Plant biostimulants - Determination of inorganic arsenic

This document specifies a method for extraction, separation, and determination of inorganic arsenic (iAs) in plant biostimulants using anion-exchange high performance liquid chromatography (HPLC) or ion chromatography (IC) coupled to ICP-MS.
This document is also applicable to the blends of fertilizing products where plant biostimulants are the main part of the blend. Otherwise, the Technical Specification for the main part of the blend applies.

Pflanzen-Biostimulanzien - Bestimmung von anorganischem Arsen

Dieses Dokument legt ein Verfahren zur Extraktion, Trennung und Bestimmung von anorganischem Arsen in Planzen-Biostimulanzien mit Anionenaustausch Hochleistungs-Flüssigchromatograph (HPLC) oder Ionenchromatographie (IC) gekoppelt mit ICP MS fest.
Dieses Dokument ist auch anzuwenden für die Mischungen von Düngeprodukten, in denen die Planzen-Biostimulanzien der Hauptbestandteil der Mischung sind. Andernfalls ist die Technische Spezifikation für den Hauptbestandteil der Mischung anzuwenden.

Biostimulants des végétaux - Dosage de l'arsenic inorganique

Le présent document spécifie une méthode d’extraction, de séparation et de dosage de l’arsenic inorganique (iAs) dans les biostimulants des végétaux par chromatographie liquide haute performance (HPLC) ou chromatographie ionique (IC) couplée à une ICP-MS.
Le présent document est également applicable aux mélanges de fertilisants dans lesquels les biostimulants des végétaux représentent la majorité du mélange. Dans le cas contraire, c’est la Spécification technique correspondant au fertilisant majoritairement présent dans le mélange qui s’applique.

Rastlinski biostimulanti - Določevanje anorganskega arzena

General Information

Status
Published
Current Stage
6060 - Definitive text made available (DAV) - Publishing
Due Date
23-Mar-2022
Completion Date
23-Mar-2022

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SLOVENSKI STANDARD
kSIST-TS FprCEN/TS 17706:2021
01-november-2021
Rastlinski biostimulansi - Določevanje anorganskega arzena
Plant biostimulants - Determination of inorganic arsenic

Biostimulanzien für die pflanzliche Anwendung - Bestimmung von anorganischem Arsen

Biostimulants des végétaux - Dosage de l'arsenic inorganique
Ta slovenski standard je istoveten z: FprCEN/TS 17706
ICS:
65.080 Gnojila Fertilizers
kSIST-TS FprCEN/TS 17706:2021 en,fr,de

2003-01.Slovenski inštitut za standardizacijo. Razmnoževanje celote ali delov tega standarda ni dovoljeno.

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kSIST-TS FprCEN/TS 17706:2021
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kSIST-TS FprCEN/TS 17706:2021
FINAL DRAFT
TECHNICAL SPECIFICATION
FprCEN/TS 17706
SPÉCIFICATION TECHNIQUE
TECHNISCHE SPEZIFIKATION
September 2021
ICS 07.080
English Version
Plant biostimulants - Determination of inorganic arsenic

Biostimulants des végétaux - Dosage de l'arsenic Biostimulanzien für die pflanzliche Anwendung -

inorganique Bestimmung von anorganischem Arsen

This draft Technical Specification is submitted to CEN members for Vote. It has been drawn up by the Technical Committee

CEN/TC 455.

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.

Recipients of this draft are invited to submit, with their comments, notification of any relevant patent rights of which they are

aware and to provide supporting documentation.

Warning : This document is not a Technical Specification. It is distributed for review and comments. It is subject to change

without notice and shall not be referred to as a Technical Specification.
EUROPEAN COMMITTEE FOR STANDARDIZATION
COMITÉ EUROPÉEN DE NORMALISATION
EUROPÄISCHES KOMITEE FÜR NORMUNG
CEN-CENELEC Management Centre: Rue de la Science 23, B-1040 Brussels

© 2021 CEN All rights of exploitation in any form and by any means reserved Ref. No. FprCEN/TS 17706:2021 E

worldwide for CEN national Members.
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kSIST-TS FprCEN/TS 17706:2021
FprCEN/TS 17706:2021 (E)
Contents Page

European foreword ....................................................................................................................................................... 3

Introduction .................................................................................................................................................................... 4

1 Scope .................................................................................................................................................................... 5

2 Normative references .................................................................................................................................... 5

3 Terms and definitions ................................................................................................................................... 5

4 Principle ............................................................................................................................................................. 5

5 Reagents ............................................................................................................................................................. 6

6 Apparatus ........................................................................................................................................................... 7

7 Sampling ............................................................................................................................................................. 8

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

8.4.1 General instrumental conditions .............................................................................................................. 9

8.4.2 HPLC-ICP/MS measurement of inorganic arsenic ............................................................................... 9

9 Calculation and expression of the results ........................................................................................... 11

9.1 Integration of peaks .................................................................................................................................... 11

9.2 Calculation of inorganic arsenic in the samples ............................................................................... 11

10 Test report ...................................................................................................................................................... 11

Annex A (informative) Examples of typical chromatographic separation ............................................. 13

Bibliography ................................................................................................................................................................. 16

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kSIST-TS FprCEN/TS 17706:2021
FprCEN/TS 17706:2021 (E)
European foreword

This document (FprCEN/TS 17706:2021) has been prepared by Technical Committee CEN/TC 455 “Plant

biostimulants”, the secretariat of which is held by AFNOR.
This document is currently submitted to the Vote on TS.

This document has been prepared under a Standardization Request given to CEN by the European

Commission and the European Free Trade Association.
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kSIST-TS FprCEN/TS 17706:2021
FprCEN/TS 17706:2021 (E)
Introduction

This document was prepared by the experts of CEN/TC 455 ‘Plant Biostimulants’. The European

Committee for Standardization (CEN) was requested by the European Commission (EC) to draft

European standards or European standardization deliverables to support the implementation of

Regulation (EU) 2019/1009 of 5 June 2019 laying down rules on the making available on the market of

EU fertilising products (“FPR” or “Fertilising Products Regulation”).

This request, presented as SR M/564, also contributes to the Communication on “Innovating for

Sustainable Growth: A Bio economy for Europe”. The Working Group 4 “Other safety parameters”, was

created to develop a work program as part of this Request. The technical committee CEN/TC 455 ‘Plant

Biostimulants’ was established to carry out the work program that will prepare a series of standards. The

interest in biostimulants has increased significantly in Europe as a valuable tool to use in agriculture.

Standardization was identified as having an important role in order to promote the use of biostimulants.

The work of CEN/TC 455 seeks to improve the reliability of the supply chain, thereby improving the

confidence of farmers, industry, and consumers in biostimulants, and will promote and support

commercialisation of the European biostimulant industry. The preparation of this document is based on

a standardization request to CEN by the European Commission and the European Free Trade Association

(Mandate M/564) concerning the modernization of methods of analysis of fertilizers in the framework of

Regulation (EU) 2019/1009 of the European Parliament and of the Council.

This document describes procedure of extraction and measurement for the determination of inorganic

arsenic in plant biostimulants. The standard is based on a mild acid oxidative extraction of the arsenic

species followed by liquid chromatography (HPLC or IC) coupled to the element-specific detector ICP-MS

for the determination of the mass fraction of iAs.

This document is also applicable to the blends of fertilizing products where plant biostimulants are the

main part of the blend. Otherwise, the Technical Specification for the main part of the blend apply.

WARNING – Persons using this document should be familiar with usual laboratory practice. This

document does not purport to address all of the safety issues, if any, associated with its use. It is

the responsibility of the user to establish appropriate health and safety practices and to ensure

compliance with any national regulatory conditions.

IMPORTANT – It is absolutely essential that tests conducted according to this document are

carried out by suitably trained staff.
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kSIST-TS FprCEN/TS 17706:2021
FprCEN/TS 17706:2021 (E)
1 Scope

This document specifies a method for extraction, separation, and determination of inorganic arsenic (iAs)

in plant biostimulants using anion-exchange HPLC or IC coupled to ICP-MS.

This document is also applicable to the blends of fertilizing products where plant biostimulants are the

main part of the blend. Otherwise, the Technical Specification for the main part of the blend apply.

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.

FprCEN/TS 17704, Plant biostimulants — Determination of dry matter
3 Terms and definitions
For the purposes of this document, the following terms and definitions apply.

ISO and IEC maintain terminological databases for use in standardization at the following addresses:

• IEC Electropedia: available at https://www.electropedia.org/
• ISO Online browsing platform: available at https://www.iso.org/obp
3.1
analyte
parameter to be determined
3.2
blank calibration solution

solution prepared in the same way as the calibration solution but leaving out the analytes

3.3
blank test solution

solution prepared in the same way as the test sample solution but omitting the test portion

3.4
calibration solution

solution used to calibrate the instrument, prepared from stock solutions by adding acids, buffer, reference

element and salts as needed
3.5
stock solution

solution with accurately known analyte concentration(s), prepared from pure chemicals

4 Principle

This document describes a method for the determination of inorganic arsenic in plant biostimulants.

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 oxidized to

As(V). The inorganic arsenic is selectively separated from other arsenic compounds using anion exchange

HPLC (High Performance Liquid Chromatography) coupled online to the element-specific detector ICP-

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kSIST-TS FprCEN/TS 17706:2021
FprCEN/TS 17706:2021 (E)

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 ICP-AES (FprCEN/TS 17701-1

and FprCEN/TS 17701-2) 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 Reagents

When using a method of high sensitivity like ICP-MS and HPLC 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 from

a purification system and nitric acid of minimum p.a. quality is recommended.

5.1 Water with an electrical conductivity not higher than 0,1 mS/m at 25 °C, having a resistivity

greater than 18,2 MΩ⋅cm.

5.2 Nitric acid (HNO ), concentrated, ≥ 65 % (mass fraction), mass concentration of approximately ρ

(HNO ) 1,4 g/ml.

Use only nitric acid available with high purity (minimum p.a. quality) in order to avoid potential

contamination.
5.3 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.
5.4 Extraction solution, 0,1 mol/l HNO in 3 %(V/V) H O
3 2 2

Add 6,5 ml of HNO (5.2) and thereafter 100 ml of hydrogen peroxide (5.3) into 800 ml water (5.1) in

a 1 000 ml volumetric flask. Fill the flask to the mark with water (5.1.). 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.

5.5 Ammonium carbonate, (NH ) CO , mass fraction w ≥ 99,999 %, for preparation of the mobile

4 2 3
phase solution.

5.6 Aqueous ammonia, (NH (aq).) w ≥ 25 %, for adjustment of pH in the mobile phase.

5.7 Methanol, (CH OH), HPLC grade, for preparation of the mobile phase solution.
5.8 Mobile phase, e.g. 50 mmol/l ammonium carbonate in 3 % methanol at pH 10,3

Dissolve 4,80 g of ammonium carbonate (5.5) in approximately 800 ml water (5.1). Adjust the pH to 10,3

with aqueous ammonia (5.6) and add 30 ml of methanol (5.7) and then fill up to 1 000 ml with water

(5.1). Prior to use filter the mobile phase solution through a 0,45 µm filter using a filtering device (6.4).

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kSIST-TS FprCEN/TS 17706:2021
FprCEN/TS 17706:2021 (E)

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 and 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.

Different mobile phase may be also used according to the instructions of the manufacturer of th

...

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