ASTM D3694-96
(Practice)Standard Practices for Preparation of Sample Containers and for Preservation of Organic Constituents
Standard Practices for Preparation of Sample Containers and for Preservation of Organic Constituents
SCOPE
1.1 These practices cover the various means of (1) preparing sample containers used for collection of waters to be analyzed for organic constituents and (2) preservation of such samples from the time of sample collection until the time of analysis.
1.2 The sample preservation practice is dependent upon the specific analysis to be conducted. See Section 9 for preservation practices listed with the corresponding applicable general and specific constituent test method. The preservation method for waterborne oils is given in Practice D3325. Use of the information given herein will make it possible to choose the minimum number of sample preservation practices necessary to ensure the integrity of a sample designated for multiple analysis. For further considerations of sample preservation, see the Manual on Water .
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 6.7, 6.24, and 8.1.3.
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An American National Standard
Designation: D 3694 – 96
Standard Practices for
Preparation of Sample Containers and for Preservation of
Organic Constituents
This standard is issued under the fixed designation D 3694; 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 (e) indicates an editorial change since the last revision or reapproval.
1. Scope D 2580 Test Method for Phenols in Water by Gas-Liquid
Chromatography
1.1 These practices cover the various means of (1) preparing
D 2908 Practice for Measuring Volatile Organic Matter in
sample containers used for collection of waters to be analyzed
Water by Aqueous-Injection Gas Chromatography
for organic constituents and (2) preservation of such samples
D 3113 Test Methods for Sodium Salts of EDTA in Water
from the time of sample collection until the time of analysis.
D 3325 Practice for Preservation of Waterborne Oil
1.2 The sample preservation practice is dependent upon the
Samples
specific analysis to be conducted. See Section 9 for preserva-
D 3371 Test Method for Nitriles in Aqueous Solution by
tion practices listed with the corresponding applicable general
Gas-Liquid Chromatography
and specific constituent test method. The preservation method
D 3534 Test Method for Polychlorinated Biphenyls (PCBs)
for waterborne oils is given in Practice D 3325. Use of the
in Water
information given herein will make it possible to choose the
D 3590 Test Methods for Total Kjeldahl Nitrogen in Water
minimum number of sample preservation practices necessary
D 3695 Test Method for Volatile Alcohols in Water by
to ensure the integrity of a sample designated for multiple
Direct Aqueous-Injection Gas Chromatography
analysis. For further considerations of sample preservation, see
D 3871 Test Method for Purgeable Organic Compounds in
the Manual on Water.
Water Using Headspace Sampling
1.3 This standard does not purport to address all of the
D 3921 Test Method for Oil and Grease and Petroleum
safety concerns, if any, associated with its use. It is the
Hydrocarbons in Water
responsibility of the user of this standard to establish appro-
D 3973 Test Method for Low-Molecular Weight Haloge-
priate safety and health practices and determine the applica-
nated Hydrocarbons in Water
bility of regulatory limitations prior to use. For specific hazard
D 4129 Test Method for Total and Organic Carbon in Water
statements, see 6.7, 6.24, and 8.1.3.
by High-Temperature Oxidation and Coulometric Detec-
2. Referenced Documents tion
D 4165 Test Method for Cyanogen Chloride in Water
2.1 ASTM Standards:
D 4193 Test Method for Thiocyanate in Water
D 1129 Terminology Relating to Water
D 4281 Test Method for Oil and Grease (Fluorocarbon
D 1193 Specification for Reagent Water
Extractable Substances) by Gravimetric Determination
D 1252 Test Methods for Chemical Oxygen Demand
D 4282 Test Method for Determination of Free Cyanide in
(Dichromate Oxygen Demand) of Water
Water and Wastewater by Microdiffusion
D 1783 Test Methods for Phenolic Compounds in Water
D 4374 Test Methods for Cyanide in Water—Automated
D 2036 Test Methods for Cyanides in Water
Methods for Total Cyanide, Dissociable Cyanide, and
D 2330 Test Method for Methylene Blue Active Sub-
Thiocyanate
stances
D 4515 Practice for Estimation of Holding Time for Water
D 2579 Test Methods for Total and Organic Carbon in
Samples Containing Organic Constituents
Water
D 4657 Test Method for Polynuclear Aromatic Hydrocar-
bons in Water
These practices are under the jurisdiction of ASTM Committee D-19 on Water
D 4744 Test Method for Organic Halides in Water by
and are the direct responsibilities of Subcommittee D19.06 on Methods for Analysis 4
Carbon Adsorption Microcoulometric Detection
for Organic Substances in Water.
D 4763 Practice for Identification of Chemicals in Water by
Current edition approved Dec. 10, 1996. Published March 1997. Originally
Fluorescence Spectroscopy
published as D 3694 – 78. Last previous edition D 3694 – 95.
Manual on Water, ASTM STP 442, ASTM, 1969.
Annual Book of ASTM Standards, Vol 11.01.
Annual Book of ASTM Standards, Vol 11.02.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.
D 3694 – 96
except pesticides, herbicides, polychlorinated biphenyls, and volatile
D 4779 Test Method for Total, Organic, and Inorganic
organics. However, this bottle cannot be recycled.
Carbon in High Purity Water by Ultraviolet (UV) or
Persulfate Oxidation, or Both, and Infrared Detection
5.3 Sample Bottle Cap, TFE-fluorocarbon or aluminum
D 4839 Test Method for Total Carbon and Organic Carbon
foil-lined.
in Water by Ultraviolet, or Persulfate Oxidation, or Both,
NOTE 2—Even these liners have some disadvantages. TFE is known to
and Infrared Detection
collect some organic constituents, for example, PCBs. Aluminum foil will
D 4841 Practice for Estimation of Holding Time for Water
react with samples that are strongly acid or alkaline. Clean TFE liners as
Samples Containing Organic and Inorganic Constituents
described in 7.1. Replace aluminum foil with new foil after each use.
D 4983 Test Method for Cyclohexylamine, Morpholine,
5.4 Sample Vial, glass.
and Diethylaminoethanol in Water and Condensed Steam
5.5 Septa, PTFE-faced with screw cap lid and matching
by Direct Aqueous Injection Gas Chromatography
aluminum foil disks.
D 5175 Test Method for Organohalide Pesticides and Poly-
chlorinated Biphenyls in Water by Microextraction and
6. Reagents and Materials
Gas Chromatography
6.1 Purity of Reagents—Reagent grade chemicals shall be
D 5176 Test Method for Total Chemically Bound Nitrogen
used in all tests. Unless otherwise indicated, it is intended that
in Water by Pyrolysis and Chemiluminescence Detection
all reagents shall conform to the specifications of the Commit-
D 5315 Test Method for N-Methyl-Carbamoyloximes and
tee on Analytical Reagents of the American Chemical Society.
N-Methylcarbamates in Water by Direct Aqueous Injection
Other grades may be used, provided it is first ascertained that
HPLC with Post-Column Derivation
the reagent is of sufficiently high purity to permit its use
D 5316 Test Method for 1,2-Dibromoethane and 1,2-
without lessening the accuracy of the determination.
Dibromo-3-Chloropropane in Water by Microextraction
6.2 Purity of Water—Unless otherwise indicated, reference
and Gas Chromatography
to water shall be understood to mean reagent water conforming
D 5317 Test Method for the Determination of Chlorinated
to Specification D 1193, Type II and demonstrated to be free of
Organic Acid Compounds in Water by Gas Chromatogra-
specific interference for the test being performed.
phy with an Electron Capture Detector
6.3 Acetic Acid Buffer Solution (pH 4)—Dissolve 6.0 g of
D 5412 Test Method for Quantification of Complex Poly-
sodium acetate in 75 mL of water. Add 30 mL of glacial acetic
cyclic Aromatic Hydrocarbon Mixtures or Petroleum Oils
4 acid, with stirring.
in Water
6.4 Acetone.
D 5475 Test Method for Nitrogen and Phosphorus Contain-
6.5 Acid Buffer Solution (pH 3.75)—Dissolve 125 g of
ing Pesticides in Water by Gas Chromatography with a
potassium chloride and 70 g of sodium acetate trihydrate in 500
Nitrogen-Phosphorus Detector
mL of water. Add 300 mL of glacial acetic acid and dilute to 1
D 5790 Test Method for Measurement of Purgeable Organic
L.
Compounds in Water by Capillary Column Gas
6.6 Ascorbic Acid.
Chromatography/Mass Spectrometry
6.7 Chromic Acid Cleaning Solution—To a 2-L beaker, add
D 5812 Test Method for Determination of Organochlorine
35 mL of saturated sodium dichromate solution followed by 1
Pesticides in Water by Capillary Column Gas Chromatog-
L of sulfuric acid (sp gr 1.84) with stirring. Warning—Use
raphy
rubber gloves, safety goggles, and protective clothing when
preparing and handling this corrosive cleaning agent that is a
3. Terminology
powerful oxidant. Store the reagent in a glass bottle with a
3.1 Definitions—For definitions of terms used in this prac-
glass stopper.
tice, refer to Terminology D 1129.
6.8 Detergent, formulated for cleaning laboratory glass-
ware.
4. Significance and Use
6.9 Hydrochloric Acid—Concentrated HCl (sp gr 1.19).
4.1 There are four basic steps necessary to obtain meaning-
6.10 Hydrochloric Acid (1 + 2)—To 200 mL of water,
ful analytical data: preparation of the sample container, sam-
carefully add 100 mL of hydrochloric acid (see 6.9). Store in a
pling, sample preservation, and analysis. In fact these four
glass-stoppered reagent bottle.
basic steps comprise the analytical method and for this reason
6.11 Ice, crushed wet.
no step should be overlooked. Although the significance of
6.12 Lead Acetate Test Paper.
preservation is dependent upon the time between sampling and
6.13 Lead Acetate Solution—Dissolve 50 g of lead acetate
the analysis, unless the analysis is accomplished within 2 h
in water and dilute to 1 L.
after sampling, preservation is preferred and usually required.
6.14 Lead Carbonate, powdered.
5. Apparatus
5.1 Forced Draft Oven, capable of operating at 275 to
Reagent Chemicals, American Chemical Society Specifications, American
325°C.
Chemical Society, Washington, DC. For suggestions on the testing of reagents not
listed by the American Chemical Society, see Analar Standards for Laboratory
5.2 Sample Bottle, borosilicate or flint glass.
Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia
NOTE 1—High density polyethylene (HDPE) bottles and caps have
and National Formulary, U.S. Pharmaceutical Convention, Inc. (USPC), Rockville,
been demonstrated to be of sufficient quality to be compatible for all tests MD.
D 3694 – 96
6.15 Lime, Hydrated, powdered. 8.1.4 Rinse the container with water until sulfurous acid and
its vapors have been removed. Test rinsings for acid with a pH
6.16 Mercuric Chloride.
meter or an appropriate narrow range pH paper. Rinsings
6.17 Monochloroacetic Acid Buffer (pH 3)—Prepare by
should have a pH approximately the same as the water used for
mixing 156 mL of chloroacetic acid solution (236.2 g/L) and
rinsing.
100 mL of potassium acetate solution (245.4 g/L).
8.1.5 When the last trace of NaHSO has been removed,
6.18 Nitric Acid—Concentrated HNO (sp gr 1.42).
wash with three additional 100-mL portions of water. Allow to
6.19 Phosphate Buffer—Dissolve 138 g of sodium dihydro-
drain. This procedure is for 1-L sample containers, therefore,
gen phosphate in water and dilute to 1 L. Refrigerate this
use proportionate volumes for washing and rinsing sample
solution.
containers of a different volume.
6.20 Phosphate Solution—Dissolve 33.8 g of potassium
8.1.6 Heat for a minimum of 4 h (mouth up) in a forced draft
dihydrogen phosphate in 250 mL of water.
oven at 275 to 325°C. Upon cooling, fit the bottles with caps
6.21 Phosphoric Acid—Concentrated H PO (sp gr 1.83).
and the vials with septa.
3 4
6.22 Phosphoric Acid Solution (1 + 1)—Dilute 1 vol of
NOTE 3—For some tests, heating may not be required. Refer to the
phosphoric acid (sp gr 1.83).
individual method to determine the necessity for this treatment.
6.23 pH Paper, narrow range for pH < 2, pH > 12, and pH
8.2 Machine Washing Glass Sample Bottles and Vials:
5to7.
NOTE 4—Machine washing of narrow mouth sample bottles may not
6.24 Potassium Iodide–Starch Test Paper.
yield acceptable results.
6.25 Sodium Bisulfate.
8.2.1 Rinse the container with 100 mL of chromic acid
6.26 Sodium Bisulfite Solution—Dissolve2gof sodium
solution, returning the chromic acid to its original container
bisulfite in 1 L of water and adjust to pH 2 by the slow addition
after use. Then rinse with at least three 100-mL portions of tap
of H SO (1 + 1). Warning—Prepare and use this reagent in a
2 4
water.
well ventilated hood to avoid exposure to SO fumes.
8.2.2 Machine wash in accordance with the machine manu-
6.27 Sodium Sulfite Solution (0.1 M)—Transfer approxi-
facturer’s instructions using a detergent and 90°C water.
mately 10.3 g of sodium sulfite to a 1-L volumetric flask.
8.2.3 Remove the bottles from the machine and rinse them
Dilute to volume with water.
with two 100-mL portions of HCl (1 + 2), followed with three
6.28 Sodium Thiosulfate.
100-mL portions of water.
6.29 Sodium Hydroxide Pellets.
8.2.4 Heat for a minimum of 4 h (mouth up) in a forced draft
oven at 275 to 325°C. Upon cooling, fit the bottles with caps
6.30 Mercuric Chloride (10 mg/mL)—Dissolve 100 mg of
and the vials with septa (see Note 3).
HgCl in reagent water and dilute to 10 mL.
6.31 Sulfuric Acid (1 + 1)— —Slowly and carefully add 1
9. Sample Preservation
vol of sulfuric acid (see 6.27) to 1 vol of water, stirring and
9.1 Depending upon the type of analysis required, use any
cooling the solution during addition.
one or a combination of the following methods of sample
preservation (see Tables 1-3, Annex A1, and Annex A2).
7. Preparation of HDPE Sample Bottles
9.1.1 Adjust the pH. An adjustment to neutral pH is usually
7.1 Wash the bottles with two 100-mL portions of HCl
prescribed when chemical reactions, such as hydrolysis, are to
(1 + 2) and rinse with three 100-mL portions of water. These
be avoided. Adjustment to an extreme pH, for example, <2, is
volumes of wash and rinse portions are recommended for 1-L
usually prescribed to inhibit biological activity for biodegrad-
sample bottles; therefore, use proportionate volumes for wash-
able organic chemicals.
ing and rinsing sample bottles of a different volume.
NOTE 5—To confirm the adjustment of the pH of samples to the proper
value, place a drop of sample on an appropriate pH test paper or measure
8. Preparation of Glass Sample Bottles and Vials
with a pH meter.
8.1 Solvent-Detergent/Chromic Acid Preparation of Glass
9.1.1.1 Sulfuric Acid—To the sample bottle partially filled
Sample Bottles:
with sample, slowly add 2 mL of H SO (sp gr 1.84) and mix
2 4
8.1.1 Rinse the container with 100 mL of dilute detergent or
thoroughly. Confirm that the pH is less than 2. If the pH is
acetone. For some residues, a few alternative detergent and
greater than 2, add additional acid until the pH is less than 2.
acetone rinses may be more satisfactory. Then rinse at least
This procedure is based on a 1-L sample bottle; therefore, use
three times with tap water followed by a reagent water rinse to
proportionate volumes for sample bottles with a different
remove the residual detergent or acetone, or both.
volume.
8.1.2 Rinse the container with 100 mL of chromic acid
9.1.1.2 Hydrochloric Acid—To a sample bottle pa
...
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