ASTM D4374-06
(Test Method)Standard Test Methods for Cyanides in Water-Automated Methods for Total Cyanide, Weak Acid Dissociable Cyanide, and Thiocyanate (Withdrawn 2013)
Standard Test Methods for Cyanides in Water-Automated Methods for Total Cyanide, Weak Acid Dissociable Cyanide, and Thiocyanate (Withdrawn 2013)
SIGNIFICANCE AND USE
Cyanides are known to be toxic to man, but more so to fish and other aquatic life. The complexity of the chemistry of cyanides has led to the coexistence of several cyanide species in the environment. The presence of cyanides in industrial, domestic, and surface water is cause for concern. Several regulations and standards require continuous monitoring of cyanides in different types of water and wastes. The automated test methods presented offer useful tools for such monitoring. (See also Practice D 4193.)
SCOPE
1.1 These test methods cover the determination of different species of cyanides and thiocyanate in water and waste water, namely weak acid dissociable cyanide, total cyanide, and thiocyanate ().
1.1.1 Total Cyanide This test method determines all the weak acid dissociable cyanides and the strong metal-cyano-complexes, such as ferrocyanide [Fe(CN)6] 4, ferricyanide [Fe(CN)6]3, hexacyanocolbaltate [Co(CN) 6]3, and those of gold and platinum.
1.1.2 Weak Acid Dissociable CyanideThis test method basically determines free cyanides, as CN and HCN, and weak metal-cyano-complexes such as [Cd(CN) 4] 2 and [Mn(CN)6] 3. Iron complexes are not included.
1.1.3 Strong cyanide complexes, like those of iron, cobalt, etc., can be determined by difference, that is, cyanide complexes = total cyanides weak acid dissociable cyanides.
1.1.4 Thiocyanate This test method determines the thiocyanate as the difference between another measurement that includes total cyanide plus thiocyanate and the value of total cyanide, that is, thiocyanate = total cyanide plus thiocyanate total cyanide.
1.2 Cyanates and cyanogen halides are not detected. Cyanogen chloride hydrolyzes to cyanate at the pH of sample preservation (12).
1.3 Most of the organo-cyano-complexes are not measured, with the exception of the weak cyanohydrins.
1.4 These test methods apply to different types of water, waste water (raw sewage, sludge, and effluent), sludge, some industrial waste, and sediments. Sample matrixes should be evaluated by the user. The reported precision and bias (see Section ) may not apply to all samples.
1.5 The values stated in SI units are to be regarded as the standard.
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 precautionary statements, see Section 9.
WITHDRAWN RATIONALE
Formerly under the jurisdiction of Committee D19 on Water, this test method was withdrawn in December 2012. This standard is being withdrawn without replacement due to its limited use by industry.
General Information
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Standards Content (Sample)
NOTICE: This standard has either been superseded and replaced by a new version or withdrawn.
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Designation: D4374 − 06
StandardTest Methods for
Cyanides in Water—Automated Methods for Total Cyanide,
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Weak Acid Dissociable Cyanide, and Thiocyanate
This standard is issued under the fixed designation D4374; the number immediately following the designation indicates the year of
original adoption or, in the case of revision, the year of last revision.Anumber in parentheses indicates the year of last reapproval.A
superscript epsilon (´) indicates an editorial change since the last revision or reapproval.
1. Scope 1.5 The values stated in SI units are to be regarded as the
standard.
1.1 These test methods cover the determination of different
1.6 This standard does not purport to address all of the
species of cyanides and thiocyanate in water and waste water,
safety concerns, if any, associated with its use. It is the
namely weak acid dissociable cyanide, total cyanide, and
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responsibility of the user of this standard to establish appro-
thiocyanate (1).
priate safety and health practices and determine the applica-
1.1.1 Total Cyanide— This test method determines all the
bility of regulatory limitations prior to use. For specific
weak acid dissociable cyanides and the strong metal-cyano-
4−
precautionary statements, see Section 9.
complexes, such as ferrocyanide [Fe(CN) ] , ferricyanide
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3− 3−
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[Fe(CN)] , hexacyanocolbaltate [Co(CN) ] , and those of
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2. Referenced Documents
gold and platinum.
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2.1 ASTM Standards:
1.1.2 Weak Acid Dissociable Cyanide—This test method
−
D1129Terminology Relating to Water
basically determines free cyanides, as CN and HCN, and
2−
D1193Specification for Reagent Water
weak metal-cyano-complexes such as [Cd(CN) ] and
4
3−
6
D2036Test Methods for Cyanides in Water
[Mn(CN)] . Iron complexes are not included.
D3370Practices for Sampling Water from Closed Conduits
1.1.3 Strong cyanide complexes, like those of iron, cobalt,
D3864Guide for Continual On-Line Monitoring Systems
etc., can be determined by difference, that is, cyanide com-
for Water Analysis
plexes=total cyanides−weak acid dissociable cyanides.
D4193Test Method for Thiocyanate in Water
1.1.4 Thiocyanate— This test method determines the thio-
D5847Practice for Writing Quality Control Specifications
cyanate as the difference between another measurement that
for Standard Test Methods for Water Analysis
includes total cyanide plus thiocyanate and the value of total
D6696Guide for Understanding Cyanide Species
cyanide, that is, thiocyanate=total cyanide plus thiocya-
nate−total cyanide.
3. Terminology
1.2 Cyanates and cyanogen halides are not detected. Cya-
3.1 Definitions—For definition of terms relating to water,
nogen chloride hydrolyzes to cyanate at the pH of sample
refer to Terminology D1129.
preservation (≥12).
3.1.1 For definitions related to cyanide terminologies, refer
1.3 Most of the organo-cyano-complexes are not measured,
to Guide D6696.
with the exception of the weak cyanohydrins.
3.2 Definitions of Terms Specific to This Standard:
1.4 These test methods apply to different types of water, 3.2.1 distillation ratio,
waste water (raw sewage, sludge, and effluent), sludge, some
volumeofdistilledportionofsample
industrial waste, and sediments. Sample matrixes should be % 5 3100
totalvolumeofacidifiedsample
evaluated by the user. The reported precision and bias (see
Section 16) may not apply to all samples.
4. Summary of Test Method
4.1 Some automated continuous flow modules are used (see
Guide D3864) in addition to the newly developed on-line thin
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These test methods are under the jurisdiction of ASTM Committee D19 on
film distillation (2) and ultraviolet (UV) irradiation (3).
Water and are the direct responsibility of Subcommittee D19.06 on Methods for
Analysis for Organic Substances in Water.
CurrenteditionapprovedJuly1,2006.PublishedJuly2006.Originallyapproved
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in 1984. Last previous edition approved in 2000 as D4374–00. DOI: 10.1520/ For referenced ASTM standards, visit the ASTM website, www.astm.org, or
D4374-06. contact ASTM Customer Service at service@astm.org. For Annual Book of ASTM
2
Theboldfacenumbersinparenthesesrefertothelistofreferencesattheendof Standards volume information, refer to the standard’s Document Summary page on
the text. the ASTM website.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States
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D4374 − 06
4.2 Threefactorscontroltheseparationofcyanidesfromthe
samples, namely (a) UV irradiation, (b) pH and acidification,
and (c) temperature and time of distillation (see 7.4, 7.5, and
7.3).
4.3 Acidification is made to pH < 1, but the sample
exposure to heat treatment in the continuous thin film distilla-
tion is very short (few seconds).Thus the liberation of HCN is
only from the free cyanides and the weak cyanide complexes,
t
...
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