ASTM D1783-91(1995)
(Test Method)Standard Test Methods for Phenolic Compounds in Water
Standard Test Methods for Phenolic Compounds in Water
SCOPE
1.1 These test methods cover the preparation of the sample and the determination of the concentration of phenolic compounds in water. They are based on the color reaction of phenol (C6H 5OH) with 4-aminoantipyrine and any color produced by the reaction of other phenolic compounds is reported as phenol. The concentration of phenol measured represents the minimum concentration of phenolic compounds present in the sample.
1.2 Phenolic compounds with a substituent in the para position may not quantitatively produce color with 4-aminoantipyrine. However, para substituents of phenol such as carboxyl, halogen, hydroxyl, methoxyl, or sulfonic acid groups do produce color with 4-aminoantipyrine.
1.3 These test methods address specific applications as follows:
RangeSectionsTest Method A-Chloroform Extraction 0 to 100 µg/L11 to 17Test Method B-Direct Photometric>0.1 mg/L 18 to 24(100 µg/L)
1.4 It is the users' responsibility to assure the validity of the standard test method for use in their particular matrix of interest.
1.5 This standard does not purport to address all 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 Note 1 and Note 3.
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NOTICE: This standard has either been superseded and replaced by a new version or
withdrawn.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: D 1783 – 91 (Reapproved 1995)
AMERICAN SOCIETY FOR TESTING AND MATERIALS
100 Barr Harbor Dr., West Conshohocken, PA 19428
Reprinted from the Annual Book of ASTM Standards. Copyright ASTM
Standard Test Methods for
Phenolic Compounds in Water
This standard is issued under the fixed designation D 1783; the number immediately following the designation indicates the year of
original adoption or, in the case of revision, the year of last revision. A number in parentheses indicates the year of last reapproval. A
superscript epsilon (e) indicates an editorial change since the last revision or reapproval.
This standard has been approved for use by agencies of the Department of Defense. Consult the DoD Index of Specifications and
Standards for the specific year of issue which has been adopted by the Department of Defense.
1. Scope Applicable Methods of Committee D–19 on Water
D 3370 Practices for Sampling Water from Closed Con-
1.1 These test methods cover the preparation of the sample
duits
and the determination of the concentration of phenolic com-
pounds in water. They are based on the color reaction of phenol
3. Terminology
(C H OH) with 4-aminoantipyrine and any color produced by
6 5
3.1 Definitions—For definitions of terms used in these test
the reaction of other phenolic compounds is reported as phenol.
methods, refer to Terminology D 1129.
The concentration of phenol measured represents the minimum
3.2 Definitions of Terms Specific to This Standard:
concentration of phenolic compounds present in the sample.
3.2.1 phenolic compounds—hydroxy derivatives of benzene
1.2 Phenolic compounds with a substituent in the para
and its condensed nuclei.
position may not quantitatively produce color with
4-aminoantipyrine. However, para substituents of phenol such
4. Summary of Test Methods
as carboxyl, halogen, hydroxyl, methoxyl, or sulfonic acid
4.1 Test Methods A and B are photometric procedures based
groups do produce color with 4-aminoantipyrine.
on the reaction of steam-distillable phenolic compounds with
1.3 These test methods address specific applications as
4-aminoantipyrine.
follows:
4.2 Test Method A differs from B mainly in that the sample
Range Sections
is extracted with chloroform, thereby providing 20-fold greater
Test Method A—Chloroform Extraction 0 to 100 μg/L 11 to 17
Test Method B—Direct Photometric >0.1 mg/L 18 to 24
sensitivity.
(100 μg/L)
4.3 Both procedures involve first separating the phenolic
compounds from the background matrix by distillation. Due to
1.4 It is the users’ responsibility to assure the validity of the
standard test method for use in their particular matrix of the differing solubilities and boiling points of the various
phenolic compounds, each phenolic comes over in the distil-
interest.
1.5 This standard does not purport to address all the safety lation at a different rate. Some phenolics will be substantially
transferred near the beginning of the distillation and some will
concerns, if any, associated with its use. It is the responsibility
of the user of this standard to establish appropriate safety and not start to distill until near the end. For this reason some
phenolics may not have been quantitatively transferred to the
health practices and determine the applicability of regulatory
limitations prior to use. For specific hazard statements see receiving flask when the specified volume of distillate has been
collected.
Note 1 and Note 3.
5. Significance and Use
2. Referenced Documents
5.1 Phenolic compounds are sometimes found in surface
2.1 ASTM Standards:
2 waters from natural and industrial sources. Their presence in
D 1129 Terminology Relating to Water
streams and other waterways frequently will cause off flavor in
D 1192 Specification for Equipment for Sampling Water
2 fish tissue and other aquatic food.
and Steam in Closed Conduits
2 5.2 Chlorination of waters containing phenols may produce
D 1193 Specification for Reagent Water
2 chlorophenols that are odoriferous and objectionable tasting.
D 1293 Test Methods for pH of Water
D 2777 Practice for Determination of Precision and Bias of
6. Interferences
6.1 Common interferences that may occur in waters are
phenol-decomposing bacteria, reducing substances, and
These test methods are under the jurisdiction of D-19 on Water and are the
direct responsibility of Subcommittee D19.06 on Methods for Analysis for Organic
strongly alkaline conditions of the sample. Provisions incorpo-
Substances in Water.
rated in these test methods will minimize the effects of such
Current edition approved Sept. 15, 1991. Published December 1991. Originally
interferences.
published as D 1783 – 60 T. Last previous edition D 1783 – 87.
Annual Book of ASTM Standards, Vol 11.01. 6.2 Treatment procedures required prior to the analysis for
D 1783
removal of interfering compounds may result in the unavoid- Method B), and accommodating a cell that gives a light path of
able elimination or loss of certain types of phenolic com- 1.0 to 10 cm shall be used. The size of the cell used will depend
pounds. It is beyond the scope of these test methods to describe on the absorbance of the colored solutions being measured and
procedures for overcoming all of the possible interferences that the characteristics of the photometer. In general, if the absor-
may be encountered in the test methods, particularly with bances are greater than 1.0 with a larger cell, the next smaller
highly contaminated water and industrial waste water. The size cell should be used.
procedures used must be revised to meet the specific require- 7.3 Distillation Apparatus—A 1-L, heat-resistant, distilling
ments. flask attached to a Graham condenser by means of a glass joint.
6.3 A few methods for eliminating certain interferences are 7.4 pH Meter—This apparatus shall conform to the require-
suggested. (See Section 8 for descriptions of reagents re- ments in Test Methods D 1293.
quired.)
8. Reagents
6.3.1 Oxidizing Agents—If the sample smells of chlorine, or
NOTE 3—Warning: Phenol, carbon tetrachloride, and chloroform are
if iodine is liberated from potassium iodide on acidification of
potentially hazardous to human health. Caution—Avoid inhalation and
the sample, remove the oxidizing agents so indicated immedi-
direct contact. Use in a well-ventilated hood.
ately after sampling. The presence of oxidizing agents in the
8.1 Purity of Reagents—Reagent grade chemicals shall be
sample may oxidize some or all of the phenols in a short time.
used in all tests. Unless otherwise indicated, it is intended that
Ferrous sulfate or sodium arsenite solution may be added to
all reagents shall conform to the specifications of the Commit-
destroy all of the oxidizing substances. Excess ferrous sulfate
tee on Analytical Reagents of the American Chemical Society,
or sodium arsenite do not interfere since they are removed in
where such specifications are available. Other grades may be
the distillation procedure.
used, provided it is first ascertained that the reagent is of
6.3.2 Sulfur Compounds—Compounds that liberate hydro-
sufficiently high purity to permit its use without lessening the
gen sulfide (H S) or sulfur dioxide (SO ) on acidification may
2 2
accuracy of the determination.
interfere with the phenol determination. Treatment of the
8.2 Purity of Water—Unless otherwise indicated, references
acidified sample with copper sulfate usually eliminates such
to water shall be understood to mean water conforming to
interferences. Acidify the sample with sulfuric acid (H SO )or
2 4
Specification D 1193 Types I, II, III, or IV. Water used for these
hydrochloric acid (HCl) until just acid to methyl orange. Then
test methods shall be free of phenolic compounds, residual
add a sufficient quantity of copper sulfate (CuSO ) solution to
chlorine, and substances that interfere with the test. Water
give a light blue color to the sample or until no more copper
sufficiently free of phenolics can be generated by boiling the
sulfide (CuS) precipitate is formed. Excessive amounts of H S
water for 20 minutes.
or SO may be removed from the acidified sample by a brief
8.3 Aminoantipyrine Solution (20 g/L)—Dissolve 2.0 g of
aeration treatment or stirring before the addition of the CuSO
4-aminoantipyrine in water and dilute to 100 mL. Prepare this
solution or both.
reagent fresh as used.
NOTE 1—Warning: Acidification of certain samples may produce vig-
NOTE 4—The melting point of a satisfactory grade of
orous evolution of carbon dioxide (CO ), SO,H S, or other gases.
2 2 2
4-aminoantipyrine ranges from 108.0 to 109.5°C.
Therefore, perform the acidification cautiously and stir the samples during
the process. Complete the evolution of gases before the sample is
8.4 Ammonium Chloride Solution (20 g/L)—Dissolve 20 g
stoppered.
of ammonium chloride (NH Cl) in water and dilute to 1 L.
6.3.3 Oils and Tars—If the sample contains oil or tar, some
8.5 Ammonium Hydroxide (NH OH) (sp gr 0.90)—
phenolic compounds may be dissolved in these materials. An
Concentrated ammonium hydroxide (NH OH).
alkaline extraction, in the absence of CuSO (Note 1), may be
4 8.6 Carbon Tetrachloride (CCl ).
used to eliminate the tar and oil. Adjust the pH of the sample
8.7 Chloroform (CHCl ).
between 12 and 12.5 with sodium hydroxide (NaOH) pellets to
8.8 Hydrochloric Acid (HCl) (sp gr 1.19)—Concentrated
avoid extraction of the phenols. Extract the mixture with
hydrochloric acid (HCl).
carbon tetrachloride (CCl ). Discard the oil- or tar-containing
4 8.9 Phenol Solution, Stock (1 mL 5 10 mg phenol)—
layer. Remove any CCl remaining in the aqueous portion of
4 Dissolve 1.00 g of phenol (C H OH) in freshly boiled and
6 5
the sample by gentle heating.
cooled water. Dilute to 1 000 mL with freshly boiled cooled
water. Prepare a fresh stock solution within 30 days of use.
NOTE 2—The presence of CuSO is detrimental since it is converted to
8.10 Phenol Solution, Intermediate—(C H OH) (1
cupric hydroxide (Cu(OH) ) by the NaOH. The Cu(OH) acts as an
6 5
2 2
oxidizing agent on phenols. mL 5 10 μg phenol)—Dilute 10.0 mL of the stock solution to
1 000 mL with freshly boiled and cooled water. Prepare this
7. Apparatus
solution fresh on the day it is used.
7.1 Buchner-Type Funnel with Coarse Fritted Disk—At
8.11 Phenol Solution, Standard —(C H OH) (1 mL 5 1.0
6 5
least three funnels are needed for determination of phenolic
compounds by Test Method A. Alternatively, standard glass
funnels and pre-fluted filter paper may be used. The funnel
Reagent Chemicals, American Chemical Society Specifications, American
Chemical Society, Washington, DC. For suggestions on the testing of reagents not
paper must be large enough to hold5gof sodium sulfate.
listed by the American Chemical Society, see Analar Standards for Laboratory
These funnels are not used in Test Method B.
Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia
7.2 Photometer—A spectrophotometer or filter photometer,
and National Formulary, U.S. Pharmaceutical Convention, Inc. (USPC), Rockville,
suitable for use at 460 nm (Test Method A) or at 510 nm (Test MD.
D 1783
μg phenol)—Dilute 50 mL of the intermediate solution to 500 aqueous solution with chloroform and the absorbance is
mL with freshly boiled and cooled water. Prepare this solution measured at 460 nm. The concentration of phenolic com-
fresh within2hof use. pounds in the sample is expressed in terms of micrograms per
8.12 Potassium Ferricyanide Solution (K Fe(CN) ) (80 litre of phenol C H OH.
3 6 6 5
g/L)—Dissolve 8.0 g of (K Fe(CN) ) in water and dilute to 100
3 6
13. Calibration
mL. Filter if necessary. Prepare fresh weekly.
13.1 Prepare a series of 500-mL C H OH standards in
6 5
8.13 Sodium Bisulfate (NaHSO ).
freshly boiled and cooled water containing 0, 5, 10, 20, 30, 40,
8.14 Sodium Sulfate (Na SO ), anhydrous and granular.
2 4
and 50 mL of standard C H OH solution (1 mL 5 1.0 μg
6 5
8.15 Sulfuric Acid (H SO ) (sp gr 1.84)—Concentrated
2 4
C H OH). Use all solutions at room temperature.
6 5
sulfuric acid (H SO ).
2 4
13.2 Develop color in the series of standards and prepare the
8.16 Sulfuric Acid Solution (H SO ) (1 + 9)—Cautiously
2 4
chloroform extracts in accordance with the procedures pre-
add one volume of concentrated H SO to nine volumes of
2 4
scribed in Section 14 and 15.
water with continuous cooling and mixing. Solution will
13.3 Measure the absorbance of each standard at 460 nm
become hot.
against the reagent blank as zero absorbance. Plot the absor-
bances against the corresponding weights in micrograms of
9. Sampling
phenol.
9.1 Collect the sample in accordance with Specification
D 1192 and Practices D 3370. NOTE 5—Make a separate calibration curve for each spectrophotometer
or photoelectric colorimeter. Check each curve periodically to ensure
9.2 When samples are composited, chill the samples or the
reproducibility.
composite sample immediately and keep at a temperature of
not more than 4°C during the compositing period. The collec-
14. Distillation Procedure
tion time for a single composite sample shall not exceed 4 h. If
14.1 Measure 500 mL of the sample into a beaker. Adjust
longer sampling periods are necessary, collect a series of
the pH of the sample to between pH 0.5 and 4 with H SO
2 4
composite samples. Then preserve such composite samples in
solution (1 + 9). Use methyl orange indicator solution or a pH
accordance with Section 10 until analyzed.
meter to aid in the pH adjustment. If the sample has been
10. Preservation of Samples previously preserved according to 10.1, this pH adjustment
step may be omitted. Transfer the mixture to the distillation
10.1 Phenolic compounds in water are subject to both
apparatus. Use a 500-mL graduated cylinder as a receiver.
chemical and biochemical oxidation. Preserve samples within
14.2 Distill 450 mL of the sample. Stop the distillation and,
4 h of collection. Acidify the samples to a pH between 0.5 and
when boiling ceases, add 50 mL of water to the distillation
2.0 with H PO , HCl, H SO , or NaHSO .
3 4 2 4 4
flask. Continue the distillation until a total of 500 mL has been
10.2 To further minimize any changes in the phenolic
collected.
content of the sample, keep it cold, preferably between 2°C and
14.3 If the distillate is turbid, a second distillation may
4°C until analysis. The preserved samples should be in glass,
prove helpful. Acidify the turbid distillate with H SO solution
2 4
not plastic bottles, and preferably analyzed within 28 days after
(1 + 9) and repeat the previously described distillation. The
collection.
second distillation usually eliminates the turbidity. However, if
the second distillate is also turbid, the screening procedure
TEST METHOD A—CHLOROFORM EXTRACTION
must be
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