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1. Scope
1.1 This test method covers the determination of 1,2dibromoethane (commonly referred to as ethylene dibromide
or EDB) and 1,2-dibromo-3-chloropropane (commonly referred to as DBCP) in water at a minimum detection level of
0.010 g/L by liquid-liquid extraction combined with gasliquid chromatography. This test method is applicable to the
analysis of drinking waters and groundwaters. It is not recommended for wastewaters, due to the potential for interferences
from high concentrations of other extractable organics. Similar
information can be found in EPA Method 504.
1.2 This test method was used successfully with reagent
water and groundwater. It is the users responsibility to ensure
the validity of this test method for waters of untested matrices.
1.3 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 Sections 6 and 9.
2. Referenced Documents
2.1 ASTM Standards:
D 1066 Practice for Sampling Steam2
D 1129 Terminology Relating to Water2
D 1192 Specification for Equipment for Sampling Water
and Steam in Closed Conduits2
D 1193 Specification for Reagent Water2
D 3370 Practices for Sampling Water from Closed Conduits2
D 3896 Guide for Good Laboratory Practices in Laboratories Engaged in the Sampling and Analysis of Water2
D 4210 Practice for Interlaboratory Quality Control Procedures and a Discussion on Reporting Low-Level Data2
D 5789 Practice for Writing Quality Control Specifications
for Standard Test Methods for Organic Constituents2
1
This test method is under the jurisdiction of ASTM Committee D-19 on Water
and is the direct responsibility of Subcommittee D19.06 on Methods for Analysis for
Organic Substances in Water.
Current edition approved July 10, 1998. Published March 1999. Originally
published as D 531692. Last previous edition D 531692.
2
Annual Book of ASTM Standards, Vol 11.01.
3
Available from U.S. Environmental Protection Agency, 26 W. Martin Luther
King Ave., Cincinnati, OH 45268.
D 5316
capillary with dimethyl silicone mixed phase.5 The linear
velocity of the helium carrier gas should be about 25 cm/s at
100C. The column temperature is programmed to hold at
40C for 4 min, to increase to 190C at 8C/min, and hold at
190C for 25 min or until all expected compounds have eluted.
(See Fig. 1 for a sample chromatogram.)
7.1.4 Column B (alternative column)A 0.32-mm ID by
30-m long fused silica capillary with methyl polysiloxane
phase.6 The linear velocity of the helium carrier gas should be
about 25 cm/s at 100C. The column temperature is programmed to hold at 40C for 4 min, to increase to 270C at
10C/min, and hold at 270C for 10 min or until all expected
compounds have eluted.
7.1.5 Column C4 (alternative column, wide bore)A 0.53mm ID by 30-m long fused silica capillary with dimethyl
diphenyl polysiloxane, bonded phase with 2.0 m film.7 The
hydrogen carrier gas flow is about 80 cm/s linear velocity,
measured at 50C. The oven temperature is programmed to
hold at 200C until all expected compounds have eluted.
7.1.6 Other Heated ZonesInjector temperature: 250C.
Detector temperature: 350C.8
7.2 Sample ContainersForty-mL screw cap vials, each
equipped with a size 24 cap, with a flat, disc-like PTFE-faced
6.2 This liquid-liquid extraction technique efficiently extracts a wide boiling range of nonpolar organic compounds
and, in addition, extracts polar organic components of the
sample with varying efficiencies.
6.3 Current column technology suffers from the fact that
EDB at low concentrations may be masked by very high levels
of dibromochloromethane (DBCM), a common disinfection
by-product of chlorinated drinking waters.
5
J & W Durawax DX-3, 0.25 m, available from J & W Scientific, 91 Blue
Ravine Rd., Folsom, CA 95630, or its equivalent, has been found suitable for this
purpose.
6
J & W DB-1, 1.0 m film, available from J & W Scientific, or its equivalent,
has been found suitable for this purpose.
7
RtxVolatiles, 2.0 m film thickness. Restek part #10902, available from Restek
Corp., 110 Benner Circle, Bellefonte, PA 16823, or its equivalent has been found
suitable for this purpose.
8
These parameters were obtained by Restek Corporation during preliminary
attempts to improve the separation of EDB and DBCM.
4
An alternative column has been recommended by the Restek Corporation and
is described in 7.1.5 as Column C.
Column A
9.5
17.3
Column C
4.1
12.8
D 5316
8.10.4 Store stock standard solutions in 15-mL bottles
equipped with PTFE-lined screw caps. Methanol solutions
prepared from liquid analytes are stable for at least four weeks
when stored at 4C.
8.11 Standard Solutions, Primary DilutionUse stock standard solutions to prepare primary dilution standard solutions
that contain both analytes in methanol. The primary dilution
standards should be prepared at concentrations that can be
easily diluted to prepare aqueous calibration standards (see
12.1.1) that will bracket the working concentration range. Store
the primary dilution standard solutions with minimal headspace, and check frequently for signs of deterioration or
evaporation, especially just before preparing calibration standards. The storage time described for stock standard solutions
also applies to primary dilution standard solutions.
9. Hazards
9.1 The toxicity and carcinogenicity of chemicals used in
this test method have not been precisely defined; each chemical
should be treated as a potential health hazard, and 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 test method.
Additional references to laboratory safety need to be made
available to the analyst.
9.2 EDB and DBCP have been tentatively classified as
known or suspected human or mammalian carcinogens. Pure
standard materials and stock standard solutions of these compounds should be handled in a hood or glovebox. A NIOSH/
MESA approved toxic gas respirator should be worn when the
analyst handles high concentrations of these toxic compounds.
NOTE 2Caution: When a solvent is purified, stabilizers put into the
solvent by the manufacturer are removed, thus potentially making the
solvent hazardous.
9
Reagent Chemicals, American Chemical Society Specifications, American
Chemical Society, Washington, DC. For suggestions on the testing of reagents not
listed by the American Chemical Society, see Standards for Laboratory Chemicals, BDH Limited, Poole, Dorset, UK, and the United States Pharmacopeia.
D 5316
an aliquot of water in a volumetric flask. If less than 20 L of
an alcoholic standard is added to the reagent water, poor
precision may result. Use a 25-L microsyringe and rapidly
inject the alcoholic standard into the expanded area of the filled
volumetric flask. Remove the needle as quickly as possible
after injection. Mix by inverting the flask several times.
Aqueous standards should be prepared fresh and extracted
immediately after preparation unless sealed and stored without
headspace as described in 8.11.
12.1.3 Each day, analyze each calibration standard according to Section 12 and tabulate peak height or area response
versus the concentration in the standard. Use the results to
prepare a calibration curve for each compound. Alternatively, if
the ratio of concentration to response (calibration factor) is a
constant over the working range (< 20 % relative standard
deviation), linearity through the origin may be assumed and the
average ratio or calibration factor may be used in place of a
calibration curve.
12.1.4 Single point calibration is a viable alternative to a
calibration curve. Prepare single point standards from the
secondary dilution standard solutions. Prepare the single point
calibration standard at a concentration that produces a response
close to that of the unknowns, that is, no more than 20 %
deviation between response of the standard and response of the
sample.
10.2.2 The addition of sodium thiosulfate as a dechlorinating agent or acidification, or both, to pH 2 with HCl (1 + 1),
common preservative procedures for purgeable compounds,
has been shown to have no effect on EDB or DBCP (see Table
2). Nonetheless, sodium thiosulfate must be added to avoid the
possibility of reactions that may occur between residual
chlorine and indeterminate contaminants present in some
solvents, yielding compounds which may subsequently interfere with the analysis. The presence of sodium thiosulfate will
arrest the formation of DBCM (see 6.3). Also, samples should
be acidified to avoid the possibility of microbial degradation
that may periodically affect these analytes contained in other
groundwater matrices.
10.3 Sample Storage:
10.3.1 Store samples and field reagent blanks together at
4C until analysis. The sample storage area must be free of
organic solvent vapors.
10.3.2 Analyze all samples within 28 days of collection.
11. Preparation of Apparatus
11.1 Set up the gas chromatograph in accordance with the
manufacturers instructions. Install the capillary column(s) and
test for leaks using techniques recommended by the instruments or capillary columns manufacturer.
11.2 Instrument PerformanceCheck the performance of
the entire analytical system daily using data gathered from
analyses of water blanks and standards.
11.2.1 Correct significant peak tailing in excess of that
shown for the target compounds in the method chromatogram
(Fig. 1).
11.2.2 Check the precision between replicate analyses. A
properly operating system will exhibit an average relative
standard deviation of less than 10 %.
13. Procedure
13.1 Sample Preparation:
13.1.1 Remove samples and standards from storage and
allow them to reach room temperature.
13.1.2 For samples and field reagent blanks, contained in
40-mL bottles, remove container cap. Discard a 5-mL volume
using a 5-mL transfer pipet or 10-mL graduated cylinder.
Replace the container cap and weigh the container with
contents to the nearest 0.1 g and record this weight for
subsequent sample volume determination (13.3).
13.1.3 For calibration standards, laboratory fortified blanks,
and laboratory reagent blanks, measure a 35-mL volume using
a 50-mL graduated cylinder and transfer it to a 40-mL sample
container.
13.2 Microextraction and Analysis:
13.2.1 Remove the container cap and add 6 g NaCl (see 8.8)
to the sample.
13.2.2 Recap the sample container and dissolve the NaCl by
shaking by hand for about 20 s.
13.2.3 Remove the cap and, using a transfer pipet, add 2.0
mL of hexane. Recap and shake vigorously by hand for 1 min.
Allow the water and hexane phases to separate. (If stored at
this state, keep the container upside down.)
13.2.4 Remove the cap and carefully transfer 0.5 mL of the
hexane layer into an auto-injector using a disposable glass
pipet.
13.2.5 Transfer the remaining hexane phase, being careful
not to include any of the water phase, into a second autoinjector vial. Reserve this second vial at 4C for a reanalysis if
necessary.
13.2.6 Transfer the first sample vial to an auto-injector set
up to inject 2.0 L portions into the gas chromatograph for
analysis. Alternatively, manually inject 2.0 L portions of
DBCP
Matrix A
RW-A
GW
GW-A
TW
TW-A
RW-A
GW
GW-A
TW
TW-A
Concentration
(g/L)
Average Bias
(%)
Relative
Standard
Deviation (%)
16
15
16
16
16
16
16
16
16
16
+4
+1
4
7
7
+5
+5
+1
5
6
4.7
2.5
4.7
6.3
6.1
8.2
6.2
8.4
10.1
6.9
A
Matrix Identities: RW-A 5 Reagent water at pH 2, GW 5 Groundwater, ambient pH, GW-A 5 Groundwater at pH 2, TW 5 Tap water, ambient pH, TW-A 5 Tap
water at pH 2.
D 5316
TABLE 4 Interlaboratory Study of EDB and DBCP Regression
Equations for Recovery and PrecisionA
Water Type
Applicable Conc. Range
Reagent Water:
Single-Analyst Precision
Overall Precision
Recovery
Groundwater:
Single-Analyst Precision
Overall Precision
Recovery
A
(1)
35
Concentration, g/L 5 Ci 3 V
s
(2)
EDB
DBCP
Number of
Samples
Concentration
(g/L)
Average Bias
(%)
Relative
Standard
Deviation (%)
7
7
7
7
7
7
0.03
0.24
50.0
0.03
0.24
50.0
+ 14
2
5
10
+2
6
9.5
11.8
4.7
11.4
8.3
4.8
SR 5 0.041X + 0.004
S 5 0.075X + 0.008
X 5 1.072C 0.006
SR 5 0.065X + 0.000
S 5 0.143X 0.000
X 5 0.987C 0.000
SR 5 0.046X + 0.002
S 5 0.102X + 0.006
X 5 1.077C 0.001
SR 5 0.076X 0.000
S 5 0.160X + 0.006
X 5 0.972C + 0.007
X 5 Mean recovery
C 5 True value for the concentration
Analyte
1,2-dibromo3-chloropropane
14. Calculation
14.1 Identify EDB and DBCP in the sample chromatogram
by comparing the retention time of the suspect peak to the
retention times generated by the calibration standards and the
laboratory control standard.
14.2 Use single point calibrations (12.1.4) or use the calibration curve or calibration factor (12.1.3) to directly calculate
the uncorrected concentration (Ci) of each analyte in the
sample (for example, calibration factor 3 response).
14.3 Calculate the sample volume (Vs) as equal to the net
sample weight:
Vs 5 gross weight ~13.1.2! 2 bottle tare ~13.3.3!
1,2-dibromoethane
0.240 (EDB)
0.240 (DBCP)
Proficiency
Acceptable
Standard
Deviation, max
0.0276 g/L
0.0312 g/L
Demonstration
QC Check
Acceptance Range
for Mean Recovery
Acceptance Range
for QC Check
D 5316
17.5 Recovery SpikesTo insure that the test method is in
control for each sample matrix, analyze a sample spiked with
the target analytes in 17.4. If the unspiked sample is essentially
free of analyte or the spike to background concentration is ten
or more, the percent recovery should fall within the limits in
Table 6. If recoveries are outside of established limits, examine
the performance of the system. If calibration and QC results are
Recovery Spike
0.240 (EDB)
0.240 (DBCP)
Acceptance Range
for Recovery Spike
0.149 0.331 g/L
0.107 0.373 g/L
18. Keywords
18.1 DBCP; 1,2-dibromo-3-chloropropane; 1,2-dibromoethane; EDB; ethylene dibromide; gas chromatography; microextraction
APPENDIX
(Nonmandatory Information)
X1. Reference Statistics
=401 5 0.0276.
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