ASTM D1682-2012-Cr in Water PDF
ASTM D1682-2012-Cr in Water PDF
ASTM D1682-2012-Cr in Water PDF
1. Scope* 1.5 This standard does not purport to address all of the
1.1 These test methods cover the determination of hexava- safety concerns, if any, associated with its use. It is the
lent and total chromium in water. Three test methods are responsibility of the user of this standard to establish appro-
included as follows: priate safety and health practices and determine the applica-
Test Method Concentration Sections
bility of regulatory limitations prior to use. For specific hazard
Range statements, see 4.2 and Note 6 and Note 7.
A—Photometric Diphenyl- 0.01 to 0.5 7-15
carbohydrazide mg/L
B—Atomic 0.1 to 10 16-24 2. Referenced Documents
Absorption, Direct mg/L
C—Atomic Absorption, 5 to 100 25-33 2.1 ASTM Standards:2
Graphite Furnace µg/L D858 Test Methods for Manganese in Water
1.2 Test Method A is a photometric method that measures D1066 Practice for Sampling Steam
dissolved hexavalent chromium only. Test Methods B and C D1068 Test Methods for Iron in Water
are atomic absorption methods that are generally applicable to D1129 Terminology Relating to Water
the determination of dissolved or total recoverable chromium D1193 Specification for Reagent Water
in water without regard to valence state. D1688 Test Methods for Copper in Water
1.3 Test Method A has been used successfully with reagent D1691 Test Methods for Zinc in Water
grade water Types I, II, and III, tap water, 10 % NaCl solution, D1886 Test Methods for Nickel in Water
treated water from a synthetic organic industrial plant that D2777 Practice for Determination of Precision and Bias of
meets National Pollution Discharge Elimination System Applicable Test Methods of Committee D19 on Water
(NPDES) permit requirements, and EPA-extraction procedure D3370 Practices for Sampling Water from Closed Conduits
leachate water, process water, lake water, effluent treatment, D3557 Test Methods for Cadmium in Water
that is, lime neutralization and precipitation of spent pickle D3558 Test Methods for Cobalt in Water
liquor and associated rinse water from stainless steel pickling. D3559 Test Methods for Lead in Water
Test Method C has been used successfully with reagent water, D3919 Practice for Measuring Trace Elements in Water by
stock scrubber water, lake water, filtered tap water, river water, Graphite Furnace Atomic Absorption Spectrophotometry
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well water, production plant water, and a condensate from a D4691 Practice for Measuring Elements in Water by Flame
medium BTU coal gasification process. Matrices used, except Atomic Absorption Spectrophotometry
for reagent water, are not available for Test Method B. It is the D4841 Practice for Estimation of Holding Time for Water
user’s responsibility to ensure the validity of these test methods Samples Containing Organic and Inorganic Constituents
for waters of untested matrices. D5810 Guide for Spiking into Aqueous Samples
1.4 The values stated in either SI units or inch-pound units D5847 Practice for Writing Quality Control Specifications
are to be regarded separately as standard. The values stated in for Standard Test Methods for Water Analysis
each system are mathematical conversions and may not be E60 Practice for Analysis of Metals, Ores, and Related
exact equivalents; therefore, each system shall be used inde- Materials by Spectrophotometry
pendently of the other. E275 Practice for Describing and Measuring Performance of
Ultraviolet and Visible Spectrophotometers
1
These test methods are under the jurisdiction of ASTM Committee D19 on
Water and are the direct responsibility of Subcommittee D19.05 on Inorganic
2
Constituents in Water. For referenced ASTM standards, visit the ASTM website, www.astm.org, or
Current edition approved Sept. 1, 2012. Published August 2007. Originally contact ASTM Customer Service at service@astm.org. For Annual Book of ASTM
approved in 1959. Last previous edition approved in 2007 as D1687 – 02(2007)E01. Standards volume information, refer to the standard’s Document Summary page on
DOI: 10.1520/D1687-12. the ASTM website.
4.2 The hexavalent state of chromium is toxic to humans, TEST METHOD A—PHOTOMETRIC
animals, and aquatic life. It can produce lung tumors when DIPHENYLCARBOHYDRAZIDE
inhaled and readily induces skin sensitization.
7. Scope
5. Purity of Reagents
7.1 This test method covers the determination of dissolved
5.1 Reagent grade chemicals shall be used in all tests. hexavalent chromium in water.
Unless otherwise indicated, it is intended that all reagents shall
conform to the specifications of the Committee on Analytical 7.2 The test method is applicable in the range from 0.01 to
Reagents of the American Chemical Society3 where such 0.5 mg/L chromium. The range may be extended by appropri-
specifications are available. Other grades may be used, pro- ate sample dilution.
vided it is first ascertained that the reagent is of sufficiently 7.3 This test method has been used successfully with
high purity to permit its use without lessening the accuracy of reagent grade water Types I, II, and III, tap water, 10 % NaCl
the determination. solution, treated water from a synthetic organic industrial plant
5.2 Purity of Water—Unless otherwise indicated, references that meets NPDES permit requirements, EPA-extraction pro-
to water shall be understood to mean reagent water conforming cedure leachate water, process water, lake water, effluent from
to Specification D1193, Type I, II, or III water. Type I is treatment that is, lime neutralization and precipitation of spent
preferred and more commonly used. Type II water was pickle liquor and associated rinse water from stainless steel
specified at the time of round robin testing of these test pickling. It is the responsibility of the user to ensure the
methods. validity of the test method to waters of untested matrices.
NOTE 1—The user must ensure the type of reagent water chosen is
8. Summary of Test Method
sufficiently free of interferences. The water should be analyzed using the
test method. 8.1 Hexavalent chromium reacts with 1.5-
diphenylcarbohydrazide (s-diphenylcarbazide) in an acid me-
6. Sampling dium to produce a reddish-purple color. The intensity of the
6.1 Collect the sample in accordance with the applicable color formed is proportional to the hexavalent chromium
ASTM standard as follows: Practice D1066, or Practice concentration.
D3370. The holding time for the samples may be calculated in
accordance with Practice D4841. 9. Interferences
6.2 Samples to be analyzed by Test Method A should be 9.1 Vanadium, titanium, or iron present at concentrations of
stabilized upon collection by addition of sodium hydroxide 5 mg/L yield a 10 to 30 % reduction in recovery of chromium.
solution to a pH greater than or equal to 8, or analyzed Copper at 100 mg/L yields a 20 to 30 % reduction in recovery
immediately. Minor delays in stabilization or analyses of in the presence of sulfate. Mercury gives a blue-purple color,
samples containing sulfur reduction compounds can produce but the reaction is not very sensitive at the pH employed for the
significant loss in hexavalent chromium. Acidic samples con- test.
9.2 Nitrite concentrations in excess of 10 mg/L as NO2 yield
3
Reagent Chemicals, American Chemical Society Specifications , American low test results. Sulfamic acid may be added (;10.1 g) prior to
Chemical Society, Washington, DC. For suggestions on the testing of reagents not the addition of diphenylcarbazide solution to minimize nitrite
listed by the American Chemical Society, see Analar Standards for Laboratory
interference. Add sulfamic acid only when the presence of
Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia
and National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville, nitrite has been positively established. Excess sulfamic acid
MD. itself creates a slightly positive interference.
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15.2 Single-operator and overall precision of this test Methods D3559), manganese (Test Methods D858) and zinc
method within its designated range and recovery data for the (Test Methods D1691).
above waters for 16 laboratories, which include a total of 16
operators analyzing each sample on three different days, is 18. Interferences
given in Table 1. 18.1 Iron, nickel, and cobalt at 100 µg/L and magnesium at
15.3 Single-operator and overall precision of this test 30 mg/L interfere by depressing the absorption of chromium.
method within its designated range and recovery data for a These interferences are eliminated in solutions containing
prepared leachate water for 8 laboratories, which include a 10,000 mg/L of 8-hydroxyquinoline. Samples adjusted to this
total of 8 operators analyzing each sample on three different concentration show no interference from 700 mg/L of iron and
days, is also given in Table 1. 10 mg/L each of nickel and cobalt, or from 1000 mg/L of
15.4 It is the user’s responsibility to ensure the validity of magnesium.
the test method for waters of untested matrices. 18.2 Potassium above 500 mg/L enhances the chromium
15.5 Precision and bias for this test method conforms to absorption.
Practice D2777 – 77, which was in place at the time of 18.3 Sodium, sulfate, and chloride (9000 mg/L each), cal-
collaborative testing. Under the allowances made in 1.4 of cium and magnesium (4000 mg/L each), nitrate (2000 mg/L),
D2777 – 08, these precision and bias data do meet existing and cadmium, lead, copper, and zinc, (10 mg/L each) do not
requirements for interlaboratory studies of Committee D19 test interfere.
methods.
19. Apparatus and Materials
TEST METHOD B—ATOMIC ABSORPTION,
DIRECT 19.1 Atomic Absorption Spectrophotometer , for use at
357.9 nm. A general guide for the use of flame atomic
16. Scope absorption applications is given in Practice D4691.
16.1 This test method covers the determination of dissolved NOTE 5—The manufacturer’s instructions should be followed for all
and total recoverable chromium in most waters, wastewaters, instrumental parameters. Wavelengths other than 357.9 nm may be used if
and brines. they have been determined to be equally suitable.
16.2 The test method is applicable in the range from 0.1 to 19.1.1 Chromium Hollow Cathode Lamp, multielement
10 mg/L of chromium. The range may be extended to concen- hollow-cathode lamps.
trations greater than 10 mg/L by dilution of the sample. 19.2 Oxidant:
16.3 It is the user’s responsibility to ensure the validity of 19.2.1 Air that has been passed through a suitable filter to
this test method for waters of untested matrices. remove oil, water, and other foreign substances, is the usual
oxidant.
17. Summary of Test Method 19.2.2 Nitrous Oxide, medical grade, is satisfactory.
17.1 Chromium is determined by atomic absorption spec- 19.3 Fuel:
trophotometry. Dissolved chromium is determined by aspirat- 19.3.1 Acetylene—Standard, commercially available acety-
ing a portion of the filtered sample directly with no pretreat- lene is the usual fuel. Acetone, always present in acetylene
ment. Total recoverable chromium is determined by aspirating cylinders, can affect analytical results. The cylinder should be
the sample following hydrochloric-nitric acid digestion and replaced at 345 kPa (50 psi).
filtration. The same digestion procedure is used to determine
NOTE 6—Warning: “Purified” grade acetylene containing a special
total recoverable cadmium (Test Methods D3557), nickel (Test proprietary solvent rather than acetone should not be used with poly(vinyl
Methods D1886), cobalt (Test Methods D3558), copper (Test chloride) tubing as weakening of the tubing walls can cause a hazardous
Methods D1688), iron (Test Methods D1068), lead (Test situation.
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21.1 Prepare 100 mL each of a blank and at least four 24.1 The overall precision (ST) of this test method within its
standard solutions, containing 1 mL of 8-hydroxyquinoline designated range for six laboratories, which include a total of
solution (100 g/L)/10 mL of standard, to bracket the expected nine operators analyzing each sample on three different days,
chromium concentration range of the samples to be analyzed, varies linearly with the chromium concentration, X, in milli-
by diluting the standard chromium solution (see 20.2) with grams per liter.
HNO3 (1 + 499). Prepare the standards each time the test is to 24.1.1 For reagent water:
be performed. S T 5 0.097X10.010 (2)
21.2 To determine the total recoverable chromium, add 0.5 24.1.2 For selected water matrices:
mL of HNO3 (sp gr 1.42) and proceed as directed in 22.2-22.4.
S T 5 0.079X10.019 (3)
To determine dissolved chromium, proceed with 21.3.
21.3 Aspirate the blank and standards and record the absor- where:
bance or concentration at 357.9 nm. Aspirate HNO3 (1 + 499) ST = overall precision, mg/L, and
between each standard. X = concentration of chromium, mg/L.
21.4 Prepare an analytical curve by plotting the absorbance 24.2 Single-operator precision did not differ significantly
versus concentration for each standard on linear graph paper. from overall precision.
Alternatively, read directly in concentration if this capability is 24.3 Recoveries of known amounts of chromium from
provided with the instrument. reagent water and selected water matrices are given in Table 2.
22. Procedure
22.1 Measure 100.0 mL of a well-mixed acidified sample 4
Supporting data are available from ASTM Headquarters. Request RR:D19-
into a 125-mL beaker or flask. 1036.
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32.1 Determine the concentration of chromium in each
minimum frequency of 10 % throughout the batch analysis.
sample by referring to Practice D3919.
The value of the instrument check standard shall fall between
33. Precision and Bias5 80 % and 120 % of the true value.
33.1 The precision of this test method was tested by 15 34.4 Two method blanks shall be prepared ensuring that an
laboratories in reagent water, stack scrubber water, lake water, adequate method blank volume is present for a minimum of
filtered tap water, river water, tap water, condensate from a seven repetitive analyses. The standard deviation of the method
medium BTU coal gasification process, well water, and pro- blank is used to determine the minimum detectable concentra-
duction plant water. The round-robin study upon which these tion of each sample and control in the batch.
precision data are based involved the determination of numer- 34.5 A Laboratory Control Sample shall be analyzed with
ous other metals. Replicate determinations were not requested each batch of samples at a minimum frequency of 10 %.
in order to simplify the study and ensure generation of data for
all metals. Thus, no single-operator precision data can be 34.6 If the QC for the sample batch is not within the
calculated. Bias data and overall precision data are given in established control limits, reanalyze the samples or qualify the
Table 3 and Table 4. results with the appropriate flags, or both. (Practice D5847)
34.7 Blind control samples should be submitted by an
5
Supporting data are available from ASTM Headquarters. Request RR:D19- outside agency in order to determine the laboratory perfor-
1103. mance capabilities.
SUMMARY OF CHANGES
Committee D19 has identified the location of selected changes to this standard since the last issue
(D1687 – 02(2007)E01) that may impact the use of this standard.
(1) The SI statement was added to section 1. (5) Reagent references were added to sections 8, 9, 10, 11, 12.
(2) D1192 was removed from section 2 and section 6.1. (6) Sections 22 and 31 were modified to include note about the
(3) Section 6 was modified to allow for pH of the samples in use of block digestion systems.
the laboratory.
(4) Sections 11.1 and 20.1 were modified to allow for commer-
cial standards.
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