ASTM D6889-03(2011)

Standard Practice for Fast Screening for Volatile Organic Compounds in Water Using Solid Phase Microextraction (SPME)

SIGNIFICANCE AND USE
This practice provides a general procedure for the solid-phase microextraction (SPME) of volatile organic compounds from the headspace of an aqueous matrix. Absorbent extraction is used as the initial step in the extraction of organic constituents for the purpose of screening and subsequently estimating the concentration of the volatile organic components found in water samples. This information may then be used to determine whether a sample may be analyzed directly by purge and trap or headspace or will require dilution prior to analysis.
Typical detection limits that can be achieved using SPME techniques with gas chromatography (GC) with a flame ionization detector (FlD) range from milligrams per litre (mg/L) to micrograms per litre (μg/L). The detection limit, linear concentration range, and sensitivity of this test method for a specific organic compound will depend upon the aqueous matrix, the fiber phase, the sample temperature, sample volume, sample mixing, and the determinative technique employed.
Solid phase microextraction has the advantage of speed, reproducibility, simplicity, no solvent, small sample size, and automation.
Extraction devices vary from a manual SPME fiber holder to automated commercial devices specifically designed for SPME.
A partial list of volatile organic compounds that can be screened by this practice is shown in Table 1.
SCOPE
1.1 This practice covers a procedure for the screening of trace levels of volatile organic compounds in water samples by headspace solid phase microextraction (SPME) in combination with fast gas chromatography with flame ionization detection.
1.2 The results from this screening procedure are used to estimate analyte concentrations to prevent contamination of purge and trap or headspace analytical systems.
1.3 The compounds of interest must have a greater affinity for the SPME absorbent polymer or adsorbent than the sample matrix or headspace phase in which they reside.
1.4 Not all of the analytes which can be determined by SPME are addressed in this practice. The applicability of the absorbent polymer, adsorbent or combination to extract the compound(s) of interest must be demonstrated before use.
1.5 Where used it is the responsibility of the user to validate the application of SPME to the analytes of interest.
1.6 The values stated in SI units are to be regarded as standard. No other units of measurement are included in this standard.
1.7 This standard does not purport to address all of the safety concerns, if any, associated with its use. It is the responsibility of the user of this standard to establish appropriate safety and health practices and determine the applicability of regulatory limitations prior to use. For specific hazard statements, see Section 9.

General Information

• Status: Historical
• Publication Date: 30-Apr-2011
• 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 D6889-03 - Standard Practice for Fast Screening for Volatile Organic Compounds in Water Using Solid Phase Microextraction (SPME)
• Effective Date: 01-May-2011
• Replaced By: ASTM D6889-03(2017) - Standard Practice for Fast Screening for Volatile Organic Compounds in Water Using Solid Phase Microextraction (SPME)
• Effective Date: 15-Dec-2017
• Referred By: ASTM E3373-23 - Standard Test Method for Scour of Hydrodynamic Separators and Settling Devices
• Effective Date: 01-May-2011

Standards Content (Sample)

NOTICE: This standard has either been superseded and replaced by a new version or withdrawn.
Contact ASTM International (www.astm.org) for the latest information
Designation: D6889 − 03 (Reapproved 2011)
Standard Practice for
Fast Screening for Volatile Organic Compounds in Water
Using Solid Phase Microextraction (SPME)
This standard is issued under the fixed designation D6889; 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 D3694 Practices for Preparation of Sample Containers and
for Preservation of Organic Constituents
1.1 This practice covers a procedure for the screening of
D3856 Guide for Management Systems in Laboratories
trace levels of volatile organic compounds in water samples by
Engaged in Analysis of Water
headspace solid phase microextraction (SPME) in combination
D4210 Practice for Intralaboratory Quality Control Proce-
with fast gas chromatography with flame ionization detection.
dures and a Discussion on Reporting Low-Level Data
1.2 The results from this screening procedure are used to 3
(Withdrawn 2002)
estimate analyte concentrations to prevent contamination of
D6520 Practice for the Solid Phase Micro Extraction
purge and trap or headspace analytical systems.
(SPME) of Water and its Headspace for the Analysis of
Volatile and Semi-Volatile Organic Compounds
1.3 The compounds of interest must have a greater affinity
for the SPME absorbent polymer or adsorbent than the sample
3. Summary of Practice
matrix or headspace phase in which they reside.
3.1 This practice employs adsorbent/gas extraction to iso-
1.4 Not all of the analytes which can be determined by
late compounds of interest, see Practice D6520. An aqueous
SPME are addressed in this practice. The applicability of the
sample is added to a small (2 mL) septum sealed vial. Salt is
absorbent polymer, adsorbent or combination to extract the
used to improve analyte recovery. After the addition of a
compound(s) of interest must be demonstrated before use.
surrogate standard and a short mixing cycle, a SPME fused
1.5 Where used it is the responsibility of the user to validate
silica fiber coated with a thick polymer film is then exposed to
the application of SPME to the analytes of interest.
the aqueous headspace for a few seconds. The fiber is then
1.6 The values stated in SI units are to be regarded as desorbed in the heated injection port of a GC/FID or GC-MS
standard. No other units of measurement are included in this and the resulting analytes chromatographed on a short narrow
standard. borecapillarycolumn.Thetotalanalysistimeisapproximately
3 min.
1.7 This standard does not purport to address all of the
safety concerns, if any, associated with its use. It is the
3.2 The concentrations of the volatile organics in the water
responsibility of the user of this standard to establish appro-
sample are estimated to determine whether the sample may be
priate safety and health practices and determine the applica-
analyzed directly or first diluted prior to purge and trap or
bility of regulatory limitations prior to use. For specific hazard
headspace analysis.
statements, see Section 9.
4. Significance and Use
2. Referenced Documents
4.1 This practice provides a general procedure for the
2.1 ASTM Standards:
solid-phase microextraction (SPME) of volatile organic com-
D1129 Terminology Relating to Water
pounds from the headspace of an aqueous matrix. Absorbent
D1193 Specification for Reagent Water
extraction is used as the initial step in the extraction of organic
constituents for the purpose of screening and subsequently
estimating the concentration of the volatile organic compo-
This practice is under the jurisdiction ofASTM Committee D19 on Water and
nents found in water samples. This information may then be
is the direct responsibility of Subcommittee D19.06 on Methods for Analysis for
Organic Substances in Water.
used to determine whether a sample may be analyzed directly
Current edition approved May 1, 2011. Published June 2011. Originally
by purge and trap or headspace or will require dilution prior to
approved in 2003. Last previous edition approved in 2003 as D6889 – 03. DOI:
analysis.
10.1520/D6889-03R11.
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.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States
D6889 − 03 (2011)
4.2 Typical detection limits that can be achieved using C 5 C V K K //V 1K V 1K K V (5)
F 0 L 1 2 G 1 L 1 2 F
SPME techniques with gas chromatography (GC) with a flame
ionization detector (FlD) range from milligrams per litre 6. Interferences
(mg/L) to micrograms per litre (µg/L). The detection limit,
6.1 Reagents, glassware, septa, fiber coatings and other
linear concentration range, and sensitivity of this test method
sample processing hardware may yield discrete artifacts or
for a specific organic compound will depend upon the aqueous
elevated baselines that can cause poor precision and accuracy.
matrix, the fiber phase, the sample temperature, sample
See Terminology D1129.
volume, sample mixing, and the determinative technique
6.1.1 Plastics other than PTFE-fluorocarbon should be
employed.
avoided. They are a significant source of interference and can
4.3 Solid phase microextraction has the advantage of speed,
adsorb some organics.
reproducibility, simplicity, no solvent, small sample size, and
automation.
7. Apparatus
4.3.1 Extraction devices vary from a manual SPME fiber
7.1 SPME Holder, manual or automated sampling.
holder to automated commercial devices specifically designed
7.1.1 SPME Fiber Assembly—Polydimethylsiloxane
for SPME.
(PDMS), 30uM or equivalent fiber suitable for volatiles ad-
4.3.2 Apartiallistofvolatileorganiccompoundsthatcanbe
sorption.
screened by this practice is shown in Table 1.
7.2 Vials with Septa and Caps, for manual or automated
5. Principles of SPME
SPME. Vials for automation, 2 mL.
5.1 Solid phase microextraction is an equilibrium technique
7.3 Gas Chromatograph, with flame ionization detector.
where analytes are not completely extracted from the matrix.
7.3.1 GC Column, 10 m by 0.25 mm, 1uM film Methyl
With liquid samples, the recovery is dependent on the parti-
Silicone, or equivalent.
tioning or equilibrium of analytes among the three phases
7.3.2 GC Guard Column, 1m by 0.32 mm uncoated, or
presentinthesamplingvial:theaqueoussampleandheadspace
equivalent.
(Eq 1), the fiber coating and aqueous sample (Eq 2), and the
7.3.3 Split/splitless Injector, with 0.75 to 1.0 mm inside
fiber coating and the headspace (Eq 3):
diameter insert.
K 5 C /C (1)
1 L g
7.3.4 Optional Septum Replacement Device.
K 5 C /C (2)
2 F L 7.3.5 Optional SPME Autosampler.
K 5 C /C (3) 7.3.6 GC Compatible Workstation.
3 F G
where:
8. Reagents
C,C , and C = concentrations of the analyte in these
L G F
8.1 Purity of Water—Unless otherwise indicated, reference
phases.
towatershallbeunderstoodtomeanreagentwaterconforming
5.1.1 Distribution of the analyte among the three phases:
to Type II of Specification D1193.
C V 5 C V 1C V 1C V (4)
0 L G G L L F F
8.2 Chemicals, standard materials and surrogates should be
5.1.2 Concentration of analyte in fiber: reagent orACS grade or better. When they are not available as
reagent grade, they should have an assay of 90 % or better.
TABLE 1 Check Standard Composition for Screening VOCs
8.3 Sodium Chloride (NaCl), reagent grade, granular.
in Water
8.4 Surrogate Standard, 30 mg/L, 1,4-dichlorobenzene-d
Sample
Detection Limit,
Analyte Composition,
in methanol.
µg/L
µg/L
8.5 CheckStandard—Prepare a check standard in methanol.
TBA 100 000 10 000
Methyl-t-butyl ether 1000 150 Check standard should contain 30 mg/L 1,4-
cis-1,2-Dichloroethene 3000 300
dichlorobenzene-d plus VOCs that will be screened.Atypical
1,1,1-Trichloroethane 1000 200
check standard will provide aqueous concentrations shown in
Benzene 400 40
1,1,1-Trichloroethane 700 120 Table 1 when spiking 4 µL of check standard to 700 µL water
Toluene 200 10
sample.
Tetrachloroethene 300 50
Chlorobenzene 150 10
Ethylbenzene 100 5
9. Hazards
m-Xylene 100 5
styrene 100 5 9.1 The toxicity and carcinogenicity of chemicals used or
o-Xylene 100 5
that could be used in this practice have not been precisely
Isopropylbenzene 100 5
defined. Each chemical should be treated as a potential health
2-Chlorotoluene 100 5
1,2,4-Trimethylbenzene 100 5 hazard. Exposure to these chemicals should be minimized.
1,4-Dichlorobenzene-d4 150 5
Each laboratory is responsible for maintaining awareness of
1,2-Dichlorobenzene 100 5
OSHA regulations regarding safe handling of chemicals used
Napthalene 100 5
in this practice.
D6889 − 03 (2011)
FIG. 3 Injection Followed by Desorption of SPME Fiber in Injec-
FIG. 1 Fiber Holder
tion Port of Chromatograph
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 biologi-
cal activity is expected, adjust the pH of the sample to about 2
by adding HCI. The constituents of concern must be stable
under acid conditions. For additional information, see Practice
D3694.
10.4.2 If residual chlorine is present, add sodium thiosulfate
as a preservative (30 mg/4 oz bottle).
11. Q
...

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: D6889 − 03 (Reapproved 2011) D6889 − 03 (Reapproved 2011)
Standard Practice for
Fast Screening for Volatile Organic Compounds in Water
Using Solid Phase Microextraction (SPME)
This standard is issued under the fixed designation D6889; 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 a procedure for the screening of trace levels of volatile organic compounds in water samples by
headspace solid phase microextraction (SPME) in combination with fast gas chromatography with flame ionization detection.
1.2 The results from this screening procedure are used to estimate analyte concentrations to prevent contamination of purge and
trap or headspace analytical systems.
1.3 The compounds of interest must have a greater affinity for the SPME absorbent polymer or adsorbent than the sample matrix
or headspace phase in which they reside.
1.4 Not all of the analytes which can be determined by SPME are addressed in this practice. The applicability of the absorbent
polymer, adsorbent or combination to extract the compound(s) of interest must be demonstrated before use.
1.5 Where used it is the responsibility of the user to validate the application of SPME to the analytes of interest.
1.6 The values stated in SI units are to be regarded as standard. No other units of measurement are included in this standard.
1.7 This standard does not purport to address all of the safety concerns, if any, associated with its use. It is the responsibility
of the user of this standard to establish appropriate safety and health practices and determine the applicability of regulatory
limitations prior to use. For specific hazard statements, see Section 9.
2. Referenced Documents
2.1 ASTM Standards:
D1129 Terminology Relating to Water
D1193 Specification for Reagent Water
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
D4210 Practice for Intralaboratory Quality Control Procedures and a Discussion on Reporting Low-Level Data (Withdrawn
2002)
D6520 Practice for the Solid Phase Micro Extraction (SPME) of Water and its Headspace for the Analysis of Volatile and
Semi-Volatile Organic Compounds
3. Summary of Practice
3.1 This practice employs adsorbent/gas extraction to isolate compounds of interest, see Practice D6520. An aqueous sample
is added to a small (2 mL) septum sealed vial. Salt is used to improve analyte recovery. After the addition of a surrogate standard
and a short mixing cycle, a SPME fused silica fiber coated with a thick polymer film is then exposed to the aqueous headspace
for a few seconds. The fiber is then desorbed in the heated injection port of a GC/FID or GC-MS and the resulting analytes
chromatographed on a short narrow bore capillary column. The total analysis time is approximately 3 min.
3.2 The concentrations of the volatile organics in the water sample are estimated to determine whether the sample may be
analyzed directly or first diluted prior to purge and trap or headspace analysis.
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, 2011. Published June 2011. Originally approved in 2003. Last previous edition approved in 2003 as D6889–03. DOI:
10.1520/D6889-03R11.
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 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
D6889 − 03 (2011)
4. Significance and Use
4.1 This practice provides a general procedure for the solid-phase microextraction (SPME) of volatile organic compounds from
the headspace of an aqueous matrix. Absorbent extraction is used as the initial step in the extraction of organic constituents for
the purpose of screening and subsequently estimating the concentration of the volatile organic components found in water samples.
This information may then be used to determine whether a sample may be analyzed directly by purge and trap or headspace or
will require dilution prior to analysis.
4.2 Typical detection limits that can be achieved using SPME techniques with gas chromatography (GC) with a flame ionization
detector (FlD) range from milligrams per litre (mg/L) to micrograms per litre (μg/L). The detection limit, linear concentration
range, and sensitivity of this test method for a specific organic compound will depend upon the aqueous matrix, the fiber phase,
the sample temperature, sample volume, sample mixing, and the determinative technique employed.
4.3 Solid phase microextraction has the advantage of speed, reproducibility, simplicity, no solvent, small sample size, and
automation.
4.3.1 Extraction devices vary from a manual SPME fiber holder to automated commercial devices specifically designed for
SPME.
4.3.2 A partial list of volatile organic compounds that can be screened by this practice is shown in Table 1.
5. Principles of SPME
5.1 Solid phase microextraction is an equilibrium technique where analytes are not completely extracted from the matrix. With
liquid samples, the recovery is dependent on the partitioning or equilibrium of analytes among the three phases present in the
sampling vial: the aqueous sample and headspace (Eq 1), the fiber coating and aqueous sample (Eq 2), and the fiber coating and
the headspace (Eq 3):
K 5 C /C (1)
1 L g
K 5 C /C (2)
2 F L
K 5 C /C (3)
3 F G
where:
C , C , and C = concentrations of the analyte in these phases.
L G F
5.1.1 Distribution of the analyte among the three phases:
C V 5 C V 1C V 1C V (4)
0 L G G L L F F
C V 5 C V 1C V 1C V (4)
0 L G G L L F F
5.1.2 Concentration of analyte in fiber:
C 5 C V K K //V 1K V 1K K V (5)
F 0 L 1 2 G 1 L 1 2 F
C 5 C V K K //V 1K V 1K K V (5)
F 0 L 1 2 G 1 L 1 2 F
TABLE 1 Check Standard Composition for Screening VOCs
in Water
Sample
Detection Limit,
Analyte Composition,
μg/L
μg/L
TBA 100 000 10 000
Methyl-t-butyl ether 1000 150
cis-1,2-Dichloroethene 3000 300
1,1,1-Trichloroethane 1000 200
Benzene 400 40
1,1,1-Trichloroethane 700 120
Toluene 200 10
Tetrachloroethene 300 50
Chlorobenzene 150 10
Ethylbenzene 100 5
m-Xylene 100 5
styrene 100 5
o-Xylene 100 5
Isopropylbenzene 100 5
2-Chlorotoluene 100 5
1,2,4-Trimethylbenzene 100 5
1,4-Dichlorobenzene-d4 150 5
1,2-Dichlorobenzene 100 5
Napthalene 100 5
D6889 − 03 (2011)
6. Interferences
6.1 Reagents, glassware, septa, fiber coatings and other sample processing hardware may yield discrete artifacts or elevated
baselines that can cause poor precision and accuracy. See Terminology D1129.
6.1.1 Plastics other than PTFE-fluorocarbon should be avoided. They are a significant source of interference and can adsorb
some organics.
7. Apparatus
7.1 SPME Holder, manual or automated sampling.
7.1.1 SPME Fiber Assembly—Polydimethylsiloxane (PDMS), 30uM or equivalent fiber suitable for volatiles adsorption.
7.2 Vials with Septa and Caps, for manual or automated SPME. Vials for automation, 2 mL.
7.3 Gas Chromatograph, with flame ionization detector.
7.3.1 GC Column, 10 m by 0.25 mm, 1uM film Methyl Silicone, or equivalent.
7.3.2 GC Guard Column, 1m by 0.32 mm uncoated, or equivalent.
7.3.3 Split/splitless Injector, with 0.75 to 1.0 mm inside diameter insert.
7.3.4 Optional Septum Replacement Device.
7.3.5 Optional SPME Autosampler . Autosampler.
7.3.6 GC Compatible Workstation . Workstation.
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 Chemicals, 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.
8.3 Sodium Chloride (NaCl),reagent grade, granular.
8.4 Surrogate Standard, 30 mg/L, 1,4-dichlorobenzene-d in methanol.
8.5 Check Standard—Prepare a check standard in methanol. Check standard should contain 30 mg/L 1,4-dichlorobenzene-d
plus VOCs that will be screened. A typical check standard will provide aqueous concentrations shown in Table 1 when spiking 4
μL of check standard to 700 μL water sample.
FIG. 1 Fiber Holder
D6889 − 03 (2011)
FIG. 2 Process for Adsorption of Analytes from Sample Vial with SPME Fiber
FIG. 3 Injection Followed by Desorption of SPME Fiber in Injection Port of Chromatograph
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.
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.
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-mill
...