International Standard

INTERNATIONAL ORGANIZATION FOR STANDARDIZATIONWME~YHAPO~HAR OPl-AHM3AUWR fl0 CTAH~PTM3AL(MM.ORGANISATION INTERNATIONALE DE NORMALISATION

Fruits, vegetables and derived products - Determination

of arsenic content - Silver diethyldithiocarbamate
spectrophotometric method
Fruits, Egumes et produits d&iv& - DtStermina tion de Ia teneur en arsenic - Methode spectrophotometrique au
di&th yldithiocarbama te d iprgen t iTeh STANDARD PREVIEW
First edition - 1982-12-01 (standards.iteh.ai)
ISO 6634:1982
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477d03dacc3d/iso-6634-1982

UDC 634.V635.6 : 543.42 : 546.19 Ref. No. ISO 6634-1982 (E)

Descriptors : agricultural products, fruits, vegetables, Chemical analysis, determination of content, arsenic.

Price based on 5 pages

Foreword
ISO (the International Organization for Standardization) is a worldwide federation of
national Standards institutes (lS0 member bedies). The work of developing lnter-
national Standards is carried out through ISO technical committees. Every member
body interested in a subject for which a technical committee has been set up has the
right to be represented on that committee. International organizations, governmental
and non-governmental, in liaison with ISO, also take part in the work.

Draft International Standards adopted by the technical committees are circulated to

the member bodies for approval before their acceptance as International Standards by
the ISO Council.

iTeh STANDARD PREVIEW

International Standard ISO 6634 was developed by Technical Committee ISO/TC 34,
Agricultural food products, and was circulated to the member bodies in June 1981.
(standards.iteh.ai)
lt has been approved by the member bodies of the following countries :
ISO 6634:1982
Austria https://standards.iteh.ai/catalog/standards/sist/0c395f07-953b-4f6b-9f3f-
Iran Portugal
Brazil Israel 477d03dacc3d/iso-6634-1982
Romania
Canada Kenya South Africa, Rep. of
Czechoslovakia Korea, Dem. P. Rep. of Spain
Egypt, Arab Rep. of Korea, Rep. of Sri Lanka
Ethiopia Malaysia Tanzania
France Netherlands Thailand
Germany, F. R. New Zealand Turkey
Hungary Philippines Y ugoslavia
India Poland

The member body of the following country expressed disapproval of the document on
tech nical grounds

0 International Organkation for Standardkation, 1982

_
Printed in Switzerland
INTERNATIONAL STANDARD ISO 6634-1982 (E)

Fruits, vegetables and derived products - Determination

of arsenic content - Silver diethyldithiocarbamate
spectrophotometric method

1 Scope and field of application of blotting-Paper folded into several layers, and allow to dry.
Store in a dry bottle.
This International Standard specifies a method for the determi-
nation of the arsenic content of fruits, vegetables and derived The platinized zinc thus prepared shall be submitted to the
products. preliminary test (see 6.1.1).

NOTE - Non-platinized zinc granules may be used if the product is

shown to be suitable by the preliminary test.
2 Reference iTeh STANDARD PREVIEW
ISO 5515, Fruits, vegetables
Position of organic
(standards.iteh.ai)
4.5 Potassium hydroxide,
and derived products - Decom-
matter Prior to analysis - Wet method.
in pellets.

4.6 TinW) chloride solution, prepared as follows.

ISO 6634:1982
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Carry out a cold attack on 20 g of pure granulated tin with
3 Principle 477d03dacc3d/iso-6634-1982
100 ml of concentrated hydrochloric acid (en, = 1,19 g/ml).

Decomposition of a test Portion, reduction of arsenic(V) to Store in the presence of metallic tin, protected from air, in a
arsenic(lll) with tinUl) chloride and transformation of the bottle provided with a security device (to avoid overpressures
arsenic into arsine by the action of nascent hydrogen. Forma- caused by the Iiberation of hydrogen).
tion of a red coloured complex by the action of the arsine on
silver diethyldithiocarbamate and spectrophotometric measure-
ment at a wavelength of 520 nm. 4.7 Potassium iodide, 100 g/l Solution.

4.8 Sodium hydroxide, Standard volumetric Solution,

c(NaOH) = 1 mol/l.
4 Reagents

All reagents shall be of recognized analytical purity and shall, in 4.9 Arsenic, Standard Solution corresponding to 10 mg of
particular, be free from arsenic [with the exception of the stan- arsenic(V) per litre, prepared as follows.
dard arsenic Solution (4.911. The water used shall be distilled
water or water of at least equivalent quality. 4.9.1 Dissolve, in a 500 ml flask, 264 mg of pure, dry arsenic
trioxide in IO ml of the sodium hydroxide Solution (4.81, make
4.1 Sulphuric acid, e20 = 1,84 g/ml. up the volume to about 100 ml with water, add 15 ml of 1 mol/1
hydrochloric acid Solution and two drops of bromine; heat to
boiling in Order to expel the excess bromine, cool, transfer
4.2 Nitrit acid, e20 = 1,38 g/mI. quantitatively to a 200 ml volumetric flask and make up to the
mark with water.
4.3 Perchlorit acid, e20 = 1,67 g/ml.
1 ml of this Solution contains 1 mg of arsenic.
4.4 Platinized zinc, prepared as follows.
4.9.2 By means of a pipette, transfer 10 ml of the Solution
Place a Portion of granulated zinc in a capsule, and pour in a (4.9.1) to a 1 000 ml volumetric flask. Make up to the mark with
volume of 0,05 g/l platinum chloride solution sufficient to water.
cover the zinc. Leave in contact for 30 min, pour off the liquid,
wash with water, leave the platinized zinc to drain on a Square 1 ml of this Standard Solution contains IO pg of arsenic(VL
ISO 66344982 (E)

4. IO Silver diethyldithiocarbamate, Standard solution, 5.6 Apparatus fo r the determination Of arsenic, for
prepared as follows.1) example as shown in the fig ure, comprising

4.10.1 Dissolve 3,4 g of silver nitrate in 200 ml of water; cool 56.1 Conical flask, sf capacity 100 ml, fitted with a screw
the Solution to a temperature close to 10 OC. thread joint System for connection to the column 5.6.2.

4.10.2 Dissolve 4,5 g of sodium diethyldithiocarbamate in 5.6.2 Column, of height 200 mm and diameter 15 mm, to fit
200 ml of water; cool this Solution to the same temperature as the flask (5.6.1) at its base and fitted with a screw thread joint
the silver nitrate Solution (4.10.12. at the top.

4.10.3 Add slowly, and with constant shaking, the sodium 56.3 Delivery tube, of internal diameter 4 mm, bent twice,
diethyldithiocarbamate solution to the silver nitrate Solution; at right angles 80 mm apart, to fit the column (5.6.2) at one end
collect the precipitate on a fritted glass crucible of porosity and tapered at the opposite end.
grade P 40, wash with water previously cooled to a tem-
perature close to 10 OC, then dry under reduced pressure at 5.6.4 Bubbler, which may consist of a measuring cylinder sf
ambient temperature, in the dark.
capacity IO ml graduated in 0,l ml divisions.
Dissolve the dried silver diethyldithiocarbamate in cold
pyridine. Add cold water to precipitate the product. Filter the 5.7 Spectrophotometer, suitable for use in the visible
precipitate and wash with cold water until all traces of pyridine region of the spectrum, for measurements of absorbance at
have been eliminated (this tan be verified using a pH indicator 520 nm, fitted with suitable cells of optical.path length 10 mm.
Paper : the pH of the washings shall not be greater than 6,5).
Dry the light yellow crystals of silver diethyldithiocarbamate in a 5.8 Analytical balance.
desiccator under reduced pressure.

iTeh STANDARD
The crystals shall be kept in a cold, dark place in a glass bottle
fitted with a ground glass stopper.
PREVIEW
6 Procedure

4.10.4 Dissolve 0,4 g of

(standards.iteh.ai)
L-ephedrine in about 200 ml sf 6.1 Preliminary tests on reagentsz)
chloroform, add 0,6 g of the silver diethyldithiocarbamate
crystals (4.10.31, Shake for 15 to 20 min, filter, and make up the
ISO 6634:1982
of the reactivity sf the zinc and
volume to 250 ml with chloroform. https://standards.iteh.ai/catalog/standards/sist/0c395f07-953b-4f6b-9f3f-
6.1.1 Verification
diethyldithiocarbamate
477d03dacc3d/iso-6634-1982 solution
This reagen t may be stored in a refrigerator in the dark for up to
tW0 ?weeks in a well stoppered bottle. 6.1.1.1 Place, at the bottom of the column (5.6.2) of the ap-
paratus (5.6), a plug of giass wo01 and add potassium hydrox-
4.11 Phenolphthalein, 30 g/l ethanolic solution. ide pellets (4.5) to a height of 6 to 8 cm. Fit the delivery tube
(5.6.3) to the column (5.6.2).

5 Apparatus Place the end of the delivery tube (5.6.3) in the bubbjer (5.6.4)
into which 4 ml of the silver diethyldithiocarbamate solution
Ordinary laboratory equipment, and in particular (4.10) have been placed. Cool the reagent by placing the bub-
bler in an ice-water bath.

51. Round-bottomed flasks, sf capacity 1 000 ml.

6.1 .1.2 Place in the conical flask (5.6.1) 0,5 ml of the Standard
arsenic solution (4.9) and sufficient water to make the volume
5.2 Volumetric flasks, of capacity 50 and 250 ml. up to about 35 ml; add 5 ml of the sulphuric acid (4.1), cool,
add 2 drops of the tin(ll) chloride solution (4.61, and then 5 ml
5.3 Beakers, of capacity 50 ml. of the potassium iodide Solution (4.7). Leave in contact for
15 min, add 5 g of the platinized zinc (4.4), and plug rapidly by
fitting the column (5.6.2) and the delivery tube (5.6.3).
5.4 Pipettes, of capacity 1, 2, 5, 10, 20 and 50 ml.
Place the conical flask in a cold water and put the
5.5 Burette. apparatus in a da rk place.

1) This Jeagent is also available commercially.

2) These tests shall only be carried out when using a new SUPPlY of reagents.

2
 ISO 66344982 0

6.“1.1.3 Allow the reaction to proceed for at least 1 h. Remove 6.4 Blank test
the delivery tube (5.6.3). If necessary, adjust the volume in the
bubbler to 4 ml with the silver diethyldithiocarbamate Solution Carry out a blank test follow ng the Same procedur ‘es as for the
(4.10). Mix. determination, but replacing the test portion by 50 ml of water.

By means of the spectrophotometer (5.7), measure the NOTE - The blank test is not necessary if the absence of
absorbance at 520 nm of the solution in the bubbler, using as reagents used for decomposition has been verified.
the reference Solution the silver diethyldithiocarbamate Solution
(4.10). The absorbance shall be at least 0,12.
6.5 Decomposition
6.12 Verification of the absence of arsenic in the
reagents Add to the contents of the flask 10 ml of the sulphuric acid
(4.1) and 20 to 30 ml of the nitric acid (4.2) and, if necessary, a
few drops of the perchloric acid (4.3). Proceed as described in
6.1.2.1 Prepare the column (5.6.2), the delivery tube (5.6.3) ISO 5515.
and the bubbler (5.6.4) of the apparatus (5.6) in the same way
as for the test specified in 6.1 .l. 1. When decomposition is complete, transfer the Solution to a
50 ml volumetric flask (5.2), rinse the original flask with water,
6.1.2.2 Place in the conical flask (5.6.1) 35 ml of water and and use the rinsings to make up the volume in the volumetric
5 ml of the sulphuric acid (4.1) and cool; then add 2 drops of flask to the mark. Mix by shaking.
the tin(ll) chloride Solution (4.6), and 5 ml of the potassium
iodide Solution (4.7). Leave in contact for 15 min, add 5 g of
the platinized zinc (4.4), plug rapidly by fitting the column 6.6 Titration of the acidity of the solution
(5.6.2) and the delivery tube (5.6.3) and place the apparatus in a
dark place. Transfer, by means of a pipette, 2 ml of the Solution obtained in
6.5 to a beaker (5.3), dilute with a few millilitres of water, and
Proceed as described in 6.1 J.3. iTeh STANDARD PREVIEW titrate against the sodium hydroxide Solution (4.8) in the
presence of two drops of phenolphthalein (4.11).
The absorbance,
diethyldithiocarbamate
compared with
(standards.iteh.ai)
that of the silver
Solution as reference Solution (4. IO), The concentration, C, of sulphuric acid the Solution obtained
shall be less than 0,015. in 6.5, expressed in grams per 100 ml, IS equal to
ISO 6634:1982
NOTE - The a bsen ce of arsenic in the nitric and perch loric acids is
verified by the blank test (6.4).
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0,049 x n x 50
477d03dacc3d/iso-6634-1982
where n is the volume, in millilitres, of sodium hydroxide solu-
6.2 Preparation of the test Sample tion (4.8) used,

Mix the laboratory Sample thoroughly. If necessary, first or, expressed in millilitres of sulphuric acid
remove seeds and hard seed-cavity Walls and pass the re- k?20= 184 g/ml) per 100 ml of solution
mainder through a mechanical grinder.
c
Allow frozen or deep-frozen products to thaw beforehand in a C’ =-
closed vessel and add the liquid formed during this process to 1184
the product before homogenization.

6.7 Colorimetric determination

6.3 T’est Portion
6.7.1 Prepare the column (5.6.2), the delivery tube (5.6.3) and
6.3.1 Liquid products the bubbler (5.6.4) of the apparatus (5.6) as indicated in
6.1.1.1.
By means of a pipette, transfer 50 ml of the test Sample (6.2) to
a 1 000 ml flask (5.1).

lf the liquid contains ethanol, expel it by boiling, and allow to

cool.
5 x 100
6.3.2 Pastyp solid or dehydrated products v=-
C’
Weigh, to the nearest 0,Ol g, a mass of the test Sample (6.2)
If necessary, add to obtain a volume of about 40 ml.
corresponding to 50 to 100 g of fresh product, according to the
Allow to cool
nature of the Sample, and place it in a 1 000 ml flask (5.1).

NOTE - If the Sample is rich in organic matter, decomposition will re-

quire more time and the mass of the test Portion should, therefore, be
minimal.

3
ISO 66344982 (El

conical flask (5.6.1). Rapidly stopper the flask by fitting the 7.1.2 Pasty, solid or dehydrated products
column (5.6.2) and the delivery tube (5.6.3) and place the
apparatus in the dark, with the conical flask placed in a cold The arsenic content, expressed In milligrams Per kilogram of
water bath. product as received, is equal to

6.7.3 Allow the reaction to proceed for at least 1 h. Remove rnl x 50

the delivery tube. Adjust the volume in the bubber to 4 ml with V x m.
diethyldithiocarbamate Solution (4.10).

By means of the spectrophotometer (5.71, measure the ab-

sorbance at 520 nm of the Solution obtained, using the blank .
test Solution (6.41, or the silver diethyldithiocarbamate Solution m. is the mass, in grams, of the test Portion (6.3.2);
(4.101, as the reference Solution, according to the case.
ml is the mass of arsenic, expressed in micrograms, ob-
tained from the calibration graph and corresponding to the
6.8 Calibration curve absorbance measured in 6.7.3;

Proceed as described in 6.1.1 using 0,5 - 1 - 1,5 and 2 ml V is the volume, in millilitres, of Solution taken for the
of the Standard arsenic Solution (4.9.2) corresponding to determination in 6.7.2.
5 - 10 - 15 and 20 pg of arsenic, and plot a graph having,
for example, the mass in micrograms of arsenic as abscissae
and the corresponding values of absorbance as If it is desired to express the arsenic content in relation to the
ordinates. dry product, take this fact into account in the calculation.

7 Expression of results 7.2 Repeatability

7.1 Method of calculation

iTeh STANDARD
and formulae +
PREVIEW
The differente between the results of two determinations, car-
ried out simultaneously or in rapid succession by the same
7.1.1 Liquid products
(standards.iteh.ai)
analyst, on the same Sample, shall not exceed 10 % as a
relative value.
The arsenic content, expressed in milligrams per litre of prod uctISO 6634:1982
as received, is equal to https://standards.iteh.ai/catalog/standards/sist/0c395f07-953b-4f6b-9f3f-
477d03dacc3d/iso-6634-1982
8 Test report

where The test report shall show the method used and the result ob-
tained. It shall also mention the method of expression used and
any operating conditions not specified in this International
ml is the mass of arsenic, expressed in micrograms, Standard, or regarded as optional, as well as any circum-
obtained from the calibration graph and corresponding to
stances that may have influenced the result.
the absorbance measured in 6.7.3;

V is the volume, in millilitres, of Solution taken for the The test report shall include all the information necessary for
determination in 6.7.2. the complete identification of the Sample.
 Dimensions in millimetres

80
015
---l

@int15, [email protected]

Column .--- - Delivery tube

0
Ei
,@ext. 6

iTeh STANDARD PREVIEW

(standards.iteh.ai)
ISO 6634:1982
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477d03dacc3d/iso-6634-1982 - Bubbler

,@int.11

Capacity

IOOmL

Figure - Example of apparatus for the determination of arsenic (5.6)

 iTeh STANDARD PREVIEW
(standards.iteh.ai)
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ISO 6634:1982
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477d03dacc3d/iso-6634-1982