ASTM D3694-96(2017)
(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
Buy Standard
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 2017)
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
1.1 Thesepracticescoverthevariousmeansof(1)preparing 2.1 ASTM Standards:
sample containers used for collection of waters to be analyzed D1129 Terminology Relating to Water
for organic constituents and (2) preservation of such samples D1193 Specification for Reagent Water
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
(Withdrawn 2011)
for waterborne oils is given in Practice D3325. Use of the
D2579 Test Method for Total Organic Carbon in Water
information given herein will make it possible to choose the
(Withdrawn 2002)
minimum number of sample preservation practices necessary
D2580 Test Method for Phenols in Water by Gas-Liquid
to ensure the integrity of a sample designated for multiple
Chromatography
analysis. For further considerations of sample preservation, see
D2908 Practice for Measuring Volatile Organic Matter in
the Manual on Water.
Water by Aqueous-Injection Gas Chromatography
1.3 The values stated in SI units are to be regarded as
D3113 Test Methods for Sodium Salts of EDTA in Water
standard. No other units of measurement are included in this
(Withdrawn 2005)
standard.
D3325 Practice for Preservation of Waterborne Oil Samples
1.4 This standard does not purport to address all of the
D3371 Test Method for Nitriles in Aqueous Solution by
safety concerns, if any, associated with its use. It is the Gas-Liquid Chromatography (Withdrawn 2002)
responsibility of the user of this standard to establish appro-
D3534 Test Method for Polychlorinated Biphenyls (PCBs)
priate safety, health, and environmental practices and deter- in Water (Withdrawn 2003)
mine the applicability of regulatory limitations prior to use.
D3590 Test Methods for Total Kjeldahl Nitrogen in Water
For specific hazard statements, see 6.7, 6.24, and 8.1.3. D3695 Test Method for VolatileAlcohols in Water by Direct
1.5 This international standard was developed in accor-
Aqueous-Injection Gas Chromatography
dance with internationally recognized principles on standard- D3856 Guide for Management Systems in Laboratories
ization established in the Decision on Principles for the
Engaged in Analysis of Water
Development of International Standards, Guides and Recom- D3871 Test Method for Purgeable Organic Compounds in
mendations issued by the World Trade Organization Technical
Water Using Headspace Sampling
Barriers to Trade (TBT) Committee. D3921 Test Method For Oil and Grease and Petroleum
Hydrocarbons in Water (Withdrawn 2013)
These practices are under the jurisdiction of ASTM Committee D19 on Water
and are the direct responsibilities of Subcommittee D19.06 on Methods forAnalysis 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 Dec. 15, 2017. Published December 2017. Originally Standards volume information, refer to the standard’s Document Summary page on
approved in 1978. Last previous edition approved in 2011 as D3694 – 96 (2011). the ASTM website.
DOI: 10.1520/D3694-96R17. 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 (2017)
D3973 TestMethodforLow-MolecularWeightHalogenated D5475 Test Method for Nitrogen- and Phosphorus-
Hydrocarbons in Water Containing Pesticides in Water by Gas Chromatography
with a Nitrogen-Phosphorus Detector (Withdrawn 2011)
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
Detection
Chromatography/Mass Spectrometry
D4165 Test Method for Cyanogen Chloride in Water
D5812 Test Method for Determination of Organochlorine
D4193 Test Method for Thiocyanate in Water
Pesticides in Water by Capillary Column Gas Chromatog-
D4281 Test Method for Oil and Grease (Fluorocarbon Ex-
raphy (Withdrawn 2011)
tractable Substances) by Gravimetric Determination
(Withdrawn 2012)
3. Terminology
D4282 Test Method for Determination of Free Cyanide in
3.1 Definitions:
Water and Wastewater by Microdiffusion
3.1.1 For definitions of terms used in this standard, refer to
D4374 Test Methods for Cyanides in Water—Automated
Terminology D1129.
Methods for Total Cyanide, Weak Acid Dissociable
Cyanide, and Thiocyanate (Withdrawn 2012)
4. Significance and Use
D4515 Practice for Estimation of Holding Time for Water
4.1 There are four basic steps necessary to obtain meaning-
Samples Containing Organic Constituents (Withdrawn
ful analytical data: preparation of the sample container,
2006)
sampling, sample preservation, and analysis. In fact these four
D4657 TestMethodforPolynuclearAromaticHydrocarbons
basic steps comprise the analytical method and for this reason
in Water (Withdrawn 2005)
no step should be overlooked. Although the significance of
D4744 Test Method for Organic Halides inWater by Carbon
preservation is dependent upon the time between sampling and
AdsorptionMicrocoulometric Detection (Withdrawn
the analysis, unless the analysis is accomplished within 2 h
2002) after sampling, preservation is preferred and usually required.
D4763 Practice for Identification of Chemicals in Water by
5. Apparatus
Fluorescence Spectroscopy
D4779 Test Method for Total, Organic, and Inorganic Car- 5.1 Forced Draft Oven, capable of operating at 275 to
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)
NOTE1—Highdensitypolyethylene(HDPE)bottlesandcapshavebeen
D4839 Test Method forTotal Carbon and Organic Carbon in
demonstrated to be of sufficient quality to be compatible for all tests
WaterbyUltraviolet,orPersulfateOxidation,orBoth,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 forTotal Chemically Bound Nitrogen in
6. Reagents and Materials
Water by Pyrolysis and Chemiluminescence Detection
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 onAnalytical Reagents of theAmerican Chemical Society.
Other grades may be used, provided it is first ascertained that
D5316 Test Method for 1,2-Dibromoethane and 1,2-
the reagent is of sufficiently high purity to permit its use
Dibromo-3-Chloropropane in Water by Microextraction
without lessening the accuracy of the determination.
and Gas Chromatography
D5317 Test Method for Determination of Chlorinated Or-
ganicAcid Compounds in Water by Gas Chromatography 5
Reagent Chemicals, American Chemical Society Specifications, American
with an Electron Capture Detector Chemical Society, Washington, DC. For suggestions on the testing of reagents not
listed by the American Chemical Society, see Analar Standards for Laboratory
D5412 Test Method for Quantification of Complex Polycy-
Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia
clicAromatic Hydrocarbon Mixtures or Petroleum Oils in
and National Formulary, U.S. Pharmaceutical Convention, Inc. (USPC), Rockville,
Water MD.
D3694 − 96 (2017)
6.2 Purity of Water—Unless otherwise indicated, reference 6.26 Sodium Bisulfite Solution—Dissolve2gof sodium
towatershallbeunderstoodtomeanreagentwaterconforming bisulfite in 1 Lof water and adjust to pH 2 by the slow addition
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-
mately 10.3 g of sodium sulfite to a 1-L volumetric flask.
sodium acetate in 75 mLof water.Add 30 mLof glacial acetic
Dilute to volume with water.
acid, with stirring.
6.28 Sodium Thiosulfate.
6.4 Acetone.
6.29 Sodium Hydroxide Pellets.
6.5 Acid Buffer Solution (pH 3.75)—Dissolve 125 g of
potassiumchlorideand70gofsodiumacetatetrihydratein500
6.30 Mercuric Chloride (10 mg/mL)—Dissolve 100 mg of
mLof water.Add 300 mLof glacial acetic acid and dilute to 1
HgCl in reagent water and dilute to 10 mL.
L.
6.31 Sulfuric Acid(1+1)—Slowly and carefully add 1 vol
6.6 Ascorbic Acid.
ofsulfuricacid(see6.27)to1volofwater,stirringandcooling
the solution during addition.
6.7 Chromic Acid Cleaning Solution—To a 2-L beaker, add
35 mL of saturated sodium dichromate solution followed by 1
7. Preparation of HDPE Sample Bottles
L of sulfuric acid (sp gr 1.84) with stirring. (Warning—Use
rubber gloves, safety goggles, and protective clothing when
7.1 Wash the bottles with two 100-mL portions of HCl
preparing and handling this corrosive cleaning agent that is a
(1 + 2) and rinse with three 100-mL portions of water. These
powerful oxidant. Store the reagent in a glass bottle with a
volumes of wash and rinse portions are recommended for 1-L
glass stopper.)
sample bottles; therefore, use proportionate volumes for wash-
ing and rinsing sample bottles of a different volume.
6.8 Detergent, formulated for cleaning laboratory glass-
ware.
8. Preparation of Glass Sample Bottles and Vials
6.9 Hydrochloric Acid—Concentrated HCl (sp gr 1.19).
8.1 Solvent-Detergent/Chromic Acid Preparation of Glass
6.10 Hydrochloric Acid(1+2)—To 200 mL of water, care-
Sample Bottles:
fully add 100 mL of hydrochloric acid (see 6.9). Store in a
8.1.1 Rinse the container with 100 mLof dilute detergent or
glass-stoppered reagent bottle.
acetone. For some residues, a few alternative detergent and
acetone rinses may be more satisfactory. Then rinse at least
6.11 Ice, crushed wet.
three times with tap water followed by a reagent water rinse to
6.12 Lead Acetate Test Paper.
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
after use. Then rinse with at least three 100-mLportions of tap
6.14 Lead Carbonate, powdered.
water followed by a reagent water rinse.
6.15 Lime, Hydrated, powdered.
8.1.3 Rinse the container with 100 mL of NaHSO solution
to remove residual hexavalent chromium. (Warning—Carry
6.16 Mercuric Chloride.
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). 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
6.23 pH Paper, narrow range for pH < 2, pH > 12, and pH
individual method to determine the necessity for this treatment.
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
6.25 Sodium Bisulfate. yield acceptable results.
D3694 − 96 (2017)
TABLE 2 Recommended Preservation Practice for Specific
8.2.1 Rinse the container with 100 mL of chromic acid
Organic Constituent Test Met
...
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 2017)
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
1.1 These practices cover the various means of (1) preparing 2.1 ASTM Standards:
sample containers used for collection of waters to be analyzed D1129 Terminology Relating to Water
for organic constituents and (2) preservation of such samples D1193 Specification for Reagent Water
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
(Withdrawn 2011)
for waterborne oils is given in Practice D3325. Use of the
D2579 Test Method for Total Organic Carbon in Water
information given herein will make it possible to choose the
(Withdrawn 2002)
minimum number of sample preservation practices necessary
D2580 Test Method for Phenols in Water by Gas-Liquid
to ensure the integrity of a sample designated for multiple
Chromatography
analysis. For further considerations of sample preservation, see
2 D2908 Practice for Measuring Volatile Organic Matter in
the Manual on Water.
Water by Aqueous-Injection Gas Chromatography
1.3 The values stated in SI units are to be regarded as
D3113 Test Methods for Sodium Salts of EDTA in Water
standard. No other units of measurement are included in this
(Withdrawn 2005)
standard.
D3325 Practice for Preservation of Waterborne Oil Samples
1.4 This standard does not purport to address all of the D3371 Test Method for Nitriles in Aqueous Solution by
safety concerns, if any, associated with its use. It is the
Gas-Liquid Chromatography (Withdrawn 2002)
responsibility of the user of this standard to establish appro- D3534 Test Method for Polychlorinated Biphenyls (PCBs)
priate safety, health, and environmental practices and deter-
in Water (Withdrawn 2003)
mine the applicability of regulatory limitations prior to use. D3590 Test Methods for Total Kjeldahl Nitrogen in Water
For specific hazard statements, see 6.7, 6.24, and 8.1.3.
D3695 Test Method for Volatile Alcohols in Water by Direct
1.5 This international standard was developed in accor- Aqueous-Injection Gas Chromatography
dance with internationally recognized principles on standard-
D3856 Guide for Management Systems in Laboratories
ization established in the Decision on Principles for the Engaged in Analysis of Water
Development of International Standards, Guides and Recom-
D3871 Test Method for Purgeable Organic Compounds in
mendations issued by the World Trade Organization Technical Water Using Headspace Sampling
Barriers to Trade (TBT) Committee.
D3921 Test Method For Oil and Grease and Petroleum
Hydrocarbons in Water (Withdrawn 2013)
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 Dec. 15, 2017. Published December 2017. Originally Standards volume information, refer to the standard’s Document Summary page on
approved in 1978. Last previous edition approved in 2011 as D3694 – 96 (2011). the ASTM website.
DOI: 10.1520/D3694-96R17. 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 (2017)
D3973 Test Method for Low-Molecular Weight Halogenated D5475 Test Method for Nitrogen- and Phosphorus-
Containing Pesticides in Water by Gas Chromatography
Hydrocarbons in Water
with a Nitrogen-Phosphorus Detector (Withdrawn 2011)
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
Detection
Chromatography/Mass Spectrometry
D4165 Test Method for Cyanogen Chloride in Water
D5812 Test Method for Determination of Organochlorine
D4193 Test Method for Thiocyanate in Water
Pesticides in Water by Capillary Column Gas Chromatog-
D4281 Test Method for Oil and Grease (Fluorocarbon Ex-
raphy (Withdrawn 2011)
tractable Substances) by Gravimetric Determination
(Withdrawn 2012)
3. Terminology
D4282 Test Method for Determination of Free Cyanide in
3.1 Definitions:
Water and Wastewater by Microdiffusion
3.1.1 For definitions of terms used in this standard, refer to
D4374 Test Methods for Cyanides in Water—Automated
Terminology D1129.
Methods for Total Cyanide, Weak Acid Dissociable
Cyanide, and Thiocyanate (Withdrawn 2012)
4. Significance and Use
D4515 Practice for Estimation of Holding Time for Water
4.1 There are four basic steps necessary to obtain meaning-
Samples Containing Organic Constituents (Withdrawn
ful analytical data: preparation of the sample container,
2006)
sampling, sample preservation, and analysis. In fact these four
D4657 Test Method for Polynuclear Aromatic Hydrocarbons
basic steps comprise the analytical method and for this reason
in Water (Withdrawn 2005)
no step should be overlooked. Although the significance of
D4744 Test Method for Organic Halides in Water by Carbon
preservation is dependent upon the time between sampling and
AdsorptionMicrocoulometric Detection (Withdrawn
the analysis, unless the analysis is accomplished within 2 h
2002)
after sampling, preservation is preferred and usually required.
D4763 Practice for Identification of Chemicals in Water by
5. Apparatus
Fluorescence Spectroscopy
5.1 Forced Draft Oven, capable of operating at 275 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
6. Reagents and Materials
Water by Pyrolysis and Chemiluminescence Detection
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
the reagent is of sufficiently high purity to permit its use
Dibromo-3-Chloropropane in Water by Microextraction
without lessening the accuracy of the determination.
and Gas Chromatography
D5317 Test Method for Determination of Chlorinated Or-
ganic Acid Compounds in Water by Gas Chromatography
Reagent Chemicals, American Chemical Society Specifications, American
with an Electron Capture Detector
Chemical Society, Washington, DC. For suggestions on the testing of reagents not
listed by the American Chemical Society, see Analar Standards for Laboratory
D5412 Test Method for Quantification of Complex Polycy-
Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia
clic Aromatic Hydrocarbon Mixtures or Petroleum Oils in
and National Formulary, U.S. Pharmaceutical Convention, Inc. (USPC), Rockville,
Water MD.
D3694 − 96 (2017)
6.2 Purity of Water—Unless otherwise indicated, reference 6.26 Sodium Bisulfite Solution—Dissolve 2 g of sodium
to water shall be understood to mean reagent water conforming bisulfite in 1 L of water and adjust to pH 2 by the slow addition
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.)
6.27 Sodium Sulfite Solution (0.1 M)—Transfer approxi-
6.3 Acetic Acid Buffer Solution (pH 4)—Dissolve 6.0 g of
mately 10.3 g of sodium sulfite to a 1-L volumetric flask.
sodium acetate in 75 mL of water. Add 30 mL of glacial acetic
Dilute to volume with water.
acid, with stirring.
6.28 Sodium Thiosulfate.
6.4 Acetone.
6.29 Sodium Hydroxide Pellets.
6.5 Acid Buffer Solution (pH 3.75)—Dissolve 125 g of
potassium chloride and 70 g of sodium acetate trihydrate in 500
6.30 Mercuric Chloride (10 mg/mL)—Dissolve 100 mg of
mL of water. Add 300 mL of glacial acetic acid and dilute to 1
HgCl in reagent water and dilute to 10 mL.
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
the solution during addition.
6.7 Chromic Acid Cleaning Solution—To a 2-L beaker, add
35 mL of saturated sodium dichromate solution followed by 1
7. Preparation of HDPE Sample Bottles
L of sulfuric acid (sp gr 1.84) with stirring. (Warning—Use
rubber gloves, safety goggles, and protective clothing when
7.1 Wash the bottles with two 100-mL portions of HCl
preparing and handling this corrosive cleaning agent that is a
(1 + 2) and rinse with three 100-mL portions of water. These
powerful oxidant. Store the reagent in a glass bottle with a
volumes of wash and rinse portions are recommended for 1-L
glass stopper.)
sample bottles; therefore, use proportionate volumes for wash-
ing and rinsing sample bottles of a different volume.
6.8 Detergent, formulated for cleaning laboratory glass-
ware.
8. Preparation of Glass Sample Bottles and Vials
6.9 Hydrochloric Acid—Concentrated HCl (sp gr 1.19).
8.1 Solvent-Detergent/Chromic Acid Preparation of Glass
6.10 Hydrochloric Acid (1 + 2)—To 200 mL of water, care-
Sample Bottles:
fully add 100 mL of hydrochloric acid (see 6.9). Store in a
8.1.1 Rinse the container with 100 mL of dilute detergent or
glass-stoppered reagent bottle.
acetone. For some residues, a few alternative detergent and
6.11 Ice, crushed wet. acetone rinses may be more satisfactory. Then rinse at least
three times with tap water followed by a reagent water rinse to
6.12 Lead Acetate Test Paper.
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
after use. Then rinse with at least three 100-mL portions of tap
6.14 Lead Carbonate, powdered.
water followed by a reagent water rinse.
6.15 Lime, Hydrated, powdered.
8.1.3 Rinse the container with 100 mL of NaHSO solution
to remove residual hexavalent chromium. (Warning—Carry
6.16 Mercuric Chloride.
out this step in a hood to prevent exposure to SO fumes.)
6.17 Monochloroacetic Acid Buffer (pH 3)—Prepare by
8.1.4 Rinse the container with water until sulfurous acid and
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).
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-mL portions 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 Heat for a minimum of 4 h (mouth up) in a forced draft
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
6.23 pH Paper, narrow range for pH < 2, pH > 12, and pH
individual method to determine the necessity for this treatment.
5 to 7.
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
6.25 Sodium Bisulfate. yield acceptable results.
D3694 − 96 (2017)
TABLE 2 Recommended Preservation Practice for Specific
8.2.1 Rinse the container with 100 mL of chromic acid
Organic Constituent Test Methods
solutio
...
This document is not an ASTM standard and is intended only to provide the user of an ASTM standard an indication of what changes have been made to the previous version. Because
it may not be technically possible to adequately depict all changes accurately, ASTM recommends that users consult prior editions as appropriate. In all cases only the current version
of the standard as published by ASTM is to be considered the official document.
Designation: D3694 − 96 (Reapproved 2011) D3694 − 96 (Reapproved 2017)
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
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 safety, health, and healthenvironmental 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.
2. Referenced Documents
2.1 ASTM Standards:
D1129 Terminology Relating to Water
D1193 Specification for Reagent Water
D1252 Test Methods for Chemical Oxygen Demand (Dichromate Oxygen Demand) of Water
D1783 Test Methods for Phenolic Compounds in Water
D2036 Test Methods for Cyanides in Water
D2330 Test Method for Methylene Blue Active Substances (Withdrawn 2011)
D2579 Test Method for Total Organic Carbon in Water (Withdrawn 2002)
D2580 Test Method for Phenols in Water by Gas-Liquid Chromatography
D2908 Practice for Measuring Volatile Organic Matter in Water by Aqueous-Injection Gas Chromatography
D3113 Test Methods for Sodium Salts of EDTA in Water (Withdrawn 2005)
D3325 Practice for Preservation of Waterborne Oil Samples
D3371 Test Method for Nitriles in Aqueous Solution by Gas-Liquid Chromatography (Withdrawn 2002)
D3534 Test Method for Polychlorinated Biphenyls (PCBs) in Water (Withdrawn 2003)
D3590 Test Methods for Total Kjeldahl Nitrogen in Water
D3695 Test Method for Volatile Alcohols in Water by Direct Aqueous-Injection Gas Chromatography
D3856 Guide for Management Systems in Laboratories Engaged in Analysis of 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
Organic Substances in Water.
Current edition approved May 1, 2011Dec. 15, 2017. Published June 2011December 2017. Originally approved in 1978. Last previous edition approved in 20042011 as
D3694 – 96 (2011). (2004). DOI: 10.1520/D3694-96R11.10.1520/D3694-96R17.
Manual on Water, ASTM STP 442, ASTM, 1969.Manual on Water, ASTM STP 442, ASTM International, 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 ASTM website.
The last approved version of this historical standard is referenced on www.astm.org.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States
D3694 − 96 (2017)
D3871 Test Method for Purgeable Organic Compounds in Water Using Headspace Sampling
D3921 Test Method For Oil and Grease and Petroleum Hydrocarbons in Water (Withdrawn 2013)
D3973 Test Method for Low-Molecular Weight Halogenated Hydrocarbons in Water
D4129 Test Method for Total and Organic Carbon in Water by High Temperature Oxidation and by Coulometric Detection
D4165 Test Method for Cyanogen Chloride in Water
D4193 Test Method for Thiocyanate in Water
D4281 Test Method for Oil and Grease (Fluorocarbon Extractable Substances) by Gravimetric Determination (Withdrawn
2012)
D4282 Test Method for Determination of Free Cyanide in Water and Wastewater by Microdiffusion
D4374 Test Methods for Cyanides in Water—Automated Methods for Total Cyanide, Weak Acid Dissociable Cyanide, and
Thiocyanate (Withdrawn 2012)
D4515 Practice for Estimation of Holding Time for Water Samples Containing Organic Constituents (Withdrawn 2006)
D4657 Test Method for Polynuclear Aromatic Hydrocarbons in Water (Withdrawn 2005)
D4744 Test Method for Organic Halides in Water by Carbon AdsorptionMicrocoulometric Detection (Withdrawn 2002)
D4763 Practice for Identification of Chemicals in Water by Fluorescence Spectroscopy
D4779 Test Method for Total, Organic, and Inorganic Carbon in High Purity Water by Ultraviolet (UV) or Persulfate Oxidation,
or Both, and Infrared Detection (Withdrawn 2002)
D4839 Test Method for Total Carbon and Organic Carbon in Water by Ultraviolet, or Persulfate Oxidation, or Both, and Infrared
Detection
D4841 Practice for Estimation of Holding Time for Water Samples Containing Organic and Inorganic Constituents
D4983 Test Method for Cyclohexylamine, Morpholine, and Diethylaminoethanol in Water and Condensed Steam by Direct
Aqueous Injection Gas Chromatography (Withdrawn 2002)
D5175 Test Method for Organohalide Pesticides and Polychlorinated Biphenyls in Water by Microextraction and Gas
Chromatography
D5176 Test Method for Total Chemically Bound Nitrogen in Water by Pyrolysis and Chemiluminescence Detection
D5315 Test Method for Determination of N-Methyl-Carbamoyloximes and N-Methylcarbamates in Water by Direct Aqueous
Injection HPLC with Post-Column Derivatization
D5316 Test Method for 1,2-Dibromoethane and 1,2-Dibromo-3-Chloropropane in Water by Microextraction and Gas
Chromatography
D5317 Test Method for Determination of Chlorinated Organic Acid Compounds in Water by Gas Chromatography with an
Electron Capture Detector
D5412 Test Method for Quantification of Complex Polycyclic Aromatic Hydrocarbon Mixtures or Petroleum Oils in Water
D5475 Test Method for Nitrogen- and Phosphorus-Containing Pesticides in Water by Gas Chromatography with a Nitrogen-
Phosphorus Detector (Withdrawn 2011)
D5790 Test Method for Measurement of Purgeable Organic Compounds in Water by Capillary Column Gas Chromatography/
Mass Spectrometry
D5812 Test Method for Determination of Organochlorine Pesticides in Water by Capillary Column Gas Chromatography
(Withdrawn 2011)
3. Terminology
3.1 Definitions—For definitions of terms used in this practice, refer to Terminology D1129.
3.1 Definitions:
3.1.1 For definitions of terms used in this standard, refer to Terminology D1129.
4. 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.
5. Apparatus
5.1 Forced Draft Oven, capable of operating at 275 to 325°C.
5.2 Sample Bottle, borosilicate or flint glass.
NOTE 1—High density polyethylene (HDPE) bottles and caps have been demonstrated to be of sufficient quality to be compatible for all tests except
pesticides, herbicides, polychlorinated biphenyls, and volatile organics. However, this bottle cannot be recycled.
5.3 Sample Bottle Cap, TFE-fluorocarbon or aluminum foil-lined.
NOTE 2—Even these liners have some disadvantages. TFE is known to collect some organic constituents, for example, PCBs. Aluminum foil will react
D3694 − 96 (2017)
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.
5.4 Sample Vial, glass.
5.5 Septa, PTFE-faced with screw cap lid and matching aluminum foil disks.
6. Reagents and Materials
6.1 Purity of Reagents—Reagent grade chemicals shall be used in all tests. Unless otherwise indicated, it is intended that all
reagents shall conform to the specifications of the Committee on Analytical Reagents of the American Chemical Society. Other
grades may be used, provided it is first ascertained that the reagent is of sufficiently high purity to permit its use without lessening
the accuracy of the determination.
6.2 Purity of Water—Unless otherwise indicated, reference to water shall be understood to mean reagent water conforming to
Specification D1193, Type II and demonstrated to be free of specific interference for the test being performed.
6.3 Acetic Acid Buffer Solution (pH 4)—Dissolve 6.0 g of sodium acetate in 75 mL of water. Add 30 mL of glacial acetic acid,
with stirring.
6.4 Acetone.
6.5 Acid Buffer Solution (pH 3.75)—Dissolve 125 g of potassium chloride and 70 g of sodium acetate trihydrate in 500 mL of
water. Add 300 mL of glacial acetic acid and dilute to 1 L.
6.6 Ascorbic Acid.
6.7 Chromic Acid Cleaning Solution—To a 2-L beaker, add 35 mL of saturated sodium dichromate solution followed by 1 L of
sulfuric acid (sp gr 1.84) with stirring. (Warning—Use rubber gloves, safety goggles, and protective clothing when preparing and
handling this corrosive cleaning agent that is a powerful oxidant. Store the reagent in a glass bottle with a glass stopper.)
6.8 Detergent, formulated for cleaning laboratory glassware.
6.9 Hydrochloric Acid—Concentrated HCl (sp gr 1.19).
6.10 Hydrochloric Acid (1 + 2)—To 200 mL of water, carefully add 100 mL of hydrochloric acid (see 6.9). Store in a
glass-stoppered reagent bottle.
6.11 Ice, crushed wet.
6.12 Lead Acetate Test Paper.
6.13 Lead Acetate Solution—Dissolve 50 g of lead acetate in water and dilute to 1 L.
6.14 Lead Carbonate, powdered.
6.15 Lime, Hydrated, powdered.
6.16 Mercuric Chloride.
6.17 Monochloroacetic Acid Buffer (pH 3)—Prepare by mixing 156 mL of chloroacetic acid solution (236.2 g/L) and 100 mL
of potassium acetate solution (245.4 g/L).
6.18 Nitric Acid—Concentrated HNO (sp gr 1.42).
6.19 Phosphate Buffer—Dissolve 138 g of sodium dihydrogen phosphate in water and dilute to 1 L. Refrigerate this solution.
6.20 Phosphate Solution—Dissolve 33.8 g of potassium dihydrogen phosphate in 250 mL of water.
6.21 Phosphoric Acid—Concentrated H PO (sp gr 1.83).
3 4
6.22 Phosphoric Acid Solution (1 + 1)—Dilute 1 vol of phosphoric acid (sp gr 1.83).
6.23 pH Paper, narrow range for pH < 2, pH > 12, and pH 5 to 7.
6.24 Potassium Iodide–Starch Test Paper.
6.25 Sodium Bisulfate.
6.26 Sodium Bisulfite Solution—Dissolve 2 g of sodium bisulfite in 1 L of water and adjust to pH 2 by the slow addition of
H SO (1 + 1). (Warning—Prepare and use this reagent in a well ventilated hood to avoid exposure to SO fumes.)
2 4 2
6.27 Sodium Sulfite Solution (0.1 M)—Transfer approximately 10.3 g of sodium sulfite to a 1-L volumetric flask. Dilute to
volume with water.
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 Analar Standards for Laboratory Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia and National
Formulary, U.S. Pharmaceutical Convention, Inc. (USPC), Rockville, MD.
D3694 − 96 (2017)
6.28 Sodium Thiosulfate.
6.29 Sodium Hydroxide Pellets.
6.30 Mercuric Chloride (10 mg/mL)—Dissolve 100 mg of HgCl in reagent water and dilute to 10 mL.
6.31 Sulfuric Acid (1 + 1)—Slowly and carefully add 1 vol of sulfuric acid (see 6.27) to 1 vol of water, stirring and cooling the
solution during addition.
7. Preparation of HDPE Sample Bottles
7.1 Wash the bottles with two 100-mL portions of HCl (1 + 2) and rinse with three 100-mL portions of water. These volumes
of wash and rinse portions are recommended for 1-L sample bottles; therefore, use proportionate volumes for washing and rinsing
sample bottles of a different volume.
8. Preparation of Glass Sample Bottles and Vials
8.1 Solvent-Detergent/Chromic Acid Preparation of Glass Sample Bottles:
8.1.1 Rinse the container with 100 mL of dilute detergent or acetone. For some residues, a few alternative detergent and acetone
rinses may be more satisfactory. Then rinse at least three times with tap water followed by a reagent water rinse to remove the
residual detergent or acetone, or both.
8.1.2 Rinse the container with 100 mL of chromic acid solution, returning the chromic acid to its original container after use.
Then rinse with at least three 100-mL portions of tap water followed by a reagent water rinse.
8.1.3 Rinse the container with 100 mL of NaHSO solution to remove residual hexavalent chromium. (Warning—Carry out this
step in a hood to prevent exposure to SO fumes.)
8.1.4 Rinse the container with water until sulfurous acid and its vapors have been removed. Test rinsings for acid with a pH
meter or an appropriate narrow range pH paper. Rinsings should have a pH approximately the same as the water used for rinsing.
8.1.5 When the last trace of NaHSO has been removed, wash with three additional 100-mL portions of water. Allow to drain.
This procedure is for 1-L sample containers, therefore, use proportionate volumes for washing and rinsing sample containers of
a different volume.
8.1.6 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 and
the vials
...
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