ASTM D3694-96(2024)
(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
SIGNIFICANCE AND USE
4.1 There are four basic steps necessary to obtain meaningful analytical data: preparation of the sample container, sampling, sample preservation, and analysis. In fact these four basic steps comprise the analytical method and for this reason no step should be overlooked. Although the significance of preservation is dependent upon the time between sampling and the analysis, unless the analysis is accomplished within 2 h after sampling, preservation is preferred and usually required.
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.2
1.3 The values stated in SI units are to be regarded as standard. No other units of measurement are included in this standard.
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, health, and environmental practices and determine the applicability of regulatory limitations prior to use. For specific hazard statements, see 6.7, 6.24, and 8.1.3.
1.5 This international standard was developed in accordance with internationally recognized principles on standardization established in the Decision on Principles for the Development of International Standards, Guides and Recommendations issued by the World Trade Organization Technical Barriers to Trade (TBT) Committee.
General Information
Relations
Standards Content (Sample)
This international standard was developed in accordance with internationally recognized principles on standardization established in the Decision on Principles for the
Development of International Standards, Guides and Recommendations issued by the World Trade Organization Technical Barriers to Trade (TBT) Committee.
Designation: D3694 − 96 (Reapproved 2024)
Standard Practices for
Preparation of Sample Containers and for Preservation of
Organic Constituents
This standard is issued under the fixed designation D3694; 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 2. Referenced Documents
2.1 ASTM Standards:
1.1 These practices cover the various means of (1) preparing
sample containers used for collection of waters to be analyzed D1129 Terminology Relating to Water
D1193 Specification for Reagent Water
for organic constituents and (2) preservation of such samples
from the time of sample collection until the time of analysis. D1252 Test Methods for Chemical Oxygen Demand (Di-
chromate Oxygen Demand) of Water
1.2 The sample preservation practice is dependent upon the
D1783 Test Methods for Phenolic Compounds in Water
specific analysis to be conducted. See Section 9 for preserva-
D2036 Test Methods for Cyanides in Water
tion practices listed with the corresponding applicable general
D2330 Test Method for Methylene Blue Active Substances
and specific constituent test method. The preservation method
D2579 Test Method for Total Organic Carbon in Water
for waterborne oils is given in Practice D3325. Use of the
(Withdrawn 2002)
information given herein will make it possible to choose the
D2580 Test Method for Phenols in Water by Gas-Liquid
minimum number of sample preservation practices necessary
Chromatography (Withdrawn 2021)
to ensure the integrity of a sample designated for multiple
D2908 Practice for Measuring Volatile Organic Matter in
analysis. For further considerations of sample preservation, see
2 Water by Aqueous-Injection Gas Chromatography
the Manual on Water.
D3113 Test Methods for Sodium Salts of EDTA in Water
1.3 The values stated in SI units are to be regarded as
(Withdrawn 2005)
standard. No other units of measurement are included in this
D3325 Practice for Preservation of Waterborne Oil Samples
standard.
D3371 Test Method for Nitriles in Aqueous Solution by
Gas-Liquid Chromatography (Withdrawn 2002)
1.4 This standard does not purport to address all of the
D3534 Test Method for Polychlorinated Biphenyls (PCBs)
safety concerns, if any, associated with its use. It is the
in Water (Withdrawn 2003)
responsibility of the user of this standard to establish appro-
D3590 Test Methods for Total Kjeldahl Nitrogen in Water
priate safety, health, and environmental practices and deter-
D3695 Test Method for Volatile Alcohols in Water by Direct
mine the applicability of regulatory limitations prior to use.
Aqueous-Injection Gas Chromatography
For specific hazard statements, see 6.7, 6.24, and 8.1.3.
D3856 Guide for Management Systems in Laboratories
1.5 This international standard was developed in accor-
Engaged in Analysis of Water (Withdrawn 2024)
dance with internationally recognized principles on standard-
D3871 Test Method for Purgeable Organic Compounds in
ization established in the Decision on Principles for the
Water Using Headspace Sampling
Development of International Standards, Guides and Recom-
D3921 Test Method For Oil and Grease and Petroleum
mendations issued by the World Trade Organization Technical
Hydrocarbons in Water (Withdrawn 2013)
Barriers to Trade (TBT) Committee.
D3973 Test Method for Low-Molecular Weight Halogenated
Hydrocarbons in Water
These practices are under the jurisdiction of ASTM Committee D19 on Water
and are the direct responsibilities of Subcommittee D19.06 on Methods for Analysis For referenced ASTM standards, visit the ASTM website, www.astm.org, or
for Organic Substances in Water. contact ASTM Customer Service at service@astm.org. For Annual Book of ASTM
Current edition approved April 1, 2024. Published April 2024. Originally Standards volume information, refer to the standard’s Document Summary page on
approved in 1978. Last previous edition approved in 2017 as D3694 – 96 (2017). the ASTM website.
DOI: 10.1520/D3694-96R24. The last approved version of this historical standard is referenced on
Manual on Water, ASTM STP 442, ASTM International, 1969. www.astm.org.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States
D3694 − 96 (2024)
D4129 Test Method for Total and Organic Carbon in Water D5790 Test Method for Measurement of Purgeable Organic
by High Temperature Oxidation and by Coulometric Compounds in Water by Capillary Column Gas
Chromatography/Mass Spectrometry
Detection
D5812 Test Method for Determination of Organochlorine
D4165 Test Method for Cyanogen Chloride in Water
Pesticides in Water by Capillary Column Gas Chromatog-
D4193 Test Method for Thiocyanate in Water
raphy (Withdrawn 2011)
D4281 Test Method for Oil and Grease (Fluorocarbon Ex-
tractable Substances) by Gravimetric Determination
4 3. Terminology
(Withdrawn 2012)
3.1 Definitions:
D4282 Test Method for Determination of Free Cyanide in
3.1.1 For definitions of terms used in this standard, refer to
Water and Wastewater by Microdiffusion
Terminology D1129.
D4374 Test Methods for Cyanides in Water—Automated
Methods for Total Cyanide, Weak Acid Dissociable
4. Significance and Use
Cyanide, and Thiocyanate (Withdrawn 2012)
4.1 There are four basic steps necessary to obtain meaning-
D4515 Practice for Estimation of Holding Time for Water
ful analytical data: preparation of the sample container,
Samples Containing Organic Constituents (Withdrawn
sampling, sample preservation, and analysis. In fact these four
2006)
basic steps comprise the analytical method and for this reason
D4657 Test Method for Polynuclear Aromatic Hydrocarbons
no step should be overlooked. Although the significance of
in Water (Withdrawn 2005)
preservation is dependent upon the time between sampling and
D4744 Test Method for Organic Halides in Water by Carbon
the analysis, unless the analysis is accomplished within 2 h
AdsorptionMicrocoulometric Detection (Withdrawn
4 after sampling, preservation is preferred and usually required.
2002)
D4763 Practice for Identification of Chemicals in Water by
5. Apparatus
Fluorescence Spectroscopy
5.1 Forced Draft Oven, capable of operating at 275 °C to
D4779 Test Method for Total, Organic, and Inorganic Car-
325 °C.
bon in High Purity Water by Ultraviolet (UV) or Persul-
fate Oxidation, or Both, and Infrared Detection (With-
5.2 Sample Bottle, borosilicate or flint glass.
drawn 2002)
NOTE 1—High density polyethylene (HDPE) bottles and caps have been
D4839 Test Method for Total Carbon and Organic Carbon in
demonstrated to be of sufficient quality to be compatible for all tests
Water by Ultraviolet, or Persulfate Oxidation, or Both, and except pesticides, herbicides, polychlorinated biphenyls, and volatile
organics. However, this bottle cannot be recycled.
Infrared Detection
D4841 Practice for Estimation of Holding Time for Water
5.3 Sample Bottle Cap, TFE-fluorocarbon or aluminum
Samples Containing Organic and Inorganic Constituents foil-lined.
D4983 Test Method for Cyclohexylamine, Morpholine, and
NOTE 2—Even these liners have some disadvantages. TFE is known to
Diethylaminoethanol in Water and Condensed Steam by
collect some organic constituents, for example, PCBs. Aluminum foil will
Direct Aqueous Injection Gas Chromatography (With- react with samples that are strongly acid or alkaline. Clean TFE liners as
described in 7.1. Replace aluminum foil with new foil after each use.
drawn 2002)
D5175 Test Method for Organohalide Pesticides and Poly- 5.4 Sample Vial, glass.
chlorinated Biphenyls in Water by Microextraction and
5.5 Septa, PTFE-faced with screw cap lid and matching
Gas Chromatography
aluminum foil disks.
D5176 Test Method for Total Chemically Bound Nitrogen in
Water by Pyrolysis and Chemiluminescence Detection
6. Reagents and Materials
D5315 Test Method for Determination of N-Methyl-
6.1 Purity of Reagents—Reagent grade chemicals shall be
Carbamoyloximes and N-Methylcarbamates in Water by
used in all tests. Unless otherwise indicated, it is intended that
Direct Aqueous Injection HPLC with Post-Column De-
all reagents shall conform to the specifications of the Commit-
rivatization
tee on Analytical Reagents of the American Chemical Society.
D5316 Test Method for 1,2-Dibromoethane and 1,2-
Other grades may be used, provided it is first ascertained that
Dibromo-3-Chloropropane in Water by Microextraction
the reagent is of sufficiently high purity to permit its use
and Gas Chromatography
without lessening the accuracy of the determination.
D5317 Test Method for Determination of Chlorinated Or-
6.2 Purity of Water—Unless otherwise indicated, reference
ganic Acid Compounds in Water by Gas Chromatography
to water shall be understood to mean reagent water conforming
with an Electron Capture Detector
D5412 Test Method for Quantification of Complex Polycy-
clic Aromatic Hydrocarbon Mixtures or Petroleum Oils in
ACS Reagent Chemicals, Specifications and Procedures for Reagents and
Standard-Grade Reference Materials, American Chemical Society, Washington,
Water
DC. For suggestions on the testing of reagents not listed by the American Chemical
D5475 Test Method for Nitrogen- and Phosphorus-
Society, see Analar Standards for Laboratory Chemicals, BDH Ltd., Poole, Dorset,
Containing Pesticides in Water by Gas Chromatography
U.K., and the United States Pharmacopeia and National Formulary, U.S. Pharma-
with a Nitrogen-Phosphorus Detector (Withdrawn 2011) copeial Convention, Inc. (USPC), Rockville, MD.
D3694 − 96 (2024)
to Specification D1193, Type II and demonstrated to be free of of H SO (1 + 1). (Warning—Prepare and use this reagent in
2 4
specific interference for the test being performed. a well ventilated hood to avoid exposure to SO fumes.)
6.3 Acetic Acid Buffer Solution (pH 4)—Dissolve 6.0 g of
6.27 Sodium Sulfite Solution (0.1 M)—Transfer approxi-
sodium acetate in 75 mL of water. Add 30 mL of glacial acetic
mately 10.3 g of sodium sulfite to a 1 L volumetric flask. Dilute
acid, with stirring.
to volume with water.
6.4 Acetone.
6.28 Sodium Thiosulfate.
6.5 Acid Buffer Solution (pH 3.75)—Dissolve 125 g of
6.29 Sodium Hydroxide Pellets.
potassium chloride and 70 g of sodium acetate trihydrate in
6.30 Mercuric Chloride (10 mg/mL)—Dissolve 100 mg of
500 mL of water. Add 300 mL of glacial acetic acid and dilute
HgCl in reagent water and dilute to 10 mL.
to 1 L.
6.31 Sulfuric Acid (1 + 1)—Slowly and carefully add 1 vol
6.6 Ascorbic Acid.
of sulfuric acid (see 6.27) to 1 vol of water, stirring and cooling
6.7 Chromic Acid Cleaning Solution—To a 2 L beaker, add
the solution during addition.
35 mL of saturated sodium dichromate solution followed by
1 L of sulfuric acid (sp gr 1.84) with stirring. (Warning—Use
7. Preparation of HDPE Sample Bottles
rubber gloves, safety goggles, and protective clothing when
preparing and handling this corrosive cleaning agent that is a 7.1 Wash the bottles with two 100 mL portions of HCl
powerful oxidant. Store the reagent in a glass bottle with a
(1 + 2) and rinse with three 100 mL portions of water. These
glass stopper.) volumes of wash and rinse portions are recommended for 1 L
sample bottles; therefore, use proportionate volumes for wash-
6.8 Detergent, formulated for cleaning laboratory glass-
ing and rinsing sample bottles of a different volume.
ware.
6.9 Hydrochloric Acid—Concentrated HCl (sp gr 1.19).
8. Preparation of Glass Sample Bottles and Vials
6.10 Hydrochloric Acid (1 + 2)—To 200 mL of water, care-
8.1 Solvent-Detergent/Chromic Acid Preparation of Glass
fully add 100 mL of hydrochloric acid (see 6.9). Store in a
Sample Bottles:
glass-stoppered reagent bottle.
8.1.1 Rinse the container with 100 mL of dilute detergent or
6.11 Ice, crushed wet.
acetone. For some residues, a few alternative detergent and
acetone rinses may be more satisfactory. Then rinse at least
6.12 Lead Acetate Test Paper.
three times with tap water followed by a reagent water rinse to
6.13 Lead Acetate Solution—Dissolve 50 g of lead acetate
remove the residual detergent or acetone, or both.
in water and dilute to 1 L.
8.1.2 Rinse the container with 100 mL of chromic acid
6.14 Lead Carbonate, powdered. solution, returning the chromic acid to its original container
after use. Then rinse with at least three 100 mL portions of tap
6.15 Lime, Hydrated, powdered.
water followed by a reagent water rinse.
6.16 Mercuric Chloride.
8.1.3 Rinse the container with 100 mL of NaHSO solution
6.17 Monochloroacetic Acid Buffer (pH 3)—Prepare by to remove residual hexavalent chromium. (Warning—Carry
out this step in a hood to prevent exposure to SO fumes.)
mixing 156 mL of chloroacetic acid solution (236.2 g/L) and
100 mL of potassium acetate solution (245.4 g/L).
8.1.4 Rinse the container with water until sulfurous acid and
its vapors have been removed. Test rinsings for acid with a pH
6.18 Nitric Acid—Concentrated HNO (sp gr 1.42).
meter or an appropriate narrow range pH paper. Rinsings
6.19 Phosphate Buffer—Dissolve 138 g of sodium dihydro-
should have a pH approximately the same as the water used for
gen phosphate in water and dilute to 1 L. Refrigerate this
rinsing.
solution.
8.1.5 When the last trace of NaHSO has been removed,
6.20 Phosphate Solution—Dissolve 33.8 g of potassium di- wash with three additional 100 mL portions of water. Allow to
hydrogen phosphate in 250 mL of water.
drain. This procedure is for 1 L sample containers, therefore,
use proportionate volumes for washing and rinsing sample
6.21 Phosphoric Acid—Concentrated H PO (sp gr 1.83).
3 4
containers of a different volume.
6.22 Phosphoric Acid Solution (1 + 1)—Dilute 1 vol of
8.1.6 Heat for a minimum of 4 h (mouth up) in a forced draft
phosphoric acid (sp gr 1.83).
oven at 275 °C to 325 °C. Upon cooling, fit the bottles with
6.23 pH Paper, narrow range for pH < 2, pH > 12, and pH caps and the vials with septa.
5 to 7.
NOTE 3—For some tests, heating may not be required. Refer to the
6.24 Potassium Iodide–Starch Test Paper. individual method to determine the necessity for this treatment.
6.25 Sodium Bisulfate. 8.2 Machine Washing Glass Sample Bottles and Vials:
6.26 Sodium Bisulfite Solution—Dissolve 2 g of sodium
NOTE 4—Machine washing of narrow mouth sample bottles may not
bisulfite in 1 L of water and adjust to pH 2 by the slow addition yield acceptable results.
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