🌱 Total and water-soluble calcium in fertilizers — manganimetric determination of calcium precipitated as oxalate from an extract according to PN-EN 15960 or PN-EN 15961, PN-EN 16196

Physicochemistry PN-EN 16196

Overview

WHAT THE STANDARD COVERS. The scope from the PKN catalogue card, quoted in full: "This European Standard specifies a manganimetric method for the determination of the calcium content in fertilizer extracts. This method is applicable to EC fertilizers for which Regulation (EC) No 2003/2003, Annex I [3] provides for a declaration of the total and/or water-soluble calcium content." (our translation of the Polish card). The title adds the principle: the extracted calcium is precipitated in the form of oxalate and determined manganimetrically. The standard does not prepare the extracts — laboratories take them from PN-EN 15960 (total calcium) or PN-EN 15961 (water-soluble calcium); the latter has a separate entry in this knowledge base.

STATUS (state of the card on 29 September 2026). The card of PN-EN 16196:2013-05 (Polish version) has no withdrawal note — the standard is CURRENT. Polish version published 06-09-2016, 14 pages, PKN technical committee KT 156 (Fertilizers), ICS 65.080; "Introduces: EN 16196:2012 [IDT]"; there is no "Supersedes" field. The PKN search for "PN-EN 16196" (29 September 2026) shows the Polish and the English version of the 2013-05 edition, neither labelled "Wycofana" (withdrawn). Regulation: Regulation (EU) 2019/1009, Article 51, repeals Regulation (EC) No 2003/2003 with effect from 16 July 2022 and treats references to it as references to Regulation 2019/1009; how the condition in the scope of the standard should be read today — WE DO NOT DECIDE.

HOW MANY LABORATORIES AND IN WHAT FORM (copy of the accreditation scope database, data up to 17 September 2026, read on 28 September 2026). All records of number 16196: 21 entries at 14 laboratories. Forms: "PN-EN 16196:2013-05" — 11 laboratories, "PN-EN 16196:2013" — AB 789, AB 820 and AB 827. The "Laboratories" tab searches for records BEGINNING with "PN-EN 16196" and will show 13 laboratories — checked with the tab query on the labcoda.pl production server on 29 September 2026: 13; AB 1186 remains outside it (it records "PN-EN 15960:2011 PN-EN 16196:2013-05" in one string). Current scopes on the PCA website (read on 29 September 2026, issues from 7 March 2025 to 5 August 2026): all entries stand in the valid issues, every pair of range numbers from the copy appears in the current document and no entry is suspended; the full records of the reference documents agree with the copy.

WHAT THEY DETERMINE. Total calcium (with PN-EN 15960:2011) and water-soluble calcium (with PN-EN 15961:2017-02) — as separate entries at AB 006, AB 180, AB 284, AB 317, AB 759, AB 779 and AB 787; as one entry with both extraction standards — AB 312, AB 333, AB 820, AB 827 and AB 921; total calcium only — AB 789 and AB 1186. Technique: titrimetric method (at AB 827 "manganimetric"). Ranges as CaO in percent: lower limits from 0.50 (among others AB 312, AB 787, AB 827) and 0.5 (AB 284, AB 820) to 2.0 (AB 789) and 2.00 (AB 317, AB 787 for water-soluble calcium); upper limits from 32.0 (AB 787, total calcium) to 60.0 (AB 312, AB 820, AB 827, AB 921, AB 1186); AB 006 and AB 180 also give the range as Ca — (0.50 – 40.0) %, AB 333 — (1.5 – 70.0) % without stating the form. Object: mineral (inorganic) fertilizers; AB 006 — also organo-mineral and organic fertilizers, compost, growing media and plant growth aids.

ALONGSIDE THIS STANDARD. Apart from this standard, calcium in mineral fertilizers is determined by ICP-OES — as one of the elements in an entry "Zawartość pierwiastków" (content of elements) — by AB 1095 (organic, natural and mineral fertilizers; PN-EN 16319+A1:2016-02) and AB 696 (inorganic, organic, natural and organo-mineral fertilizers; procedure PT-LCAW-13, and for raw materials for fertilizer production PT-LCAW-16). For natural, organic and organo-mineral fertilizers laboratories have in-house procedures (AB 277, AB 312, AB 339, AB 779, AB 823, AB 921 — by flame methods, AB 312 and AB 339 also by ICP-OES), and calcium is also determined by ICP-OES according to standards by AB 700 (compost; PN-EN ISO 11885:2009 with PN-EN 16173 and PN-EN 16174), AB 1249 (compost; PN-EN 16170:2017-02) and AB 213 (compost, biomass, stabilised material; PN-EN 16174 with PN-EN 22036). For agricultural limes the scopes cite PN-EN 13475:2003 (AB 006, AB 180, AB 339), PN-EN 12946:2023-11 (AB 006, entry "Zawartość pierwiastków": calcium and magnesium), PN-C-87006-11:1990 (magnesium-containing limes) and PN-C-87007-06:1993 (entry in this knowledge base). For plant cultivation aids calcium is determined by ICP-OES by AB 213 (with PN-EN 15960, PN-EN 15961 and PN-EN ISO 11885), AB 1365 (PN-EN ISO 11885 with procedure ILB3b-25) and AB 1748 (PB-80). Magnesium in the same extracts — according to PN-EN 16197 (separate entry).

WHAT WE DO NOT GIVE. We did not have the text of the standard — PKN sells it (14 pages). We do not give the conditions of oxalate precipitation, the reagents, the concentration of the potassium permanganate solution, the calculations or the precision.

Method principle

According to the card and the title of the standard, calcium from a fertilizer extract (prepared according to PN-EN 15960 or PN-EN 15961) is precipitated in the form of oxalate and determined manganimetrically; the result is expressed as calcium content (in the scopes usually as CaO). We DO NOT GIVE the precipitation and titration conditions — we did not have the text of the standard.

Applications

• Declared content of total and water-soluble calcium in mineral fertilizers — in the scopes of 14 laboratories
• Fertilizer control together with extraction according to PN-EN 15960 or PN-EN 15961

Key parameters

Standard

Standard number

PN-EN 16196:2013-05 (wersja polska; wprowadza EN 16196:2012 [IDT])

Title (PL)

Nawozy — Manganometryczne oznaczanie wyekstrahowanego wapnia wytrąconego w postaci szczawianu

Title (EN)

Fertilizers — Manganimetric determination of extracted calcium following precipitation in the form of oxalate

Step-by-step procedure

1. Extract

   Fertilizer extract according to PN-EN 15960 (total calcium) or PN-EN 15961 (water-soluble calcium).

2. Precipitation

   Calcium from an aliquot of the extract is precipitated in the form of oxalate (title); conditions NOT GIVEN.

3. Determination

   Manganimetric determination; in the scopes — titrimetric method.

4. Result

   Calcium content, in the scopes usually as CaO in percent.

Reagents, media and consumables

Health and safety (OHS)

• Potassium permanganate is a strong oxidant and oxalates are harmful — the safety data sheets apply
• NOTE ON SUBSTANCE: the scope of the standard refers to the repealed Regulation 2003/2003; for organic fertilizers laboratories use in-house procedures, not this standard

Frequently asked questions