ASTM D5241-92(2017)
(Practice)Standard Practice for Micro-Extraction of Water for Analysis of Volatile and Semi-Volatile Organic Compounds in Water
Standard Practice for Micro-Extraction of Water for Analysis of Volatile and Semi-Volatile Organic Compounds in Water
SIGNIFICANCE AND USE
4.1 This practice provides a general procedure for the solvent extraction of volatile and semi-volatile organic compounds from a water matrix. Solvent extraction is used as the initial step in the solvent extraction of organic constituents for the purpose of quantifying extractable organic compounds.
4.2 Typical detection limits that can be achieved using micro-extraction techniques with gas chromatography (GC) with flame ionization detector (FID), electron capture detector (ECD), or with a mass spectrometer (GC/MS) range from milligrams per litre (mg/L) to nanograms per litre (ng/L). The detection limit, linear concentration range, and sensitivity of the test method for a specific organic compound will depend upon the sample clean-up, injection volume, solvent to sample ratio, solvent concentration methods used, and the determinative technique employed.
4.3 Micro-extraction has the advantage of speed, simple extraction devices, and the use of small amounts of sample and solvents.
4.3.1 Selectivity can be improved by the choice of solvent (usually hexane or pentane) or mixed solvents, extraction time and temperature, and ionic strength of the solution.
4.3.2 Extraction devices can vary from the sample container itself to commercial devices specifically designed for micro-extraction. See 7.1 and 7.2.
4.3.3 A list of chlorinated organic compounds that can be determined by this practice includes both high and low boiling compounds or chemicals (see Table 1). (A) Based on the injection of chlorinated compounds in pentane solution, taking into consideration the 100:1 concentration of a water sample by the microextraction technique.
SCOPE
1.1 This practice covers standard procedures for extraction of volatile and semi-volatile organic compounds from water using small volumes of solvents.
1.2 The compounds of interest must have a greater solubility in the organic solvent than the water phase.
1.3 Not all of the solvents that can be used in micro extraction are addressed in this practice. The applicability of a solvent to extract the compound(s) of interest must be demonstrated before use.
1.4 This practice provides sample extracts suitable for any technique amenable to solvent injection such as gas chromatography or high performance liquid chromatography (HPLC).
1.5 The values stated in SI units are to be regarded as standard. No other units of measurement are included in this standard.
1.6 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
1.7 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.
General Information
Relations
Buy Standard
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: D5241 − 92 (Reapproved 2017)
Standard Practice for
Micro-Extraction of Water for Analysis of Volatile and Semi-
Volatile Organic Compounds in Water
This standard is issued under the fixed designation D5241; 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 D1193 Specification for Reagent Water
D3370 Practices for Sampling Water from Closed Conduits
1.1 This practice covers standard procedures for extraction
D3694 Practices for Preparation of Sample Containers and
of volatile and semi-volatile organic compounds from water
for Preservation of Organic Constituents
using small volumes of solvents.
D3856 Guide for Management Systems in Laboratories
1.2 The compounds of interest must have a greater solubil-
Engaged in Analysis of Water
ity in the organic solvent than the water phase.
D3973 TestMethodforLow-MolecularWeightHalogenated
Hydrocarbons in Water
1.3 Not all of the solvents that can be used in micro
extraction are addressed in this practice. The applicability of a D4210 Practice for Intralaboratory Quality Control Proce-
dures and a Discussion on Reporting Low-Level Data
solvent to extract the compound(s) of interest must be demon-
strated before use. (Withdrawn 2002)
D4448 Guide for Sampling Ground-Water MonitoringWells
1.4 This practice provides sample extracts suitable for any
D5175 Test Method for Organohalide Pesticides and Poly-
technique amenable to solvent injection such as gas chroma-
chlorinated Biphenyls in Water by Microextraction and
tography or high performance liquid chromatography (HPLC).
Gas Chromatography
1.5 The values stated in SI units are to be regarded as
3. Summary of Practice
standard. No other units of measurement are included in this
standard.
3.1 This practice employs liquid/liquid extraction to isolate
1.6 This standard does not purport to address all of the compounds of interest. The sample is added to an extraction
safety concerns, if any, associated with its use. It is the
device.Thesolventmaybeaddedtothesamplecontaineroran
responsibility of the user of this standard to establish appro- extraction device and extracted for a period of 5 min. The
priate safety, health, and environmental practices and deter- solvent is then ready for analysis. If required, the pH may be
mine the applicability of regulatory limitations prior to use.
adjusted and salt may be added prior to extraction to increase
For specific hazard statements, see Section 9 the extraction specificity and efficiency.
1.7 This international standard was developed in accor-
3.2 The solvent extract may be further processed using
dance with internationally recognized principles on standard-
sample clean-up and concentration techniques. The analytes in
ization established in the Decision on Principles for the
the solvent may be analyzed using instrumental methods for
Development of International Standards, Guides and Recom-
specific volatile or semivolatile organic compounds. This
mendations issued by the World Trade Organization Technical
practice does not include sample extract clean-up methods.
Barriers to Trade (TBT) Committee.
4. Significance and Use
2. Referenced Documents
4.1 This practice provides a general procedure for the
2.1 ASTM Standards:
solvent extraction of volatile and semi-volatile organic com-
D1129 Terminology Relating to Water
pounds from a water matrix. Solvent extraction is used as the
initial step in the solvent extraction of organic constituents for
This practice is under the jurisdiction ofASTM Committee D19 on Water and
the purpose of quantifying extractable organic compounds.
is the direct responsibility of Subcommittee D19.06 on Methods for Analysis for
Organic Substances in Water.
4.2 Typical detection limits that can be achieved using
Current edition approved Dec. 15, 2017. Published January 2018. Originally
micro-extraction techniques with gas chromatography (GC)
approved in 1992. Last previous edition approved in 2011 as D5241 – 92 (2011).
DOI: 10.1520/D5241-92R17. with flame ionization detector (FID), electron capture detector
For referenced ASTM standards, visit the ASTM website, www.astm.org, or
contact ASTM Customer Service at service@astm.org. 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.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States
D5241 − 92 (2017)
(ECD), or with a mass spectrometer (GC/MS) range from 5.1.2 Plastics other than PTFE-fluorocarbon should be
milligrams per litre (mg/L) to nanograms per litre (ng/L). The avoided. They are a significant source of interference and can
detection limit, linear concentration range, and sensitivity of adsorb some organics.
the test method for a specific organic compound will depend 5.1.3 Afield blank prepared from water and carried through
upon the sample clean-up, injection volume, solvent to sample sampling, subsequent storage, and handling can serve as a
ratio, solvent concentration methods used, and the determina- check on sources of interferences from the containers.
tive technique employed.
5.2 When performing analyses for specific organic
4.3 Micro-extraction has the advantage of speed, simple compounds, matrix interferences may be caused by materials
extraction devices, and the use of small amounts of sample and and constituents that are coextracted from the sample. The
solvents. extent of such matrix interferences will vary considerably
4.3.1 Selectivity can be improved by the choice of solvent depending on the sample and the specific instrumental analysis
(usually hexane or pentane) or mixed solvents, extraction time method used. Matrix interferences may be reduced by the
and temperature, and ionic strength of the solution. choice of extracting solvent, or by using a clean-up technique
on the extract.
4.3.2 Extraction devices can vary from the sample container
itself to commercial devices specifically designed for micro-
extraction. See 7.1 and 7.2. 6. Selection of the Extraction Solvent
4.3.3 A list of chlorinated organic compounds that can be
6.1 The selection of solvent for extraction will depend upon
determined by this practice includes both high and low boiling
many factors, including the following:
compounds or chemicals (see Table 1).
6.1.1 Solvent compatibility with analytical instrumentation,
6.1.2 Solubility of the organic constituent in the solvent
5. Interferences
versus its solubility in water. The water/solvent ratio has been
5.1 Solvents,reagents,glassware,andothersampleprocess- found to be critical to achieve optimum recovery of some
ing hardware may yield discrete artifacts or elevated baselines analytes (see Test Method D3973). Typical solvent to sample
that can cause poor precision and accuracy. See Terminology ratios are 1 to 10 or 20. The ratio should be optimized for
D1129. maximum recovery or detection of an analyte, or both,
5.1.1 Glassware should be washed with detergent, rinsed
6.1.3 The availability and purity of the solvent,
with water, followed by a rinse with distilled in glass acetone. 6.1.4 The boiling point and viscosity of the solvent,
Final drying is done by air or 103°C oven.Additional cleaning
6.1.5 The tendency of the solvent and matrix to form
steps may be required when the analysis requires levels of emulsions, and
micrograms per litre or below. Once the glassware has been
6.1.6 Solubility of the solvent in the water.
cleaned, it should be used immediately or stored wrapped in
6.2 The analyst should analyze sample blank using the
aluminum foil (shiny side out) or by stretching a sheet of
potential solvent and demonstrate a recovery using a spiking
PTFE-fluorocarbon over the top for storage.
procedure in the matrix of interest before applying this
procedure for sample analysis.
7. Apparatus
TABLE 1 Results of Flame Ionization Detector (FID) and Electron
A
Capture Detector (ECD) Detectability
7.1 Volumetric Flasks, 110 mL.
NOTE 1—Lowest levels tested.
7.2 Liquid/Liquid Extractor.
FID (µg/L) ECD (ng/L)
7.3 Vials, auto sampler with septa and caps. Vials should be
Trichloroethene 2 5
compatiblewiththeautomaticsampleinjectorandshouldhave
Tetrachloroethene 2 5
Monochlorobenzene 1 500
an internal volume of not greater than 2 mL.
para-Chlorobenzotrifluoride 1 5
ortho-Chlorobenzotrifluoride 1 5 7.4 Vial, crimper.
ortho-Chlorotoluene 1 100
7.5 Bottles, glass narrow mouth with TFE fluorocarbon-
meta-Chlorotoluene 1 100
para-Chlorotoluene 1 100
lined septum screw caps.
1,2,4-Trichlorobenzene 1 5
1,2,3-Trichlorobenzene 1 5 7.6 Shaker, wrist.
Hexachlorobutadiene 1 5
1,2,4,5-Tetrachlorobenzene 1 5
8. Reagents
Hexachlorocyclopentadiene 2 5
2,4,5-Trichlorophenol 2 100
8.1 Purity of Water—Unless otherwise indicated, reference
1,2,3,4-Tetrachlorobenzene 1 5
towatershallbeunderstoodtomeanreagentwaterconforming
alpha-Hexachlorocyclohexane 1 5
beta-Hexachlorocyclohexane 1 5
to Type II of Specification D1193.
Hexachlorobenzene 1 5
gamma-Hexachlorocyclohexane 1 5
delta-Hexachlorocyclohexane 1 5
A
Cassia, available from Baxter, 1430Waukegan Rd., McGaw Park, IL60085, or
Based on the injection of chlorinated compounds in pentane solution, taking into
equivalent, has been found suitable for this purpose.
consideration the 100:1 concentration of a water sample by the microextraction
Available from J & W Scientific, 91 Blue Ravine Rd., Folsom, CA 95630, or
technique.
equivalent, has been found suitable for this purpose.
D5241 − 92 (2017)
8.2 Chromatographic grade solvents that have been distilled 10.3 Sample Storage:
in glass should be used in all tests. Other grades may be used, 10.3.1 All samples must be iced or refrigerated to 4°C from
if it is first ascertained that the solvent is of sufficiently high the time of collection until ready for extraction.
purity to permit its use without lessening the accuracy of the 10.3.2 Samples should be stored in a clean dry place away
determination. from samples containing high concentrations of organics.
8.3 The extraction solvent of choice should be appropriate 10.4 Sample Preservation:
for the matrix and compounds of interest. This choice is 10.4.1 Some compounds are susceptible to rapid biological
dependent upon the chemical properties of the organic con- degradation under certain environmental conditions. If biologi-
stituents of interest and the matrix being extracted. cal activity is expected, adjust the pH of the sample to about 2
by adding HCl. The constituent of concern must be stable
8.4 The spiking, standard materials and surrogates should
underacidconditions.Foradditionalinformation,seePractices
be reagent orACS grade or better. When they are not available
D3694.
as reagent grade, they should have an assay of 90 % or better.
10.4.2 If residual chlorine is present, add sodium thiosulfate
8.5 Hydrochloric Acid (HCl) or Sulfuric Acid Solution—
as a preservative (30 mg/4 oz bottle).
(H SO ) (1:1 v:v), prepared by slowly adding 50 mLof acid to
2 4
NOTE 2—Any reagents added to the sample at the time of collection or
50 mL of water.
before analysis must be added to the laboratory blank and standard. See
8.6 Sodium Hydroxide Solution (NaOH), prepared by dis-
11.3.
solving 40 g NaOH in water and diluting to 100 mL.
11. Quality Control
8.7 Sodium Sulfate (Na SO ), reagent grade, granular,
2 4
anhydrous, prepared by heating to 300°C under a flow of 11.1 Minimum quality control requirements are an initial
nitrogen. demonstration of laboratory capability, analysis of method
blanks, a laboratory fortified blank, a laboratory fortified
NOTE 1—Nitrogen is only required when trace work using ECD is
sample matrix and, if available, quality control samples. For a
required.
general discussion of good laboratory practices, see Guide
8.8 Magnesium Sulfate (MgSO ), reagent grade, granular,
D3856 and Practice D4210.
anhydrous, prepared by heating at 400°C for a minimum of 4
11.2 Selectarepresentativespikeconcentration(aboutthree
h in a shallow tray to eliminate interfering organics.
times the estimated detection limit or expected concentration)
8.9 Sodium Chloride (NaCl), reagent grade, granular.
for each analyte. Extract according to Section 12 and analyze.
8.10 Sodium Thiosulfate—(Na S O ), reagent grade, granu-
2 2 3
11.3 Method blanks must be prepared using reagent grade
lar.
water and contain all the reagents used in sample preservation
and preparation. The blanks must be carried through the entire
9. Hazards
analytical procedure with the samples. Each time a group of
9.1 The toxicity and carcinogenicity of chemicals used or
samples are run that contain different reagents or reagent
that could be used in this practice have not been precisely
concentrations, a new method blank must be run.
defined. Each chemical should be treated as a potential health
11.4 All calibration and quality control standards must be
hazard. Exposure to these chemicals should be minimized.
extracted using the same reagents, procedures, and conditions
Each laboratory is responsible for maintaining awareness of
as the samples.
OSHA regulations regarding safe handling of chemicals used
in this practice.
11.5 Precision and bias must be established for each matrix
and laboratory analytical method.
9.2 If using ether solvents, the hazard of peroxides forma-
11.5.1 Precision should be determined by splitting spiked
tion should be considered by testing for the presence of
samples or analytes in the batch into two equal portions. The
peroxide prior to use.
replicate samples should then be extracted and analyzed.
10. Sample Handling
11.5.2 Bias should be determined in the laboratory by
spiking the samples with the analytes of interest at a concen-
10.1 There are many procedures for acquiring representa-
tration three times the concentration found in the samples or
tive samples of water. The procedure chosen will be site and
less.
analysis specific. There are several guides and practices for
sampling listed in the ASTM subject index under Sampling-
NOTE 3—The bias may be decreased by keeping the temperature,
Water Applications. Two good sources are Practices D3370 shaking speed and time, ionic strength, and solvent and sample volumes
constant.
and Guide D4448.
10.2 The recommended sample size is 40 to 1
...
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: D5241 − 92 (Reapproved 2017)
Standard Practice for
Micro-Extraction of Water for Analysis of Volatile and Semi-
Volatile Organic Compounds in Water
This standard is issued under the fixed designation D5241; 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 D1193 Specification for Reagent Water
D3370 Practices for Sampling Water from Closed Conduits
1.1 This practice covers standard procedures for extraction
D3694 Practices for Preparation of Sample Containers and
of volatile and semi-volatile organic compounds from water
for Preservation of Organic Constituents
using small volumes of solvents.
D3856 Guide for Management Systems in Laboratories
1.2 The compounds of interest must have a greater solubil-
Engaged in Analysis of Water
ity in the organic solvent than the water phase.
D3973 Test Method for Low-Molecular Weight Halogenated
1.3 Not all of the solvents that can be used in micro Hydrocarbons in Water
D4210 Practice for Intralaboratory Quality Control Proce-
extraction are addressed in this practice. The applicability of a
solvent to extract the compound(s) of interest must be demon- dures and a Discussion on Reporting Low-Level Data
(Withdrawn 2002)
strated before use.
D4448 Guide for Sampling Ground-Water Monitoring Wells
1.4 This practice provides sample extracts suitable for any
D5175 Test Method for Organohalide Pesticides and Poly-
technique amenable to solvent injection such as gas chroma-
chlorinated Biphenyls in Water by Microextraction and
tography or high performance liquid chromatography (HPLC).
Gas Chromatography
1.5 The values stated in SI units are to be regarded as
standard. No other units of measurement are included in this 3. Summary of Practice
standard.
3.1 This practice employs liquid/liquid extraction to isolate
1.6 This standard does not purport to address all of the
compounds of interest. The sample is added to an extraction
safety concerns, if any, associated with its use. It is the device. The solvent may be added to the sample container or an
responsibility of the user of this standard to establish appro- extraction device and extracted for a period of 5 min. The
priate safety, health, and environmental practices and deter-
solvent is then ready for analysis. If required, the pH may be
mine the applicability of regulatory limitations prior to use. adjusted and salt may be added prior to extraction to increase
For specific hazard statements, see Section 9
the extraction specificity and efficiency.
1.7 This international standard was developed in accor-
3.2 The solvent extract may be further processed using
dance with internationally recognized principles on standard-
sample clean-up and concentration techniques. The analytes in
ization established in the Decision on Principles for the
the solvent may be analyzed using instrumental methods for
Development of International Standards, Guides and Recom-
specific volatile or semivolatile organic compounds. This
mendations issued by the World Trade Organization Technical
practice does not include sample extract clean-up methods.
Barriers to Trade (TBT) Committee.
4. Significance and Use
2. Referenced Documents
4.1 This practice provides a general procedure for the
2.1 ASTM Standards:
solvent extraction of volatile and semi-volatile organic com-
D1129 Terminology Relating to Water
pounds from a water matrix. Solvent extraction is used as the
initial step in the solvent extraction of organic constituents for
This practice is under the jurisdiction of ASTM Committee D19 on Water and
the purpose of quantifying extractable organic compounds.
is the direct responsibility of Subcommittee D19.06 on Methods for Analysis for
Organic Substances in Water.
4.2 Typical detection limits that can be achieved using
Current edition approved Dec. 15, 2017. Published January 2018. Originally
micro-extraction techniques with gas chromatography (GC)
approved in 1992. Last previous edition approved in 2011 as D5241 – 92 (2011).
DOI: 10.1520/D5241-92R17. with flame ionization detector (FID), electron capture detector
For referenced ASTM standards, visit the ASTM website, www.astm.org, or
contact ASTM Customer Service at service@astm.org. 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.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States
D5241 − 92 (2017)
(ECD), or with a mass spectrometer (GC/MS) range from 5.1.2 Plastics other than PTFE-fluorocarbon should be
milligrams per litre (mg/L) to nanograms per litre (ng/L). The avoided. They are a significant source of interference and can
detection limit, linear concentration range, and sensitivity of adsorb some organics.
the test method for a specific organic compound will depend 5.1.3 A field blank prepared from water and carried through
upon the sample clean-up, injection volume, solvent to sample sampling, subsequent storage, and handling can serve as a
ratio, solvent concentration methods used, and the determina- check on sources of interferences from the containers.
tive technique employed.
5.2 When performing analyses for specific organic
4.3 Micro-extraction has the advantage of speed, simple compounds, matrix interferences may be caused by materials
extraction devices, and the use of small amounts of sample and and constituents that are coextracted from the sample. The
solvents. extent of such matrix interferences will vary considerably
4.3.1 Selectivity can be improved by the choice of solvent depending on the sample and the specific instrumental analysis
(usually hexane or pentane) or mixed solvents, extraction time method used. Matrix interferences may be reduced by the
and temperature, and ionic strength of the solution. choice of extracting solvent, or by using a clean-up technique
4.3.2 Extraction devices can vary from the sample container on the extract.
itself to commercial devices specifically designed for micro-
6. Selection of the Extraction Solvent
extraction. See 7.1 and 7.2.
4.3.3 A list of chlorinated organic compounds that can be
6.1 The selection of solvent for extraction will depend upon
determined by this practice includes both high and low boiling
many factors, including the following:
compounds or chemicals (see Table 1).
6.1.1 Solvent compatibility with analytical instrumentation,
6.1.2 Solubility of the organic constituent in the solvent
5. Interferences
versus its solubility in water. The water/solvent ratio has been
5.1 Solvents, reagents, glassware, and other sample process- found to be critical to achieve optimum recovery of some
ing hardware may yield discrete artifacts or elevated baselines analytes (see Test Method D3973). Typical solvent to sample
that can cause poor precision and accuracy. See Terminology ratios are 1 to 10 or 20. The ratio should be optimized for
D1129.
maximum recovery or detection of an analyte, or both,
5.1.1 Glassware should be washed with detergent, rinsed 6.1.3 The availability and purity of the solvent,
with water, followed by a rinse with distilled in glass acetone.
6.1.4 The boiling point and viscosity of the solvent,
Final drying is done by air or 103°C oven. Additional cleaning 6.1.5 The tendency of the solvent and matrix to form
steps may be required when the analysis requires levels of
emulsions, and
micrograms per litre or below. Once the glassware has been 6.1.6 Solubility of the solvent in the water.
cleaned, it should be used immediately or stored wrapped in
6.2 The analyst should analyze sample blank using the
aluminum foil (shiny side out) or by stretching a sheet of
potential solvent and demonstrate a recovery using a spiking
PTFE-fluorocarbon over the top for storage.
procedure in the matrix of interest before applying this
procedure for sample analysis.
7. Apparatus
TABLE 1 Results of Flame Ionization Detector (FID) and Electron
A
Capture Detector (ECD) Detectability 4
7.1 Volumetric Flasks, 110 mL.
NOTE 1—Lowest levels tested. 5
7.2 Liquid/Liquid Extractor.
FID (µg/L) ECD (ng/L)
7.3 Vials, auto sampler with septa and caps. Vials should be
Trichloroethene 2 5
compatible with the automatic sample injector and should have
Tetrachloroethene 2 5
Monochlorobenzene 1 500
an internal volume of not greater than 2 mL.
para-Chlorobenzotrifluoride 1 5
ortho-Chlorobenzotrifluoride 1 5 7.4 Vial, crimper.
ortho-Chlorotoluene 1 100
7.5 Bottles, glass narrow mouth with TFE fluorocarbon-
meta-Chlorotoluene 1 100
para-Chlorotoluene 1 100
lined septum screw caps.
1,2,4-Trichlorobenzene 1 5
1,2,3-Trichlorobenzene 1 5 7.6 Shaker, wrist.
Hexachlorobutadiene 1 5
1,2,4,5-Tetrachlorobenzene 1 5
8. Reagents
Hexachlorocyclopentadiene 2 5
2,4,5-Trichlorophenol 2 100
8.1 Purity of Water—Unless otherwise indicated, reference
1,2,3,4-Tetrachlorobenzene 1 5
to water shall be understood to mean reagent water conforming
alpha-Hexachlorocyclohexane 1 5
beta-Hexachlorocyclohexane 1 5 to Type II of Specification D1193.
Hexachlorobenzene 1 5
gamma-Hexachlorocyclohexane 1 5
delta-Hexachlorocyclohexane 1 5
A
Cassia, available from Baxter, 1430 Waukegan Rd., McGaw Park, IL 60085, or
Based on the injection of chlorinated compounds in pentane solution, taking into
equivalent, has been found suitable for this purpose.
consideration the 100:1 concentration of a water sample by the microextraction
technique. Available from J & W Scientific, 91 Blue Ravine Rd., Folsom, CA 95630, or
equivalent, has been found suitable for this purpose.
D5241 − 92 (2017)
8.2 Chromatographic grade solvents that have been distilled 10.3 Sample Storage:
in glass should be used in all tests. Other grades may be used, 10.3.1 All samples must be iced or refrigerated to 4°C from
if it is first ascertained that the solvent is of sufficiently high the time of collection until ready for extraction.
purity to permit its use without lessening the accuracy of the 10.3.2 Samples should be stored in a clean dry place away
determination. from samples containing high concentrations of organics.
8.3 The extraction solvent of choice should be appropriate 10.4 Sample Preservation:
for the matrix and compounds of interest. This choice is 10.4.1 Some compounds are susceptible to rapid biological
dependent upon the chemical properties of the organic con- degradation under certain environmental conditions. If biologi-
stituents of interest and the matrix being extracted. cal activity is expected, adjust the pH of the sample to about 2
by adding HCl. The constituent of concern must be stable
8.4 The spiking, standard materials and surrogates should
under acid conditions. For additional information, see Practices
be reagent or ACS grade or better. When they are not available
D3694.
as reagent grade, they should have an assay of 90 % or better.
10.4.2 If residual chlorine is present, add sodium thiosulfate
8.5 Hydrochloric Acid (HCl) or Sulfuric Acid Solution—
as a preservative (30 mg/4 oz bottle).
(H SO ) (1:1 v:v), prepared by slowly adding 50 mL of acid to
2 4
NOTE 2—Any reagents added to the sample at the time of collection or
50 mL of water.
before analysis must be added to the laboratory blank and standard. See
8.6 Sodium Hydroxide Solution (NaOH), prepared by dis- 11.3.
solving 40 g NaOH in water and diluting to 100 mL.
11. Quality Control
8.7 Sodium Sulfate (Na SO ), reagent grade, granular,
2 4
anhydrous, prepared by heating to 300°C under a flow of 11.1 Minimum quality control requirements are an initial
nitrogen. demonstration of laboratory capability, analysis of method
blanks, a laboratory fortified blank, a laboratory fortified
NOTE 1—Nitrogen is only required when trace work using ECD is
sample matrix and, if available, quality control samples. For a
required.
general discussion of good laboratory practices, see Guide
8.8 Magnesium Sulfate (MgSO ), reagent grade, granular,
D3856 and Practice D4210.
anhydrous, prepared by heating at 400°C for a minimum of 4
11.2 Select a representative spike concentration (about three
h in a shallow tray to eliminate interfering organics.
times the estimated detection limit or expected concentration)
8.9 Sodium Chloride (NaCl), reagent grade, granular.
for each analyte. Extract according to Section 12 and analyze.
8.10 Sodium Thiosulfate—(Na S O ), reagent grade, granu-
2 2 3
11.3 Method blanks must be prepared using reagent grade
lar.
water and contain all the reagents used in sample preservation
and preparation. The blanks must be carried through the entire
9. Hazards
analytical procedure with the samples. Each time a group of
9.1 The toxicity and carcinogenicity of chemicals used or
samples are run that contain different reagents or reagent
that could be used in this practice have not been precisely
concentrations, a new method blank must be run.
defined. Each chemical should be treated as a potential health
11.4 All calibration and quality control standards must be
hazard. Exposure to these chemicals should be minimized.
extracted using the same reagents, procedures, and conditions
Each laboratory is responsible for maintaining awareness of
as the samples.
OSHA regulations regarding safe handling of chemicals used
in this practice.
11.5 Precision and bias must be established for each matrix
and laboratory analytical method.
9.2 If using ether solvents, the hazard of peroxides forma-
11.5.1 Precision should be determined by splitting spiked
tion should be considered by testing for the presence of
samples or analytes in the batch into two equal portions. The
peroxide prior to use.
replicate samples should then be extracted and analyzed.
10. Sample Handling
11.5.2 Bias should be determined in the laboratory by
spiking the samples with the analytes of interest at a concen-
10.1 There are many procedures for acquiring representa-
tration three times the concentration found in the samples or
tive samples of water. The procedure chosen will be site and
less.
analysis specific. There are several guides and practices for
sampling listed in the ASTM subject index under Sampling-
NOTE 3—The bias may be decreased by keeping the temperature,
shaking speed and time, ionic strength, and solvent and sample volumes
Water Applications. Two good sources are Practices D3370
constant.
and Guide D4448.
10.2 The recommended sample size is 40 to 100 mL. More
12. Procedure
or less sample can be used depending upon th
...
This document is not an ASTM standard and is intended only to provide the user of an ASTM standard an indication of what changes have been made to the previous version. Because
it may not be technically possible to adequately depict all changes accurately, ASTM recommends that users consult prior editions as appropriate. In all cases only the current version
of the standard as published by ASTM is to be considered the official document.
Designation: D5241 − 92 (Reapproved 2011) D5241 − 92 (Reapproved 2017)
Standard Practice for
Micro-Extraction of Water for Analysis of Volatile and Semi-
Volatile Organic Compounds in Water
This standard is issued under the fixed designation D5241; 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
1.1 This practice covers standard procedures for extraction of volatile and semi-volatile organic compounds from water using
small volumes of solvents.
1.2 The compounds of interest must have a greater solubility in the organic solvent than the water phase.
1.3 Not all of the solvents that can be used in micro extraction are addressed in this practice. The applicability of a solvent to
extract the compound(s) of interest must be demonstrated before use.
1.4 This practice provides sample extracts suitable for any technique amenable to solvent injection such as gas chromatography
or high performance liquid chromatography (HPLC).
1.5 The values stated in SI units are to be regarded as the standard. No other units of measurement are included in this standard.
1.6 The values stated in SI units are to be regarded as standard. No other units of measurement are included in this standard.
1.6 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 safety, health, and healthenvironmental practices and determine the
applicability of regulatory limitations prior to use. For specific hazard statements, see Section 9.
1.7 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.
2. Referenced Documents
2.1 ASTM Standards:
D1129 Terminology Relating to Water
D1193 Specification for Reagent Water
D3370 Practices for Sampling Water from Closed Conduits
D3694 Practices for Preparation of Sample Containers and for Preservation of Organic Constituents
D3856 Guide for Management Systems in Laboratories Engaged in Analysis of Water
D3973 Test Method for Low-Molecular Weight Halogenated Hydrocarbons in Water
D4210 Practice for Intralaboratory Quality Control Procedures and a Discussion on Reporting Low-Level Data (Withdrawn
2002)
D4448 Guide for Sampling Ground-Water Monitoring Wells
D5175 Test Method for Organohalide Pesticides and Polychlorinated Biphenyls in Water by Microextraction and Gas
Chromatography
3. Summary of Practice
3.1 This practice employs liquid/liquid extraction to isolate compounds of interest. The sample is added to an extraction device.
The solvent may be added to the sample container or an extraction device and extracted for a period of 5 min. The solvent is then
ready for analysis. If required, the pH may be adjusted and salt may be added prior to extraction to increase the extraction
specificity and efficiency.
This practice is under the jurisdiction of ASTM Committee D19 on Water and is the direct responsibility of Subcommittee D19.06 on Methods for Analysis for Organic
Substances in Water.
Current edition approved May 1, 2011Dec. 15, 2017. Published June 2011January 2018. Originally approved in 1992. Last previous edition approved in 20042011 as
D5241 – 92 (2011). (2004). DOI: 10.1520/D5241-92R11.10.1520/D5241-92R17.
For referenced ASTM standards, visit the ASTM website, www.astm.org, or contact ASTM Customer Service at service@astm.org. For Annual Book of ASTM Standards
volume information, refer to the standard’s Document Summary page on the ASTM website.
The last approved version of this historical standard is referenced on www.astm.org.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States
D5241 − 92 (2017)
3.2 The solvent extract may be further processed using sample clean-up and concentration techniques. The analytes in the
solvent may be analyzed using instrumental methods for specific volatile or semivolatile organic compounds. This practice does
not include sample extract clean-up methods.
4. Significance and Use
4.1 This practice provides a general procedure for the solvent extraction of volatile and semi-volatile organic compounds from
a water matrix. Solvent extraction is used as the initial step in the solvent extraction of organic constituents for the purpose of
quantifying extractable organic compounds.
4.2 Typical detection limits that can be achieved using micro-extraction techniques with gas chromatography (GC) with flame
ionization detector (FID), electron capture detector (ECD), or with a mass spectrometer (GC/MS) range from milligrams per litre
(mg/L) to nanograms per litre (ng/L). The detection limit, linear concentration range, and sensitivity of the test method for a
specific organic compound will depend upon the sample clean-up, injection volume, solvent to sample ratio, solvent concentration
methods used, and the determinative technique employed.
4.3 Micro-extraction has the advantage of speed, simple extraction devices, and the use of small amounts of sample and
solvents.
4.3.1 Selectivity can be improved by the choice of solvent (usually hexane or pentane) or mixed solvents, extraction time and
temperature, and ionic strength of the solution.
4.3.2 Extraction devices can vary from the sample container itself to commercial devices specifically designed for
micro-extraction. See 7.1 and 7.2.
4.3.3 A list of chlorinated organic compounds that can be determined by this practice includes both high and low boiling
compounds or chemicals (see Table 1).
5. Interferences
5.1 Solvents, reagents, glassware, and other sample processing hardware may yield discrete artifacts or elevated baselines that
can cause poor precision and accuracy. See Terminology D1129.
5.1.1 Glassware should be washed with detergent, rinsed with water, followed by a rinse with distilled in glass acetone. Final
drying is done by air or 103°C oven. Additional cleaning steps may be required when the analysis requires levels of micrograms
per litre or below. Once the glassware has been cleaned, it should be used immediately or stored wrapped in aluminum foil (shiny
side out) or by stretching a sheet of PTFE-fluorocarbon over the top for storage.
5.1.2 Plastics other than PTFE-fluorocarbon should be avoided. They are a significant source of interference and can adsorb
some organics.
5.1.3 A field blank prepared from water and carried through sampling, subsequent storage, and handling can serve as a check
on sources of interferences from the containers.
TABLE 1 Results of Flame Ionization Detector (FID) and Electron
A
Capture Detector (ECD) Detectability
NOTE 1—Lowest levels tested.
FID (μg/L) ECD (ng/L)
Trichloroethene 2 5
Tetrachloroethene 2 5
Monochlorobenzene 1 500
para-Chlorobenzotrifluoride 1 5
ortho-Chlorobenzotrifluoride 1 5
ortho-Chlorotoluene 1 100
meta-Chlorotoluene 1 100
para-Chlorotoluene 1 100
1,2,4-Trichlorobenzene 1 5
1,2,3-Trichlorobenzene 1 5
Hexachlorobutadiene 1 5
1,2,4,5-Tetrachlorobenzene 1 5
Hexachlorocyclopentadiene 2 5
2,4,5-Trichlorophenol 2 100
1,2,3,4-Tetrachlorobenzene 1 5
alpha-Hexachlorocyclohexane 1 5
beta-Hexachlorocyclohexane 1 5
Hexachlorobenzene 1 5
gamma-Hexachlorocyclohexane 1 5
delta-Hexachlorocyclohexane 1 5
A
Based on the injection of chlorinated compounds in pentane solution, taking into
consideration the 100:1 concentration of a water sample by the microextraction
technique.
D5241 − 92 (2017)
5.2 When performing analyses for specific organic compounds, matrix interferences may be caused by materials and
constituents that are coextracted from the sample. The extent of such matrix interferences will vary considerably depending on the
sample and the specific instrumental analysis method used. Matrix interferences may be reduced by the choice of extracting
solvent, or by using a clean-up technique on the extract.
6. Selection of the Extraction Solvent
6.1 The selection of solvent for extraction will depend upon many factors, including the following:
6.1.1 Solvent compatibility with analytical instrumentation,
6.1.2 Solubility of the organic constituent in the solvent versus its solubility in water. The water/solvent ratio has been found
to be critical to achieve optimum recovery of some analytes (see Test Method D3973). Typical solvent to sample ratios are 1 to
10 or 20. The ratio should be optimized for maximum recovery or detection of an analyte, or both,
6.1.3 The availability and purity of the solvent,
6.1.4 The boiling point and viscosity of the solvent,
6.1.5 The tendency of the solvent and matrix to form emulsions, and
6.1.6 Solubility of the solvent in the water.
6.2 The analyst should analyze sample blank using the potential solvent and demonstrate a recovery using a spiking procedure
in the matrix of interest before applying this procedure for sample analysis.
7. Apparatus
7.1 Volumetric Flasks, 110 mL.
7.2 Liquid/Liquid Extractor.
7.3 Vials, auto sampler with septa and caps. Vials should be compatible with the automatic sample injector and should have an
internal volume of not greater than 2 mL.
7.4 Vial, crimper.
7.5 Bottles, glass narrow mouth with TFE fluorocarbon-lined septum screw caps.
7.6 Shaker, wrist.
8. Reagents
8.1 Purity of Water—Unless otherwise indicated, reference to water shall be understood to mean reagent water conforming to
Type II of Specification D1193.
8.2 Chromatographic grade solvents that have been distilled in glass should be used in all tests. Other grades may be used, if
it is first ascertained that the solvent is of sufficiently high purity to permit its use without lessening the accuracy of the
determination.
8.3 The extraction solvent of choice should be appropriate for the matrix and compounds of interest. This choice is dependent
upon the chemical properties of the organic constituents of interest and the matrix being extracted.
8.4 The spiking, standard materials and surrogates should be reagent or ACS grade or better. When they are not available as
reagent grade, they should have an assay of 90 % or better.
8.5 Hydrochloric Acid (HCl) or Sulfuric Acid Solution—(H SO ) (1:1 v:v), prepared by slowly adding 50 mL of acid to 50 mL
2 4
of water.
8.6 Sodium Hydroxide Solution (NaOH), prepared by dissolving 40 g NaOH in water and diluting to 100 mL.
8.7 Sodium Sulfate (Na SO ), reagent grade, granular, anhydrous, prepared by heating to 300°C under a flow of nitrogen.
2 4
NOTE 1—Nitrogen is only required when trace work using ECD is required.
8.8 Magnesium Sulfate (MgSO ), reagent grade, granular, anhydrous, prepared by heating at 400°C for a minimum of 4 h in
a shallow tray to eliminate interfering organics.
8.9 Sodium Chloride (NaCl), reagent grade, granular.
8.10 Sodium Thiosulfate—(Na S O ), reagent grade, granular.
2 2 3
9. Hazards
9.1 The toxicity and carcinogenicity of chemicals used or that could be used in this practice have not been precisely defined.
Each chemical should be treated as a potential health hazard. Exposure to these chemicals should be minimized. Each laboratory
is responsible for maintaining awareness of OSHA regulations regarding safe handling of chemicals used in this practice.
Cassia, available from Baxter, 1430 Waukegan Rd., McGaw Park, IL 60085, or equivalent, has been found suitable for this purpose.
Available from J & W Scientific, 91 Blue Ravine Rd., Folsom, CA 95630, or equivalent, has been found suitable for this purpose.
D5241 − 92 (2017)
9.2 If using ether solvents, the hazard of peroxides formation should be considered by testing for the presence of peroxide prior
to use.
10. Sample Handling
10.1 There are many procedures for acquiring representative samples of water. The procedure chosen will be site and analysis
specific. There are several guides and practices for sampling listed in the ASTM subject index under Sampling-Water
Applications. Two good sources are Practices D3370 and Guide D4448.
10.2 The recommended sample size is 40 to 100 mL. More or less sample can be used depending upon the sample availability,
detection limits required, and the expected concentration level of the analyte. Forty millilitre VOA vials are commonly used as
sampling containers. Head space should be eliminated if volatiles analysis is required.
D5241 − 92 (2017)
10.3 Sample Storage:
10.3.1 All samples must be iced or refrigerated to 4°C from the time of collection until ready for extraction.
10.3.2 Samples should be stored in a clean dry place away from samples containing high concentrations of organics.
10.4 Sample Preservation:
10.4.1 Some compounds are susceptible to rapid biological degradation under certain environmental conditions. If biological
activity is expected, adjust the pH of the sample to about 2 by adding HCl. The constituent of concern must be stable under acid
conditions. For additional information, see Practices D3694.
10.4.2 If residual chlorine is present, add sodium thiosulfate as a preservative (30 mg/4 oz bottle).
NOTE 2—Any reagents added to the sample at the time of collection or before analysis must be added to the laboratory blank and standard. See 11.3.
11. Quality Control
11.1 Minimum quality control requirements are an initial demonstration of laboratory capability, analysis of method blanks, a
laboratory fortified blank, a laboratory fortified sample matrix and, if available, quality control samples. For a general discussion
of good laboratory practices, see Guide D3856 and Practice D4210.
11.2 Select a representative spike concentration (about three times the estimated detection limit or expected concentration) for
each analyte. Extract according to Section 12 and analyze.
11.3 Method blanks must be prepared using reagent grade water and contain all the reagents used in sample preservation and
preparation. The blanks must be carried through the entire analytical procedure with the samples. Each time a group of samples
are run that cont
...
Questions, Comments and Discussion
Ask us and Technical Secretary will try to provide an answer. You can facilitate discussion about the standard in here.