SIST-TS CEN/TS 17775:2023

SLOVENSKI STANDARD
SIST-TS CEN/TS 17775:2023
01-februar-2023
Organska in organsko-mineralna gnojila - Določevanje anorganskega arzena
Organic and organo-mineral fertilizers - Determination of the inorganic arsenic content
Organische und organisch-mineralische Düngemittel - Bestimmung des Gehalts an
anorganischem Arsen
Engrais organiques et organo-minéraux - Détermination de la teneur en arsenic
inorganique
Ta slovenski standard je istoveten z: CEN/TS 17775:2022
ICS:
65.080 Gnojila Fertilizers
SIST-TS CEN/TS 17775:2023 en,fr,de
2003-01.Slovenski inštitut za standardizacijo. Razmnoževanje celote ali delov tega standarda ni dovoljeno.

---------------------- Page: 1 ----------------------
SIST-TS CEN/TS 17775:2023

---------------------- Page: 2 ----------------------
SIST-TS CEN/TS 17775:2023


CEN/TS 17775
TECHNICAL SPECIFICATION

SPÉCIFICATION TECHNIQUE

April 2022
TECHNISCHE SPEZIFIKATION
ICS 65.080
English Version

Organic and organo-mineral fertilizers - Determination of
the inorganic arsenic content
Engrais organiques et organo-minéraux - Organische und organisch-mineralische Düngemittel -
Détermination de la teneur en arsenic inorganique Bestimmung des Gehalts an anorganischem Arsen

This Technical Specification (CEN/TS) was approved by CEN on 13 March 2022 for provisional application.

The period of validity of this CEN/TS is limited initially to three years. After two years the members of CEN will be requested to
submit their comments, particularly on the question whether the CEN/TS can be converted into a European Standard.

CEN members are required to announce the existence of this CEN/TS in the same way as for an EN and to make the CEN/TS
available promptly at national level in an appropriate form. It is permissible to keep conflicting national standards in force (in
parallel to the CEN/TS) until the final decision about the possible conversion of the CEN/TS into an EN is reached.

CEN members are the national standards bodies of Austria, Belgium, Bulgaria, Croatia, Cyprus, Czech Republic, Denmark, Estonia,
Finland, France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway,
Poland, Portugal, Republic of North Macedonia, Romania, Serbia, Slovakia, Slovenia, Spain, Sweden, Switzerland, Turkey and
United Kingdom.





EUROPEAN COMMITTEE FOR STANDARDIZATION
COMITÉ EUROPÉEN DE NORMALISATIO N

EUROPÄISCHES KOMITEE FÜR NORMUN G

CEN-CENELEC Management Centre: Rue de la Science 23, B-1040 Brussels
© 2022 CEN All rights of exploitation in any form and by any means reserved Ref. No. CEN/TS 17775:2022 E
worldwide for CEN national Members.

---------------------- Page: 3 ----------------------
SIST-TS CEN/TS 17775:2023
CEN/TS 17775:2022 (E)
Contents Page
European foreword . 3
Introduction . 4
1 Scope . 5
2 Normative references . 5
3 Terms and definitions . 5
4 Principle . 5
5 Sampling . 5
6 Reagents . 6
7 Apparatus . 7
8 Procedure. 8
8.1 Sample preparation . 8
8.2 Water bath extraction . 8
8.3 Preparation of the calibration solutions . 8
8.4 Measurement . 9
9 Calculation and expression of the results . 10
9.1 Integration of peaks . 10
9.2 Calculation of inorganic arsenic in the samples . 11
10 Test report . 11
Annex A (informative) Examples of typical chromatographic separation . 12
Bibliography . 16

2

---------------------- Page: 4 ----------------------
SIST-TS CEN/TS 17775:2023
CEN/TS 17775:2022 (E)
European foreword
This document (CEN/TS 17775:2022) has been prepared by Technical Committee CEN/TC 260
“Fertilizers and liming materials”, the secretariat of which is held by DIN.
Attention is drawn to the possibility that some of the elements of this document may be the subject of
patent rights. CEN shall not be held responsible for identifying any or all such patent rights.
This document has been prepared under a standardization request given to CEN by the European
Commission and the European Free Trade Association.
Any feedback and questions on this document should be directed to the users’ national standards body.
A complete listing of these bodies can be found on the CEN website.
According to the CEN/CENELEC Internal Regulations, the national standards organisations of the
following countries are bound to announce this Technical Specification: Austria, Belgium, Bulgaria,
Croatia, Cyprus, Czech Republic, Denmark, Estonia, Finland, France, Germany, Greece, Hungary, Iceland,
Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Republic of
North Macedonia, Romania, Serbia, Slovakia, Slovenia, Spain, Sweden, Switzerland, Turkey and the
United Kingdom.
3

---------------------- Page: 5 ----------------------
SIST-TS CEN/TS 17775:2023
CEN/TS 17775:2022 (E)
Introduction
This document describes a procedure of extraction and measurement for the determination of
inorganic arsenic in organic or organo-mineral fertilizers. This Technical Specification is based on a
mild acid oxidative extraction of the arsenic species followed by liquid chromatography (High
Performance Liquid Chromatography [HPLC] or ion chromatography [IC]) coupled to the element-
specific detector ICP-MS (Inductively Coupled Plasma Mass Spectrometer) for the determination of the
mass fraction of inorganic arsenic (iAs).
4

---------------------- Page: 6 ----------------------
SIST-TS CEN/TS 17775:2023
CEN/TS 17775:2022 (E)
1 Scope
This document specifies a method for extraction, separation, and determination of inorganic arsenic
(iAs) in organic or organo-mineral fertilizers using anion-exchange HPLC or IC coupled to ICP-MS.
2 Normative references
The following documents are referred to in the text in such a way that some or all of their content
constitutes requirements of this document. For dated references, only the edition cited applies. For
undated references, the latest edition of the referenced document (including any amendments) applies.
EN 1482-2:2007, Fertilizers and liming materials — Sampling and sample preparation — Part 2: Sample
preparation
3 Terms and definitions
No terms and definitions are listed in this document.
ISO and IEC maintain terminological databases for use in standardization at the following addresses:
• ISO Online browsing platform: available at https://www.iso.org/obp
• IEC Electropedia: available at https://www.electropedia.org/
4 Principle
This document describes a method for the determination of inorganic arsenic in organic or organo-
mineral fertilizers. Inorganic arsenic consists of arsenite As(III) and arsenate, As(V). A representative
test portion of the sample is treated with a diluted nitric acid and hydrogen peroxide solution in a
heated water bath. By this means the sample is solubilised, arsenic species are extracted into solution
and As(III) is oxidised to As(V). The inorganic arsenic is selectively separated from other arsenic
compounds using anion exchange HPLC (High Performance Liquid Chromatography) coupled on-line to
the element-specific detector ICP-MS (Inductively Coupled Plasma Mass Spectrometer) for the
determination of the mass fraction of the inorganic arsenic. External calibration with solvent matrix-
matched standards is used for the quantification of the amount of the inorganic arsenic. Alternatively, IC
(ion chromatography) coupled to ICP-MS can be used.
A preliminary determination of the total arsenic in aqua regia extracts by inductively coupled plasma
atomic emission spectrometry [ICP-AES] (CEN/TS 17770) could reduce the number of the samples
where the determination of iAs is necessary because if the content of aqua regia (total) extractable
arsenic is lower than the legislative limit for iAs then the determination of iAs is not necessary.
5 Sampling
Sampling should be performed carefully, following principle described in EN 1482 (all parts) with
appropriate adaptations required account for specificities of organic and organo-mineral fertilizers.
5

---------------------- Page: 7 ----------------------
SIST-TS CEN/TS 17775:2023
CEN/TS 17775:2022 (E)
6 Reagents
6.1 General
When using a method of high sensitivity like ICP-MS, the control of the blank levels of water, acid and
other reagents is very important. The reagents shall be of adequate purity and of recognized analytical
grade. The concentration of arsenic species in the reagents and water used shall be negligible and low
enough not to affect the results of the determination. Generally, ultra-pure water and nitric acid of
minimum p.a. quality is recommended.
6.2 Nitric acid (HNO ), concentrated, ≥ 65 % (mass fraction), mass concentration of approximately ρ
3
(HNO ) 1,4 g/ml.
3
Use only nitric acid available with high purity (minimum p.a. quality) in order to avoid potential
contamination.
6.3 Hydrogen peroxide, H O not less than 30 % (mass fraction).
2 2
High purity is essential to avoid potential contamination. Commercially available hydrogen peroxide for
analysis should be tested for contamination of arsenic prior to use. It is necessary to prevent peroxide
degradation and ensure the stability of the solution.
6.4 Extraction solution, 0,1 mol/l HNO in 3 %(volume fraction) H O .
3 2 2
Add 6,5 ml of HNO3 (6.2) and thereafter 100 ml of hydrogen peroxide (6.3) into 800 ml water in a
1 000 ml volumetric flask. Fill the flask to the mark with water. This solution is prepared on the day of
use.
It is recommended that the total volume needed for the analysis is estimated and only this amount is
produced in the day of use.
6.5 Ammonium carbonate, (NH ) CO , mass fraction w ≥ 99,999 %, for preparation of the mobile
4 2 3
phase solution.
6.6 Aqueous ammonia, (NH (aq)), mass fraction w ≥ 25 %, for adjustment of pH in the mobile
3
phase.
6.7 Methanol, (CH OH), HPLC grade, for preparation of the mobile phase solution.
3
6.8 Mobile phase, e.g. 50 mmol/l ammonium carbonate in 3 % methanol at pH 10,3.
Dissolve 4,80 g of ammonium carbonate (6.5) in approximately 800 ml water. Adjust the pH to 10,3
with aqueous ammonia (6.6) and add 30 ml of methanol (6.7) and then fill up to 1 000 ml with water.
Prior to use filter the mobile phase solution through a 0,45 μm filter using a filtering device (7.4).
The optimal concentration of ammonium carbonate in the mobile phase depends on the analytical
column used (e.g. brand, particle size and dimensions) and should be verified in advance. The
appropriate concentration of ammonium carbonate (usually between 10 mmol/l to 50 mmol/l) is
highly dependent on the column used and is up to the discretion of the analyst. It should fulfil the
criteria for sufficient resolution of the arsenate peak.
Methanol is added to the mobile phase in order to enhance the signal intensity for arsenic. The
concentration of methanol to achieve the highest signal to noise ratio depends on the instrument used
and should be identified by the analyst.
6

---------------------- Page: 8 ----------------------
SIST-TS CEN/TS 17775:2023
CEN/TS 17775:2022 (E)
NOTE Different mobile phase can be also used according to the instructions of the manufacturer of the
column but it is necessary to verify optimal separation conditions.
1
For example, Agilent column G3154-65001 with a guard column G3154-65002 and a recommended
mobile phase for this column (dihydrogen potassium carbonate 2 mmol, EDTA 0,2 mmol, pH 6,0
adjusted with sodium hydroxide solution 1 mol) were successfully used for the analysis.
6.9 Arsenic (V) standard stock solution, with an arsenic (V) mass concentration of 1 000 mg/l.
The use of commercial standards of arsenic As(V), with a mass concentration of 1 000 mg/l is
recommended.
6.10 Arsenic (V) standard solution I, with an arsenic (V) mass concentration of 10 mg/l in 2 %
(volume fraction) HNO .
3
Pipette 1 ml of arsenic standard stock solution (6.9) into a 100 ml volumetric flask. Add 2 ml of nitric
acid (6.2), fill to the mark with water and mix well. This solution is stable in a refrigerator at least one
week.
6.11 Arsenic (V) standard solution II, with an arsenic (V) mass concentration of 1 mg/l.
Pipette 10 ml of arsenic standard solution I (6.10) into a 100 ml volumetric flask, fill to the mark with
water and mix well. This solution should be prepared on the same day of use.
6.12 Solution for checking chromatographic separation, containing organic arsenic compounds
(e.g. 10 μg/l) monomethylarsenous acid (MMA), dimethylarsinic acid (DMA) and arsenobetaine (AB), as
well as arsenate (e.g.
...