ASTM D4947-00
(Test Method)Standard Test Method for Chlordane and Heptachlor Residues in Indoor Air
Standard Test Method for Chlordane and Heptachlor Residues in Indoor Air
SCOPE
1.1 This test method covers the sampling and analysis of indoor atmospheres for residues of chlordane and heptachlor.
1.2 This test method is based upon the collection of chlordane and heptachlor from air onto polyurethane foam (PUF) and analysis by gas chromatography coupled with electron capture detection.
1.3 This test method is applicable to concentrations of chlordane varying from 0.1 to 100 μg/m and heptachlor varying from 0.01 to 80.0 μg/m with sampling periods to collect at least 0.25 m of air. Detection limits will depend upon the conditions of the gas chromatography (GC) and the length of the sampling period.
1.4 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.
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Designation: D 4947 – 00
Standard Test Method for
Chlordane and Heptachlor Residues in Indoor Air
This standard is issued under the fixed designation D4947; the number immediately following the designation indicates the year of
original adoption or, in the case of revision, the year of last revision.Anumber in parentheses indicates the year of last reapproval.A
superscript epsilon (e) indicates an editorial change since the last revision or reapproval.
1. Scope 2.2 EPA Methods:
Compendium of Methods for the Determination to Toxic
1.1 This test method covers the sampling and analysis of
Organic Compounds in Ambient Air, EPA 600/R-96/
indoor atmospheres for residues of chlordane and heptachlor.
010b
1.2 This test method is based upon the collection of chlor-
2.3 Other Documents:
dane and heptachlor from air onto polyurethane foam (PUF)
Indoor Sampling Guidelines for Termiticides
and analysis by gas chromatography coupled with electron
capture detection.
3. Terminology
1.3 This test method is applicable to concentrations of
3 3.1 Definitions:
chlordane varying from 0.1 to 100 µg/m and heptachlor
3.1.1 Refer to Terminology D1356, Practice E355, and
varying from 0.01 to 80.0 µg/m with sampling periods to
3 Practice D4861 for definitions of terms used in this test
collect at least 0.25 m of air. Detection limits will depend
method.
upon the conditions of the gas chromatography (GC) and the
3.1.2 The term “chlordane” refers to a technical-grade
length of the sampling period.
mixture consisting mostly of chlorinated Diels-Alder addition
1.4 This standard does not purport to address all of the
products of cyclopentadiene and hexachlorocyclopentadiene.
safety concerns, if any, associated with its use. It is the
The mixture consists of 50 or more compounds, 10 of which
responsibility of the user of this standard to establish appro-
are major components (1). The isomers a-(or cis-) and g-(or
priate safety and health practices and determine the applica-
trans-) chlordane, heptachlor, and trans-nonachlor are among
bility of regulatory limitations prior to use.
these.
2. Referenced Documents 3.1.2.1 The terms “chlordane” and “technical” chlordane
are used interchangeably.
2.1 ASTM Standards:
3.1.3 Heptachlorisasinglechemicalcompound,whichmay
D1356 Terminology Relating to Sampling andAnalysis of
be used alone or in formulations with technical chlordane. It is
Atmospheres
also a component of technical chlordane.
D3686 Practice for Sampling Atmospheres to Collect Or-
ganic Compound Vapors (Activated Charcoal Tube Ad-
4. Summary of Practice
sorption Method)
4.1 Alow-volume (1 to 5 L/min) sampler is used to collect
D3687 Practice forAnalysis of Organic CompoundVapors
airborne chlordane and heptachlor on a sorbent cartridge
Collected by the Activated Charcoal Tube Adsorption
2 containing PUF. The method is taken from Refs. (2) through
Method
(4) and Practice D4861.
D4185 Practice for Measurement of Metals in Workplace
2 4.2 Chlordaneandheptachlorareextractedfromthesorbent
Atmospheres by Atomic Absorption Spectrophotometry
cartridge with 5% diethyl ether in hexane and analyzed on a
D4861 Practice for Sampling and Selection of Analytical
gas chromatograph (GC) equipped with an electron capture
Techniques for Pesticides and Polychlorinated Biphenyls
detector (ECD).
in Air
E355 Practice for Gas Chromatography Terms and Rela-
tionships
This practice is under the jurisdiction of ASTM Committee D22 on Sampling
and Analysis of Atmospheres and is the direct responsibility of Subcommittee Available from the U.S. Department of Commerce, National Technical Infor-
D22.05 on Indoor Air. mation Service, Port Royal Road, Springfield, VA 22161.
Current edition approved March 10, 2000. Published June 2000. Originally Available from Wood Protection Council, National Institute for Building
published as D4947–89. Last previous edition D4947–94. Sciences, Washington, DC, 1987.
2 6
Annual Book of ASTM Standards, Vol 11.03. Theboldfacenumbersinparenthesesrefertothelistofreferencesattheendof
Annual Book of ASTM Standards, Vol 14.02. this standard.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.
D 4947
4.3 Because of the possibility of interfering materials hav- methylpolysiloxane fused-silica capillary column, film thick-
ing similar retention times to chlordane and heptachlor peaks, ness 3 µm, for quantitation; and a 30-mby0.53-mm inside
column chromatography or the use of a second chromato- diameter poly(5% -diphenyl-95% dimethylsiloxane) fused-
graphic column of a different type is necessary to obtain silica capillary column, film thickness 1.5 µm, for confirma-
accurate identification and quantification. Mass spectrometry tion.
may be required for unambiguous determination. 7.3.3 Microsyringes, 5-µL volume.
5. Significance and Use 8. Sampling Procedures
5.1 This test method is intended to be used primarily for
8.1 Follow the applicable section of Practice D4861 for
non-occupational exposure monitoring in domiciles, public clean-up and proper storage of the PUF sampling plugs.
access buildings and offices. 8.2 At least one assembled sampling cartridge from each
5.2 Chlordanehasbeenusedwidelyasageneralinsecticide batch should be analyzed as a laboratory blank prior to using.
forcrops(forexample,cotton)andasatermiticide.Heptachlor The blank level should be <0.10 µg/plug for chlordane, <0.01
isamajorcomponentoftechnicalchlordaneandaninsecticide µg/plug for heptachlor.
in its own right. Although their use in the United States was 8.3 After the sampling system has been assembled and
discontinued in 1988, residues of the chemicals may remain in calibratedasdescribedinSection9,itcanbeusedtocollectair
indoor air for many years after application. samples as described in 9.5.1 to 9.5.9 of Practice D4861.
6. Interferences
9. Calibration of Pump
6.1 Theelectroncapturedetectorrespondstoawidevariety 9.1 Refer to the applicableAnnex in Practice D3686 or the
oforganiccompounds.Itislikelythatsuchcompoundswillbe
applicable Annex Practice D4185 for procedures to calibrate
encountered as interferences during GC-ECD analysis. Al- small volume air pumps. See also Practice D4861.
though mass spectrometry can provide positive identification
10. Sample Extraction Procedure
of chlordane and heptachlor, some laboratories do not possess
such instrumentation.
10.1 All samples should be extracted within one week after
6.2 Technical chlordane is a complex mixture of
collection in accordance with the procedures outlined in
chemically-related chlorinated compounds, including 8 to
Section 10 of the Practice D4861.
10% by weight of heptachlor. Similar compounds (for ex-
10.2 Adjust final volume of sample extract to 1 mL for
ample,DDTanditsisomers)cancausedifficultyinidentifying
analysis.
and quantifying this multiple-component mixture.
6.3 In addition, contaminated glassware and sampling tubes 11. Analysis Procedures
can be a major source of error when attempting to quantitate
11.1 Prepare analytical standard solutions of technical chlo-
multiple-component mixtures with an ECD. To minimize this 10
rdane in pesticide-quality 2,2,4-trimethylpentane (“iso-
source of error, careful attention to glassware cleaning and
octane”). Analytically pure standards of technical chlordane
sample handling procedures must be followed.
and heptachlor are available from several commercial sources.
6.4 General approaches that can be followed to minimize
11.2 When not in use, store standard solutions at 4°C or
interferences are given as follows:
below and protect from light. Replace after six months, or
6.4.1 Chlordane and heptachlor can be cleaned up by
soonerifcomparisonwithcheckstandardsindicatesaproblem.
column chromatography on Florisil . See Ref (5).
11.3 Chlordane and heptachlor are responsive to detection
6.4.2 Chlordane- and heptachlor-containing samples can be
by GC/ECD at low concentrations, which will be dependent
cleaned up with sulfuric acid treatment. See Ref (6).
upon the condition of the chromatograph, columns (see 7.3.2)
and detector.
7. Apparatus
11.4 Agaschromatograph(GC)withdualinjectorportsand
7.1 Air Sampler—Refer to the appropriate section of Prac-
dual electron capture detectors is recommended.
tice D4861 for specifications on air sampling equipment.
11.5 Set up both the quantitation and confirmatory GC
7.2 Equipment and Reagents for Sample Extraction and
columns in the same GC oven.
Concentration—Refer to the applicable section of Practice
11.6 Provide helium carrier gas at a nominal flow rate of 10
D4861 for required equipment and reagents.
mL/min at approximately 170 kPa (25 psig) to each column.
7.3 Equipment for Analysis:
11.7 Set the temperature for both injectors at 235°C and the
7.3.1 Gas chromatograph equipped with a Nickel-63 elec-
ECD at 350°C.
tron capture detector.
11.8 Allowsamplesandstandardsolutionstowarmtoroom
7.3.2 Gas chromatographic columns: A 15-mby0.53 mm
temperature before analysis.
inside diameter bonded, crosslinked (50%-phenyl)-
This column is available from several commercial sources under such trade
“Florisil” is a trademark of the Floridin Corp., Tallahassee, FL 32303. It is a names as OV-17, DB-17, SPB-17, and others.
natural magnesium silicate; it is available from several commercial sources. This column is available from several commercial sources under such trade
names as DB-5, SPB-5, RTX-5, HP-5, OV-5, BP-5, and others.
Glass distilled and certified for pesticides analysis by GC/ECD.
D 4947
11.9 Set column temperature program for 60°C (2 min),
then programmed to 140°C at 25°C/min, then to 270°C at
4°C/min.
11.10 Calibrate gas chromatograph by injecting 2 µL ali-
quotsofstandardsolutions(SeePracticeD3687fortechnique)
in order to establish response factors, linearity of the ECD,
dynamic range, and retention time windows.
11.11 Set retention time windows at 60.10 min for the
quantitation primary column and 60.05 min for the confirma-
tory column.
11.12 Typical chromatograms of technical chlordane are
showninFig.1andFig.2forthequantitationandconfirmatory
columns, respectively. The ten numbered peaks are to be used
for identification and quantitation of chlordane in the sample.
11.13 Typical retention times for the two columns are given
in Table 1.
11.14 Inject 2 µl of sample extract on quantitation column
and obtain a tentative identification of technical chlordane by
NOTE 1—Refer to Table 1 for typical retention times of peaks.
comparisonofchromatographicpeaksinthesamplewiththose
FIG. 2 Typical Chromatogram of Technical Chlordane on
in the standard in accordance with the flow chart in Fig. 3 and
Confirmatory Megabore Column
the following steps:
11.14.1 On a worksheet, list the measured retention times
TABLE 1 Typical Gas Chromatographic Retention Times of
A
(in minutes) and corresponding areas of each chromatographic Technical Chlordane Components
peakthatappearstomatchanyofthetenreferencepeaksfrom
Quantitation Megabore Column Confirmatory Megabore Column
B C
the standard.
Peak RT, min Compound Peak RT, min Compound
11.14.2 Comparetheretentiontimeofeachofthetenpeaks
1 12.74 1 16.56
2 18.07 2 22.23
in the sample chromatogram to the absolute retention time of
3 18.80 Heptachlor 3 23.19 Heptachlor
the respective standard peak using a retention window of
4 21.17 4 24.98
60.10minaroundeachstandardpeak.Drawalinethroughthe
5 22.75 5 26.37
6 23.64 g-Chlordane 6 27.97 g-Chlordane
retention time and area of all sample peaks that are outside the
7 23.87 t-Nonachlor 7 28.72 a-Chlordane
retention window. However, when a consistent shift is evident
8 24.32 a-Chlordane 8 28.99 t-Nonachlor
in the retention times of many of the sample peaks, the 9 27.51 9 31.97
10 28.36 10 32.40
experienced analyst may expand the acceptable retention
A
Refer to Section 11 for chromatographic conditions.
window in the direction of the shift.
B
Refer to Fig. 1.
C
Refer to Fig. 2.
11.14.3 If all ten peaks qualify, tentative confirmation is
obtainedandthesamplemaybesubjectedtofinalconfirmation
by analysis on the DB-5 column in accordance with 11.15.
11.14.4 When only some of the ten peaks are present in the
sample chromatogram, the priority order of peak presence for
identification as chlordane is as follows:
11.14.4.1 a- and g-Chlordane (peaks 8 and 6) (highest
priority),
11.14.4.2 Heptachlor component (peak 3),
11.14.4.3 Trans -nonachlor (peak 7),
11.14.4.4 Last two components (peaks 9 and 10), and
11.14.4.5 Component immediately preceding heptachlor
(peak 2).
11.14.5 If all seven of these peaks listed in 11.14.4 are
present in the sample (for example, found to be within its
retention window as in 11.14.2), then tentative assignment of
technical chlordane is made.
NOTE 1—Refer to Table 1 for typical retention times of peaks.
11.14.6 If peaks 2, 3, 6, 8, 9, and 10 are present in the
FIG. 1 Typical Chromatogram of Technical Chlordane on
Quantitation Megabore Column sample, then the tentative assignment of chlordane is made.
D 4947
ten reference chlordane component peaks obtained from the
confirmatory column analysis of the technical chlordane stan-
dard solution.
11.15.3 On the same worksheet, list the retention times and
areas of the peaks corresponding to these ten peaks from the
sample analysis using the DB-5 confirmation column.
11.15.4 Compare the retention times of peaks 3 (hep-
tachlor), 6 (g-chlordane), 7 (a-chlordane), and 8 (trans-
nonachlor) in the confirmation analysis of the sample to the
absoluteretentiontimesoftherespectivestandardpeaks,using
a retention window of 60.05 minutes around each standard
peak.Drawalinethroughthesampleretentiontimesandareas
for both the confirmation column and the primary quantitation
column for any of these four components that are outside the
retention window (for example, not present) on the confirma-
tioncolumn.However,whenaconsistentshiftisevidentinthe
retention times of many of the sample peaks, the analyst may
expand the acceptable retention window in the direction of the
shift. (Remember that the elution sequence of trans-nonachlor
and a-chlordane are reversed on the OV-17 megabore and
DB-5 columns).
11.15.5 If either a-chlordane or g-chlordane (peaks 6 or 7
on the confirmatory column) is not present within the standard
retentiontimewindowontheconfirmationcolumn,thesample
is considered negative for chlordane.
FIG. 3 Flow Chart for Tentative Identification of Chlordane Using
11.15.6 Ifheptachlor(peak3)or trans-nonachlor(peak8)is
the Primary Column
outsideitsstandardretentiontimewindowontheconfirmation
column, cross out its respective retention times and areas for
11.14.7 As illustrated in the flow chart in Fig. 3, when the
both the con
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