ASTM D3694-96(2011)
(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
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.
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 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.
General Information
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Standards Content (Sample)
NOTICE: This standard has either been superseded and replaced by a new version or withdrawn.
Contact ASTM International (www.astm.org) for the latest information
Designation: D3694 − 96 (Reapproved 2011)
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 D1783 Test Methods for Phenolic Compounds in Water
D2036 Test Methods for Cyanides in Water
1.1 Thesepracticescoverthevariousmeansof(1)preparing
D2330 Test Method for Methylene Blue Active Substances
sample containers used for collection of waters to be analyzed
(Withdrawn 2011)
for organic constituents and (2) preservation of such samples
D2579 Test Method for Total Organic Carbon in Water
from the time of sample collection until the time of analysis.
(Withdrawn 2002)
1.2 The sample preservation practice is dependent upon the
D2580 Test Method for Phenols in Water by Gas-Liquid
specific analysis to be conducted. See Section 9 for preserva-
Chromatography
tion practices listed with the corresponding applicable general
D2908 Practice for Measuring Volatile Organic Matter in
and specific constituent test method. The preservation method
Water by Aqueous-Injection Gas Chromatography
for waterborne oils is given in Practice D3325. Use of the
D3113 Test Methods for Sodium Salts of EDTA in Water
information given herein will make it possible to choose the
(Withdrawn 2005)
minimum number of sample preservation practices necessary
D3325 Practice for Preservation of Waterborne Oil Samples
to ensure the integrity of a sample designated for multiple
D3371 Test Method for Nitriles in Aqueous Solution by
analysis. For further considerations of sample preservation, see
Gas-Liquid Chromatography (Withdrawn 2002)
the Manual on Water.
D3534 Test Method for Polychlorinated Biphenyls (PCBs)
1.3 The values stated in SI units are to be regarded as in Water (Withdrawn 2003)
D3590 Test Methods for Total Kjeldahl Nitrogen in Water
standard. No other units of measurement are included in this
standard. D3695 Test Method for VolatileAlcohols in Water by Direct
Aqueous-Injection Gas Chromatography
1.4 This standard does not purport to address all of the
D3856 Guide for Management Systems in Laboratories
safety concerns, if any, associated with its use. It is the
Engaged in Analysis of Water
responsibility of the user of this standard to establish appro-
D3871 Test Method for Purgeable Organic Compounds in
priate safety and health practices and determine the applica-
Water Using Headspace Sampling
bility of regulatory limitations prior to use. For specific hazard
D3921 Test Method For Oil and Grease and Petroleum
statements, see 6.7, 6.24, and 8.1.3.
Hydrocarbons in Water
D3973 TestMethodforLow-MolecularWeightHalogenated
2. Referenced Documents
Hydrocarbons in Water
2.1 ASTM Standards:
D4129 Test Method for Total and Organic Carbon in Water
D1129 Terminology Relating to Water
by High Temperature Oxidation and by Coulometric
D1193 Specification for Reagent Water
Detection
D1252 Test Methods for Chemical Oxygen Demand (Di-
D4165 Test Method for Cyanogen Chloride in Water
chromate Oxygen Demand) of Water
D4193 Test Method for Thiocyanate in Water
D4281 Test Method for Oil and Grease (Fluorocarbon Ex-
tractable Substances) by Gravimetric Determination
These practices are under the jurisdiction of ASTM Committee D19 on Water
and are the direct responsibilities of Subcommittee D19.06 on Methods forAnalysis
D4282 Test Method for Determination of Free Cyanide in
for Organic Substances in Water.
Water and Wastewater by Microdiffusion
Current edition approved May 1, 2011. Published June 2011. Originally
D4374 Test Methods for Cyanides in Water—Automated
approved in 1978. Last previous edition approved in 2004 as D3694 – 96 (2004).
DOI: 10.1520/D3694-96R11. Methods for Total Cyanide, Weak Acid Dissociable
Manual on Water, ASTM STP 442, ASTM, 1969.
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 The last approved version of this historical standard is referenced on
the ASTM website. www.astm.org.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States
D3694 − 96 (2011)
Cyanide, and Thiocyanate sampling, sample preservation, and analysis. In fact these four
D4515 Practice for Estimation of Holding Time for Water basic steps comprise the analytical method and for this reason
Samples Containing Organic Constituents (Withdrawn no step should be overlooked. Although the significance of
2006) preservation is dependent upon the time between sampling and
D4657 TestMethodforPolynuclearAromaticHydrocarbons the analysis, unless the analysis is accomplished within 2 h
in Water (Withdrawn 2005) after sampling, preservation is preferred and usually required.
D4744 Test Method for Organic Halides inWater by Carbon
5. Apparatus
AdsorptionMicrocoulometric Detection (Withdrawn
2002)
5.1 Forced Draft Oven, capable of operating at 275 to
D4763 Practice for Identification of Chemicals in Water by
325°C.
Fluorescence Spectroscopy
5.2 Sample Bottle, borosilicate or flint glass.
D4779 Test Method for Total, Organic, and Inorganic Car-
NOTE1—Highdensitypolyethylene(HDPE)bottlesandcapshavebeen
bon in High Purity Water by Ultraviolet (UV) or Persul-
demonstrated to be of sufficient quality to be compatible for all tests
fate Oxidation, or Both, and Infrared Detection (With-
except pesticides, herbicides, polychlorinated biphenyls, and volatile
drawn 2002)
organics. However, this bottle cannot be recycled.
D4839 Test Method forTotal Carbon and Organic Carbon in
5.3 Sample Bottle Cap, TFE-fluorocarbon or aluminum
WaterbyUltraviolet,orPersulfateOxidation,orBoth,and
foil-lined.
Infrared Detection
D4841 Practice for Estimation of Holding Time for Water
NOTE 2—Even these liners have some disadvantages. TFE is known to
collect some organic constituents, for example, PCBs.Aluminum foil will
Samples Containing Organic and Inorganic Constituents
react with samples that are strongly acid or alkaline. Clean TFE liners as
D4983 Test Method for Cyclohexylamine, Morpholine, and
described in 7.1. Replace aluminum foil with new foil after each use.
Diethylaminoethanol in Water and Condensed Steam by
5.4 Sample Vial, glass.
Direct Aqueous Injection Gas Chromatography (With-
drawn 2002)
5.5 Septa, PTFE-faced with screw cap lid and matching
D5175 Test Method for Organohalide Pesticides and Poly-
aluminum foil disks.
chlorinated Biphenyls in Water by Microextraction and
6. Reagents and Materials
Gas Chromatography
D5176 Test Method forTotal Chemically Bound Nitrogen in
6.1 Purity of Reagents—Reagent grade chemicals shall be
Water by Pyrolysis and Chemiluminescence Detection
used in all tests. Unless otherwise indicated, it is intended that
D5315 Test Method for Determination of N-Methyl-
all reagents shall conform to the specifications of the Commit-
Carbamoyloximes and N-Methylcarbamates in Water by
tee onAnalytical Reagents of theAmerican Chemical Society.
Direct Aqueous Injection HPLC with Post-Column De-
Other grades may be used, provided it is first ascertained that
rivatization
the reagent is of sufficiently high purity to permit its use
D5316 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
D5317 Test Method for Determination of Chlorinated Or-
to Specification D1193, Type II and demonstrated to be free of
ganicAcid Compounds in Water by Gas Chromatography
specific interference for the test being performed.
with an Electron Capture Detector
6.3 Acetic Acid Buffer Solution (pH 4)—Dissolve 6.0 g of
D5412 Test Method for Quantification of Complex Polycy-
clicAromatic Hydrocarbon Mixtures or Petroleum Oils in sodium acetate in 75 mLof water.Add 30 mLof glacial acetic
acid, with stirring.
Water
D5475 Test Method for Nitrogen- and Phosphorus-
6.4 Acetone.
Containing Pesticides in Water by Gas Chromatography
4 6.5 Acid Buffer Solution (pH 3.75)—Dissolve 125 g of
with a Nitrogen-Phosphorus Detector (Withdrawn 2011)
potassiumchlorideand70gofsodiumacetatetrihydratein500
D5790 Test Method for Measurement of Purgeable Organic
mL of water.Add 300 mL of glacial acetic acid and dilute to 1
Compounds in Water by Capillary Column Gas
L.
Chromatography/Mass Spectrometry
D5812 Test Method for Determination of Organochlorine 6.6 Ascorbic Acid.
Pesticides in Water by Capillary Column Gas Chromatog-
6.7 Chromic Acid Cleaning Solution—To a 2-L beaker, add
raphy (Withdrawn 2011)
35 mL of saturated sodium dichromate solution followed by 1
L of sulfuric acid (sp gr 1.84) with stirring. (Warning—Use
3. Terminology
3.1 Definitions—For definitions of terms used in this
practice, refer to Terminology D1129. Reagent Chemicals, American Chemical Society Specifications, American
Chemical Society, Washington, DC. For suggestions on the testing of reagents not
4. Significance and Use listed by the American Chemical Society, see Analar Standards for Laboratory
Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia
4.1 There are four basic steps necessary to obtain meaning-
and National Formulary, U.S. Pharmaceutical Convention, Inc. (USPC), Rockville,
ful analytical data: preparation of the sample container, MD.
D3694 − 96 (2011)
rubber gloves, safety goggles, and protective clothing when 7. Preparation of HDPE Sample Bottles
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 mLof dilute detergent or
acetone. For some residues, a few alternative detergent and
6.11 Ice, crushed wet.
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
remove the residual detergent or acetone, or both.
6.13 Lead Acetate Solution—Dissolve 50 g of lead acetate
8.1.2 Rinse the container with 100 mL of chromic acid
in water and dilute to 1 L.
solution, returning the chromic acid to its original container
6.14 Lead Carbonate, powdered.
after use. Then rinse with at least three 100-mLportions of tap
water followed by a reagent water rinse.
6.15 Lime, Hydrated, powdered.
8.1.3 Rinse the container with 100 mL of NaHSO solution
6.16 Mercuric Chloride.
to remove residual hexavalent chromium. (Warning—Carry
out this step in a hood to prevent exposure to SO fumes.)
6.17 Monochloroacetic Acid Buffer (pH 3)—Prepare by
8.1.4 Rinsethecontainerwithwateruntilsulfurousacidand
mixing 156 mL of chloroacetic acid solution (236.2 g/L) and
its vapors have been removed. Test rinsings for acid with a pH
100 mL of potassium acetate solution (245.4 g/L).
meter or an appropriate narrow range pH paper. Rinsings
6.18 Nitric Acid—Concentrated HNO (sp gr 1.42).
3 should have a pH approximately the same as the water used for
rinsing.
6.19 Phosphate Buffer—Dissolve 138 g of sodium dihydro-
8.1.5 When the last trace of NaHSO has been removed,
gen phosphate in water and dilute to 1 L. Refrigerate this
wash with three additional 100-mLportions of water.Allow to
solution.
drain. This procedure is for 1-L sample containers, therefore,
6.20 Phosphate Solution—Dissolve 33.8 g of potassium
use proportionate volumes for washing and rinsing sample
dihydrogen phosphate in 250 mL of water.
containers of a different volume.
8.1.6 Heatforaminimumof4h(mouthup)inaforceddraft
6.21 Phosphoric Acid—Concentrated H PO (sp gr 1.83).
3 4
oven at 275 to 325°C. Upon cooling, fit the bottles with caps
6.22 Phosphoric Acid Solution (1+1)—Dilute 1 vol of
and the vials with septa.
phosphoric acid (sp gr 1.83).
NOTE 3—For some tests, heating may not be required. Refer to the
individual method to determine the necessity for this treatment.
6.23 pH Paper, narrow range for pH < 2, pH > 12, and pH
5to7.
8.2 Machine Washing Glass Sample Bottles and Vials:
6.24 Potassium Iodide–Starch Test Paper.
NOTE 4—Machine washing of narrow mouth sample bottles may not
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 Lof water and adjust to pH 2 by the slow addition
after use. Then rinse with at least three 100-mLportions of tap
of H SO (1 + 1). (Warning—Prepare and use this reagent in
2 4 water.
a well ventilated hood to avoid exposure to SO fumes.)
8.2.2 Machine wash in accordance with the machine manu-
facturer’s instructions using a detergent and 90°C water.
6.27 Sodium Sulfite Solution (0.1 M)—Transfer approxi-
8.2.3 Remove the bottles from the machine and rinse them
mately 10.3 g of sodium sulfite to a 1-L volumetric flask.
with two 100-mL portions of HCl (1 + 2), followed with three
Dilute to volume with water.
100-mL portions of water.
6.28 Sodium Thiosulfate.
8.2.4 Heatforaminimumof4h(mouthup)inaforceddraft
oven at 275 to 325°C. Upon cooling, fit the bottles with caps
6.29 Sodium Hydroxide Pellets.
and the vials with septa (see Note 3).
6.30 Mercuric Chloride (10 mg/mL)—Dissolve 100 mg of
HgCl in reagent water and dilute to 10 mL.
2 9. Sample Preservation
6.31 Sulfuric Acid(1+1)—Slowly and carefully add 1 vol 9.1 Depending upon the type of analysis required, use any
ofsulfuricacid(see6.27)to1volofwater,stirringandcooling one or a combination of the following methods of sample
the solution during addition. preservation (see Tables 1-3, Annex A1, and Annex A2).
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