ASTM D3694-96(2004)
(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 D 3325. 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.
General Information
Relations
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NOTICE: This standard has either been superseded and replaced by a new version or withdrawn.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 2004)
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 D2579 Test Method for Total Organic Carbon in Water
D2580 Test Method for Phenols in Water by Gas-Liquid
1.1 Thesepracticescoverthevariousmeansof(1)preparing
Chromatography
sample containers used for collection of waters to be analyzed
D2908 Practice for Measuring Volatile Organic Matter in
for organic constituents and (2) preservation of such samples
Water by Aqueous-Injection Gas Chromatography
from the time of sample collection until the time of analysis.
D3113 Test Methods for Sodium Salts of EDTA in Water
1.2 The sample preservation practice is dependent upon the
D3325 Practice for Preservation ofWaterborne Oil Samples
specific analysis to be conducted. See Section 9 for preserva-
D3371 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
D3534 Test Method for Polychlorinated Biphenyls (PCBs)
for waterborne oils is given in Practice D3325. Use of the
in Water
information given herein will make it possible to choose the
D3590 Test Methods for Total Kjeldahl Nitrogen in Water
minimum number of sample preservation practices necessary
D3695 TestMethodforVolatileAlcoholsinWaterbyDirect
to ensure the integrity of a sample designated for multiple
Aqueous-Injection Gas Chromatography
analysis. For further considerations of sample preservation, see
D3856 Guide for Good Laboratory Practices in Laborato-
the Manual on Water.
ries Engaged in Sampling and Analysis of Water
1.3 This standard does not purport to address all of the
D3871 Test Method for Purgeable Organic Compounds in
safety concerns, if any, associated with its use. It is the
Water Using Headspace Sampling
responsibility of the user of this standard to establish appro-
D3921 Test Method for Oil and Grease and Petroleum
priate safety and health practices and determine the applica-
Hydrocarbons in Water
bility of regulatory limitations prior to use. For specific hazard
D3973 Test Method for Low-Molecular Weight Haloge-
statements, see 6.7, 6.24, and 8.1.3.
nated Hydrocarbons in Water
2. Referenced Documents D4129 Test Method for Total and Organic Carbon in Water
by High Temperature Oxidation and by Coulometric De-
2.1 ASTM Standards:
tection
D1129 Terminology Relating to Water
D4165 Test Method for Cyanogen Chloride in Water
D1193 Specification for Reagent Water
D4193 Test Method for Thiocyanate in Water
D1252 Test Methods for Chemical Oxygen Demand (Di-
D4281 Test Method for Oil and Grease (Fluorocarbon
chromate Oxygen Demand) of Water
Extractable Substances) by Gravimetric Determination
D1783 Test Methods for Phenolic Compounds in Water
D4282 Test Method for Determination of Free Cyanide in
D2036 Test Methods for Cyanides in Water
Water and Wastewater by Microdiffusion
D2330 Test Method for Methylene Blue Active Substances
D4374 Test Methods for Cyanides in Water—Automated
Methods for Total Cyanide, Weak Acid Dissociable Cya-
nide, and Thiocyanate
These practices are under the jurisdiction of ASTM Committee D19 on Water
D4515 Practice for Estimation of Holding Time for Water
and are the direct responsibilities of Subcommittee D19.06 on Methods forAnalysis
Samples Containing Organic Constituents
for Organic Substances in Water.
D4657 Test Method for Polynuclear Aromatic Hydrocar-
Current edition approved June 1, 2004. Published June 2004. Originally
approved in 1978. Last previous edition approved in 1996 as D3694 – 96. DOI:
bons in Water
10.1520/D3694-96R04.
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 Withdrawn. The last approved version of this historical standard is referenced
the ASTM website. on www.astm.org.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.
D3694 – 96 (2004)
D4744 Test Method for Organic Halides in Water by Car- 5. Apparatus
bon AdsorptionMicrocoulometric Detection
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-
NOTE 1—High density polyethylene (HDPE) bottles and caps have
boninHighPurityWaterbyUltraviolet(UV)orPersulfate
been demonstrated to be of sufficient quality to be compatible for all tests
Oxidation, or Both, and Infrared Detection
except pesticides, herbicides, polychlorinated biphenyls, and volatile
organics. However, this bottle cannot be recycled.
D4839 Test Method for Total Carbon and Organic Carbon
in Water by Ultraviolet, or Persulfate Oxidation, or Both,
5.3 Sample Bottle Cap, TFE-fluorocarbon or aluminum
and Infrared Detection
foil-lined.
D4841 Practice for Estimation of Holding Time for Water
NOTE 2—Even these liners have some disadvantages. TFE is known to
Samples Containing Organic and Inorganic Constituents
collect some organic constituents, for example, PCBs.Aluminum foil will
D4983 Test Method for Cyclohexylamine, Morpholine, and
react with samples that are strongly acid or alkaline. Clean TFE liners as
Diethylaminoethanol in Water and Condensed Steam by described in 7.1. Replace aluminum foil with new foil after each use.
Direct Aqueous Injection Gas Chromatography
5.4 Sample Vial, glass.
D5175 Test Method for Organohalide Pesticides and Poly-
5.5 Septa, PTFE-faced with screw cap lid and matching
chlorinated Biphenyls in Water by Microextraction and
aluminum foil disks.
Gas Chromatography
6. Reagents and Materials
D5176 Test Method for Total Chemically Bound Nitrogen
6.1 Purity of Reagents—Reagent grade chemicals shall be
in 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
ganic Acid 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-
sodium acetate in 75 mLof water.Add 30 mLof glacial acetic
clicAromatic Hydrocarbon Mixtures or Petroleum Oils in
acid, with stirring.
Water
6.4 Acetone.
D5475 Test Method for Nitrogen- and Phosphorus-
6.5 Acid Buffer Solution (pH 3.75)—Dissolve 125 g of
Containing Pesticides in Water by Gas Chromatography
potassiumchlorideand70gofsodiumacetatetrihydratein500
with a Nitrogen-Phosphorus Detector
mL of water.Add 300 mL of glacial acetic acid and dilute to 1
L.
D5790 Test Method for Measurement of Purgeable Organic
6.6 Ascorbic Acid.
Compounds in Water by Capillary Column Gas
6.7 Chromic Acid Cleaning Solution—To a 2-L beaker, add
Chromatography/Mass Spectrometry
35 mL of saturated sodium dichromate solution followed by 1
D5812 Test Method for Determination of Organochlorine
L of sulfuric acid (sp gr 1.84) with stirring. (Warning—Use
Pesticides in Water by Capillary Column Gas Chromatog-
rubber gloves, safety goggles, and protective clothing when
raphy
preparing and handling this corrosive cleaning agent that is a
powerful oxidant. Store the reagent in a glass bottle with a
3. Terminology
glass stopper.)
3.1 Definitions—For definitions of terms used in this prac-
6.8 Detergent, formulated for cleaning laboratory glass-
tice, refer to Terminology D1129.
ware.
6.9 Hydrochloric Acid—Concentrated HCl (sp gr 1.19).
4. Significance and Use
6.10 Hydrochloric Acid (1 + 2)—To 200 mL of water,
carefully add 100 mLof hydrochloric acid (see 6.9). Store in a
4.1 There are four basic steps necessary to obtain meaning-
glass-stoppered reagent bottle.
ful analytical data: preparation of the sample container, sam-
pling, sample preservation, and analysis. In fact these four
basic steps comprise the analytical method and for this reason
Reagent Chemicals, American Chemical Society Specifications, American
Chemical Society, Washington, DC. For suggestions on the testing of reagents not
no step should be overlooked. Although the significance of
listed by the American Chemical Society, see Analar Standards for Laboratory
preservation is dependent upon the time between sampling and
Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia
the analysis, unless the analysis is accomplished within 2 h
and National Formulary, U.S. Pharmaceutical Convention, Inc. (USPC), Rockville,
after sampling, preservation is preferred and usually required. MD.
D3694 – 96 (2004)
6.11 Ice, crushed wet. 8.1.3 Rinse the container with 100 mL of NaHSO solution
6.12 Lead Acetate Test Paper. to remove residual hexavalent chromium. (Warning—Carry
out this step in a hood to prevent exposure to SO fumes.)
6.13 Lead Acetate Solution—Dissolve 50 g of lead acetate
8.1.4 Rinsethecontainerwithwateruntilsulfurousacidand
in water and dilute to 1 L.
its vapors have been removed. Test rinsings for acid with a pH
6.14 Lead Carbonate, powdered.
meter or an appropriate narrow range pH paper. Rinsings
6.15 Lime, Hydrated, powdered.
should have a pH approximately the same as the water used for
6.16 Mercuric Chloride.
rinsing.
6.17 Monochloroacetic Acid Buffer (pH 3)—Prepare by
8.1.5 When the last trace of NaHSO has been removed,
mixing 156 mL of chloroacetic acid solution (236.2 g/L) and
wash with three additional 100-mLportions of water.Allow to
100 mL of potassium acetate solution (245.4 g/L).
drain. This procedure is for 1-L sample containers, therefore,
6.18 Nitric Acid—Concentrated HNO (sp gr 1.42).
use proportionate volumes for washing and rinsing sample
6.19 Phosphate Buffer—Dissolve 138 g of sodium dihydro-
containers of a different volume.
gen phosphate in water and dilute to 1 L. Refrigerate this
8.1.6 Heatforaminimumof4h(mouthup)inaforceddraft
solution.
oven at 275 to 325°C. Upon cooling, fit the bottles with caps
6.20 Phosphate Solution—Dissolve 33.8 g of potassium
and the vials with septa.
dihydrogen phosphate in 250 mL of water.
NOTE 3—For some tests, heating may not be required. Refer to the
6.21 Phosphoric Acid—Concentrated H PO (sp gr 1.83).
3 4
individual method to determine the necessity for this treatment.
6.22 Phosphoric Acid Solution (1 + 1)—Dilute 1 vol of
phosphoric acid (sp gr 1.83).
8.2 Machine Washing Glass Sample Bottles and Vials:
6.23 pH Paper, narrow range for pH < 2, pH > 12, and pH
NOTE 4—Machine washing of narrow mouth sample bottles may not
5to7.
yield acceptable results.
6.24 Potassium Iodide–Starch Test Paper.
8.2.1 Rinse the container with 100 mL of chromic acid
6.25 Sodium Bisulfate.
solution, returning the chromic acid to its original container
6.26 Sodium Bisulfite Solution—Dissolve2gof sodium
after use. Then rinse with at least three 100-mLportions of tap
bisulfite in 1 Lof water and adjust to pH 2 by the slow addition
water.
of H SO (1 + 1). (Warning—Prepare and use this reagent in a
2 4
8.2.2 Machine wash in accordance with the machine manu-
well ventilated hood to avoid exposure to SO fumes.)
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
6.29 Sodium Hydroxide Pellets.
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
usually prescribed to inhibit biological activity for biodegrad-
volumes of wash and rinse portions are recommended for 1-L
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 mLof 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 tha
...
Questions, Comments and Discussion
Ask us and Technical Secretary will try to provide an answer. You can facilitate discussion about the standard in here.