ASTM D6889-03
(Practice)Standard Practice for Fast Screening for Volatile Organic Compounds in Water Using Solid Phase Microextraction (SPME)
Standard Practice for Fast Screening for Volatile Organic Compounds in Water Using Solid Phase Microextraction (SPME)
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 the 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.
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Designation:D6889–03
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 D4210 Practice for Intralaboratory Quality Control Proce-
dures and a Discussion on Reporting Low-Level Data
1.1 This practice covers a procedure for the screening of
D6520 Practice for the Solid Phase Micro Extraction
trace levels of volatile organic compounds in water samples by
(SPME) of Water and its Headspace for the Analysis of
headspace solid phase microextraction (SPME) in combination
Volatile and Semi-Volatile Organic Compounds
with fast gas chromatography with flame ionization detection.
1.2 The results from this screening procedure are used to
3. Summary of Practice
estimate analyte concentrations to prevent contamination of
3.1 This practice employs adsorbent/gas extraction to iso-
purge and trap or headspace analytical systems.
late compounds of interest, see Practice D6520. An aqueous
1.3 The compounds of interest must have a greater affinity
sample is added to a small (2 mL) septum sealed vial. Salt is
for the SPME absorbent polymer or adsorbent than the sample
used to improve analyte recovery. After the addition of a
matrix or headspace phase in which they reside.
surrogate standard and a short mixing cycle, a SPME fused
1.4 Not all of the analytes which can be determined by
silica fiber coated with a thick polymer film is then exposed to
SPME are addressed in this practice. The applicability of the
the aqueous headspace for a few seconds. The fiber is then
absorbent polymer, adsorbent or combination to extract the
desorbed in the heated injection port of a GC/FID or GC-MS
compound(s) of interest must be demonstrated before use.
and the resulting analytes chromatographed on a short narrow
1.5 Where used it is the responsibility of the user to validate
borecapillarycolumn.Thetotalanalysistimeisapproximately
the application of SPME to the analytes of interest.
3 min.
1.6 The values stated in SI units are to be regarded as the
3.2 The concentrations of the volatile organics in the water
standard.
sample are estimated to determine whether the sample may be
1.7 This standard does not purport to address all of the
analyzed directly or first diluted prior to purge and trap or
safety concerns, if any, associated with its use. It is the
headspace analysis.
responsibility of the user of this standard to establish appro-
priate safety and health practices and determine the applica-
4. Significance and Use
bility of regulatory limitations prior to use. For specific hazard
4.1 This practice provides a general procedure for the
statements, see Section 9.
solid-phase microextraction (SPME) of volatile organic com-
pounds from the headspace of an aqueous matrix. Absorbent
2. Referenced Documents
2 extraction is used as the initial step in the extraction of organic
2.1 ASTM Standards:
constituents for the purpose of screening and subsequently
D1129 Terminology Relating to Water
estimating the concentration of the volatile organic compo-
D1193 Specification for Reagent Water
nents found in water samples. This information may then be
D3694 Practices for Preparation of Sample Containers and
used to determine whether a sample may be analyzed directly
for Preservation of Organic Constituents
by purge and trap or headspace or will require dilution prior to
D3856 Guide for Good Laboratory Practices in Laborato-
analysis.
ries Engaged in Sampling and Analysis of Water
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
This practice is under the jurisdiction ofASTM Committee D19 on Water and
(mg/L) to micrograms per litre (µg/L). The detection limit,
is the direct responsibility of Subcommittee D19.06 on Methods for Analysis for
Organic Substances in Water. linear concentration range, and sensitivity of this test method
Current edition approved March 10, 2003. PublishedApril 2003. DOI: 10.1520/
for a specific organic compound will depend upon the aqueous
D6889-03.
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 Withdrawn. The last approved version of this historical standard is referenced
the ASTM website. on www.astm.org.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.
D6889–03
matrix, the fiber phase, the sample temperature, sample vol- 6.1.1 Plastics other than PTFE-fluorocarbon should be
ume, sample mixing, and the determinative technique em- avoided. They are a significant source of interference and can
ployed. adsorb some organics.
4.3 Solid phase microextraction has the advantage of speed,
reproducibility, simplicity, no solvent, small sample size, and 7. Apparatus
automation.
7.1 SPME Holder, manual or automated sampling.
4.3.1 Extraction devices vary from a manual SPME fiber
7.1.1 SPME Fiber Assembly—Polydimethylsiloxane
holder to automated commercial devices specifically designed
(PDMS), 30uM or equivalent fiber suitable for volatiles ad-
for SPME.
sorption.
4.3.2 Apartiallistofvolatileorganiccompoundsthatcanbe
7.2 Vials with Septa and Caps, for manual or automated
screened by this practice is shown in Table 1.
SPME. Vials for automation, 2 mL.
7.3 Gas Chromatograph, with flame ionization detector.
5. Principles of SPME
7.3.1 GC Column, 10 m by 0.25 mm, 1uM film Methyl
5.1 Solid phase microextraction is an equilibrium technique
Silicone, or equivalent.
where analytes are not completely extracted from the matrix.
7.3.2 GC Guard Column, 1m by 0.32 mm uncoated, or
With liquid samples, the recovery is dependent on the parti-
equivalent.
tioning or equilibrium of analytes among the three phases
7.3.3 Split/splitless Injector, with 0.75 to 1.0 mm inside
presentinthesamplingvial:theaqueoussampleandheadspace
diameter insert.
(Eq 1), the fiber coating and aqueous sample (Eq 2), and the
7.3.4 Optional Septum Replacement Device.
fiber coating and the headspace (Eq 3):
7.3.5 Optional SPME Autosampler.
7.3.6 GC Compatible Workstation.
K 5 C /C (1)
1 L g
K 5 C /C (2)
2 F L
8. Reagents
K 5 C /C (3)
3 F G
8.1 Purity of Water—Unless otherwise indicated, reference
towatershallbeunderstoodtomeanreagentwaterconforming
where:
C ,C , and C = concentrations of the analyte in these to Type II of Specification D1193.
L G F
phases. 8.2 Chemicals, standard materials and surrogates should be
5.1.1 Distribution of the analyte among the three phases: reagent orACS grade or better. When they are not available as
reagent grade, they should have an assay of 90 % or better.
C V 5 C V 1 C V 1 C V (4)
0 L G G L L F F
8.3 Sodium Chloride (NaCl), reagent grade, granular.
5.1.2 Concentration of analyte in fiber:
8.4 Surrogate Standard, 30 mg/L, 1,4-dichlorobenzene-d
C 5 C V K K //V 1 K V 1 K K V (5)
F 0 L 1 2 G 1 L 1 2 F in methanol.
8.5 CheckStandard—Prepareacheckstandardinmethanol.
6. Interferences
Check standard should contain 30 mg/L 1,4-
6.1 Reagents, glassware, septa, fiber coatings and other dichlorobenzene-d plus VOCs that will be screened.Atypical
sample processing hardware may yield discrete artifacts or
check standard will provide aqueous concentrations shown in
elevated baselines that can cause poor precision and accuracy. Table 1 when spiking 4 µL of check standard to 700 µL water
See Terminology D1129.
sample.
9. Hazards
TABLE 1 Check Standard Composition for Screening VOCs
in Water 9.1 The toxicity and carcinogenicity of chemicals used or
that could be used in this practice have not been precisely
Sample Composition, Detection Limit,
Analyte
µg/L µg/L
defined. Each chemical should be treated as a potential health
TBA 100 000 10 000 hazard. Exposure to these chemicals should be minimized.
Methyl-t-butyl ether 1000 150
Each laboratory is responsible for maintaining awareness of
cis-1,2-Dichloroethene 3000 300
OSHA regulations regarding safe handling of chemicals used
1,1,1-Trichloroethane 1000 200
in this practice.
Benzene 400 40
1,1,1-Trichloroethane 700 120
Toluene 200 10
10. Sample Handling
Tetrachloroethene 300 50
Chlorobenzene 150 10
10.1 There are many procedures for acquiring representa-
Ethylbenzene 100 5
tive samples of water. The procedure chosen will be site and
m-Xylene 100 5
styrene 100 5 analysis specific. There are several guides and practices for
o-Xylene 100 5
sampling listed in the ASTM subject index under Sampling,
Isopropylbenzene 100 5
Water Applications.
2-Chlorotoluene 100 5
1,2,4-Trimethylbenzene 100 5 10.2 The recommended sample size is 40 to 100 mL. More
1,4-Dichlorobenzene-d4 150 5
or less sample can be used depending upon the sample
1,2-Dichlorobenzene 100 5
availability, detection limits required, and the expected con-
Napthalene 100 5
centration level of the analyte. Forty-milliliter VOA vials are
D6889–03
FIG. 3 Injection Followed by Desorption of SPME Fiber in
Injection Port of Chromatograph
FIG. 1 Fiber Holder
by adding HCI. The constituents of concern must be stable
under acid conditions. For additional information, see Practice
D3694.
10.4.2 If resi
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