Designation: D2036 − 09

Standard Test Methods for

Cyanides in Water1
This standard is issued under the fixed designation D2036; 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.
This standard has been approved for use by agencies of the U.S. Department of Defense.

1. Scope 1.7 This standard does not purport to address all of the
1.1 These test methods cover the determination of cyanides safety concerns, if any, associated with its use. It is the
in water. The following test methods are included: responsibility of the user of this standard to establish appro-
priate safety and health practices and determine the applica-
Sections
Test Method A—Total Cyanides after 12 to 18 bility of regulatory limitations prior to use. Specific hazard
Distillation statements are given in sections 5.1, 8.8, 8.18, 9, 11.3, and
Test Method B—Cyanides Amenable 19 to 25 16.1.9.
to Chlorination2 by Difference
Test Method C—Weak Acid 26 to 32
Dissociable Cyanides 2. Referenced Documents
Test Method D—Cyanides Amenable 33 to 39
to Chlorination without Distillation
2.1 ASTM Standards:3
(Short-Cut Method) D1129 Terminology Relating to Water
1.2 Cyanogen halides may be determined separately. D1193 Specification for Reagent Water
D2777 Practice for Determination of Precision and Bias of
NOTE 1—Cyanogen chloride is the most common of the cyanogen Applicable Test Methods of Committee D19 on Water
halide complexes as it is a reaction product and is usually present when
chlorinating cyanide-containing industrial waste water. For the presence
D3370 Practices for Sampling Water from Closed Conduits
or absence of CNCl, the spot test method given in Annex A1 can be used. D5788 Guide for Spiking Organics into Aqueous Samples
D5847 Practice for Writing Quality Control Specifications
1.3 These test methods do not distinguish between cyanide
for Standard Test Methods for Water Analysis
ions and metallocyanide compounds and complexes.
D6696 Guide for Understanding Cyanide Species
Furthermore, they do not detect the cyanates. Cyanates can be
D6888 Test Method for Available Cyanide with Ligand
determined using ion chromatography without digestion.
Displacement and Flow Injection Analysis (FIA) Utilizing
NOTE 2—The cyanate complexes are decomposed when the sample is Gas Diffusion Separation and Amperometric Detection
acidified in the distillation procedure. D6994 Test Method for Determination of Metal Cyanide
1.4 The cyanide in cyanocomplexes of gold, platinum, Complexes in Wastewater, Surface Water, Groundwater
cobalt and some other transition metals is not completely and Drinking Water Using Anion Exchange Chromatog-
recovered by these test methods. Refer to Test Method D6994 raphy with UV Detection
for the determination of cyanometal complexes. D7284 Test Method for Total Cyanide in Water by Micro
1.5 Cyanide from only a few organic cyanides are Distillation followed by Flow Injection Analysis with Gas
recovered, and those only to a minor extent. Diffusion Separation and Amperometric Detection
D7365 Practice for Sampling, Preservation and Mitigating
1.6 Part or all of these test methods have been used Interferences in Water Samples for Analysis of Cyanide
successfully with reagent water and various waste waters. It is D7511 Test Method for Total Cyanide by Segmented Flow
the user’s responsibility to assure the validity of the test Injection Analysis, In-Line Ultraviolet Digestion and Am-
method for the water matrix being tested. perometric Detection
E60 Practice for Analysis of Metals, Ores, and Related
1
These test methods are under the jurisdiction of ASTM Committee D19 on Materials by Spectrophotometry
Water and are the direct responsibility of Subcommittee D19.06 on Methods for
Analysis for Organic Substances in Water.
E275 Practice for Describing and Measuring Performance of
Current edition approved Oct. 1, 2009. Published October 2009. Originally Ultraviolet and Visible Spectrophotometers
approved in 1964. Last previous edition approved in 2006 as D2036 – 06. DOI:
10.1520/D2036-09.
2 3
For an explanation of the term cyanides amenable to alkaline chlorination, see For referenced ASTM standards, visit the ASTM website, www.astm.org, or
Lancy, L. E. and Zabban, W., “Analytical Methods and Instrumentation for contact ASTM Customer Service at [email protected]. For Annual Book of ASTM
Determining Cyanogen Compounds,” Papers on Industrial Water and Industrial Standards volume information, refer to the standard’s Document Summary page on
Waste Water, ASTM STP 337, 1962, pp. 32–45. the ASTM website.

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 D2036 − 09

FIG. 1 Cyanide Distillation Apparatus

3. Terminology a degree determined by the amount of manipulation required

3.1 Defenitions—For definitions of terms used in these test and the type of sample.
methods, refer to Terminology D1129 and Guide D6696. 4.7 Round-robin data indicate the following minimum con-
3.2 Acronyms: centrations: colorimetric 0.03 mg/L; titration 1.0 mg/L; and
3.2.1 HPLC, n—high performance liquid chromatography selective ion electrode 0.03 mg/L. Ion chromatography and
Test Method D6888 have a minimum levels equal to approxi-
3.2.2 IC, n—ion chromatography mately 0.002 mg/L.
3.2.3 PAD, n—pulsed amperometric detection
5. Significance and Use
3.2.4 FIA, n—flow injection analysis
5.1 Cyanide is highly toxic. Regulations have been estab-
4. Summary of Test Methods lished to require the monitoring of cyanide in industrial and
4.1 The cyanide as hydrocyanic acid (HCN) is released domestic wastes and in surface waters (Appendix X1).
from compounds by means of reflux distillation and absorbed 5.2 Test Method D is applicable for natural water and clean
in sodium hydroxide solution. The conditions used for the metal finishing or heat treatment effluents. It may be used for
distillation distinguish the type of cyanide. The sodium cyanide process control in wastewater treatment facilities providing its
in the absorbing solution can be determined colorimetrically, applicability has been validated by Test Method B or C.
by ion chromatography, titration, by selective ion electrode, or
5.3 The spot test outlined in Annex A1 can be used to detect
as described in Test Method D6888 using flow injection with
cyanide and thiocyanate in water or wastewater, and to
amperometric detection.
approximate its concentration.
4.2 Test Method A, Total Cyanides, is based on the decom-
position of nearly all cyanides in the presence of strong acid, 6. Interferences
magnesium chloride catalyst, and heat during a 1-h reflux 6.1 Common interferences in the analysis for cyanide in-
distillation. clude oxidizing agents, sulfides, aldehydes, glucose and other
4.3 Test Method B, Cyanide Amenable to Chlorination, is sugars, high concentration of carbonate, fatty acids,
based on chlorinating a portion of the sample under controlled thiocyanate, and other sulfur containing compounds.
conditions followed by the determination of total cyanide in 6.2 It is beyond the scope of these test methods to describe
both the original and chlorinated samples. Cyanides amenable procedures for overcoming all of the possible interferences that
to chlorination are calculated by difference. may be encountered. Refer to Practice D7365 for potential
4.3.1 This test method can be affected by compounds that interferences for the analysis of cyanide in water.
are converted during chlorination to color-producing com-
pounds or react with the reagents used, and cause interference 7. Apparatus
in the procedure employed to determine cyanide in the absorp- 7.1 Distillation Apparatus—The reaction vessel shall be a
tion solution. 1-L round bottom flask, with provision for an inlet tube and a
4.4 Test Method C, Weak Acid Dissociable Cyanides, is condenser. The inlet tube shall be a funnel with an 8-mm
based on the decomposition of cyanides in the presence of diameter stem that extends to within 6 mm of the bottom of the
weak acid, zinc acetate and heat during a 1-h reflux distillation. flask. The condenser, which is recommended, shall be a
reflux-type, cold finger, or Allihn. The condenser shall be
4.5 Test Method D, Cyanide Amenable to Chlorination connected to a vacuum-type absorber which shall be in turn
without Distillation, is a direct colorimetric procedure. connected to a vacuum line which has provision for fine
4.6 In the absence of interference, the minimum concentra- control. The flask shall be heated with an electric heater.
tion of cyanide in the absorption solution that can be accurately Examples of the apparatus are shown in Fig. 1. Equivalent
determined colorimetrically is 0.005 mg/L, ion chromatogra- apparatus is acceptable provided cyanide recoveries of 100 6
phy and Test Method D6888 are 0.002 mg/L, titration is 0.4 4 % are documented.
mg/L and by selective ion electrode is 0.05 mg/L. Pretreatment 7.1.1 Smaller distillation tubes such as 50-mL MIDI tubes
including distillation tends to increase these concentrations to or 6-mL MicroDist (trademarked) tubes described in Test

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 D2036 − 09
Method D7284 can be used if the quality control requirements 8.6 Calcium Hypochlorite Solution (50 g/L)—Dissolve 5 g
in Section 40 are satisfied. The reagents should be added of calcium hypochlorite (Ca(OCl)2) in 100 mL of water. Store
proportionately to those specified in this test method for the solution in an amber glass bottle in the dark. Prepare fresh
smaller sample sizes. While the use of smaller distillation tubes monthly.
is generally accepted, the interlaboratory study was conducted 8.7 Chloramine-T Solution (10 g/L)—Dissolve 1.0 g of the
with 500-mL samples; therefore, the user is responsible to white-colored, water-soluble grade powder chloramine-T in
determine the actual precision and bias when using a different 100 mL of water. Prepare fresh weekly.
type of distillation apparatus.
8.8 Cyanide Solution, Stock (1 mL = 250 µg CN−)—
7.2 Spectrophotometer or Filter Photometer, suitable for Dissolve 0.6258 g of potassium cyanide (KCN) in 40 mL of
measurement in the region of 578 nm, using 1.0-, 2.0-, 5.0-, sodium hydroxide solution (40 g/L). Dilute to 1 L with water.
and 10.0-cm absorption cells. Filter photometers and photo- Mix thoroughly. Standardize with standard silver nitrate solu-
metric practices used in these test methods shall conform to tion following the titration procedure (see 16.2). (Warning—
Practice E60. Spectrophotometers shall conform to Practice Because KCN is highly toxic, avoid contact or inhalation (see
E275. 9)). Commercial solutions may also be used if certified by the
7.3 Selective Ion Meter, or a pH meter with expanded manufacturer and used within the recommended storage date.
millivolt scale equipped with a cyanide activity electrode and 8.8.1 Cyanide I Solution, Standard (1 mL = 25 µg CN−)—
a reference electrode. Dilute a calculated volume (approximately 100 mL) of KCN
stock solution to 1 L with NaOH solution (1.6 g/L).
7.4 Mixer, magnetic, with a TFE-fluorocarbon-coated stir- 8.8.2 Cyanide II Solution, Standard (1 mL = 2.5 µg CN−)—
ring bar. Dilute exactly 100 mL of KCN standard solution I to 1 L with
7.5 Buret, Koch, micro, 2- or 5-mL, calibrated in 0.01 mL. NaOH solution (1.6 g/L).
8.8.3 Cyanide III Solution, Standard (1 mL = 0.25 µg
7.6 Ion Chromatograph, high performance ion chromato- CN−)— Dilute exactly 100 mL of KCN standard solution II to
graph equipped with a 10-µL sample injection device and 1 L with NaOH solution (1.6 g/L). Prepare fresh solution daily
pulsed-amperometric detector. and protect from light.
7.7 Chromatography Column, Dionex IonPac AS7 anion- 8.8.4 Cyanide IV Solution, Standard (1 mL = 0.025 µg
exchange, 4 × 250 mm and matching guard column or equiva- CN−)— Dilute exactly 100 mL of KCN standard solution III to
lent. 1 L with NaOH solution (1.6 g/L). Prepare fresh solution daily
and protect from light.
8. Reagents and Materials 8.9 Hydrogen Peroxide Solution, 3 %—Dilute 10 mL of
30 % hydrogen peroxide (H2O2) to 100 mL. Prepare fresh
8.1 Purity of Reagents—Reagent grade chemicals shall be
weekly.
used in all tests. Unless otherwise indicated, it is intended that
all reagents shall conform to the specifications of the Commit- 8.10 Isooctane, Hexane, Chloroform (solvent preference in
tee on Analytical Reagents of the American Chemical Society, the order named).
where such specifications are available.4 Other grades may be 8.11 Lead Carbonate (PbCO 3 ), Lead Acetate
used, provided it is first ascertained that the reagent is of (Pb(C2H3O2)2·3H2O), or Lead Nitrate (Pb(NO3)2)—Lead ac-
sufficiently high purity to permit its use without lessening the etate and lead nitrate can be put in solution with water, if
accuracy of the determination. desired, at a suggested concentration of 50 g/L.
8.2 Purity of Water—Unless otherwise indicated, references 8.12 Lime, hydrate (Ca(OH)2), powder.
to water shall be understood to mean reagent water that meets 8.13 Magnesium Chloride Solution—Dissolve 510 g of
the purity specifications of Type I or Type II water, presented magnesium chloride (MgCl2·6H2O) in water and dilute to 1 L.
in D1193.
8.14 Potassium Iodide-Starch Test Paper.
8.3 Acetic Acid (1 + 9) —Mix 1 volume of glacial acetic
acid with 9 volumes of water. 8.15 Pyridine-Barbituric Acid Reagent—Place 15 g of bar-
bituric acid in a 250-mL volumetric flask and add just enough
8.4 Acetate Buffer—Dissolve 410 g of sodium acetate trihy- water to wash the sides of the flask and wet the barbituric acid.
drate (NaC2H3O2·3H2O) in 500 mL of water. Add glacial acetic Add 75 mL of pyridine and mix. Add 15 mL of hydrochloric
acid to yield a solution pH of 4.5, approximately 500 mL. acid (sp gr 1.19), mix, and cool to room temperature. Dilute to
8.5 Barbituric Acid. volume with water and mix until all of the barbituric acid is
dissolved. This solution is usable for about 6 months if stored
in a cold dark place. Commercially prepared solutions may be
available; follow the manufacturer’s expiration date.
4
Reagent Chemicals, American Chemical Society Specifications , American
Chemical Society, Washington, DC. For suggestions on the testing of reagents not 8.16 Rhodanine Indicator Solution (0.2 g/L)—Dissolve 0.02
listed by the American Chemical Society, see Analar Standards for Laboratory g of (p-dimethylaminobenzylidene) in 100 mL of acetone.
Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia
and National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville, 8.17 Silver Nitrate Solution, Standard (0.01 N)—Dissolve
MD. 1.6987 g of silver nitrate (AgNO3) in water and dilute to 1 L.

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 D2036 − 09
Mix thoroughly. Commerical solutions that are certified at the 9.3 All reagents and standards should be prepared in vol-
designated normality are suitable if used within the manufac- umes consistent with laboratory use to minimize the generation
turer’s recommended storage date. Store in a dark container. of waste.
8.18 Sodium Arsenite Solution (20 g/L)—Dissolve 2 g of
10. Sample and Sample Preservation
NaAsO2 in 100 mL of water. Warning—This material has
appeared on lists of suspected and known carcinogens. Avoid 10.1 Collect the sample in accordance with Practice D7365.
contact with skin. This standard practice is applicable for the collection and
preservation of water samples for the analysis of cyanide.
8.19 Sodium Hydroxide Solution (40 g/L)—Dissolve 40 g of Responsibilities of field sampling personnel and the laboratory
sodium hydroxide (NaOH) in water and dilute to 1 L with are indicated.
water.
8.20 Sodium Hydroxide Solution (1.6 g/L)—Dilute 40 mL of 11. Elimination of Interferences
NaOH solution (40 g/L) to 1 L. 11.1 Refer to Practice D7365 for mitigating interferences
8.21 Sulfamic Acid Solution (133 g/L)—Dissolve 133 g of for the analysis of cyanide in water.
sulfamic acid in water and dilute to 1 L. 11.2 The following treatments are specific for the removal
or reduction of substances that can interfere in the various
8.22 Sodium Thiosulfate Solution (500 g/L)—Dissolve 785
methods of this test method. Care must be taken to keep time
g of sodium thiosulfate (Na2S2O3·5H2O) in water and dilute to
of pretreatment at a minimum to avoid loss of cyanide.
1 L.
11.3 Fatty acids that distill and form soaps in the absorption
8.23 Sulfuric Acid (1 + 1) —Slowly and carefully add 1 solution can be removed by extraction. Acidify the sample with
volume of sulfuric acid (H2SO4, sp gr 1.84) to 1 volume of dilute (1 + 9) acetic acid to a pH 6 to 7 (perform this operation
water, stirring and cooling the solution during the addition. in the hood and leave the sample there until it is made alkaline
8.24 Zinc Acetate Solution (100 g/L)—Dissolve 120 g of after the extraction). Extract with isooctane, hexane or chloro-
zinc acetate [Zn(C2H3O2)2·2H2] in 500 mL of water. Dilute to form (preference in order named), with a solvent volume equal
1 L. to 20 % of the sample volume. One extraction is usually
sufficient to reduce the fatty acids below the interference level.
8.25 IC Eluent Solutions, (75 mM sodium hydroxide, 250 Avoid multiple extractions or a long contact time at low pH in
mM sodium acetate, and 0.05 % (v/v) ethylenediamine) order to keep the loss of HCN to a minimum. When the
8.25.1 Eluent Preparation—Weigh 20.50 g of anhydrous extraction is complete, immediately raise the pH of the sample
NaOAc and dissolve it in 500–600 g of 18 MΩ-cm water. Fill to 12 to 12.5 with NaOH solution.
up to ~980 g with 18 MΩ-cm water. Stir thoroughly and filter
11.4 Aldehydes combine with cyanides to form cyanohy-
through a 0.2 µm Nylon filter. Add 5.97 g (3.9 mL) of 50 %
drins which can hydrolyze to acids under distillation condi-
NaOH and 0.4495 g (0.50 mL ) of ethylendiamine. Fill up to
tions. Glucose and other sugars, if present in the sample, can
1015 g (1.0 L) with 18 MΩ-cm water in the bottom container
also form cyanohydrins with cyanide at the pH of preservation.
of the filtration unit. Transfer the solution immediately to the
Aldehydes can be removed as described in Practice D7365.
eluent container, which is connected to nitrogen. Adjust the
flow rate at 0.25 mL/min (for a 2-mm ID column) or 1.00 11.5 Carbonate in high concentration can affect the distilla-
mL/min (for a 4-mm ID column) tion procedure by causing the violent release of carbon dioxide
with excessive foaming when acid is added prior to distillation,
8.26 Ethylene diamine. and by lowering the pH of the absorption solution.
8.27 Sodium Hydroxide Solution (50 % W/W). It is essential 11.6 Nitrite and nitrate in the sample can react under
to use high quality 50 % (w/w) sodium hydroxide solution for conditions of the distillation with other contaminants present to
eluent and diluent preparation for use in ion chromatography. form cyanides. The addition of an excess of sulfamic acid to
Sodium hydroxide pellets are coated with sodium carbonate the sample prior to the addition of sulfuric acid will reduce this
and, therefore, are not acceptable for this application. interference. For example, if samples are known or suspected
8.28 Sodium Acetate. to contain nitrate or nitrite, add 50 mL of 0.4 N sulfamic acid
solution (40 g/L) per 500 mL sample, then proceed with
9. Hazards distillation after 3 minutes.
11.7 Thiocyanate and other sulfur containing compounds
9.1 Warning—Because of the toxicity of cyanide, great
can decompose during distillation. Sulfur, hydrogen sulfide,
care must be exercised in its handling. Acidification of cyanide
sulfur dioxide, etc., formed can be distilled into the absorption
solutions produces toxic hydrocyanic acid (HCN). All manipu-
solution. The addition of lead ion to the absorption solution
lations must be done in the hood so that any HCN gas that
before distillation followed by filtration of the solution before
might escape is safely vented.
the titration or the colorimetric procedure is used will minimize
9.2 Warning—Many of the reagents used in these test sulfur and sulfide interference. Absorbed sulfur dioxide forms
methods are highly toxic. These reagents and their solutions sodium sulfite which reacts with chloramine-T in the colori-
must be disposed of properly. metric determination. Test for the presence of chloramine-T by

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 D2036 − 09
placing a drop of solution on a strip of potassium iodide test 13.2 For the removal of these interferences, proceed as
paper previously moistened with dilute acetic acid. If the test is instructed in Sections 10 and 11.
negative, add chloramine-T until a positive test is obtained.
11.7.1 Cyanide can be measured in the presence of sulfur 14. Apparatus
containing compounds by using IC to separate the interferences
14.1 The schematic arrangement of the distillation system is
from the cyanide (16.5). Samples or distillates containing up to
shown in Fig. 1.
50 mg/L sulfide can be analyzed with sulfide abatement
acidification reagent as described in Test Method D6888. 14.2 For the required apparatus, refer to Section 7.
11.7.2 False positive results have been observed for total
cyanide in samples containing thiocyanate in the presence of 15. Reagents and Materials
ammonia and nitrate. To avoid this interference, use a method 15.1 Refer to Section 8.
that does not require distillation such as Test Method D6888.
Adding 0.6 g/L ascorbic acid prior to distillation may also 16. Procedure
reduce the interference; treated samples should be analyzed
within 24 hours. 16.1 Distillation Procedure:
11.7.3 Separation of the cyanide from interfering substances 16.1.1 Set up the apparatus as shown in Fig. 1.
prior to electrochemical determination (see 16.5 for ion chro- 16.1.2 Add 10.0 mL of 1 M NaOH solution to the absorber.
matography procedure) should be conducted when using Test Dilute with water to obtain an adequate depth of liquid. Do not
Method A—Total Cyanides After Distillation, or Test Method use more than 225 mL of total volume in the absorber.
B—Cyanides Amenable to Chlorination by the Difference 16.1.3 Attach the absorber to the vacuum and connect to the
when sulfur, thiocyanate, or other sulfur containing compounds condenser.
are present. 16.1.4 Place 500 mL of the sample in the flask. If cyanide
11.8 Thiocyanate in the presence of ferric ion is quantita- content is suspected to be more than 10 mg/L, use an aliquot so
tively determined by the colorimetric procedure. Test Method that no more than 5 mg of cyanide is in the distilling flask and
D outlines a procedure for masking any cyanide amenable to dilute to 500 mL with water. Annex A1 describes a procedure
chlorination in order to determine thiocyanate by difference. for establishing the approximate cyanide content. Verify a
negative reaction in the spot-plate technique by using 500 mL
11.9 Substances which contribute color or turbidity interfere
of the sample.
with Test Method D.
16.1.5 Connect the flask to the condenser.
TEST METHOD A—TOTAL CYANIDES 16.1.6 Turn on the vacuum and adjust the air flow to
AFTER DISTILLATION approximately 1 bubble per second entering the boiling flask
through the air-inlet tube.
12. Scope
16.1.7 Add 20 mL of magnesium chloride solution (8.13)
12.1 This test method covers the determination of cyanides through the air inlet tube. If the sample contains nitrite or
in water, including the iron cyanide complexes (total cyanide). nitrate, add 15 mL of sulfamic acid solution (8.21).
12.2 The cyanide in some cyano complexes of transition 16.1.8 Rinse the air-inlet tube with a few mL of water and
metals, for example, cobalt, gold, platinum, etc., is not deter- allow the air flow to mix the content of the flask for
mined. approximately 3 min.
12.3 The cyanide concentration can be determined with 16.1.9 Carefully add 50 mL of H2SO4 solution (1 + 1)
titration, IC-PAD, colorimetric, selective ion electrode through the air-inlet tube. (Warning— Add slowly; heat is
procedure, or flow injection analysis with gas diffusion sepa- generated and foaming may occur.)
ration and amperometric detection as described in Test Method 16.1.10 Turn on the condenser cooling water. Heat the
D6888. solution to boiling, taking care to prevent the solution from
12.4 This test method has been used successfully on reagent backing into the air-inlet tube.
and surface water and coke plant, refinery, and sanitary waste 16.1.11 Maintain the air flow as in 16.1.6.
waters. It is the user’s responsibility to assure the validity of 16.1.12 Reflux for 1 h.
the test method for the water matrix being tested. 16.1.13 Turn off the heat, but maintain the air flow for at
12.5 Because of the sample preservation, certain suspended least an additional 15 min.
and/or colloidal forms of metal cyanide complexes such as 16.1.14 For 500-mL macro distillations, quantitatively
those from iron and copper will dissolve prior to the distillation transfer the absorption solution into a 250-mL volumetric flask.
step. The recovery of this cyanide may depend on solution Rinse absorber and its connecting tubes sparingly with water
parameters such as the cyanide concentration in suspended and add to the volumetric flask.
solids, ionic strength of the sample, sample temperature, acid 16.1.15 Dilute to volume with water and mix thoroughly.
digestion times, and so forth. 16.1.16 Determine the concentration of cyanide in the
absorption solution by one of the procedures—titration (Sec-
13. Interferences tion 16.2), colorimetric (16.3), selective ion electrode (16.4),
13.1 All the chemical compounds listed in Section 6 can ion chromatography (16.5), or flow injection with gas diffusion
interfere. separation with amperometric detection as described in Test

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TABLE 1 Guide for Selection of Appropriate Cell Paths 16.3.2.7 Calculate the concentration of cyanide (mg CN/L)
Millitres of Final Cell Length,
in the original sample following equations given in 17.2.
Standard Standard Concen- cm
Solution Solution tration, µg 16.4 Selective Ion Electrode Procedure:
No.
50 mL CN/mL 1.0 5.0 10.0 16.4.1 Standardization:
IV 5.0 0.0025 X 16.4.1.1 Place 100-mL aliquots of standard solutions I, II,
IV 10.0 0.0050 X X III, and IV in 250-mL beakers.
IV 15.0 0.0075 X X
IV 20.0 0.0100 X X
16.4.1.2 Follow 16.4.2.2 and 16.4.2.3.
IV 25.0 0.0125 X X 16.4.1.3 Pipet 10- and 50-mL aliquots of standard solution
IV 30.0 0.0150 X X IV into 250-mL beakers and dilute to 100 mL with NaOH
IV 40.0 0.0200 X
III 5.0 0.0250 X X solution (1.6 g/L).
III 10.0 0.0500 X 16.4.1.4 Follow 16.4.2.2 and 16.4.2.3 of the procedure,
III 15.0 0.0750 X starting with the lowest concentration.
III 20.0 0.1000 X
III 25.0 0.1250 X 16.4.1.5 Plot concentration values of the standardizing so-
III 30.0 0.1500 X lutions on the logarithmic axis of semilogarithmic graph paper
0.0 (blank) X X X versus the potentials developed in the standardizing solutions
on the linear axis. Follow manufacturer’s instructions for
direct-reading ion meters.
16.4.2 Procedure:
Method D6888 (16.6). See Sections 4.6 and 4.7 for minimum 16.4.2.1 Place 100 mL of the absorption solution (or an
concentration levels for each procedure prior to choosing a accurately measured aliquot diluted to 100 mL with NaOH
determinative step. solution (1.6 g/L)) in a 250-mL beaker.
16.2 Titration Procedure:
NOTE 3—Check a small portion of the solution for sulfide. If it is
16.2.1 Place 100 mL of the absorption solution or an present, add either the PbCO3 or Pb(C2H3O2)2 immediately before
accurately measured aliquot diluted to 100 mL with NaOH inserting the electrodes.
solution (1.6 g/L) in a flask or beaker. 16.4.2.2 Place the beaker on a magnetic stirrer, place a
16.2.2 Add 0.5 mL of rhodanine indicator solution. TFE-fluorocarbon-coated stirring bar in the solution, stir at a
16.2.3 Titrate with standard silver nitrate solution (8.17) predetermined constant rate, and maintain constant tempera-
using a microburet to the first change from yellow to salmon ture.
pink. 16.4.2.3 Insert the cyanide specific ion electrode and the
16.2.4 Titrate a blank of 100 mL of NaOH solution (1.6 g/L) reference electrode in the solution and measure potential or the
(8.20). cyanide concentration following the manufacturer’s instruc-
16.2.5 Record the results of the titration and calculate the tions.
cyanide concentration in the original samples according to Eq 16.4.2.4 Use values found from the graph or direct-reading
1 (17.1). ion meter to calculate the concentration in the original sample
16.3 Colorimetric Procedure: following Eq 5 (17.3).
16.3.1 Standardization:
16.5 Ion Chromatography Procedure:
16.3.1.1 Prepare a series of cyanide standards based on the
16.5.1 Standardization:
cell path which is used (Table 1). For this purpose use 50-mL
16.5.1.1 Place 2-mL of standard solutions I, II, III, and IV
glass-stoppered volumetric flasks or graduated cylinders.
into HPLC autosampler vials if using an autosampler, or other
16.3.1.2 Follow 16.3.2.2 through 16.3.2.6 of the procedure.
capped glass vial if using a manual injector.
16.3.1.3 Calculate the absorption factor (17.2.1).
16.5.1.2 Follow 16.5.2.1 through 16.5.2.4 to standardize the
16.3.2 Procedure:
IC detector response by injection of 10 µL of each standard
16.3.2.1 Pipet an aliquot of the absorption liquid, such that
solution.
the concentration falls within the standardization range, into a
50-mL glass-stoppered volumetric flask or graduated cylinder. NOTE 4—A 10-µL injection was used for the interlaboratory study.
16.3.2.2 If necessary, dilute to 40 mL with the NaOH Other levels can be used provided the analyst confirms the precision and
solution used in the absorber solution. bias is equivalent with that generated using the 10-µL injection.
16.3.2.3 Place 40 mL of the NaOH solution used in the 16.5.1.3 Measure the area under the cyanide peak. This is
absorber solutions in a flask or cylinder for a blank. (Carry out the detector response.
the following steps of the procedure on the blank also.) 16.5.1.4 Plot concentration values of the standard solution
16.3.2.4 Add 1 mL of chloramine-T solution and 1 mL of versus detector response. Follow manufacturer’s instruction for
acetate buffer, stopper, mix by inversion two or three times, and IC systems with computer controlled data stations.
allow to stand for exactly 2 min. 16.5.2 Procedure:
16.3.2.5 Add 5 mL of pyridine-barbituric acid reagent, 16.5.2.1 Set the ion chromatograph to operate at the follow-
dilute to volume with water, mix thoroughly, and allow to stand ing conditions or as required for instrument being used:
exactly 8 min for color development. (a) Flow Rate: 1.0 mL/min.
16.3.2.6 Measure at the absorbance maximum at 578 nm. (b) PAD operated in a dc amperometric mode with a
Measure absorbance (A) versus water. silver-working-electrode set at –0.05 V in relation to a standard

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TABLE 2 Waveform for Analysis of Cyanide by Ion where:
Chromatography
a = absorbance of standard solution,
Time (sec)
Potential (V) vs.
Integration c = concentration of CN− in standard, mg/L, and
Ag/AgCl, 3 M KCl
0.00 –0.10 - n = number of standard solutions.
0.20 –0.10 Start
0.90 –0.10 End
17.2.1.1 the blank concentration, 0.0 mg CN− /L, and the
0.91 –1.00 - absorbance of the blank must be included in the calculation of
0.93 –0.30 - slope and intercept.
1.00 –0.30 -
17.2.2 Concentration—Calculate the concentration of cya-
nides using Eq 4:
40 250
CN, mg/L 5 ~ ma1 1b ! X X (4)
Ag/AgCl-reference electrode or an equivalent detector. Other X Y
working electrodes such as platinum or boron-doped diamond where:
electrodes have also been shown to be effective. Optimize the
a1 = absorbance of sample solution,
waveform based on the electrode used.
X = aliquot of absorbance solution, mL, and
(c) Column, Dionex IonPac AS 7 anion-exchange, Y = original sample, mL.
4 × 250 mm and matching guard column or equivalent.
(d) Temperature: Ambient. 17.3 Selective-Ion Electrode and Ion Chromatography
(e) Sample size: 10 µL. Procedures—Calculate the concentration in milligrams of CN
16.5.2.2 Prime the IC pump and ensure that the flow rate is per litre using Eq 5:
1.0 mL/min. Allow the detector to warm up for 30-60 min to CN, mg/L 5 CN mg/L from graph or meter (5)
stabilize the baseline.
16.5.2.3 Inject 10-µL of sample solution into the IC system. 3 ~ 100/aliquot! 3 ~ 250/mL original sample!
Apply the waveform from Table 2. A 10-µL injection of 50 ppb
18. Precision and Bias5
standard of cyanide should result in a well-defined peak with
an area >1.0 nC min and with asymmetry in the range of 0.9 to 18.1 Precision: All methods have met the requirements for
2.0 for 2-mm ID column set. With a 4-mm ID column set a Practice D2777 for Determination of Precision and Bias of
50-µL injection of the same standard should generate a peak Applicable Test Methods of Committee D19 on Water.
area >0.8 nC min in the same range of asymmetry values. 18.1.1 Colorimetric—Based on the results of nine operators
16.5.2.4 Use values found from the graph or data station to in nine laboratories, the overall and single-operator precision
calculate the concentration in the original sample following Eq of this test method within its designated range may be
5 (17.3). expressed as follows:
Reagent Water ST = 0.06x + 0.003
16.6 Flow Injection Analysis with Gas Diffusion Separation So = 0.11x + 0.010
and Amperometric Detection Procedure: Selected Water Matrices ST = 0.04x + 0.018
16.6.1 For total cyanide, test the sample distillates with Test So = 0.04x + 0.008
Method D6888. 18.1.2 Electrode—Based on the results of six operators in
five laboratories, the overall and single-operator precision of
17. Calculation this test method within its designated range may be expressed
17.1 Titration Procedure—Calculate the concentration in as follows:
milligrams of CN per litre in the original sample using Eq 1: Reagent Water ST = 0.06x + 0.003
So = 0.03x + 0.008
mg CN/L 5 @ ~ A 2 B ! 3 N AgNO3 3 0.052/mL original sample# Selected Water Matrices ST = 0.05x + 0.008
3 ~ 250/mL aliquot used! 3 10 6 (1) So = 0.03x + 0.012
18.1.3 Titrimetric—Based on the results of six operators in
three laboratories, the overall and single-operator precision of
where: this test method within its designated range may be expressed
A = AgNO3 solution to titrate sample, mL, and as follows:
B = AgNO3 solution to titrate blank, mL. Reagent Water ST = 0.04x + 0.038
So = 0.01x + 0.018
17.2 Colorimetric Procedure—Calculate the concentration Selected Water Matrices ST = 0.06x + 0.711
in milligrams of CN per litre as follows: So = 0.04x + 0.027

17.2.1 Slope and Intercept of Standard Curve—Calculate 18.1.4 Ion Chromatography Procedure—The precision was
the slope on the standard curve, m, and the intercept on c-axis, determined in accordance with Practice D2777. Based on the
b, using Eq 2 and Eq 3, respectively: results of eight operators in eight laboratories, the overall and
single-operator precision of this test method within its desig-
m5 ( ca 2 ( c ( a
n
2 (2) nated range may be expressed as follows:
( a 2 ~( a!
n 2

b5( (
a c 2 ( a ( ac
2
5
(3) Supporting data have been filed at ASTM International Headquarters and may
2
n( a 2 ~( a! 2
be obtained by requesting RR:D19-1131.

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 D2036 − 09
TABLE 3 Reagent Water (Test Method A)
Statistical
Amount Added, Amount Found,
Technique n St Bias %Bias Significance,
mg/L mg/L
95 % CL
Colorimetric 0.060 0.060 26 0.0101 0.000 0 No
0.500 0.480 23 0.0258 −0.020 −4 No
0.900 0.996 27 0.0669 0.096 11 Yes
Electrode 0.060 0.059 18 0.0086 −0.001 2 No
0.500 0.459 18 0.0281 −0.041 −8 Yes
0.900 0.911 18 0.0552 0.011 1 No
5.00 5.07 18 0.297 0.07 1 No
Titrimetric 2.00 2.10 18 0.1267 0.10 5 Yes
5.00 4.65 18 0.2199 −0.35 −7 Yes
5.00 5.18 18 0.2612 0.18 4 Yes

xbar 5 1.04x10.35 TEST METHOD B—CYANIDES AMENABLE TO

S T 5 0.057x13.19 CHLORINATION (CATC) BY THE DIFFERENCE
S o 5 0.020x13.90 19. Scope
18.1.5 A weighted linear regression was used since the 19.1 This test method covers the determination of cyanides
absolute error increased with concentration. More weight was amenable to chlorination in water.
given to the smaller (lower error) concentrations than to the 19.2 Iron cyanides are the most commonly encountered
larger (higher error) ones. The weighting factor used was compounds not amenable to chlorination.
1/s.d.2 for each of the concentration levels (1).6
19.3 This test method has been used on reagent, surface, and
where: industrial waste waters. It is the user’s responsibility to assure
ST = overall precision, the validity of the test method for the water matrix being tested.
So = single operator precision, and
X = cyanide concentration, mg/L. 20. Interferences
18.1.6 The precision and bias for Test Method D6888 was 20.1 All the chemical compounds listed in Section 6 can
determined in accordance with Practice D2777. Based on the interfere. See Practice D7365 for further discussion on inter-
results of 10 operators in 10 laboratories, the overall and single ferences. Alternatively, analyze the samples for available
operator precision and method bias data are shown in Table 2 cyanide as described in Test Method D6888, which is less
of Test Method D6888. The precision and bias were deter- susceptible to interference than this method.
mined for available cyanide using a synthetic wastewater 20.2 For the removal of these interferences, proceed as
matrix. instructed in Practice D7365 and Sections 10 and 11.
18.2 Bias: 20.3 This test method can be affected by compounds that are
18.2.1 Recoveries of known amounts of cyanide from converted during chlorination to volatile compounds which are
Reagent Water Type II and selected water matrices are shown collected in the absorption solution and can interfere in the
in Table 3 and Table 4. final determination.
18.2.2 Bias was determined in alkaline reagent water (0.25 20.4 If the calculated result is significantly negative, inter-
M NaOH) for ion chromatography as the determinative step ferences are present. In this case, Test Method D6888 can be
during an interlaboratory study7 in accordance with Practice used to determine available cyanide.
D2777. The statistical summary for ion chromatography as the
determinative step is shown in Table 5. 21. Apparatus
18.3 The bias for Test Method D6888 was determined for 21.1 The schematic arrangement of the distillation system is
available cyanide in a synthetic wastewater in accordance with shown in Fig. 1.
Practice D2777. This test method can also be used as a 21.2 For the required apparatus, refer to Section 7.
determinative step for total cyanide after distillation.
22. Reagents and Materials
18.4 The precision and bias information given in this
section may not apply to waters of untested matrices. 22.1 Refer to Section 8.

23. Procedure

6
23.1 Sample Preparation—Divide the sample into two equal
The boldface numbers in parentheses refer to the list of references at the end of
portions of 500 mL or less. Determine the total cyanide in one
this standard.
7
Supporting data have been filed at ASTM International Headquarters and may portion as indicated in 23.2. Place the other portion in a 1-L
be obtained by requesting RR:D19-1161. beaker and chlorinate as outlined in the following steps.

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 D2036 − 09
TABLE 4 Selected Water Matrices (Test Method A)
Statistical
Amount Added, Amount Found,
Technique n St Bias %Bias Significance,
mg/L mg/L
95 % CL
Colorimetric 0.060 0.060 25 0.0145 0.000 0 No
0.500 0.489 26 0.0501 −0.011 −3 No
0.900 0.959 24 0.0509 0.059 7 Yes
Electrode 0.060 0.058 14 0.0071 −0.002 −3 No
0.500 0.468 21 0.0414 −0.032 −6 No
0.900 0.922 19 0.0532 0.022 2 No
5.00 5.13 20 0.2839 0.13 3 No
Titrimetric 2.00 2.80 18 0.8695 0.80 40 Yes
5.00 5.29 18 1.1160 0.29 6 No
5.00 5.75 18 0.9970 0.75 15 Yes

TABLE 5 Final Statistical Summary for Ion Chromatography as the Determinative Step
Sample A Sample D Sample B Sample E Sample C Sample F A + Sulfide D + Sulfide
Number of retained values 7 7 7 7 7 7 7 7
True Concentration (C),µ g/L 251 217 866 736 43.3 34.6 251 217
Mean Recovery (XBAR) 250 222 958 801 44 39 248 221
Percent Recovery 99.5 10.2 111 109 100 110 99.0 102
Overall Standard Deviation, 17.8 20.1 58.8 41.7 7.3 4.6 18.4 13.2
(st)
Overall Relative Standard 7.10 9.08 6.14 5.21 16 12 7.39 5.95
Deviation,%
Number of retained pairs 7 7 7 7 7 7 7 7
Single-Operator Standard 9.35 18.0 4.6 8.54
Deviation, (so)
Analyst Relative Deviation,% 4.01 2.12 11 3.72
Bias −0.46 2.11 10.61 8.83 2.6 13 −1.02 2.04

NOTE 1—Samples prepared in alkaline reagent water (0.25M NaoH). Samples A+Sulfide and D+Suflide contain 1 mg/L sulfide to test for potential
interference.

NOTE 5—Protect the solution in the beaker from ultraviolet radiation by where:
wrapping the beaker with aluminum foil or black paper and cover with a
wrapped watch glass during chlorination.
G = cyanide, determined in the unchlorinated portion of the
sample, mg/L, and
23.1.1 Place the beaker on a magnetic stirrer, insert a TFE H = cyanide determined in the chlorinated portion of the
fluorocarbon-coated stirring bar in the beaker, and start stirring. sample, mg/L.
23.1.2 If necessary, adjust the pH to between 11 and 12 with
NaOH solution (40 g/L). 25. Precision and Bias5
23.1.3 Add Ca(OCl)2 solution (50 g/L) 3 drops at a time
until there is an excess of chlorine indicated on a strip of 25.1 Precision:
potassium iodide-starch test paper previously moistened with 25.1.1 Colorimetric—Based on the results of eight operators
acetic acid solution. in seven laboratories, the overall and single-operator precision
23.1.4 Maintain the pH and excess chlorine for 1 h while of this test method within its designated range may be
stirring. Add Ca(OCl)2 solution or NaOH solution, or both, 2 expressed as follows:
drops at a time when necessary. Reagent Water ST = 0.18x + 0.005
23.1.5 At the end of the hour remove any residual chlorine So = 0.06x + 0.003
Selected Water Matrices ST = 0.20x + 0.009
by the dropwise addition of NaAsO2 solution (2 g/100 mL) or So = 0.05x + 0.005
by adding 8 drops of H2O2 solution (3 %) followed by 4 drops
25.1.2 Titrimetric—Based on the results of six operators in
of Na2S2O3 solution (500 g/L). Test with potassium iodide-
three laboratories, the overall and single-operator precision of
starch test paper.
this test method within its designated range may be expressed
23.2 Follow steps 16.1.1 through 16.1.16 for Test Method as follows:
A. Reagent Water ST = 0.01x + 0.439
So = 0.241 − 0.03x
24. Calculation Selected Water Matrices ST = 0.12x + 0.378
So = 0.209 − 0.01x
24.1 Calculate the total cyanide in each portion of the
sample following Eq 1, Eq 4, or Eq 5. 25.1.3 where:
24.2 Calculate the concentration of cyanide amenable to ST = overall precision,
chlorination using Eq 6: So = single operator precision, and
CN, mg/L 5 G 2 H (6)
x = cyanide concentration, mg/L.

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TABLE 6 Reagent Water (Test Method B)
Statistical
Amount Added, Amount Found, n
Technique St Bias % Bias Significance,
mg/L mg/L
95 % CL
0.008 0.009 21 0.0033 0.001 13 No
Colorimetric 0.019 0.023 20 0.0070 0.004 21 Yes
0.080 0.103 20 0.0304 0.018 23 Yes
0.191 0.228 21 0.0428 0.037 19 Yes
1.00 0.73 18 0.350 −0.27 −27 Yes
Titrimetric 1.00 0.81 18 0.551 −0.19 −19 No
4.00 3.29 18 0.477 −0.71 −18 Yes

25.2 Bias—Recoveries of known amounts of cyanide ame- 30.1.2 Add 10.0 mL of NaOH solution (40 g/L) to the
nable to chlorination from reagent water Type II and selected absorber. Dilute with water to obtain an adequate depth of
water matrices were as shown in Table 6 and Table 7. liquid. Do not use more than 225 mL of total volume in the
25.3 The precision and bias information given in this absorber.
section may not apply to waters of untested matrices. 30.1.3 Attach the absorber to the vacuum and connect to the
condenser.
TEST METHOD C—WEAK ACID 30.1.4 Place 500 mL of sample in the flask. If cyanide
DISSOCIABLE CYANIDES content is suspected to be more than 10 mg/L, use an aliquot so
that no more than 5 mg of cyanide are in the flask, and dilute
26. Scope to 500 mL with water.
26.1 This test method covers the determination of cyanide 30.1.5 Connect the flask to the condenser.
compounds and weak acid dissociable complexes in water. 30.1.6 Turn on the vacuum and adjust the air flow to
26.2 The thiocyanate content of a sample usually does not approximately 1 bubble per second entering the boiling flask
cause interference. through the air-inlet tube.
30.1.7 Add 20 mL each of the acetate buffer and zinc acetate
26.3 Any of the three procedures, titration, colorimetric, or solutions through the air-inlet tube. Add 2 or 3 drops of methyl
selective ion electrode, can be used to determine the cyanide red indicator solution.
content of the absorption solution. The lower limits of detect-
30.1.8 Rinse the air-inlet tube with a few mL of water and
ability are the same as for Test Method A.
allow the air flow to mix the content of the flask. (If the
26.4 This test method has been used successfully on reagent solution is not pink, add acetic acid (1 + 9) dropwise through
and surface water and coke plant, refinery and sanitary waste the air-inlet tube until there is a permanent color change.)
waters. It is the user’s responsibility to assure the validity of 30.1.9 Turn on the condenser cooling water, heat the solu-
the test method for the water matrix being tested. tion to boiling, taking care to prevent the solution from backing
into the air inlet tube.
27. Interferences
30.1.10 Maintain the air flow as in 30.1.6.
27.1 All the chemical compounds listed in Section 6 can 30.1.11 Reflux for 1 h.
interfere. See Practice D7365 for further discussion on inter- 30.1.12 Turn off the heat, but maintain the air flow for at
ferences. Alternatively, analyze the samples for available least an additional 15 min.
cyanide as described in Test Method D6888, which is less 30.1.13 Quantitatively transfer the absorption solution into
susceptible to interference than this method. a 250-mL volumetric flask. Rinse the absorber and its connect-
27.2 For the removal of these interferences proceed as ing tubes sparingly with water and add to volumetric flask.
instructed in Practice D7365 and Sections 10 and 11. 30.1.14 Dilute to volume with water and mix thoroughly.
30.1.15 Determine the concentration of cyanide in the
28. Apparatus absorption solution by one of the three procedures desceibed in
28.1 The schematic arrangement of the distillation system is 16.2, 16.3, or 16.4.
shown in Fig. 1.
28.2 The required equipment, instruments, and parts are 31. Calculation
listed in Section 7. 31.1 Calculate the concentration of weak acid dissociable
cyanide in the sample following Eq 1, Eq 4, or Eq 5.
29. Reagents and Materials
29.1 Refer to Section 8. 32. Precision and Bias5
29.2 Methyl Red Indicator Solution. 32.1 Precision:
32.1.1 Colorimetric—Based on the results of nine operators
30. Procedure in nine laboratories, the overall and single-operator precision
30.1 Distillation Procedure: of this test method within its designated range may be
30.1.1 Set up the apparatus as shown in Fig. 1. expressed as follows:

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 D2036 − 09
TABLE 7 Selected Water Matrices (Test Method B)
Statistical
Amount Added, Amount Found, n
Technique St Bias % Bias Significance,
mg/L mg/L
95 % CL
Colorimetric 0.008 0.013 17 0.0077 0.005 63 Yes
0.019 0.025 18 0.0121 0.006 32 Yes
0.080 0.100 18 0.0372 0.020 25 Yes
0.191 0.229 18 0.0503 0.038 20 Yes
1.00 1.20 18 0.703 0.20 20 No
Titrimetric 1.00 1.10 18 0.328 0.10 10 No
4.00 3.83 18 0.818 −0.17 −4 No

Reagent Water ST = 0.09x + 0.010 cyanide as described in Test Method D6888, which is less
So = 0.08x + 0.005 susceptible to interference than this method.
Selected Water Matrices ST = 0.08x + 0.012
So = 0.05x + 0.008 34.2 For the removal of these interferences, proceed as
32.1.2 Electrode—Based on the results of six operators in instructed in Practice D7365 and Sections 10 and 11.
five laboratories, the overall and single-operator precision of
34.3 The thiocyanate ion which reacts with chloramine-T
this test method within its designated range may be expressed
will give a positive error equivalent to its concentration as
as follows:
cyanide.
Reagent Water ST = 0.09x + 0.004
So = 0.02x − 0.009 34.4 Color and turbidity can interfere.
Selected Water Matrices ST = 0.08x + 0.005
So = 0.02x + 0.004 34.4.1 When color or turbidity producing substances are
32.1.3 Titrimetric—Based on the results of six operators in present, it is recommended that Test Method B or C be used.
three laboratories, the overall and single-operator precision of 34.4.2 Color and turbidity can be extracted from some
this test method within its designated range may be expressed samples with chloroform without reduction of the pH.
as follows: 34.4.3 It is possible with some samples to compensate for
Reagent Water ST = 0.532 − 0.10x color and turbidity by determining the absorbance of a second
So = 0.151 − 0.01x sample solution to which all reagents except chloramine-T
Selected Water Matrices ST = 0.604 − 0.06x have been added.
So = 0.092 + 0.02 x
32.1.4 where: 34.5 Reducing compounds such as sulfites can interfere by
preferentially reacting with chloramine-T.
ST = overall precision,
So = single-operator precision,and 34.6 The color intensity and absorption is affected by wide
x = cyanide concentration, mg/L. variations in the total dissolved solids content of the sample.
34.6.1 For samples containing high concentrations of dis-
32.2 Bias—Recoveries of known amounts of cyanide from
solved solids, 3000 to 10 000 mg/L, add 6 g of NaCl to each
reagent water Type II and selected water matrices were as
litre of NaOH solution (1.6 g/L) used to prepare the standards.
shown in Table 8 and Table 9.
For samples containing dissolved solids concentration greater
32.3 The precision and bias information given in this than 10 000 mg/L, add sufficient NaCl to the NaOH solution to
section may not apply to waters of untested matrices. approximate the dissolved solids content.
TEST METHOD D—CYANIDES AMENABLE
35. Apparatus
TO CHLORINATION WITHOUT
DISTILLATION, SHORT-CUT METHOD 35.1 Spectrophotometer or Filter Photometer, suitable for
measurements in the region of 578 nm, using 1.0-cm absorp-
33. Scope tion cells. Filter photometers and photometric practices used in
33.1 This test method covers the determination of free CN− these test methods shall conform to Practice E60. Spectropho-
and CN− complexes that are amenable to chlorination in water. tometers shall conform to Practice E275.
The procedure does not measure cyanates nor iron cyanide 35.2 Water Bath, capable of maintaining temperature at 27
complexes. It does, however, determine cyanogen chloride and 6 1°C.
thiocyanate.
33.2 Modification is outlined for its use in the presence of 36. Reagents and Materials
thiocyanate.
36.1 Refer to Section 8.
34. Interferences 36.2 Pyridine-Barbituric Acid Reagent—For the preparation
34.1 All the chemical compounds listed in Section 6 can of this reagent, refer to 8.15; however, for this test method,
interfere. See Practice D7365 for further discussion on inter- prepare a fresh solution weekly. Longer storage affects the
ferences. Alternatively, analyze the samples for available results of the test.

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 D2036 − 09
TABLE 8 Reagent Water (Test Method C)
Statistical
Amount Added, Amount Found, n
Technique St Bias % Bias Significance,
mg/L mg/L
95 % CL
Colorimetric 0.030 0.030 25 0.0089 0.000 0 No
0.100 0.117 27 0.0251 0.017 17 Yes
0.400 0.361 27 0.0400 −0.039 −10 Yes
Electrode 0.030 0.030 21 0.0059 0.000 0 No
0.100 0.095 21 0.0163 −0.005 −5 No
0.400 0.365 21 0.0316 −0.035 −9 No
1.000 0.940 21 0.0903 −0.060 −6 No
Titrimetric 1.00 1.35 18 0.4348 0.35 35 Yes
1.00 1.38 18 0.3688 0.38 38 Yes
4.00 3.67 18 0.1830 0.33 −8 No

TABLE 9 Selected Water Matrices (Test Method C)

Statistical
Amount Added, Amount Found, n
Technique St Bias % Bias Significance,
mg/L mg/L
95 % CL
Colorimetric 0.030 0.029 15 0.0062 0.001 3 No
0.100 0.118 24 0.0312 0.018 18 Yes
0.400 0.381 23 0.0389 −0.019 −5 Yes
Electrode 0.030 0.029 20 0.0048 −0.001 −3 No
0.100 0.104 21 0.0125 0.004 4 No
0.400 0.357 21 0.0372 −0.043 −11 No
1.000 0.935 21 0.0739 −0.065 −7 No
Titrimetric 1.00 1.55 18 0.5466 0.55 55 Yes
1.00 1.53 18 0.4625 0.53 53 Yes
4.00 3.90 18 0.3513 −0.10 −3 No

36.3 EDTA Solution (18.5 g/L)—Dissolve 18.5 g of the 38.2 Pipet 20.0 mL of the sample into a 50-mL volumetric
disodium salt of ethylenediamine tetraacetic acid dihydrate in flask. If the cyanide concentration is greater than 0.3 mg/L, use
water and dilute to 1 L. a smaller aliquot and dilute to 20 mL with NaOH solution (1.6
36.4 Formaldehyde Solution (10 %) —Dilute 27 mL of g/L). Do not exceed the concentration limit of 0.3 mg/L.
formaldehyde (37 %) to 100 mL. 38.3 To ensure uniform color development, both in calibra-
36.5 Hydrochloric Acid (HCl) (sp gr 1.19) (1 + 9)—Slowly tion and testing, it is necessary to maintain a uniform tempera-
add 1 volume of concentrated HCl (sp gr 1.19) to 9 volumes of ture. Immerse the flasks in a water bath held at 27 6 1°C for
water, stirring during the addition. 10 min before adding the reagent chemicals and keep the
samples in the water bath until all the reagents have been
36.6 Phosphate Buffer Solution (138 g/L)—Dissolve 159 g added.
of sodium dihydrogen phosphate (NaH2PO4·H2O) in water,
dilute to 1 L and refrigerate. 38.4 Add 4 mL of phosphate buffer and swirl to mix. Add
one drop of EDTA solution, and mix.
36.7 Sodium Carbonate (Na2CO3), anhydrous.
38.5 Add 2 mL of chloramine-T solution and swirl to mix.
36.8 Sodium Chloride (NaCl), crystals.
Place 1 drop of sample on potassium iodide-starch test paper
37. Standardization which has been previously moistened with acetate buffer
solution. Repeat the chloramine-T addition if required. After
37.1 From the cyanide standard solutions, pipet a series of exactly 3 min, add 5 mL of pyridine-barbituric acid reagent and
aliquots containing from 0.5 to 5.0 µg of cyanide in volumes swirl to mix.
not exceeding 20 mL into 50-mL volumetric flasks.
38.6 Remove the samples from the water bath, dilute to
37.2 Dilute each solution to 20 mL with NaOH solution (1.6 volume and mix. Allow 8 min from the addition of the
g/L). Follow 38.3 through 38.7 of the procedure. pyridine-barbituric acid reagent for color development.
37.3 Calculate the absorption factor (17.2.1). 38.7 Determine the absorbance at 578 nm in a 1.0-cm cell
versus water.
38. Procedure
38.8 Calculate the concentration of cyanide as milligrams
38.1 Adjust the pH of a small volume of sample (50 mL) to
per litre, in the original sample following equations given in
between 11.5 and 11.9. If the addition of acid is needed, add a
17.2.
small amount (0.2 to 0.4 g) of sodium carbonate and stir to
dissolve. Then add dropwise while stirring HCl solution 38.9 If the presence of thiocyanate is suspected, pipet a
(1 + 9). For raising the pH, use NaOH solution (40 g/L). second 20-mL aliquot of pH-adjusted sample solution into a

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TABLE 10 Reagent Water (Test Method D)
Amount Added, mg/L Statistical
Amount Found, n
St Bias % Bias Significance,
CN SCN mg/L
95 % CL
0.005 0.007 42 0.0049 0.002 40 Yes
0.027 0.036 41 0.0109 0.009 25 Yes
0.090 0.100 42 0.0167 0.010 11 Yes
0.090 0.080 0.080 39 0.0121 −0.010 11 Yes
0.270 0.276 42 0.0320 0.006 2 No

50-mL volumetric flask. Add 3 drops of 10 % formaldehyde 40.1.2 Colorimetric Procedure:

solution. Mix and allow to stand 10 min. Place in a water bath 40.1.2.1 Prepare a series of cyanide standards, including
at 27 6 1°C for an additional 10 min before the addition of the zero (blank), based on the expected concentration range of the
reagent chemicals and hold in the bath until all reagents have samples, and follow the standardization each time new re-
been added. agents are prepared or every six months.
38.10 Continue with 38.4 through 38.7. 40.1.2.2 The slope (m) of the standard curve should check
the theoretical value:
38.11 Calculate the concentration of cyanide, in milligrams
1.0-cm cell, 0.22–0.24 mg CN/L/a; 5.0-cm cell, 0.044–0.048
per litre, in the original sample following equations given in
mg CN/L/a; 10.0-cm cell, 0.022–0.024 mg CN/L/a
17.2.
40.1.2.3 At least one standard solution and one blank should
38.12 In the presence of thiocyanate, cyanide amenable to be checked each time the procedure is used.
chlorination is equal to the difference between the concentra- 40.1.3 Selective Ion Electrode Procedure:
tion of cyanide obtained in 38.8 and that obtained in 38.11. 40.1.3.1 Follow the standardization procedure each time
39. Precision and Bias8 new standard solutions are prepared.
40.1.3.2 The slope of the curve should check within 90 % of
39.1 Precision: the theoretical value: 59.2 mV/decade.
39.1.1 Based on the results of 14 operators in nine
40.1.3.3 At least two standard solutions and one blank
laboratories, the overall and single-operator precision of this
should be checked each time the procedure is used.
test method within its designated range may be expressed as
follows: 40.1.4 Ion Chromatographic Procedure:
40.1.4.1 At least three standard solutions and one blank
Reagent Water ST = 0.10x + 0.006
So = 0.07x + 0.005 should be checked each time the procedure is used.
Selected Water Matrices ST = 0.11x + 0.007 40.1.4.2 Calibrate the ion chromatograph each time the
So = 0.02x + 0.005
procedure is used or whenever the eluent is changed. If the
39.1.2 where: response or retention time for cyanide varies from the expected
value by more than 6 10 % a new calibration curve must be
ST = overall precision,
So = single-operator precision,and prepared.
x = cyanide concentration, mg/L. 40.1.4.3 One midrange standard solution and a blank should
be checked each time the procedure is used or at least every 20
39.2 Bias—Recoveries of known amounts of cyanide from samples. If the response or retention time varies from the
reagent water Type II, seven creek waters, one diluted sewage expected value by more than6 10 % repeat the test using fresh
(1 + 20) and one industrial waste water are as shown in Table standards.
10 and Table 11.
40.2 Verification of the Distillation Procedure:
39.3 This precision and bias information may not apply to
waters of untested matrices. 40.2.1 Verify the distillation procedure as described in
sections 40.3 to 40.8.
40. Quality Assurance/Quality Control NOTE 6—With careful selection of concentration all four quantification
40.1 Verification of Systems for Quantifying Cyanide in the procedures can be performed on the same distillate solution. (See Guide
Distillate: D5788).
40.1.1 Titration Procedure: 40.3 Initial Demonstration of Laboratory Capability:
40.1.1.1 Standardize the silver nitrate solution with Potas- 40.3.1 If a laboratory has not performed the test before or if
sium Chloride, NIST, at least every six months. there has been a major change in the measurement system, for
40.1.1.2 Titrate 100-mL aliquots of Cyanide I Solution example new analyst, new instrument, and so forth, a precision
Standard and 100-mL aliquots of Sodium Hydroxide Solution and bias study must be performed to demonstrate laboratory
(1.6 g/L) each time the procedure is used. Duplicate titrations capability.
should check within 0.05 mL. 40.3.2 Analyze seven replicates of a standard solution
prepared from an IRM containing a known concentration of
8
Supporting data have been filed at ASTM International Headquarters and may cyanide in reagent water. Each replicate should be taken
be obtained by requesting RR:D19-1074. through the entire analytical test (that is, the distillation and

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TABLE 11 Selected Water Matrices (Test Method D)
Amount Added, mg/L Statistical
Amount Found, n
St Bias % Bias Significance,
CN SCN mg/L
95 % CL
0.005 0.003 40 0.0042 −0.002 40 Yes
0.027 0.026 42 0.0093 −0.001 4 No
0.090 0.087 42 0.0202 −0.003 3 No
0.090 0.080 0.068 37 0.0146 −0.022 24 Yes
0.270 0.245 41 0.0319 −0.025 9 Yes

determinative step) including preservation and any pretreat- A = concentration found in spiked sample,
ment used to remove interferences. The replicates may be B = concentration found in unspiked sample,
intersected with samples. C = concentration of analyte in spiking solution,
40.3.3 Calculate the mean and standard deviation of the Vs = volume of sample use, and
seven values and refer to Test Method D5847 for information V = volume of spiking solution added.
on applying the F test and t test in evaluating the acceptability
40.6.3 The percent recovery of the spike shall fall within
of the mean and standard deviation.
70-130 % or else one of the following must be employed: the
40.4 Laboratory Control Sample (LCS): matrix interference should be removed, all samples in the batch
40.4.1 To ensure that the test method is in control, analyze must be reanalyzed by a test method not affected by the matrix
an LCS containing cyanide at the appropriate concentration interference, or the results must be qualified with an indication
range for each analytical batch of 10 samples. For batches of that the matrix spike does not fall within the performance
less than 10 samples analyze at least one LCS. The LCS should criteria of the test method.
be taken through the entire analytical procedure. The LCS is
considered in control if the recovery is 85-115 %. If the LCS 40.7 Duplicate:
falls outside these limits halt the analysis of samples until the 40.7.1 To check the precision of sample analyses, analyze a
problem is corrected, upon which the samples should be sample in duplicate with each analytical batch. If the concen-
reanalyzed if possible. If samples cannot be reanalyzed, qualify tration of cyanide is less than five times the detection limit for
the data that the LCS was not within the performance criteria the method, a matrix spike duplicate (MSD) should be used.
of the test method. Calculate the standard deviation of the duplicate values and
40.5 Method Blank: compare to the single operator precision in the collaborative
40.5.1 Analyze a reagent water test blank with each analyti- study using an F test. Refer to 6.4.4 of Test Method D5847 for
cal batch of 10 samples or at least once daily if less than 10 information applying the F test.
samples are analyzed in a given day. The concentration of 40.7.2 If the result exceeds the precision limit, the batch
cyanide should be less than the reporting limit for the corre- must be reanalyzed or the results must be qualified with an
sponding method or else sample analyses are halted until the
indication that they do not fall within the performance criteria
problem is corrected. Affected samples should be reanalyzed or
of the test method.
qualified.
40.6 Matrix Spike (MS): 40.8 Independent Reference Material (IRM):
40.6.1 To check for interferences in the specific matrix 40.8.1 In order to verify the quantitative value obtained in
being tested, perform an MS on at least one sample from each the method, analyze an IRM, preferably analyzed as a regular
analytical batch by fortifying a known concentration of cyanide sample at least once a quarter. The observed concentration
and taking it through the entire analytical procedure. should fall within the limits set by the outside source of the
40.6.2 The matrix spike must produce a concentration that IRM.
is 2 to 5 times the background concentration or 10 to 50 times
the detection limit of the test method, whichever is greater. 41. Keywords
Calculate the percent recovery of the spike (P) using the
following formula: 41.1 colorimetric; cyanides amendable to chlorination;
distillation; ion chromatography; ion electrode; titration; total
P 5 100
? A~V s 1V ! 2 BVs ? cyanide; weak acid dissociable cyanides
CV

where:

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ANNEX

(Mandatory Information)

A1. SPOT TEST FOR SAMPLE SCREENING

A1.1 Scope A1.4.3 Hydrochloric Acid (1 + 9) —Mix 1 volume of con-

A1.1.1 The spot test procedure allows a quick screening of centrated (HCl (sp gr 1.19) with 9 volumes of water.
the sample to establish if more than 0.05 mg/L (ppm) of A1.4.4 Sodium Carbonate, anhydrous Na2CO3.
cyanides amenable to chlorination, cyanogen chloride, or
thiocyanate are present in water, waste water, and saline water. A1.5 Procedure
A1.5.1 If the solution subject to spot tests is alkaline in a pH
A1.1.2 The test may also be used to establish the presence
range greater than 10, neutralize a 20 to 25-mL portion.
and absence of cyanogen chloride by omitting the addition of
A1.5.1.1 Add 1 drop of phenolphthalein indicator solution.
chloramine-T.
If the sample remains colorless, proceed to A1.5.2.
A1.1.3 With the addition of formaldehyde to the sample, the A1.5.1.2 If the sample turns red, add approximately 250 mg
amenable cyanide can be masked and under these conditions, of sodium carbonate and mix to dissolve.
the test is specific to thiocyanate. It is possible therefore to A1.5.1.3 Add HCl (1 + 9) dropwise while mixing until
distinguish between the presence of cyanide and thiocyanate or colorless.
possibly judge the relative levels of concentration for each. A1.5.2 Place 3 drops of sample and 3 drops of reagent water
A1.1.4 With practice or dilution, the test can be used to (for a blank) on a white spot plate.
estimate the approximate concentration range of these A1.5.3 To each cavity, add 1 drop of chloramine-T solution
compounds, judging from the color development and compar- and mix with a clean stirring rod.
ing it to similarly treated samples of known concentration.
A1.5.4 To each cavity add 1 drop of phosphate buffer.
A1.2 Interferences A1.5.5 Add 1 drop of pyridine-barbituric acid solution to
A1.2.1 All the chemical compounds listed in Section 6, with each and again mix with a stirring rod.
the exception of the nitrites, may interfere. For their removal, A1.5.6 After 1 min, the sample spot will turn pink to red if
refer to Sections 10 and 11. 0.05 mg/L or more of CN is present. The blank spot will be
faint yellow due to the color of the reagents. Until familiarity
A1.2.2 The thiocyanate ion reacts in the same manner as the
with the spot test is gained, it may be advisable to use, instead
cyanide. The cyanide can be masked and then the test is
of the reagent water blank, a standard solution containing 0.05
specific for thiocyanate.
mg/L CN for color comparisons. This standard can be made up
A1.2.3 The presence of large amounts of reducing sub- by diluting the KCN standard solution (8.8.3).
stances in the sample interferes by consuming the A1.5.7 If the presence of thiocyanate is suspected, test a
chloramine-T added. Repeat the chloramine-T addition, if second sample pretreated as follows: Heat a 20 to 25-mL
necessary. sample in a water bath at 50°C; add 0.1 mL of formaldehyde
A1.3 Apparatus and hold for 10 min. This treatment will mask up to 5 mg
CN/L.
A1.3.1 Spot Plate, porcelain with 6 to 12 cavities preferred.
A1.5.8 Repeat the spot test with the treated sample. Color
A1.4 Reagents and Materials development indicates the presence of thiocyanate. Comparing
the intensity of the colors in the two spot tests is useful in
A1.4.1 Refer to Sections 8 and 36. judging whether both compounds are present and, if so, the
A1.4.2 Formaldehyde, 37 %, pharmaceutical grade. relative concentration of cyanide and thiocyanate.

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APPENDIX

(Nonmandatory Information)

X1. CYANIDE

X1.1 Introductory Comments—Cyanides are used exten- pH (that is, increasing the hydrogen ion concentration by 0.3
sively in metal finishing processes and heat treatment of steel, pH units) doubles the HCN content.
and are a significant constituent of wastes from coke oven and X1.2.6 Doudoroff has found that the toxicity of zinc-,
blast furnace operations. As a toxic contaminant of effluents, cadmium-, and copper-cyanide compounds is probably greater
they usually appear in the waste waters from quenching, gas than equal concentrations of sodium cyanide. The synergistic
scrub waters, and rinse water effluent from electroplating toxic effects, when both zinc and copper ions are combined
plants. The toxic effects of cyanide are so severe and estab- with cyanide, are known. Additional evidence regarding the
lished toxicity levels so low (<0.1 mg/L) that regulatory toxicity of copper, silver, and nickel cyanide complexes in low
concern and waste treatment efforts by industry need depend- concentrations was reported (10,9,11). Doudoroff, on the other
able analytical procedures and a better understanding of the hand, shows that the iron cyanides do not dissociate to any
various cyanide complexes that may be encountered. measurable extent and therefore are not toxic to fish (2,10,12).
X1.2 Molecular Hydrogen Cyanide, Cyanides Amenable to X1.2.7 Differentiation between toxic and nontoxic cyanide
Chlorination, Iron Cyanides: was designated “cyanides amenable to chlorination” by Lancy
and Zabban(13). Differentiation is based on the oxidizing effect
X1.2.1 Toxicological investigations by Doudoroff and oth- of chlorine. Resistance of the iron cyanide compounds to
ers have indicated that the acute toxicity of polluted water is oxidation is due to lack of dissociation rendering them non-
caused by the molecular hydrogen cyanide (undissociated toxic to fish. Test for “Cyanides Amenable to Chlorination
HCN) as opposed to the cyanide ion (CN) that may be equally Without Distillation” is based on rapid dissociation of cyanide
present (2–3). Actually, Milne suggested complexing the mo- and complexing with chloramine-T. First, the sample aliquot is
lecular HCN with metal salts as a waste treatment process (4) prepared in the very low concentration ranges, aiding disso-
. ciation which is accelerated by complexing the cyanide ion
X1.2.2 A number of analytical methods were proposed to with chloramine-T. The latter frees additional cyanide ion to
allow a quantitative distinction for the molecular HCN to reestablish the equilibrium that was disturbed. The pH is
establish the acute toxicity levels of surface waters when reduced significantly by adding the pyridine-barbituric acid
cyanide toxicity is suspected (5–6). The first question we have reagent (pH 5 to 5.5), and the sample is previously heated to
to raise when evaluating these various analytical procedures is accelerate the dissociation and complexing with chloramine-T.
whether the premise regarding the distinction between molecu- The test therefore has the necessary ability to measure certain
lar or undissociated HCN hydrogen cyanide on the one hand undissociated cyanides, which could be converted by dissocia-
and cyanide ions on the other hand is valid or not. The tion to toxic cyanides as a result of pH changes or dilution of
distinction desired is actually the dissociated CN− as distinct the sample.
from the CN− tightly bound in the metal complex. Another X1.2.8 All metal cyanide complexes are in equilibrium with
term referred to by the authors in reference is “free cyanide.” the hydrolyzed HCN molecule, the concentration being depen-
This term doesn’t have any toxicological significance and is dent on the pH of the water and the dissociation constant of the
commonly used in the electroplating industry and refers to the particular metal cyanide complex present. The tightest com-
cyanide ion that can be titrated with silver nitrate (Liebig plex is formed with iron. Since there is little dissociation, we
Titration), forming an insoluble silver cyanide precipitate when may say that the ferrocyanide and ferricyanide compounds are
the free cyanide available for complexing the silver is ex- themselves nontoxic (14,15). The iron cyanide complex is so
hausted. tight that the standard alkaline chlorination procedure will not
X1.2.3 Lancy and Zabban have shown (7) that in solutions affect it. Reported analytical data showing a slight reduction in
containing the various metal cyanide complexes, the difference ferrocyanide content, either in the chlorination step or recovery
in cyanide ion activity is due to the difference in measurable in the colorimetric analysis procedure, is most likely due to
dissociation constants for each of the metal cyanide complexes impurity in the reagent or the handling of the sample.
investigated. Analytical-grade ferrocyanide when dissolved always contains
some dissociated CN−(HCN). The sample has to be handled
X1.2.4 Critical evaluation of the toxicity investigations with carefully to avoid any photodecomposition which will appear
various metal cyanide complexes reveals that these reports as an oxidizable portion of the total ferrocyanide present
confirm the great differences in dissociation by the various (16–17) . All other metal cyanide compounds will be chlori-
metal cyanide complexes. nated at a slower rate due to the slow dissociation of the metal
X1.2.5 Both Milne (8) and Doudoroff (9) show that in the cyanide complex. The equilibrium of the metal cyanide com-
critical concentration of 0.01 to 0.5 mg/L of CN at a pH of 7.5, plex and molecular HCN is continuously upset, and as the
HCN formation is favored and will be maintained if depleted dissociation occurs, the hypochlorite ion will react with the
by further dissociation of the cyanide complex. Lowering the cyanide ion, leading to further dissociation of the metal

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 D2036 − 09

FIG. X1.1 Photodecomposition Rates for Fe(CN)64 in Direct Sunlight, 20°C, pH 7, in Buffered Distilled Water,
75 mm Solution Layer, 1 h Exposure

cyanide complex and then allowing further oxidation by X1.4.2 Deliberate complexing of simple cyanides with iron
chlorination. This implies a time dependence regarding the salts as an economical means of waste treatment naturally
chlorination reaction with the cyanide ion that is complexed by should be unacceptable. Higher concentrations of iron
such metals as silver, gold, and nickel. The chlorination of cyanides, in view of the foregoing, require treatment. Suitable
nickel cyanide at a concentration of 20 mg/L CN, as an processes for the oxidative destruction of iron cyanides are
example, may not be complete after 1 h even when hypochlo- available (20), leading to the complete destruction of the
rite was added at a 10 % excess of the stoichiometric amount cyanide and precipitation of iron oxide. Insoluble iron cyanide
(13,18,19). Because iron cyanide complexes are not destroyed precipitates are soluble in alkali. Therefore, their being in-
by the practical methods of “alkaline chlorination” and cyanide soluble under normal conditions is not an ensurance that the
in contact with iron salts causes iron cyanide to be always environment is protected.
present in metal finishing waste, the question of proper waste
treatment, or its lack, was many times raised when analyzing X1.5 Cyanogen Chloride:
industrial waste using the standard analytical procedures. X1.5.1 Presently the destruction of cyanide compounds in
There is important practical value, therefore, that a distinction waste treatment processes is done by oxidation with hypochlo-
be made and analytical procedures be developed for “Cyanides rite (OCl−) because the oxidation reaction is rapid and can be
Amenable to Chlorination” (7,13). As it has been established carried to completion using near stoichiometric equivalent of
that the ferrocyanide complex is not toxic (2,10,14,15) it might the reacting chemical. The chlorination reaction has to be
be assumed that a low-cyanide concentration of 1 to 10 mg/L; conducted at an alkaline pH because the first reaction product
if not amenable to chlorination such as iron cyanides, would formed is cyanogen chloride, a toxic gas, having very low
have no toxic effect on the environment. However, this solubility. The toxicity of cyanogen chloride may exceed the
assumption is based on the following two factors: toxicity of HCN, both in water and in the atmosphere (<0.1
mg/L) (21,22). Cyanogen chloride hydrolyzes at an alkaline pH
X1.3 The Iron Cyanides Undergo Dissociation from to cyanate (CNO−). The rate of hydrolysis is dependent on the
Photodecomposition—(15 and 17). pH conditions and the available excess chlorine, the higher the
X1.3.1 Under strong sunlight, 10 mg/L iron cyanide, ex- pH or the more chlorine present, the faster will the reaction go
pressed as CN−, may release 1 mg/L HCN in 1 h (Fig. X1.1). to completion. At a pH of 9, with no excess chlorine present,
cyanogen chloride may persist in the treated water for more
X1.4 Dilution and Dispersion of the Treated Waste in the than 24 h (23–24). In view of the low solubility of cyanogen
Receiving Waters: chloride and the time dependence for its hydrolysis, it is
X1.4.1 The kind of dilution, mixing in the diluting stream, desirable to maintain the alkalinity during chlorination at pH
clarity of the receiving waters, and the quantity of HCN release 11 or higher. A pH of 12 to 13 may be required when the
that may be expected are dependent upon particular environ- chlorination reaction is carried out on a waste water containing
mental conditions, considering that only the top layers of the high concentrations of cyanide (>100 mg/L). The low solubil-
receiving waters will be subject to the strong sunlight to cause ity of cyanogen chloride is reduced further by the reaction heat
decomposition. Oxidation by air and bacterial decomposition generated upon addition of chlorine. The vapor pressure of the
in the receiving waters will be additional factors mitigating cyanogen chloride gas is increased. Rapid hydrolysis of the
against the development of toxic concentration levels. cyanogen chloride is the only means available to avoid the

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 D2036 − 09
escape of cyanogen chloride into the atmosphere. When X1.8 Total Cyanide:
conducting continuous treatment of an effluent, the pH of the X1.8.1 Cobalt cyanide is not recovered completely during
waste stream is lowered after a few minutes of reaction time the distillation. The explanation for this condition was given by
because a neutral effluent has to be discharged. After the pH is Leschber (27) and referred to by original investigations by
reduced, any cyanogen chloride that has not yet undergone Bassett and Corbet (28). Potassium cobalt cyanide, when
hydrolysis will escape as the toxic cyanogen chloride in the boiled with dilute sulfuric acid, partially breaks down to carbon
effluent. At pH 11 and at 10°C, the half-life period of cyanogen monoxide, carbon dioxide, and ammonium sulfate.
chloride before hydrolysis to CNO −, and in the absence of
excess chlorine, is 12.5 min (23–24). It is regrettable that the X1.8.2 The determination of total cyanide retains its signifi-
importance of this reaction and these conditions are not cance. As discussed earlier in X1.2, iron cyanides will not be
appreciated by Regulatory Agencies and waste treatment revealed by the Cyanides Amenable to Chlorination analysis
engineers. Analysis for cyanogen chloride is not performed, methods. To a lesser extent, some of the nickel cyanide, cobalt
whereas concern is shown for the possible cyanate content of cyanide, silver and gold cyanide will also not be completely
a treated waste. An analytical procedure for the distinction recovered. Neither will the standard alkaline chlorination
between HCN, ferro- and ferricyanide, respectively was pub- practices break down these complexes. It has been noted that
lished by Kruse and Thibault (6). the toxic effects of these compounds are also considerably less
and of a different nature: photodecomposition for iron cya-
X1.6 Cyanate Compounds: nides; slow dissociation for nickel-, cobalt-, silver-, and gold
cyanides. At the same time, there are many waste treatment
X1.6.1 As discussed in X1.5, the cyanogen chloride that is
installations that are either not designed properly, or not
formed due to the reaction of OCl− with cyanide ions and HCN
operated properly; therefore, more cyanide compounds that
during the chlorination reaction will hydrolyze to cyanate
could have been treated are discharged in the effluent. There
(CNO−). The reported toxicity of cyanate in water is >100
are also some processes generating excessively large quantities
mg/L. The reversion of cyanate to cyanide was attempted with
of these complex cyanides, thereby producing a significant
photodecomposition and reduction, but could not be accom-
pollution hazard.
plished (25). Theoretical calculations also indicate that cyanate
As examples, we should list:
cannot be reduced to cyanide.
(a) Heat treating processes;
X1.6.2 Acidification and dilution of the cyanate leads to (b) Coke and blast furnace operations;
hydrolysis of cyanate to the ammonium ion (NH4+). Ammonia (c) Cyanide-type processes used for stripping nickel and
toxicity was reported in the 2 to 2.5 mg/L range in hard water cobalt-nickel alloy deposits;
(14). Doudoroff reports toxic effects at even lower levels (<1 (d) Rinse waters from silver and gold plating operations;
mg/L), (21). It can be assumed therefore that the toxicity of (e) Accidentally mixed waste coming from nickel plating
cyanate is mainly due to the fact that it will yield ammonia. solutions and cyanide floor spill;
Since chlorination is conducted at high pH, and the treated (f ) Regeneration and backwash waters from ion exchange
waste normally then neutralized, further pH reduction may type waste treatment processes used for the removal of plating
occur due to the lower pH condition of natural waters. salts from rinse water waste. The treatment of these wastes
Therefore, we may assume that harmful concentrations of consists usually of mixing, partially deliberately, partially due
cyanate will not be easily encountered in a natural environ- to the process, and partially accidentally, nickel and iron salts
ment. A cyanate determination within ASTM has not yet been with cyanide compounds; and
formalized. Recommended analytical procedures are available (g) Some waste treatment processes still recommended the
from the literature (25–26). use of iron sulfate for the neutralization of cyanide salts, etc.
X1.7 Thiocyanate Compounds: X1.8.3 The total cyanide determination therefore must be
used to ensure good waste treatment practices. The mistaken
X1.7.1 The relatively nontoxic thiocyanate compounds (14)
belief that the enumerated cyanide compounds are not “toxic”
may become extremely toxic due to conversion to cyanogen
must be avoided. The fact is that the toxicity is only of a lesser
chloride (see X1.5.1) when a waste stream containing the
magnitude.
thiocyanate ion undergoes chlorination for disinfection (21,22).
The probable reaction is: KCNS + 4Cl2 + 4H 2 O → X1.9 Cyanide in Solid Waste:
CNCl + KCl + H2SO4 + 6 HCl.
X1.9.1 The waste treatment needs for soluble cyanide
X1.7.2 According to Doudoroff, this reaction will occur sludges is assumed, for example, sludges from plating solu-
even if the chlorine added to the waste stream is not sufficient tions; cyanide salts removed from heat treat pots or in frozen
to provide a residual (21). Thiosulfate, a common reducing condition as drag-out from heat treatment; or cyanide salts as
chemical used to detoxify chloramines, is not as effective for residue from the evaporation of processing solutions or rinse
cyanogen chloride unless a large excess is used (22). waters. The treatment requirements for these highly toxic
X1.7.3 The determination for “cyanides amenable to chlo- residues is obvious.
rination” will also include the thiocyanate ion due to the X1.9.2 Most of the metal cyanide complexes are insoluble
conversion to cyanogen chloride by chloramine-T. A specific and are made soluble in water only in the presence of excess
test for thiocyanates is contemplated. alkali metal cyanides. Milne (4) quotes a few examples which,

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TABLE X1.1 Solubility of Metal Cyanide Precipitates X1.9.4 Iron cyanide is always present in electroplating
in Water solutions. The concentration is usually in the range from 20 to
Solubility in Temperature, 25 g/L. Only a small quantity of this iron cyanide will appear
Precipitate
Water, g/L °C
Silver cyanide 0.000028 18
in the rinse water effluent, and as it escapes chlorination, it may
Zinc cyanide 0.0058 18 form insoluble iron cyanide compounds with other metals
Copper cyanide 0.014 20 present, such as copper, zinc, iron, etc. The metal iron cyanide
Nickel cyanide 0.0592 18
Cadmium cyanide 17 15 compounds may be considered insoluble and nontoxic, but can
Mercuric cyanide 93 14 become soluble in the alkaline range (pH > 9) if the solid waste
is leached with alkaline waste. The resolubilized iron cyanide
can undergo photodecomposition as discussed in X1.2. The
insoluble iron cyanide content of solid waste may be a result of
the best treatment that modern technology can do with regard
while not complete, should be sufficient to show the insolubil- to treatment and disposal of particular cyanide compounds.
ity of some metallic cyanides. The usual disposal is burial or landfill where acid conditions
X1.9.3 During waste treatment, if the process is not con- are far more common than excessive alkalinity which would
ducted carefully, as the breakdown of the alkali metal cyanide cause the redissolution.
is progressing, the metal cyanide will become insoluble, and X1.9.5 The insoluble cyanide content of a solid waste can
will precipitate as the slightly soluble cyanide compound of the be determined by placing a 500-mg sample with 500 mL of
particular metal originally present. As seen from Table X1.1, distilled water into the distillation flask and following the total
some sludges may contain high levels of relatively insoluble cyanide distillation. The calculations should consider a multi-
metallic cyanides having high potential toxicity. Lancy and plication by 1000 to give the cyanide content of the solid waste
Zabban have reported (13) the cyanide content in the precipi- sample in ppm. Insoluble iron cyanides in the solid waste can
tates when conducting slow chlorination and with no or be leached out before analysis by stirring a weighed sample for
minimal chlorine excesses. The complete treatment and re- 12 to 16 h in a 10 % caustic soda solution. The leachate and
moval of the cyanide concentration in the sludge can be wash waters of the solid waste will give the iron cyanide
accomplished only by either significant chlorine excess in the content of the sample using the distillation procedure. A
waste water, or by rapid chlorination to allow breakdown of the previous chlorination will have eliminated all cyanide ame-
metal cyanide complex before it is precipitated and buried in nable to chlorination from the sample. The sample should not
the sludge. Some newer waste treatment processes, such as be exposed to sunlight. A method allowing differentiation
treatment with peroxygen compounds, will yield considerably between HCN, ferro- and ferricyanide, as mentioned earlier, is
higher available cyanide concentrations in the sludge. referenced (6,17).

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 D2036 − 09
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