INTERNATIONAL STANDARD ISO 11262:2011(E)

Soil quality — Determination of total cyanide

WARNING — Hydrogen cyanide and its salts are toxic. Therefore, care shall be exercised when
manipulating cyanide-contaminated samples. Volatile hydrogen cyanide (with a smell of bitter
almonds) is released from acidified solutions containing cyanide salts. As a minimum, all work shall
be carried out in a fume hood and suitable plastic gloves shall be worn when handling contaminated
samples.
Analytical wastes containing cyanides shall be placed in a special container with a lid, in the
laboratory, for temporary storage. This container shall be clearly marked with labels such as “toxic
waste” or “cyanides”. Periodically, the container shall be emptied and the wastes containing cyanides
disposed of as “special waste” by an appropriate waste-management contractor.

1 Scope
This International Standard is applicable to as -received (field-moist) samples and specifies two different
procedures for the liberation of cyanide from the soil:
— direct liberation of hydrogen cyanide using orthophosphoric acid (normative);
— extraction with sodium hdroxide solution and subsequent liberation using orthophosphoric acid (informative, see Annex
B).
The liberated cyanide is determined either by a photometric method or a titrimetric method using an indicator.
The method is applicable to all types of soil.

Under the conditions specified in this International-Standard, the lower limit of application is 0,5 mg/kg of total
cyanide (expressed on the as-received basis) for photometric determination and 10 mg/kg for titrimetric
determination.
NOTE Using the alkaline extraction followed by liberation using phosphoric acid, the lower limit of application is 1 mg/kg of
total cyanide (expressed on the as-received basis) for photometric determination and 30 mg/kg for titrimetric
determination.

2 Principle

4.1 Direct liberation of hydrogen cyanide using orthophosphoric acid

The field-moist sample is homogenized and pretreated in accordance with ISO 14507, removing visible coarse
constituents. It is then treated with orthophosphoric acid and the liberated hydrogen cyanide is transported by an
airflow and absorbed into 1 mol/l sodium hydroxide. Tin(II) and copper(II) salts are added to suppress the
interference from sulfur compounds and catalyse the decomposition of complex cyanides during the liberation
process.

4.2 Determination of total cyanide content

Cyanide ion in the sodium hydroxide absorber solutions is determined either

— photometrically (see Clause 9) by a procedure based on the reaction of cyanide with chloramine-T with the
formation of cyanogen chloride; this reacts with pyridine-4-carboxylic acid and 1,3-dimethylbarbituric acid to
form a coloured complex, the absorbance of which ismeasured at 606 nm, or
— titrimetrically (see Clause 10) by a titrimetric procedure-involving titration with silver nitrate. When in excess
relative to the Ag (CN)2- ion, silver ions form a red-coloured complex with the end-point indicator,
5-(4-dimethylaminobenzylidene)rhodanine.

5 Reagents
All reagents shall be of recognized analytical grade and the water used shall conform to grade 2 of ISO 3696:1987.
All reagents are stable for at least 3 months unless stated otherwise.

5.1 Reagents for liberation and absorption of cyanide

5.1.1 Orthophosphoric acid, w(H3PO4) = 85 % (mass fraction), r = 1,69 g/ml.

5.1.2 Sodium hydroxide solution, c(NaOH) = 1 mol/l.

Dissolve 40 g of NaOH in water and dilute with water to 1 000 ml, or use commercially available solutions. Store in a
polyethylene bottle.

5.1.3 Hydrochloric acid solution, c(HCl) = 1 mol/l.

Dilute 98,6 g of concentrated hydrochloric acid (37 %, r = 1,18 g/ml) with water to 1 000 ml or use commercially
available solutions.

5.1.4 Tin(II) chloride solution.

Dissolve 50 g of tin(II) chloride dihydrate (SnCl 2·2H2O) in 40 ml of the hydrochloric acid solution (5.1.3) and dilute
with water to 100 ml. Prepare a fresh solution daily.

5.1.5 Copper(II) sulfate solution.

Dissolve 200 g of copper(II) sulfate pentahydrate (CuSO4·5H2O) in water and dilute with water to 1 000 ml.

5.2 Reagents for the photometric determination of cyanide

5.2.1 Sodium hydroxide solution, c(NaOH) = 0,8 mol/l.

Dissolve 32 g of NaOH in water and dilute with water to 1 000 ml. Store in a polyethylene bottle.

5.2.2 Glacial acetic acid, 20 % (volume fraction).

Dilute 100 ml of glacial acetic acid (r = 1,049 g/ml) to 500 ml in a measuring cylinder with water.

NOTE 100 % glacial acetic acid (r = 1,049 g/ml), as well as 96 % glacial acetic acid (r = 1,06 g/ml), are commercially
available.
5.2.3 N-Chloro-4-methylbenzenesulfonamide sodium salt (chloramine-T) solution.

Dissolve 0,5 g of chloramine-T trihydrate [C 7H7ClNO2S·Na(3H2O)] in water in a 50 ml volumetric flask and dilute to
the mark. Prepare a fresh solution daily.

5.2.4 Colour reagent.

Dilute 7,0 g of sodium hydroxide (NaOH) in500mlofwater. Add 16,8gof1,3-dimethylbarbituric acid (C 6H8O3 N2), and 13,6 g of pyridine-4 -
carboxylic acid (isonicotinic acid) (C 6H5NO2), and dilute to 1 000 ml with water. Mix well for 1 h at 30 °C and then filter
poresizeappoximately8µm) through a pleated filter. This solution can be kept for at least 1 week, provided it is stored below 10 °C in the dark,
and filtered through another pleated filter (pore size approximately 8 µm) before use.

5.2.5 Potassium cyanide stock solution, corresponding to 100 mg/l of cyanide ion.

Dissolve 250 mg of potassium cyanide (KCN) in the 0,8 mol/l sodium hydroxide solution (5.2.1) and dilute with the
same sodium hydroxide solution to 1 000 ml in a volumetric flask. Standardize this solution by titration with the 0,01
mol/l silver nitrate solution (5.3.1), once each day if determinations are carried out (see Clause 9). Commercially
available stock solutions may also be used. Store in the dark and at a temperature below 10 °C.

5.2.6 Potassium cyanide standard solution, corresponding to 10 mg/l of cyanide ion.

Dilute 10 ml of stock solution (5.2.5) to 100 ml in a volumetric flask using the 0,8 mol/l sodium hydroxide solution
(5.2.1). Prepare daily.

5.2.7 Paranitrophenol (0,1 % m/V) in ethanol.

Dissolve 0,1 g of paranitrophenol in 100 ml of ethanol.

5.3 Reagents for the titrimetric determination of cyanide

5.3.1 Silver nitrate solution, c(AgNO3) = 0,01 mol/l.

Dissolve 1,699 g of silver nitrate in approximately 400 ml of water and dilute to 1 000 ml in a volumetric flask with
water. Check the actual concentration of the 0,01 mol/l silver nitrate by titration with sodium chloride in accordance
with ISO 9297 on a two-weekly basis. Store this solution in the dark.

5.3.2 Silver nitrate solution, c(AgNO3) = 0,001 mol/l.

Prepare daily from the 0,01 mol/l silver nitrate solution (5.3.1). Add 25,00 ml of 0,01 mol/l silver nitrate solution to a
250 ml volumetric flask and dilute to 250 ml with water. Cover the flask with aluminium foil to exclude light.

5.3.3 Indicator solution.

Dissolve 0,02 g of 5-(4-dimethylaminobenzylidene) rhodanine in acetone and dilute with acetone to 100 ml.
This solution is stable for up to 1 week if kept in the dark at ambient temperature.

6 Apparatus
Usual laboratory equipment and, in particular, the following:

6.1 Apparatus for the liberation and absorption of hydrogen cyanide.

Use the apparatus shown in Figure 1. The round-bottomed flask (9) shall be triple-necked, have a capacity of at
least 500 ml and have standard conical joints (for example 29/32 central neck, 19/24 side necks). A water-cooled
Liebig condenser (3) (for example 16 cm long and 30 mm in outer diameter); a 50 ml dropping funnel (5) and an air-
inlet tube (7) are fitted. The connection to the absorption vessel (2) (for example 20 cm long and 2,5 cm in inner
diameter) is via a transfer line (1). Standard joints are fitted to this tube to enable connection to the Liebig
condenser and the absorption vessel (2). A glass tube (for example 15 cm long by 1,3 cm outer diameter) extends
into the absorption vessel and this is fitted with a No. 2 glass-frit sinter (4) to ensure efficient bubbling of the
liberated HCN through the absorption fluid (e.g. ISO 4793 P 160, porosity class 1 or 2.)

The recovery factor (Fcr) of the liberation apparatus should be determined using potassium hexacyanoferrate(III)
solution for total cyanide. A mid-range calibration standard should be used (see 9.3).
6.2 Suction.
A pump capable of sucking up to 30 l/h of air through the apparatus in Figure 1 is required. A low-power piston
pump is recommended. This shall be fitted wihfine-controlvalve (see13in Figure 1) between the pump and the
Dreschel bottle (see 6 in Figure 1). The Dreschel bottle is used to ensure that, if a sample contained a very high
level of cyanide, no HCN would be liberated to the atmosphere.
A single flowmeter (see 12 in Figure 1) can be used to give a visual estimation of a 10 l/h to 20 l/h flow rate. All
other Dreschel bottle flows can then be set visually without using flowmeters. The flow rate needs to be defined as
a function of the volume of the apparatus and should be checked by determining recovery rates.

6.3 Photometer, set to a wavelength of 606 nm, with cells of optical path length 10 mm (photometric method only,
see Clause 9).

6.4 Magnetic stirrer (titrimetric method only, see Clause 10).

Key
1 transfer line 8 heating device
9 500 ml 3-angled-neck round-bottomed reaction flask
2 absorption vessel 10 plastictubing
3 Liebig condenser 11 pump
4 glass-frit sinter 12 flowmeter
13 fine-control valve
5 dropping funnel
6 Dreschel bottle
7 air-inlet tube
a Direction of flow.

Figure 1 — Apparatus for the direct liberation of cyanide in soils

7 Sample preservation and preparation

7.1 Sample preservation

The sample shall be taken in a glass or polyethylene container which will not influence the analysis. Maintain
the sample at a temperature below 10 °C and keep it in the dark until analysed. Analyse within 48 h after
collection.
NOTE A stability study has demonstrated that refrigerated soil samples are stable for at least 4 days. See Reference [4] in
the Bibliography.

7.2 Sample preparation

7.2.1 General

The sample bottle containing the field-moist sample shall not be opened prior to the analysis and weighing
shall be carried out quickly to remove the test portion(s). If the soil sample cannot be homogenized, carry out
at least two parallel cyanide determinations depending on the precision requirements.

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