Regulation (EC) No 2003/2003 of the European Parliament and of the Council of 13 October 2003 relating to fertilisers (Text with EEA relevance)
Date: 2003-10-13
Institutions: Council of the European Union, European Parliament
Subjects: fertiliser, labelling, marketing standard, plant health control

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I

(Acts whose publication is obligatory)

REGULATION (EC) No 2003/2003 OF THE EUROPEAN PARLIAMENT AND OF THE COUNCIL

of 13 October 2003

relating to fertilisers

(Text with EEA relevance)

THE EUROPEAN PARLIAMENT AND THE COUNCIL OF THE
EUROPEAN UNION,

Having regard to the Treaty establishing the European
Community, and in particular Article 95 thereof,

European Parliament and the Council ‘Simpler legislation
for the internal market’ (SLIM) and the Action Plan for the
those Directives should be repealed and
Single Market
replaced by a single legal instrument, in the interests of
clarity.

Having regard to the proposal from the Commission (1),

Having regard to the Opinion of the European Economic and
Social Committee (2),

Acting in accordance with the procedure laid down in Article
251 of the Treaty (3),

(2) The Community legislation on fertilisers is very technical
in its content. A Regulation is therefore the most appro-
priate legal
instrument, as it imposes directly on manu-
facturers precise requirements to be applied at the same
time and in the same manner throughout the Community.

Whereas:

(3)

the laws of

(1) Council Directive 76/116/EEC of 18 December 1975 on
the approximation of
the Member States
relating to fertilisers (4), Council Directive 80/876/EEC of
15 July 1980 on the approximation of the laws of the
Member States relating to straight ammonium nitrate
fertilisers of high nitrogen content (5), Commission
Directive 87/94/EEC of 8 December 1986 on the approxi-
mation of
the Member States relating to
procedures for the control of characteristics of, limits for
and resistance to detonation of straight ammonium nitrate
fertilisers of high nitrogen content (6), and Commission
Directive 77/535/EEC of 22 June 1977 on the approxi-
mation of
the Member States relating to
methods of sampling and analysis for fertilisers (7), have
been substantially amended several times. In accordance
with the communication from the Commission to the

the laws of

the laws of

(1) OJ C 51 E, 26.2.2002, p. 1 and OJ C 227 E, 24.9.2002, p. 503.
(2) OJ C 80, 3.4.2002, p. 6.
(3) Opinion of the European Parliament of 10 April 2002 (OJ C 127 E,
29.5.2002, p. 160), Council Common Position of 14 April 2003
(OJ C 153 E, 1.7.2003, p. 56) and Decision of
the European
Parliament of 2 September 2003 (not yet published in the
Official Journal).

(4) OJ L 24, 30.1.1976, p. 21. Directive as last amended by Directive
98/97/EC of the European Parliament and the Council (OJ L 18,
23.1.1999, p. 60).

(5) OJ L 250, 23.9.1980, p. 7. Directive as amended by Directive
97/63/EC of the European Parliament and the Council (OJ L 335,
6.12.1997, p. 15).

(6) OJ L 38, 7.2.1987, p. 1. Directive as amended by Directive

88/126/EEC (OJ L 63, 9.3.1988, p. 12).

(7) OJ L 213, 22.8.1977, p. 1. Directive as last amended by Directive

95/8/EC (OJ L 86, 20.4.1995, p. 41).

down

characteristics

In each Member State fertilisers must display certain
technical
by mandatory
laid
provisions. These provisions, concerning more particularly
the composition and definition types of
the
designations of these types, their identification and their
packaging, differ from one Member State to another. By
their disparity they hinder trade within the Community
and should therefore be harmonised.

fertilisers,

the

in fertilisers,

internal market

(4) Since the objective of the proposed action, namely to
ensure
cannot be
sufficiently achieved by the Member States if there are
no common technical criteria and can therefore, by
reason of the scale of the action, be better achieved at
Community level, the Community may adopt measures
in accordance with the principle of subsidiarity as set
out in Article 5 of the Treaty. In accordance with the
principle of proportionality, as set out in that Article,
this Regulation does not go beyond what is necessary in
order to achieve this objective.

(5)

It is necessary to determine at Community level the desig-
nation, definition and composition of certain fertilisers (EC
fertilisers).

(6) Community rules on the identification,

labelling of EC fertilisers and on the closure of
packages should also be laid down.

traceability and
the

(7) A procedure should be established at Community level to
be followed in cases where a Member State deems it
necessary to restrict
the placing on the market of EC
fertilisers.

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(8) The production of fertilisers is subject to varying degrees
of fluctuation due to manufacturing techniques or basic
materials. Sampling and analytical procedures may also
contain variations. It is therefore necessary to authorise
In the
tolerances on the declared nutrient contents.
interest of the agricultural user,
it is advisable to keep
these tolerances within narrow limits.

Parliament and the Council. Where appropriate, a similar
review will be undertaken for other contaminants.

(16) It is appropriate to establish a procedure, to be observed
by any manufacturer or its representative that wishes to
include a new type of fertiliser in Annex I in order to use
the marking ‘EC fertiliser’.

(9) Official controls on the compliance of EC fertilisers with
requirements of this Regulation concerning quality and
composition should be carried out by laboratories that
are approved by the Member States and notified to the
Commission.

(17) The measures necessary for the implementation of this
Regulation should be
adopted in accordance with
Council Decision 1999/468/EC of 28 June 1999 laying
down the procedures for the exercise of implementing
powers conferred on the Commission (1).

(10) Ammonium nitrate is the essential ingredient of a variety
of products, some of which are intended for use as
fertilisers and others as explosives. It is necessary, having
regard to the particular nature of ammonium nitrate
fertilisers of high nitrogen content and to the consequent
and
requirements
protection
additional
Community rules for EC fertilisers of this type.

regarding
of workers,

public
to

safety,

health

down

lay

(11) Certain of those products could be hazardous and could in
certain instances be used for purposes other than those for
which they were intended. This could well endanger the
security of persons and property. Manufacturers should
therefore be obliged to take appropriate steps to avoid
such use, and in particular to ensure the traceability of
such fertilisers.

(12) In the interest of public safety, it is particularly important
to determine at Community level the characteristics and
properties distinguishing ammonium nitrate EC fertilisers
of high nitrogen content from varieties of ammonium
nitrate used in the manufacture of products used as
explosives.

(13) Ammonium nitrate EC fertilisers of high nitrogen content
should conform to certain characteristics to ensure that
they are harmless. Manufacturers should ensure that all
high nitrogen content ammonium nitrate fertilisers have
passed a test of resistance to detonation before those
fertilisers are placed on the market.

(14) It is necessary to establish rules on the methods of the
these methods may not
during
arising

closed thermal cycles even if
necessarily
simulate
transport and storage.

conditions

all

(15) Fertilisers can be contaminated by substances that can
potentially pose a risk to human and animal health and
the environment. Further to the opinion of the Scientific
Committee on Toxicity, Ecotoxicity and the Environment
(SCTEE), the Commission intends to address the issue of
unintentional cadmium content in mineral fertilisers and
will, where appropriate, draw up a proposal for a Regu-
to the European
lation, which it

to present

intends

(18) Member States should lay down penalties in respect of
infringements of the provisions of this Regulation. They
may provide that a manufacturer which infringes Article
27 can be fined an amount equivalent to ten times the
market value of the shipment that fails to comply.

(19) Directives 76/116/EEC, 77/535/EEC, 80/876/EEC and

87/94/EEC should be repealed,

HAVE ADOPTED THIS REGULATION:

TITLE I

GENERAL PROVISIONS

CHAPTER I

Scope and definitions

Article 1

Scope

This Regulation shall apply to products which are placed on
the market as fertilisers designated ‘EC fertiliser’.

Article 2

Definitions

For the purposes of this Regulation the following definitions
shall apply:

(a)

‘Fertiliser’ means material, the main function of which is to
provide nutrients for plants.

(b)

‘Primary nutrient’ means the elements nitrogen, phos-
phorus and potassium only.

(c)

(d)

‘Secondary
magnesium, sodium and sulphur.

nutrient’ means

the

elements

calcium,

cobalt,
‘Micro-nutrients’ means
zinc,
iron, manganese, molybdenum and
copper,
essential
for plant growth in quantities that are small
compared with those of primary and secondary nutrients.

elements boron,

the

(1) OJ L 184, 17.7.1999, p. 23.

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(e)

(f)

(g)

‘Inorganic fertiliser’ means a fertiliser in which the declared
nutrients are in the form of minerals obtained by
extraction or by physical and/or chemical
industrial
processes. Calcium cyanamide, urea and its condensation
containing
and association products,
chelated
by
convention, be classed as inorganic fertilisers.

complexed micro-nutrients may,

and fertilisers

or

‘Chelated micro-nutrient’ means a micro-nutrient that is
held by one of the organic molecules listed in section
E.3.1 of Annex I.

‘Complexed micro-nutrient’ means a micro-nutrient that is
held by one of the molecules listed in section E.3.2 of
Annex I.

(h)

‘Type of fertilisers’ means fertilisers with a common type
designation as indicated in Annex I.

(i)

(j)

(k)

‘Straight
fertiliser’ means a nitrogenous, phosphatic or
potassic fertiliser having a declarable content of only one
of the primary nutrients.

‘Compound fertiliser’ means a fertiliser having a declarable
content of at
the primary nutrients and
obtained chemically or by blending or by a combination
of both.

two of

least

‘Complex fertiliser’ means a compound fertiliser, obtained
by chemical reaction, by solution, or in its solid state by
granulation, having a declarable content of at least two of
In its solid state each granule
the primary nutrients.
contains all the nutrients in their declared composition.

(l)

‘Blended fertiliser’ means a fertiliser obtained by dry
mixing of several fertilisers, with no chemical reaction.

(m) ‘Foliar fertiliser’ means a fertiliser suitable for application

to and nutrient uptake by the foliage of a crop.

(n)

‘Fluid fertiliser’ means a fertiliser in suspension or solution.

recognised by the Community and whose reference has
been published in the Official
the European
Communities.

Journal of

(u)

‘Package’ means a sealable receptacle used to hold, protect,
handle, and distribute fertilisers and holding not more than
1 000 kg.

(v)

‘Bulk’ means a fertiliser not packaged as prescribed by this
Regulation.

(w)

(x)

fertiliser,
‘Placing on the market’ means the supply of
whether in return for payment or free of charge, or
Importation of a
storage for
fertiliser
the European
Community shall be deemed to constitute placing on the
market.

the purpose of supply.

into the customs

territory of

the natural or

legal person
‘Manufacturer’ means
responsible for placing a fertiliser on the market;
in
particular a producer, an importer, a packager working
for its own account, or any person changing the charac-
teristics of a fertiliser, shall be deemed to be a manu-
facturer. However, a distributor who does not change
the characteristics of the fertiliser shall not be deemed to
be a manufacturer.

CHAPTER II

Placing on the market

Article 3

EC Fertiliser

A fertiliser belonging to a type of fertilisers listed in Annex I
and complying with the conditions laid down in this Regu-
lation, may be designated ‘EC fertiliser’.

(o)

(p)

(q)

(r)

(s)

(t)

‘Solution fertiliser’ means a fluid fertiliser that is free of
solid particles.

The designation ‘EC fertiliser’ shall not be used for a fertiliser
which does not comply with this Regulation.

‘Suspension fertiliser’ means a two-phase fertiliser in which
solid particles are maintained in suspension in the liquid
phase.

amount of
‘Declaration’ means
nutrients, including their forms and solubility, guaranteed
within specified tolerances.

statement of

the

a

‘Declared content’ means the content of an element, or its
oxide, which, in accordance with Community legislation, is
given on a label of an EC fertiliser or on the relevant
accompanying document.

‘Tolerance’ means the permitted deviation of the measured
value of a nutrient content from its declared value.

‘European Standard’ means CEN (European Committee for
standards, which have been officially
Standardisation)

Article 4

Establishment within the Community

The manufacturer shall be established within the Community
and shall be responsible for the conformity of the ‘EC fertiliser’
with the provisions of this Regulation.

Article 5

Free circulation

States

1. Without prejudice to Article 15 and other Community
legislation, Member
of
composition, identification,
labelling or packaging, and other
provisions contained in this Regulation, prohibit, restrict or
hinder the placing on the market of fertilisers marked ‘EC
fertiliser’ which comply with the provisions of this Regulation.

on grounds

shall not,

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Fertilisers that are marked ‘EC fertiliser’

2.
with this Regulation shall
Community.

circulate

in accordance
freely within the

Article 6

Compulsory statements

1.
In order to satisfy the requirements of Article 9, Member
States may prescribe that the indication of the nitrogen, phos-
phorus and potassium contents of fertilisers placed on their
market is to be expressed in the following way:

(a) nitrogen solely in the elemental form (N); and either

(b) phosphorus and potassium solely in the elemental form (P,

K); or

(c) phosphorus and potassium solely in the oxide form (P2O5,

K2O); or

(d) phosphorus and potassium in both elemental and oxide

forms simultaneously.

Where the option is chosen to prescribe that the phosphorus
and potassium contents be expressed in the form of elements,
all references in the Annexes to the oxide form shall be read as
being in elemental form and the numerical values shall be
converted using the following factors:

(a) phosphorus (P) = phosphorus pentoxide (P2O5) × 0,436;

(b) potassium (K) = potassium oxide (K2O) × 0,830.

prescribe

States may

sodium and sulphur

2. Member
magnesium,
nutrient
are fulfilled, of primary nutrient
markets are to be expressed:

calcium,
secondary
fertilisers and, where the conditions of Article 17
fertilisers placed on their

the
that
contents of

(a)

in the oxide form (CaO, MgO, Na2O, SO3); or

(b) in the elemental form (Ca, Mg, Na, S); or

(c)

in both of these forms.

To convert the calcium oxide, magnesium oxide, sodium oxide
and sulphur
into calcium, magnesium,
sodium and sulphur contents, the following factors shall be
used:

contents

trioxide

(a) calcium (Ca) = calcium oxide (CaO) × 0,715;

(b) magnesium (Mg) = magnesium oxide (MgO) × 0,603;

(c) sodium (Na) = sodium oxide (Na2O) × 0,742;

(d) sulphur (S) = sulphur trioxide (SO3) × 0,400.

the calculated oxide or elemental content,
For
declared shall be rounded to the nearest decimal place.

the figure

3. Member States shall not prevent
market of an ‘EC fertiliser’
mentioned in paragraphs 1 and 2.

labelled in both of

the placing on the
the forms

The content of one or more of the micro-nutrients boron,
4.
cobalt, copper, iron, manganese, molybdenum, or zinc in the
EC fertilisers belonging to the types of
fertilisers listed in
sections A, B, C and D of Annex I shall be declared where
the following conditions are fulfilled:

(a) the micro-nutrients are added at least in the minimum
quantities specified in section E.2.2 and E.2.3 of Annex I;

(b) the EC fertiliser continues to satisfy the requirements of

sections A, B, C and D of Annex I.

5. Where the micro-nutrients are the normal ingredients of
the raw materials intended to supply primary (N, P, K) and
secondary (Ca, Mg, Na, S) nutrients, they may be declared,
provided that these micro-nutrients are present at least in the
minimum quantities specified in sections E.2.2 and E.2.3 of
Annex I.

The micro-nutrient content shall be declared in the

6.
following manner:

(a)

for fertilisers belonging to the types of fertilisers listed in
section E.1 of Annex
in accordance with the
I,
requirements set out in column 6 of that section;

two different micro-nutrients

(b) for mixtures of fertilisers referred to in (a) containing at
least
and meeting the
requirements of section E.2.1 of Annex I and for fertilisers
belonging to the types of fertilisers listed in sections A, B, C
and D of Annex I, by indicating:

(i) the total content, expressed as a percentage of

the

fertiliser by mass,

(ii) the water-soluble content, expressed as a percentage of
the fertiliser by mass, where the soluble content is at
least half of the total content.

Where a micro-nutrient is totally water-soluble, only the water-
soluble content shall be declared.

the content of the micro-nutrient present

Where a micro-nutrient is chemically linked with an organic
in the
molecule,
fertiliser shall be declared immediately following the water-
soluble content as a percentage by mass of
the product,
followed by one of the terms ‘chelated by’, or ‘complexed
by’, with the name of the organic molecule as set out in
section E.3 of Annex I. The name of the organic molecule
may be replaced by its initials.

Article 7

Identification

The manufacturer shall provide EC fertilisers with the

1.
identification markings listed in Article 9.

2.
If the fertilisers are packed, these identification markings
shall appear on the packages or labels attached. If the fertilisers
are in bulk, these markings shall appear on the accompanying
documents.

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Article 8

Traceability

Without prejudice to Article 26(3), the manufacturer shall, to
ensure traceability of EC fertilisers, maintain records of the
origin of the fertilisers. These records shall be available for
inspection by Member States for as long as the fertiliser is
being supplied to the market, and for a further period of 2
years after the manufacturer stopped supplying it.

Article 9

Markings

1. Without prejudice
the
packages, labels and accompanying documents, referred to in
Article 7 shall bear the following markings:

to other Community rules,

(a) Compulsory identification

— The words ‘EC FERTILISER’ in capital letters;

— Where it exists, the designation of the type of fertiliser

as set out in Annex 1;

— Quantities of fluid fertilisers, expressed by mass. The
expression of quantities of fluid fertilisers by volume
or in terms of mass versus volume (kilograms per
hectolitre or grams per litre) shall be optional;

— Net or gross mass and, optionally, volume for fluid
the tare mass
If the gross mass is given,

fertilisers.
must be indicated beside it;

— The name or trade name and the address of the manu-

facturer.

(b) Optional identification

— As listed in Annex I;

— The directions for the storage and handling, and for
fertilisers not listed in Annex I, sections E.1 and E.2,
the specific directions for the use of the fertiliser;

— Indications of

the dose rates and conditions of use
suitable for the soil and crop conditions under which
the fertiliser is used;

— The mark of the manufacturer and the trade description

— For blended fertilisers,
designation of the type;

the marking ‘blend’ after the

of the product.

— The additional markings specified in Article 19, 21 or

23;

— Nutrients shall be indicated both in words and by the
appropriate chemical symbols, e.g. nitrogen (N), phos-
phorus (P), phosphorus pentoxide (P2O5), potassium
(K), potassium oxide (K2O), calcium (Ca), calcium
oxide
(CaO), magnesium (Mg), magnesium oxide
(MgO), sodium (Na), sodium oxide (Na2O), sulphur
(S), sulphur trioxide (SO3), boron (B), copper (Cu),
cobalt (Co),
iron (Fe), manganese (Mn), molybdenum
(Mo), zinc (Zn);

— If the fertiliser contains micro-nutrients of which all or
part are chemically linked with an organic molecule,
the name of the micro-nutrient shall be followed by
one of the following qualifiers:

(i) ‘chelated by . . .’

(name of chelating agent or its
abbreviation as set out in section E.3.1 of Annex I);

(ii) ‘complexed by . . .’ (name of complexing agent as

set out in section E.3.2 of Annex I);

— Micro-nutrients contained in the fertiliser, listed in the
alphabetical order of their chemical symbols: B, Co, Cu,
Fe, Mn, Mo, Zn;

— For products listed in sections E.1 and E.2 of Annex I,

the specific directions for use;

The indications referred to in (b) must not conflict with those
referred to in (a) and must be clearly separated from them.

All the markings referred to in paragraph 1 must be
information on the

2.
clearly
separated from any other
packages, labels and accompanying documents.

3.
Fluid fertilisers may be placed on the market only if the
manufacturer provides suitable additional instructions covering,
in particular, storage temperature and prevention of accidents
during storage.

Detailed rules for the application of this Article shall be

4.
adopted under the procedure referred to in Article 32(2).

Article 10

Labelling

The labels or markings printed on the package and giving
1.
the particulars mentioned under Article 9 must be placed in a
conspicuous position. Labels must be attached to the package
or to whatever system is used for closing it. If this system
consists of a seal, that seal must bear the name or mark of
the packager.

The markings referred to in paragraph 1 must be and

2.
must remain indelible and clearly legible.

3.
In the cases of fertilisers in bulk referred to in the second
sentence of Article 7(2) a copy of the documents containing
the identification markings must accompany the goods and be
accessible for inspection purposes.

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Article 11

Languages

The label, the markings on the package and the accompanying
language or
documents must appear in at least the national
languages of the Member State in which the EC fertiliser is
marketed.

Article 12

Packaging

In the case of packaged EC fertilisers, the package must be
closed in such a way or by such a device that, when it is
opened, the fastening, fastening seal or the package itself is
irreparably damaged. Valve sacks may be used.

Article 13

Tolerances

1.
The nutrient content of EC fertilisers shall comply with
the tolerances established in Annex II, which are intended to
allow for deviations in manufacture, sampling and analysis.

The manufacturer shall not take systematic advantage of

2.
the tolerances given in Annex II.

No tolerances are allowed in respect of the minimum and

3.
maximum contents specified in Annex I.

Article 14

Fertiliser requirements

A type of fertiliser may only be included in Annex I if:

(a)

it provides nutrients in an effective manner;

market of that fertiliser in its territory or make it subject to
special conditions.
immediately inform the other
Member States and the Commission thereof, giving the
reasons for its decision.

shall

It

The Commission shall adopt a decision on the matter
the information in

2.
within 90 days
from the receipt of
accordance with the procedure referred to in Article 32(2).

3.
The provisions of this Regulation shall not preclude the
taking of measures by the Commission or by a Member State
which are justified on grounds of public security to prohibit,
restrict or hinder the placing on the market of EC fertilisers.

TITLE II

PROVISIONS FOR SPECIFIC TYPES OF FERTILISERS

CHAPTER I

Inorganic primary nutrient fertilisers

Article 16

Scope

shall apply to inorganic primary nutrient
This
chapter
fertilisers, solid or
including
those containing secondary nutrients and/or micro-nutrients,
with the minimum nutrient content established in sections A,
B, C, E.2.2 or E.2.3 of Annex I.

fluid, straight or compound,

Article 17

Declaration of secondary nutrients in primary nutrient
fertilisers

secondary nutrient

Calcium, magnesium, sodium and sulphur content may be
declared as
content of EC fertilisers
belonging to the types of fertiliser listed in sections A, B and
C of Annex I, provided that these elements are present in at
least the following minimum quantities:

(b) relevant sampling, analysis, and if required, test methods

are being provided.

(a) 2 % calcium oxide (CaO), i.e. 1,4 % Ca;

(c) under normal conditions of use it does not adversely affect
human, animal, or plant health, or the environment.

(b) 2 % of magnesium oxide (MgO), i.e. 1,2 % Mg;

Article 15

Safeguard clause

1. Where a Member State has
for
believing that a specific EC fertiliser, although satisfying the
requirements of this Regulation, constitutes a risk to safety
or health of humans, animals or plants or a risk to the
environment, it may temporarily prohibit the placing on the

justifiable grounds

(c) 3 % of sodium oxide (Na2O), i.e. 2,2 % Na;

(d) 5 % of sulphur trioxide (SO3), i.e. 2 % S.

In such a case,
19(2)(ii) shall be added to the type designation.

the additional marking specified in Article

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Article 18

Calcium, magnesium, sodium and sulphur

1.
The declaration of the magnesium, sodium and sulphur
content of the fertilisers listed in sections A, B, and C of Annex
I shall be expressed in one of the following ways:

(a) the total content expressed as a percentage of the fertiliser

by mass;

The declared content of micro-nutrients shall give the name
and symbol of each micro-nutrient, indicating the percentage
by mass as specified in sections E.2.2 and E.2.3 of Annex I and
according to solubility.

6.
The forms and solubility of the nutrients shall also be
expressed as a percentage by mass of fertiliser, except where
Annex I explicitly provides that this content shall be otherwise
expressed.

(b) the total content and the content

soluble in water,
expressed as a percentage of the fertiliser by mass where
the soluble content is at least a quarter of the total content;

The number of decimal places shall be one, except for micro-
nutrients where it shall be as specified in sections E.2.2 and
E.2.3 of Annex I.

(c) where an element

is totally soluble in water, only the
content soluble in water shall be declared as a percentage
of the mass.

2.
Unless otherwise stated in Annex I, a declaration of the
calcium content shall only be made if it is soluble in water and
shall be expressed as a percentage of the fertiliser by mass.

Article 19

Identification

In addition to the compulsory identification markings
in

1.
referred to in Article 9(1)(a),
set out
paragraphs 2, 3, 4, 5 and 6 of this Article shall be stated.

the markings

The following shall be stated after the type designation of

2.
compound fertilisers:

(i) The chemical symbols of the declared secondary nutrients,
between brackets and after the symbols of the primary
nutrients.

(ii) Numbers indicating the primary nutrient content. The
declared secondary nutrient content shall be indicated
between brackets after the primary nutrient content.

The fertiliser type designation shall only be followed by

3.
figures indicating primary and secondary nutrient content.

the words ‘with
4. Where micro-nutrients are declared,
micro-nutrients’ or the word ‘with’ followed by the name or
names and chemical symbols of the micro-nutrients present
shall be given.

5.
The declared content of primary nutrients and secondary
nutrients shall be given as a percentage by mass, as whole
numbers or, where necessary, where an appropriate method
of analysis exists, to one decimal place.

CHAPTER II

Inorganic secondary nutrient fertilisers

Article 20

Scope

shall apply to inorganic secondary nutrient
This chapter
fertilisers, solid or fluid,
including those containing micro-
nutrients, with the minimum nutrient content established in
sections D, E.2.2, and E.2.3 of Annex I.

Article 21

Identification

In addition to the compulsory identification markings
in

1.
referred to in Article 9(1)(a),
paragraphs 2, 3, 4 and 5 of this Article shall be stated.

the markings

set out

2. Where micro-nutrients are declared,
the words ‘with
micro-nutrients’ or the word ‘with’, followed by the name or
names and chemical symbols of the micro-nutrients present,
shall be given.

3.
The declared content of secondary nutrients shall be
given as a percentage by mass, as whole numbers or, where
necessary, where an appropriate method of analysis exists, to
one decimal place.

Where more than one secondary nutrient is present, the order
shall be:

CaO and/or Ca, MgO and/or Mg, Na2O and/or Na, SO3 and/or
S.

In fertilisers containing more than one declared nutrient, the
order shall be for primary nutrients: N, P2O5 and/or P, K2O
and/or K, and for secondary nutrients: CaO and/or Ca, MgO
and/or Mg, Na2O and/or Na, SO3 and/or S.

The declared content of micro-nutrients shall give the name
and symbol of each micro-nutrient, indicating the percentage
by mass as specified in sections E.2.2 and E.2.3 of Annex I and
according to solubility.

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The forms and solubility of the nutrients shall also be
4.
expressed as a percentage by mass of fertiliser, except where
Annex I explicitly provides that this content shall be otherwise
expressed.

The number of decimal places shall be one, except for micro-
nutrients where it shall be as specified in sections E.2.2 and
E.2.3 of Annex I.

Unless otherwise stated in Annex I, a declaration of the
5.
calcium content shall only be made if it is soluble in water and
shall be expressed as a percentage of the fertiliser by mass.

CHAPTER III

Inorganic micro-nutrient fertilisers

Article 22

Scope

This chapter shall apply to inorganic micro-nutrient fertilisers,
solid or fluid, with the minimum nutrient content established
in sections E.1 and E.2.1 of Annex I.

Article 23

Identification

1.
In addition to the compulsory identification markings
referred to in Article 9(1)(a) the markings set out in paragraphs
2, 3, 4 and 5 of this Article shall be stated.

2. Where the fertiliser contains more than one micro-
the type designation ‘mixture of micro-nutrients’
nutrient,
followed by the names of
the micro-nutrients present and
their chemical symbols, shall be given.

3.
For fertilisers containing only one micro-nutrient (section
E.1 of Annex I), the declared micro-nutrient content shall be
given as a percentage by mass, in whole numbers or, where
necessary, to one decimal place.

4.
The forms and solubility of micro-nutrients shall be
expressed as a percentage by mass of fertiliser, except where
Annex I explicitly provides that this content shall be otherwise
expressed.

The number of decimal places for micro-nutrients shall be as
specified in section E.2.1 of Annex I.

5.
the
Below the compulsory or optional declarations
following shall be entered on the label and accompanying
documents with regard to the products appearing in sections
E.1 and E.2.1 of Annex I:

‘To be used only where there is a recognised need. Do not
exceed the appropriate dose rates.’

Article 24

Packaging

EC fertilisers covered by the provisions of this chapter shall be
packaged.

CHAPTER IV

Ammonium nitrate fertilisers of high nitrogen content

Article 25

Scope

For the purpose of this chapter, ammonium nitrate fertilisers of
high nitrogen content, straight or compound, are ammonium
nitrate based products manufactured for use as fertilisers and
containing more than 28 % by mass of nitrogen in relation to
ammonium nitrate.

type of

This
substances.

fertiliser may contain inorganic or

inert

The substances used in the manufacturing of
fertiliser must not
tendency to detonate.

increase its

sensitivity to heat or

this type of
its

Article 26

Safety measures and controls

1.
The manufacturer shall ensure that straight ammonium
nitrate fertilisers of high nitrogen content comply with the
provisions of section 1 of Annex III.

2.
The checking, analysis and testing for official controls of
straight ammonium nitrate fertilisers of high nitrogen content
provided for by this chapter shall be carried out in accordance
with the methods described in section 3 of Annex III.

shall maintain records of

3.
To ensure the traceability of ammonium nitrate EC
fertilisers of high nitrogen content placed on the market, the
manufacturer
the names and
addresses of the sites, and of the operators of the sites, at
components were
and its principal
which the
produced. These records shall be available for inspection by
Member States for as long as the fertiliser is being supplied
to the market, and for a further period of 2 years after the
manufacturer stopped supplying it.

fertiliser

Article 27

Test of resistance to detonation

Without prejudice to the measures referred to in Article 26, the
manufacturer shall ensure that each type of EC high nitrogen
content ammonium nitrate fertiliser placed on the market has
passed the test of resistance to detonation described in sections
2, 3 (method 1, point 3) and 4 of Annex III of this Regulation.
This test shall be carried out by one of the approved labora-
tories referred to in Article 30(1) or 33(1). Manufacturers shall
submit the results of the test to the competent authority of the
Member State concerned at least 5 days before placing the
fertiliser on the market, or at least 5 days before the arrival
of the fertiliser at the borders of the European Community in
the case of imports. Thereafter, the manufacturer shall continue
to guarantee that all supplies of the fertiliser placed on the
market are capable of passing the abovementioned test.

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Article 28

Packaging

Ammonium nitrate fertilisers of high nitrogen content shall be
made available to the final user only in packaged form.

TITLE III

CONFORMITY ASSESSMENT OF FERTILISERS

Article 29

Control measures

1. Member States may subject
fertiliser’
to official control measures
verifying that they comply with this Regulation.

fertilisers marked ‘EC
the purpose of

for

Member States may charge fees not exceeding the cost of tests
needed for such control measures, but this shall not oblige
manufacturers to repeat
tests or to pay for repeated tests
where the first test was made by a laboratory which fulfilled
the conditions of Article 30 and where the test showed
compliance of the fertiliser in question.

2. Member States shall ensure that sampling and analysis for
official controls of EC fertilisers belonging to types of fertilisers
in accordance with the
listed in Annex I are carried out
methods described in Annex III and IV.

Compliance with this Regulation in respect of conformity
3.
to types of fertiliser and compliance with the declared nutrient
content and/or the declared content expressed as forms and
solubilities of
such nutrients may be verified at official
inspections only by means of sampling and analysis methods
established in accordance with Annex III and IV and taking
into account the tolerances specified in Annex II.

The

adaptation and modernisation of measuring,
4.
sampling and analysis methods shall
follow the procedure
referred to in Article 32(2), and shall, wherever possible, use
European Standards. The same procedure shall apply to the
adoption of implementing rules needed to specify the control
measures provided for in this Article and in Articles 8, 26 and
27 of this Regulation. Such rules shall in particular address the
question of the frequency with which tests need to be repeated,
as well as measures that are designed to ensure that
the
fertiliser put on the market is identical with the fertiliser tested.

Article 30

Laboratories

1. Member States shall notify to the Commission the list of
those approved laboratories on their
that are
competent
to provide the necessary services for checking
compliance of EC fertilisers with the requirements of this Regu-

territories

lation. Such laboratories must meet the standards mentioned in
section B of Annex V. Such notification shall be made by 11
June 2004 and on the occasion of each subsequent modifi-
cation.

The Commission shall publish the list of approved labo-

2.
ratories in the Official Journal of the European Union.

for
justifiable grounds
3. Where a Member State has
believing that an approved laboratory does not meet
the
standards referred to in paragraph 1, it shall raise this matter
in the committee referred to in Article 32. If the committee
agrees that the laboratory does not meet the standards, the
Commission shall remove the name from the list referred to
in paragraph 2.

The Commission shall adopt a decision on the matter
the information in

4.
from the receipt of
within 90 days
accordance with the procedure referred to in Article 32(2).

The Commission shall publish the amended list in the

5.
Official Journal of the European Union.

TITLE IV

FINAL PROVISIONS

CHAPTER I

Adaptation of the Annexes

Article 31

New EC fertilisers

The inclusion of a new type of fertiliser in Annex I of this
1.
Regulation shall be adopted in accordance with the procedure
referred to in Article 32(2).

2.
A manufacturer or its representative which wishes to
propose a new type of fertiliser for inclusion in Annex I and
is required to compile a technical file for that purpose shall do
so by taking into account the technical documents referred to
in section A of Annex V.

3.
Amendments required to adapt the Annexes to technical
progress shall be adopted in accordance with the procedure
referred to in Article 32(2).

Article 32

Committee procedure

1.

The Commission shall be assisted by a committee.

2. Where reference is made to this paragraph, Articles 5 and
7 of Decision 1999/468/EC shall apply, having regard to the
provisions of Article 8 thereof.

The period laid down in Article 5(6) of Decision 1999/468/EC
shall be set at three months.

3.

The committee shall adopt its rules of procedure.

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CHAPTER II

Transitional provisions

Article 33

Competent laboratories

1. Without prejudice to the provisions of Article 30(1),
Member States may for a transitional period until 11
December 2007 continue to apply their national provisions
for
the
necessary services for checking compliance of EC fertilisers
with the requirements of this Regulation.

to provide

laboratories

authorising

competent

2. Member States shall notify the list of these laboratories to
the Commission, giving details of their authorisation scheme.
Such notification shall be made by 11 June 2004 and on the
occasion of each subsequent modification.

Article 34

Packaging and labelling

Notwithstanding Article
EC fertiliser markings,
35(1),
packagings, labels and accompanying documents provided for
by earlier Directives may continue to be used until 11 June
2005.

CHAPTER III

Final provisions

Article 35

Repealed Directives

Directives 76/116/EEC, 77/535/EEC, 80/876/EEC and

1.
87/94/EEC are hereby repealed.

References to the Directives repealed shall be construed
2.
as references to this Regulation. In particular, derogations from
Article 7 of Directive 76/116/EEC that were granted by the
Commission under Article 95(6) of
the Treaty shall be
construed as derogations from Article 5 of the present Regu-
lation and shall continue to produce their effects notwith-
standing the entry into force of this Regulation. Pending the
adoption of penalties under Article 36, Member States may
continue to apply penalties for
infringements of national
rules implementing the Directives mentioned in paragraph 1.

Article 36

Penalties

The Member States shall
lay down the rules on penalties
applicable to infringements of the provisions of this Regulation
and shall take all measures necessary to ensure that they are
implemented. The penalties provided for must be effective,
proportionate and dissuasive.

Article 37

National provisions

The Member States shall notify the Commission by 11 June
2005 of any national provisions adopted pursuant to Articles
6(1), 6(2), 29(1) and 36 of this Regulation, and shall notify it
without delay of any subsequent amendment affecting them.

Article 38

Entry into force

This Regulation shall enter into force on the twentieth day after
its publication in the Official Journal of the European Union with
the exception of Articles 8 and 26(3), which shall enter into
force 11 June 2005.

This Regulation shall be binding in its entirety and directly applicable in all Member States.

Done at Luxembourg, 13 October 2003.

For the European Parliament

The President

P. COX

For the Council

The President

G. ALEMANNO

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TABLE OF CONTENTS

Page

ANNEX I — List of types of EC fertilisers ......................................................................................... ..................................

15

A.

Inorganic straight primary nutrient fertilisers .............................................................................. ..................................

15

A.1. Nitrogenous fertilisers ........................................................................................................................................................ ..

15

A.2.

Phosphatic fertilisers .............................................................................. ...............................................................................

19

A.3.

Potassic fertilisers ....................................................................................................................................................... ...........

22

B.

Inorganic compound primary nutrient fertilisers ......................................................................................... ................

23

B.1. NPK fertilisers ......................................................................................... ...............................................................................

23

B.2. NP fertilisers ....................................................................................................................................................... ....................

27

B.3. NK fertilisers ....................................................................................................................................................... ....................

30

B.4.

PK fertilisers ....................................................................................................................................................... ....................

32

C.

Inorganic fluid fertilisers ........................................................................................ .............................................................

34

C.1.

Straight fluid fertilisers ................................................................................................ ........................................................

34

C.2. Compound fluid fertilisers ................................................................... ...............................................................................

36

D.

E.

Inorganic secondary nutrient fertilisers ......................................................................................... ..................................

42

Inorganic micro-nutrient fertilisers ........................................................................................ ...........................................

43

E.1.

Fertilisers containing only one micro-nutrient ................................................................... ...........................................

43

E.1.1. Boron ................................................................... ................................................................................................ ....................

43

E.1.2. Cobalt ................................................................... ................................................................................................ ....................

44

E.1.3. Copper ........................................................................................................................................................ .............................

45

E.1.4 Iron ......................................................................................... ................................................................................................ ..

46

E.1.5. Manganese ................................................................... ................................................................................................ ...........

46

E.1.6. Molybdenum ................................................................................................ ................................................................... .......

47

E.1.7. Zinc ........................................................................................ ................................................................................................ ..

48

E.2. Minimum micro-nutrient content, percentage weight of fertiliser ...........................................................................

49

E.3.

List of authorised organic chelating and complexing agents for micro-nutrients ...............................................

50

ANNEX II — Tolerances ......................................................................................... ......................................................................

51

1. Inorganic straight primary nutrient fertilisers — absolute value in percentage by mass expressed as N, P2O5,
K2O, MgO, CL ................................................................... ................................................................................................ ...........

51

2. Inorganic compound primary nutrient fertilisers .............................................................................. ..................................

52

3. Secondary nutrients in fertilisers ......................................................................................... ....................................................

52

4. Micro-nutrients in fertilisers ......................................................................................... .............................................................

52

ANNEX III — Technical provisions for Ammonium Nitrate Fertilisers of High Nitrogen Content ...............

53

1. Characteristics of and limits for straight ammonium nitrate fertilisers of high nitrogen content .........................

53

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2. Description of the test of resistance to detonation concerning ammonium nitrate fertilisers of high nitrogen
......................................................................................... ................................................................................................ ..

content

53

3. Methods of checking compliance with the limits specified in annexes III-1 and III-2 .............................................

54

4. Determination of resistance to detonation ................................................................................................ ............................

66

ANNEX IV — Methods of Sampling and Analysis .................................................................. ...........................................

73

A. Method of sampling for the control of fertilisers ............................................................................. ..................................

73

1. Purpose and scope ............................................................................. .........................................................................................

73

2. Sampling officers ................................................................................................ .................................................................. .......

73

3. Definitions ........................................................................................................................................................ .............................

73

4. Apparatus .................................................................. ................................................................................................ ....................

73

5. Quantitative requirements ....................................................................................................................................................... ..

74

6. Instructions for taking, preparing and Packaging the samples ........................................................................................

75

7. Packaging of final samples ................................................................................................ ........................................................

76

8. Sampling record ....................................................................................................................................................... ....................

76

9. Destination of samples ......................................................................................... ......................................................................

76

B. Methods for the analysis of fertilisers ......................................................................................... ...........................................

76

General observations ........................................................................................................................................................ ...........

76

General provisions relating to method of analysing fertilisers ........................................................................................

76

Method 1

— Preparation of the sample for analysis......................................................................................... .......

76

Methods 2

— Nitrogen ........................................................................................ .............................................................

78

Method 2.1

— Determination of ammoniacal nitrogen ................................................................... .........................

78

Methods 2.2

— Determination of nitric and ammoniacal nitrogen .................................................................. .......

87

Method 2.2.1

— Determination of nitric and ammoniacal nitrogen according to Ulsch ....................................

87

Method 2.2.2

— Determination of nitric and ammoniacal nitrogen according to Arnd .....................................

88

Method 2.2.3

— Determination of nitric and ammoniacal nitrogen according to Devarda ...............................

90

Method 2.3

— Determination of total nitrogen ................................................................................................ ..........

94

Method 2.3.1

— Determination of the total nitrogen in calcium cyanamide nitrate free ...................................

94

Method 2.3.2

— Determination of total nitrogen in calcium cyanamide containing nitrates ............................

95

Method 2.3.3

— Determination of total nitrogen in urea .................................................................. .........................

98

Method 2.4

— Determination of cyanamide nitrogen ........................................................................................ .......

99

Method 2.5

— Spectrophotometric determination of biuret in urea ..................................................................... 101

Methods 2.6

— Determination of different forms of nitrogen in the same sample ........................................... 104

Method 2.6.1

— Determination of different forms of nitrogen in the same sample in fertilisers containing

nitrogen as nitric, ammoniacal, urea and cyanamide nitrogen ................................................... 104

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Method 2.6.2

— Determination of different forms of nitrogen in fertilisers containing nitrogen only as nitric,

ammoniacal and urea nitrogen ............................................................................................................ 116

Methods 3

— Phosphorus ................................................................................................................................................ 122

Methods 3.1

— Extractions ................................................................................................................................................. 122

Method 3.1.1

— Extraction of phosphorus soluble in mineral acids ........................................................................ 122

Method 3.1.2

— Extraction of the phosphorus soluble in 2 % formic acid (20 g per litre)

............................. 123

Method 3.1.3

— Extraction of phosphorus soluble in 2 % citric acid (20 g per litre) ........................................ 123

Method 3.1.4

— Extraction of phosphorus which is soluble in neutral ammonium citrate .............................. 124

Method 3.1.5

— Extraction by alkaline ammonium citrate ......................................................................................... 126

Method 3.1.5.1 — Extraction of soluble phosphorus according to petermann at 65 °C ........................................ 126

Method 3.1.5.2 — Extraction of the soluble phosphorus according to Petermann at ambient temperature ..... 128

Method 3.1.5.3 — Extraction of the phosphorus soluble in joulie's alkaline ammonium citrate ......................... 129

Method 3.1.6

— Extraction of water soluble phosphorus ................................................................... ......................... 130

Method 3.2

— Eetermination of extracted phosphorus (gravimetric method using quinoline phosphomo-

lybdate) ................................................................................................ ....................................................... 131

Method 4

— Potassium ............................................................................. ...................................................................... 134

Method 4.1

— Determination of the water soluble potassium content ................................................................ 134

Method 5

— .............................................................................. ......................................................................................... 137

Method 6

— Chlorine 116 ........................................................................................ .................................................... 137

Method 6.1

— Determination of chlorides in the absence of organic material .................................................. 137

Methods 7

— Fineness of grinding .................................................................. ............................................................. 139

Method 7.1

— Determination of fineness of grinding (dry procedure) ................................................................. 139

Method 7.2

— Determination of the fineness of grinding of soft natural phosphates ..................................... 140

Method 8

— Secondary nutrients .............................................................................. .................................................... 141

Method 8.1

— Extraction of total calcium, total magnesium, total sodium and total sulphur in the form of

sulphates .............................................................................. ...................................................................... 141

Method 8.2

— Extraction of total sulphur present in various forms .................................................................... 142

Method 8.3

— Extraction of water-soluble calcium, magnesium, sodium and sulphur (in the form of

sulphates) ............................................................................. ...................................................................... 143

Method 8.4

— Extraction of water-soluble sulphur where the sulphur is in various forms ........................... 144

Method 8.5

— Extraction and determination of elemental sulphur ....................................................................... 145

Method 8.6

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

oxalate ................................................................................................ ........................................................ 147

Method 8.7

— Determination of magnesium by atomic absorption spectrometry ............................................ 148

Method 8.8

— Determination of magnesium by complexometry ................................................................... ....... 150

Method 8.9

— Determination of sulphates ................................................................................................ ................... 153

Method 8.10

— Determination of the sodium extracted ............................................................................. ................ 154

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Methods 9

— Micro-nutrients at a concentration of less than or equal to 10 % .............................................. 156

Method 9.1

— Extraction of total micro-nutrients ................................................................... .................................. 156

Method 9.2

— Extraction of water-soluble micro-nutrients .............................................................................. ....... 158

Method 9.3

— Removal of organic compounds from fertiliser extracts ............................................................... 159

Method 9.4

— Determination of micro-nutrients in fertiliser extracts by atomic absorption spectrometry

(general procedure) ........................................................................................ ........................................... 160

Method 9.5

— Determination of boron in fertiliser extracts by means of spectrometry with azomethine-H 162

Method 9.6

— Determination of cobalt in fertiliser extracts by atomic absorption spectrometry ................ 164

Method 9.7

— Determination of copper in fertiliser extracts by atomic absorption spectrometry ............... 166

Method 9.8

— Determination of iron in fertiliser extracts by atomic absorption spectrometry .................... 167

Method 9.9

— Determination of manganese in fertiliser extracts by atomic absorption spectrometry ....... 169

Method 9.10

— Determination of molybdenum in fertiliser extracts by spectrometry of a complex with

ammonium thiocyanate .............................................................................. ........................................... 171

Method 9.11

— Determination of zinc in fertiliser extracts by atomic absorption spectrometry .................... 173

Methods 10

— Micro-nutrients at a concentration greater than 10 % .................................................................. 175

Method 10.1

— Extraction of total micro-nutrients .............................................................................. ......................... 175

Method 10.2

— Extraction of water-soluble micro-nutrients .............................................................................. ....... 176

Method 10.3

— Removal of organic compounds from fertiliser extracts ............................................................... 178

Method 10.4

— Determination of micro-nutrients in fertiliser extracts by atomic absorption spectrometry

(general procedure) .............................................................................. .................................................... 179

Method 10.5

— Determination of boron in fertiliser extracts by means of acidimetric titration .................... 181

Method 10.6

— Determination of cobalt in fertiliser extracts by the gravimetric method with 1-nitroso-

2-naphthol ................................................................................................................................................. 183

Method 10.7

— Determination of copper in fertiliser extracts by the titrimetric method ................................. 184

Method 10.8

— Determination of iron in fertiliser extracts by atomic absorption spectrometry .................... 186

Method 10.9

— Determination of manganese in fertiliser extracts by titration .................................................... 188

Method 10.10

— Determination of molybdenum in fertiliser extracts by the gravimetric method with

8-hydroxyquinoline ............................................................................. .................................................... 190

Method 10.11

— Determination of zinc in fertiliser extracts by atomic absorption spectrometry .................... 191

ANNEX V ................................................................................................ ................................................................... ......................... 194

A. List of documents to be consulted by manufacturers or their representatives in order to compile a technical file

for a new type of fertilisers to be added to annex I of this regulation.................................................................. ....... 194

B. Standards of accreditation concerning the laboratories that are competent and authorised to provide the
necessary service for checking compliance of EC fertilisers with the requirements of this regulation and its
annexes ......................................................................................... ................................................................................................ .. 194

A.

Inorganic straight primary nutrient fertilisers

A.1. Nitrogenous fertilisers

ANNEX I

LIST OF TYPES OF EC FERTILISERS

No

Type designation

Data on method of production and
essential ingredients

Minimum content of nutrients
(percentage by weight)
Data on the expression of nutrients
Other requirements

Other data on the type designation

Nutrient content to be declared
Forms and solubilities of the nutrients
Other criteria

2

3

4

5

6

1

1(a)

1(b)

Calcium nitrate
lime)

(nitrate

of

Calcium magnesium nitrate
and
(nitrate
magnesium)

lime

of

obtained
calcium nitrate

Chemically
containing
essential
ammonium nitrate

ingredient

and

product
its
as
possibly

15 % N
Nitrogen expressed as total nitrogen
ammoniacal
or
of
nitrogen. Maximum content
ammoniacal nitrogen: 1,5 % N

nitric

and

as

obtained

Chemically
containing
magnesium nitrate
ingredients

as

calcium nitrate

product
and
essential

1(c)

Magnesium nitrate

Chemically
containing as its essential
hexahydrated magnesium nitrate

obtained

product
ingredient

13 % N
Nitrogen expressed as nitric nitrogen.
Minimum content of magnesium in
the
salts
form of water-soluble
expressed as magnesium oxide: 5 %
MgO

10 % N
Nitrogen expressed as nitric nitrogen

14 % MgO
Magnesium expressed as water-soluble
magnesium oxide

2(a)

Sodium nitrate (nitrate of soda) Chemically
containing
essential ingredient

obtained
sodium nitrate

product
its
as

15 % N
Nitrogen expressed as nitric nitrogen

2(b)

Chile nitrate

3(a)

Calcium cyanamide

prepared

Product
containing
essential ingredient

sodium nitrate

from caliche,
its

as

obtained

Chemically
product
containing calcium cyanamide as its
calcium oxide
essential
and
of
quantities
ammonium salts and urea

ingredient,
small

possibly

15 % N
Nitrogen expressed as nitric nitrogen

18 % N
Nitrogen expressed as total nitrogen,
at least 75 % of the nitrogen declared
being bound in the form of cyanamide

Total nitrogen

Additional optional particulars:

Nitric nitrogen

Ammoniacal nitrogen

Nitric nitrogen

Water-soluble magnesium oxide

When marketed in the form of crystals
as note ‘in crystallised form’ may be
added

Nitric nitrogen

Water-soluble magnesium oxide

Nitric nitrogen

Nitric nitrogen

Total nitrogen

.

2
1
1
1
2
0
0
3

.

E
N

O

f
f
i
c
i
a
l

J
o
u
r
n
a
l

o
f

t
h
e

E
u
r
o
p
e
a
n
U
n
o
n

i

L

3
0
4
/
1
5

2

3

4

5

6

1

3(b)

4

5

Nitrogenous
mide

calcium cyana-

obtained

Chemically
product
containing calcium cyanamide as its
essential
calcium
oxide and possibly small quantities of
ammonium salts and urea, plus added
nitrate

ingredient,

and

least 75 % of

18 % N
Nitrogen expressed as total nitrogen,
at
the non-nitric
nitrogen declared being bound in the
form of cyanamide. Nitric nitrogen
content:
— minimum: 1 % N
— maximum: 3 % N

Sulphate of ammonia

Chemically
product
containing ammonium sulphate as its
essential ingredient

obtained

20 % N
Nitrogen expressed as
nitrogen

ammoniacal

Ammonium nitrate or calcium
ammonium nitrate

obtained

Chemically
product
containing ammonium nitrate as its
ingredient, which may
essential
ground
fillers
contain
limestone, calcium sulphate, ground
dolomite,
sulphate,
magnesium
kieserite

such

as

20 % N
Nitrogen expressed as nitric nitrogen
and ammoniacal nitrogen, each of
nitrogen
forms
these
accounting
the
for
nitrogen present.
See Annexes III.1 and III.2 of
regulation, if required.

about

two

half

this

of

6

Ammonium sulphate-nitrate

product
Chemically
containing
ingredients
ammonium nitrate and ammonium
sulphate

obtained
essential

as

25 % N
Nitrogen expressed as
ammoniacal
and nitric nitrogen. Minimum nitric
nitrogen content: 5 %

7

Magnesium sulphonitrate

obtained
ammonium

product
Chemically
containing
nitrate,
ammonium sulphate and magnesium
sulphate as essential ingredients

19 % N
Nitrogen expressed as
ammoniacal
and nitric nitrogen. Minimum nitric
nitrogen content: 6 % N

(for

only

instance

containing

The designation ‘calcium ammonium
is exclusively reserved for a
nitrate’
calcium
fertiliser
limestone)
carbonate
and/or magnesium carbonate
and
calcium carbonate
instance
(for
dolomite)
in addition to ammonium
nitrate. The minimum content of
these carbonates must be 20 % and
their purity level at least 90 %

Total nitrogen

Nitric nitrogen

Ammoniacal nitrogen

Total nitrogen

Nitric nitrogen

Ammoniacal nitrogen

Total nitrogen

Ammoniacal nitrogen

Nitric nitrogen

Total nitrogen

Ammoniacal nitrogen

8

Magnesium ammonium nitrate Chemically

obtained

product
containing ammonium nitrates and
magnesium compound salts (dolomite
and/or
magnesium
magnesium sulphate)
essential
ingredients

carbonate
as

5 % MgO
Magnesium in the form of water-
soluble salts expressed as magnesium
oxide

19 % N
Nitrogen expressed as
ammoniacal
nitrogen.
nitric
nitrogen
Minimum nitric nitrogen content 6 %
N

and

5 % MgO
Magnesium expressed
magnesium oxide

as

total

Nitric nitrogen

Water-soluble magnesium oxide

Total nitrogen

Ammoniacal nitrogen

Nitric nitrogen

Total magnesium oxide and possibly,
water-soluble magnesium oxide

L

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E
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O

f
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a
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2

3

4

5

6

9

Urea

Chemically
containing
(carbamide) as its essential

obtained
carbonyl

product
diamide
ingredient

44 % N
Total ureic nitrogen (including biuret).
Maximum biuret content: 1,2 %

10

Crotonylidene diurea

Product obtained by reaction of urea
with crotonaldehyde

28 % N
Nitrogen expressed as total nitrogen

Monomeric compound

least 25 % N from the croto-

At
nylidene diurea

Maximum ureic nitrogen content: 3 %

11

Isobutylidene diurea

Product obtained by reaction of urea
with
isobutyraldehyde Monomeric
compound

Monomeric compound

28 % N
Nitrogen expressed as total nitrogen

least 25 % N from isobutylidene

At
diurea

Maximum ureic nitrogen content: 3 %

12

Urea formaldehyde

Product obtained by reaction of urea
with formaldehyde and containing as
its essential
ingredients molecules of
urea formaldehyde

Polymeric compound

13

Nitrogenous fertiliser contain-
ing crotonylidene diurea

obtained

chemically
Product
containing crotonylidene diurea and
a straight nitrogen fertiliser [List A-1,
excluding products 3(a), 3(b) and 5]

36 % N total nitrogen
Nitrogen expressed as total nitrogen

least 3/5 of

the declared total
At
nitrogen content must be soluble in
hot water

least 31 % N from urea formal-

At
dehyde

Maximum ureic nitrogen content: 5 %

18 % N expressed as total nitrogen

At least 3 % nitrogen in ammoniacal
and/or nitric and/or ureic form

least 1/3 of

At
the declared total
nitrogen content must be derived
from crotonylidene diurea

Maximum biuret content:

(ureic
N) × 0,026

N + crotonylidene

diurea

Total nitrogen,
nitrogen

expressed as ureic

Total nitrogen

Ureic nitrogen where this is at least 1 %
by weight

Nitrogen from crotonylidene diurea

Total nitrogen

Ureic nitrogen where this is at least 1 %
by weight

Nitrogen from isobutylidene diurea

Total nitrogen

Ureic nitrogen where this is at least 1 %
by weight

Nitrogen from formaldehyde urea that
is soluble in cold water

Nitrogen from formaldehyde urea that
is only soluble in hot water

Total nitrogen

For each form amounting to at least
1 %:

— nitric nitrogen

— ammoniacal nitrogen

— ureic nitrogen

Nitrogen from crotonylidene diurea

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14

Nitrogenous fertiliser contain-
ing isobutylidene diurea

obtained

Product
chemically
containing isobutylidene diurea and a
straight nitrogenous fertiliser [List A-1,
excluding products 3(a), 3(b) and 5]

18 % N expressed as total nitrogen

At least 3 % nitrogen in ammoniacal
and/or nitric and/or ureic form

A least 1/3 of
the declared total
nitrogen content must derive from
isobutylidene diurea

Maximum biuret content:

(Ureic N + isobutylidene diurea N) ×
0,026

18 % N expressed as total nitrogen

At least 3 % nitrogen in ammoniacal
and/or nitric and/or ureic form

least 1/3 of

At
the declared total
nitrogen content must derive from
urea formaldehyde

The nitrogen from the urea formal-
dehyde must contain at
least 3/5
nitrogen that is soluble in hot water

Maximum biuret content:

(Ureic N + urea formaldehyde) ×
0,026

20 % N
Nitrogen expressed as total nitrogen

Minimum
content: 18 %

ammoniacal

nitrogen

Minimum content of nitrogen from
dicyandiamide: 1,5 %

24 % N
Nitrogen expressed as total nitrogen

Minimum nitric nitrogen content: 3 %

Minimum content of nitrogen from
dicyandiamide: 1,5 %

Total nitrogen

For each form amounting to at least
1 %:

— nitric nitrogen

— ammoniacal nitrogen

— ureic nitrogen

Nitrogen from isobutylidene diurea

Total nitrogen

For each form amounting to at least
1 %:

— nitric nitrogen

— ammoniacal nitrogen

— ureic nitrogen

Nitrogen from urea formaldehyde

Nitrogen from urea formaldehyde that
is soluble in cold water

Nitrogen from urea formaldehyde that
is only soluble in hot water

Total nitrogen

Ammoniacal nitrogen

Nitrogen from dicyandiamide

Technical information (a)

Total nitrogen

Nitric nitrogen

Ammoniacal nitrogen

Nitrogen from dicyandiamide

Technical information (a)

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.

15

Nitrogenous fertiliser contain-
ing urea formaldehyde

obtained

Product
chemically
containing urea formaldehyde and a
straight nitrogenous
[List
A-1, excluding products 3(a), 3(b)
and 5]

fertiliser

16

Ammonium sulphate with
nitrification inhibitor (dicyan-
diamide)

product
Chemically
containing ammonium sulphate and
dicyandiamide

obtained

17

Ammonium sulphonitrate with
nitrification inhibitor (dicyan-
diamide)

product
Chemically
containing ammonium sulphonitrate
and dicyandiamide

obtained

1

2

3

4

5

6

18

Urea-ammonium sulphate

Product obtained chemically from urea
and ammonium sulphate

30 % N
Nitrogen expressed as
and ureic nitrogen

ammoniacal

Minimum
content: 4 %

ammoniacal

nitrogen

Minimum sulphur content expressed
as sulphur trioxide: 12 %

Maximum biuret content: 0,9 %

Total nitrogen

Ammoniacal nitrogen

Ureic nitrogen

Water-soluble sulphur trioxide

(a) Technical information as complete as possible must be provided with each package or bulk consignment by the person responsible for marketing. This information must in particular enable the user to determine the rates and timing

of application in relation to the crop being grown.

A.2. Phosphatic fertilisers

Where a particle size criterion is prescribed for the basic constituent materials of fertilisers sold in granular form (fertilisers 1, 3, 4, 5, 6 and 7), it will be established by an appropriate analytical method.

No

1

Type designation

Data on method of production and
essential ingredients

Minimum content of nutrients
(percentage by weight)
Data on the expression of nutrients
Other requirements

Other data on the type designation

Nutrient content to be declared
Forms and solubilities of the nutrients
Other criteria

2

3

4

5

6

1

Basic slag:

— Thomas phosphates

— Thomas slag

Product obtained in iron-smelting by
treatment of
the phosphorus melts
and containing calcium silicophos-
phates as its essential ingredients

12 % P2O5
Phosphorus expressed as phosphorus
pentoxide soluble in mineral acids, at
least 75 % of the declared content of
phosphorus pentoxide being soluble in
2 % citric acid

or P2O5

Phosphorus expressed as phosphorus
pentoxide soluble in 2 % citric acid

Particle size:
— at least 75 % able to pass through
a sieve with a mesh of 0,160 mm
— at least 96 % able to pass through
a sieve with a mesh of 0,630 mm

Total phosphorus pentoxide (soluble in
mineral acids) 75 % of which (to be
indicated as % by weight) is soluble in
2 % citric acid (for marketing in France,
Italy, Spain, Portugal and Greece)

Total phosphorus pentoxide (soluble in
mineral
phosphorus
pentoxide soluble in 2 % citric acid
(for marketing in the United Kingdom)

acids)

and

Phosphorus pentoxide soluble in 2 %
citric acid (for marketing in Germany,
Ireland,
Denmark,
Belgium,
Luxembourg,
and
the Netherlands
Austria)

.

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1

2

3

4

5

6

2(a)

Single superphosphate

2(b)

Concentrated superphosphate

Product obtained
by
reaction of
phosphate with
ground mineral
sulphuric acid and containing mono-
calcium phosphate as an essential
ingredient as well as calcium sulphate

16 % P2O5
Phosphorus expressed as P2O5 soluble
in neutral ammonium citrate, at least
93 % of the declared content of P2O5
being water-soluble

Test sample: 1 g

by
reaction of
Product obtained
ground mineral
phosphate with
sulphuric acid and phosphoric acid
monocalcium
containing
and
phosphate as an essential
ingredient
as well as calcium sulphate

25 % P2O5
Phosphorus expressed as P2O5 soluble
in neutral ammonium citrate, at least
93 % of the declared content of P2O5
being water-soluble

Test sample: 1 g

2(c)

Triple superphosphate

3

Partially
phosphate

solubilised

rock

by

Product obtained
reaction of
ground mineral phosphate with phos-
phoric acid and containing mono-
calcium phosphate as
essential
ingredient

its

Product obtained by partial solubili-
sation of ground rock phosphate
with sulphuric acid or phosphoric
acid
essential
ingredients monocalcium phosphate,
tricalcium phosphate
and calcium
sulphate

containing

and

as

4

Dicalcium phosphate

Product obtained by precipitation of
solubilised
from
phosphoric
mineral phosphates or bones, and
phosphate
dicalcium
containing
dihydrate as its essential ingredient

acid

38 % P2O5
Phosphorus expressed as P2O5 soluble
in neutral ammonium citrate, at least
93 % of the declared content of P2O5
being water-soluble

Test sample: 3 g

20 % P2O5
Phosphorus expressed as P2O5 soluble
in mineral acids, at least 40 % of the
declared content of P2O5 being water-
soluble

Particle size:

— at least 90 % able to pass through
a sieve with a mesh of 0,160 mm

— at least 98 % able to pass through
a sieve with a mesh of 0,630 mm

38 % P2O5
Phosphorus expressed as P2O5 soluble
in
ammonium citrate
(Petermann)

alkaline

Particle size:

— at least 90 % able to pass through
a sieve with a mesh of 0,160 mm

— at least 98 % able to pass through
a sieve with a mesh of 0,630 mm

Phosphorus
neutral ammonium citrate

pentoxide

soluble

in

Water-soluble phosphorus pentoxide

Phosphorus
neutral ammonium citrate

pentoxide

soluble

in

Water-soluble phosphorus pentoxide

Phosphorus
neutral ammonium citrate

pentoxide

soluble

in

Water-soluble phosphorus pentoxide

Total phosphorus pentoxide (soluble in
mineral acids)

Phosphorus pentoxide soluble in water

Phosphorus
alkaline ammonium citrate

pentoxide

soluble

in

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5

Calcined phosphate

Product obtained by heat treatment of
ground rock phosphate with alkaline
and
compounds
calcium
containing
phosphate
as
essential ingredients

and calcium silicate

silicic
alkaline

acid,

and

25 % P2O5
Phosphorus expressed as P2O5 soluble
in
ammonium citrate
(Petermann)

alkaline

Particle size:

— at least 75 % able to pass through
a sieve with a mesh of 0,160 mm

— at least 96 % able to pass through
a sieve with a mesh of 0,630 mm

30 % P2O5
Phosphorus expressed as P2O5 soluble
in mineral acids, at least 75 % of the
declared content of P2O5 being soluble
in alkaline ammonium citrate (Joulie)

Particle size:

— at least 90 % able to pass through
a sieve with a mesh of 0,160 mm

— at least 98 % able to pass through
a sieve with a mesh of 0,630 mm

6

Aluminium-calcium phosphate

Product obtained in amorphous form
by heat
grinding,
containing aluminium and calcium
phosphates as essential ingredients

treatment

and

7

Soft ground rock phosphate

Product obtained by grinding soft
mineral phosphates and containing
and calcium
tricalcium phosphate
carbonate as essential ingredients

25 % P2O5
Phosphorus expressed as P2O5 soluble
in mineral acids, at least 55 % of the
declared content of P2O5 being soluble
in 2 % formic acid

Particle size:

— at least 90 % able to pass through
a sieve with a mesh of 0,063 mm

— at least 99 % able to pass through
a sieve with a mesh of 0,125 mm

Phosphorus
alkaline ammonium citrate

pentoxide

soluble

in

Total phosphorus pentoxide (soluble in
mineral acids)

Phosphorus
alkaline ammonium citrate

pentoxide

soluble

in

Total phosphorus pentoxide (soluble in
mineral acids)

Phosphorus pentoxide soluble in 2 %
formic acid

Percentage by weight of material able to
pass through a sieve with a mesh of
0,063 mm

.

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A.3. Potassic fertilisers

No

1

1

Kainit

2

Enriched kainit salt

3

Muriate of potash

4

Potassium chloride containing
magnesium salts

Type designation

Data on method of production and
essential ingredients

Minimum content of nutrients
(percentage by weight)
Data on the expression of nutrients
Other requirements

Other data on the type designation

Nutrient content to be declared
Forms and solubilities of the nutrients
Other criteria

2

3

4

5

6

Product
potassium salts

obtained

from

crude

obtained

Product
crude
potassium salts enriched by blending
with potassium chloride

from

obtained

Product
and
potassium salts
potassium chloride as
ingredient

from

crude
containing
its essential

from
with

crude
obtained
Product
added
potassium
salts
magnesium salts
containing
potassium chloride and magnesium
salts as essential ingredients

and

Usual trade names may be added

Water-soluble potassium oxide

Water-soluble magnesium oxide

Usual trade names may be added

Water-soluble potassium oxide

Optional mention of the water-soluble
magnesium oxide content where higher
than 5 % MgO

Usual trade names may be added

Water-soluble potassium oxide

Water-soluble potassium oxide

Water-soluble magnesium oxide

10 % K2O
Potassium expressed as water-soluble
K2O

5 % MgO
Magnesium in the form of water-
soluble salts, expressed as magnesium
oxide

18 % K2O
Potassium expressed as water-soluble
K2O

37 % K2O
Potassium expressed as water-soluble
K2O

37 % K2O
Potassium expressed as water-soluble
K2O

5 % MgO
Magnesium in the form of water-
soluble salts, expressed as magnesium
oxide

5

Sulphate of potash

Product obtained chemically
potassium salts
and
potassium sulphate as
ingredient

from
containing
its essential

47 % K2O
Potassium expressed as water-soluble
K2O
Maximum chloride content: 3 % Cl

Water-soluble potassium oxide

Optional mention of
content

the

chloride

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3

4

5

6

1

6

Sulphate of potash containing
magnesium salt

from
Product obtained chemically
with
possibly
potassium salts,
addition of magnesium salts,
and
containing potassium sulphate and
magnesium sulphate
essential
ingredients

as

7

Kieserite
sulphate

with

potassium

Product obtained from Kieserite with
potassium sulphate added

Usual trade names may be added

Water-soluble potassium oxide

Water-soluble magnesium oxide

Optional mention of
content

the

chloride

Usual trade names may be added

Water-soluble magnesium oxide

Water-soluble potassium oxide

Optional mention of
content

the

chloride

22 % K2O
Potassium expressed as water-soluble
K2O

8 % MgO
Magnesium in the form of water-
soluble salts, expressed as magnesium
oxide

Maximum chloride content: 3 % Cl

8 % MgO
Magnesium expressed as water-soluble
MgO

6 % K2O
Potassium expressed as water-soluble
K2O
Total MgO + K2O: 20 %
Maximum chloride content: 3 % Cl

B.

Inorganic compound primary nutrient fertilisers

B.1. NPK fertilisers

Type designation:

NPK fertilisers.

Data on method of production:

B.1.1.

Product obtained chemically or by blending, without addition of organic nutrients of animal or vegetable origin.

Minimum content of nutrients (percentage by weight):

— Total: 20 % (N + P2O5 + K2O);

— For each of the nutrients: 3 % N, 5 % P2O5, 5 % K2O.

.

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Forms, solubilities and nutrient content to be declared as specified in columns 4, 5 and 6
Particle size

Data for identification of the fertilisers
Other requirements

N

1

P2O5

2

K2O

3

N

4

P2O5

5

(1) Total nitrogen

(1) Water-soluble P2O5

Water soluble K2O

(1) Total nitrogen

(2) Nitric nitrogen

(2) P2O5 soluble in neutral ammonium citrate

(3) Ammoniacal
nitrogen

(3) P2O5 soluble in neutral ammonium citrate

and in water

(4) Ureic nitrogen

(4) P2O5 soluble in mineral acids only

(5) Cyanamide nitrogen

(5) P2O5 soluble in alkaline ammonium citrate

(Petermann)

(2) If any of the forms
of nitrogen (2)
to
(5) amounts to at
1 %
least
by
weight,
it must be
declared

(3) If above 28 %, see

Annex III.2

(6a) P2O5 soluble in mineral acids, of which at
least 75 % of the declared P2O5 content is
soluble in 2 % citric acid

(6b) P2O5 soluble in 2 % citric acid

(7) P2O5 soluble in mineral acids, of which at
least 75 % of the declared P2O5 content is
soluble in alkaline ammonium citrate (Joulie)

(8) P2O5 soluble in mineral acids, of which at
least 55 % of the declared P2O5 content is
soluble in 2 % formic acid

1. An NPK fertiliser

free from Thomas

phosphate,
partially

slag,
aluminium-calcium
calcined
rock
solubilised
phosphate,
phosphate and soft ground rock phosphate
must be declared in accordance with solu-
bilities (1), (2) or (3):

— when the water-soluble P2O5 does not
to 2 %, solubility (2) only shall

amount
be declared;

— when the water-soluble P2O5 is at

least
2 %, solubility (3) shall be declared, and
the water-soluble P2O5 content must be
indicated [solubility (1)].

The P2O5 content soluble in mineral acids only
must not exceed 2 %.

For this type 1, the test sample for determining
solubilities (2) and (3) shall be 1 g.

phosphate must

2 (a) An NPK fertiliser containing soft ground
rock phosphate or partially solubilised
from
rock
and
Thomas
aluminium-calcium phosphate.
It shall be
declared in accordance with solubilities (1),
(3) and (4)

calcined phosphate

slag,

free

be

This type of fertiliser must contain:

— at least 2 % P2O5 soluble in mineral

acids only [solubility (4)];

— at least 5 % P2O5 soluble in water and
neutral ammonium citrate [solubility
(3)];

— at least 2,5 % water-soluble P2O5 [solu-

bility (1)].

This type of fertiliser must be marketed under the
designation ‘NPK fertiliser containing soft ground
‘NPK fertiliser containing
rock phosphate’ or
partially solubilised rock phosphate’. For
this
type 2(a), the test sample for determining solu-
bility (3) shall be 3 g.

K2O

6

(1) Water-soluble

potassium oxide

(2) The indication ‘low
is
in
linked
a
maximum content
of 2 % Cl

chloride’
to

(3) Chloride

content

may be declared

L

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2

3

4

5

6

Particle size of the basic phosphatic ingredients

Thomas slag:

at least 75 % able to pass through a sieve with a mesh of 0,160 mm

Aluminium-calcium phosphate: at least 90 % able to pass through a sieve with a mesh of 0,160 mm

Calcined phosphate:

at least 75 % able to pass through a sieve with a mesh of 0,160 mm

Soft ground rock phosphate:

at least 90 % able to pass through a sieve with a mesh of 0,063 mm

Partially solubilised rock
phosphate:

at least 90 % able to pass through a sieve with a mesh of 0,160 mm

2 (b) An NPK fertiliser containing aluminium-
from
calcium phosphate must be
soft
Thomas
ground rock phosphate and partially solu-
bilised rock phosphate.

free
calcined phosphate,

slag,

It shall be declared in accordance with solubilities
(1) and (7), the latter applying after deduction of
the solubility in water.

This type of fertiliser must contain:

— at least 2 % of water-soluble P2O5 [solubility

(1)];

— at least 5 % of P2O5 according to solubility (7).

This type of fertiliser must be marketed under the
designation ‘NPK fertiliser containing aluminium-
calcium phosphate’.

3.

In the case of NPK fertilisers containing only
one of
the following types of phosphatic
fertiliser: Thomas slag, calcined phosphate,
aluminium-calcium phosphate,
soft ground
the type designation must
rock phosphate,
be
the
indication
followed
phosphate ingredient.

by

an

of

The declaration of the solubility of the P2O5 must
be given in accordance with the following solu-
bilities:

— for fertilisers based on Thomas slag: solubility
Italy, Spain, Portugal, Greece),
(6a)
(6b)
Ireland,
Luxembourg, Netherlands, United Kingdom
and Austria);

(France,
(Germany, Belgium, Denmark,

— for fertilisers based on calcined phosphate:

solubility (5);

— for

fertilisers based on aluminium-calcium

phosphate: solubility (7);

— for

fertilisers based on soft ground rock

phosphate: solubility (8).

.

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u
r
o
p
e
a
n
U
n
o
n

i

L

3
0
4
/
2
5

B.1. NPK fertilisers (cont’d)

Type designation:

Data on method of production:

NPK fertiliser containing crotonylidene diurea or isobutylidene diurea or urea formaldehyde (as appropriate).

Product obtained chemically without addition of organic nutrients of animal or vegetable origin and containing crotonylidene diurea or
isobutylidene diurea or urea formaldehyde.

Minimum content of nutrients (percentage by weight):

B.1.2.

— Total: 20 % (N + P2O5 + K2O);

— For each of the nutrients:

— 5 % N. At least ¼ of the declared content of total nitrogen must derive from nitrogen form (5) or (6) or (7). At least 3/5 of the

declared nitrogen content (7) must be soluble in hot water,

— 5 % P2O5,

— 5 % K2O.

Forms, solubilities and nutrient content to be declared as specified in columns 4, 5 and 6
Particle size

Data for identification of the fertilisers
Other requirements

P2O5

2

K2O

3

N

4

P2O5

5

(1) Water-soluble P2O5
(2) P2O5 soluble in neutral ammonium citrate
(3) P2O5 soluble in neutral ammonium citrate

and in water

Water-soluble K2O

(1) Total nitrogen

(2) If any of the forms
of nitrogen (2)
to
(4) amounts to at
1 %
least
by
it must be
weight,
declared

(3) One of

the forms
of nitrogen (5)
to
(7) (as appropriate).
Nitrogen form (7)
must be declared
in
form of
nitrogen (8) and (9)

the

An NPK fertiliser free from Thomas slag, calcined
phosphate,
phosphate,
aluminium-calcium
partially solubilised rock phosphate and rock
phosphate must be declared in accordance with
solubilities (1), (2) or (3):
— when the water-soluble P2O5 does not amount
to 2 %, solubility (2) only shall be declared,
— when the water-soluble P2O5 is at least 2 %,
solubility (3) shall be declared, and the water-
soluble P2O5 content must be indicated [solu-
bility (1)].

The P2O5 content soluble in mineral acids only
must not exceed 2 %.

The test sample for determining solubilities (2)
and (3) shall be 1 g.

K2O

6

(1) Water-soluble

potassium oxide

(2) The indication ‘low
is
in
linked
a
maximum content
of 2 % Cl

chloride’
to

(3) Chloride

content

may be declared

N

1

(1) Total nitrogen

(2) Nitric nitrogen

(3) Ammoniacal
nitrogen

(4) Ureic nitrogen

(5) Nitrogen

from
crotonylidene diurea

(6) Nitrogen

from
isobutylidene diurea

(7) Nitrogen from urea

formaldehyde

(8) Nitrogen from urea
formaldehyde
that
is only soluble in
hot water

(9) Nitrogen from urea
that
soluble in cold

formaldehyde
is
water

L

3
0
4
/
2
6

E
N

O

f
f
i
c
i
a
l

J
o
u
r
n
a
l

o
f

t
h
e

E
u
r
o
p
e
a
n
U
n
o
n

i

.

2
1
1
1
2
0
0
3

.

B.2. NP fertilisers

Type designation:

Data on method of production:

B.2.1.

NP fertilisers.

Product obtained chemically or by blending without addition of organic nutrients of animal or vegetable origin.

Minimum content of nutrients (percentage by weight):

— Total: 18 % (N + P2O5);

— For each of the nutrients: 3 % N, 5 % P2O5.

Forms, solubilities and nutrient content to be declared as specified in columns 4, 5 and 6
Particle size

Data for identification of the fertilisers
Other requirements

N

1

(1) Total nitrogen

(2) Nitric nitrogen

(3) Ammoniacal
nitrogen

(4) Ureic nitrogen

(5) Cyanamide nitrogen

P2O5

2

K2O

3

N

4

P2O5

5

K2O

6

(1) Total nitrogen

(2) If any of the forms
of nitrogen (2)
to
(5) amounts to at
by
1 %
least
weight,
it must be
declared

(1) Water-soluble P2O5
(2) P2O5 soluble in neutral ammonium citrate
(3) P2O5 soluble in neutral ammonium citrate

and in water

(4) P2O5 soluble in mineral acids only
(5) P2O5 soluble in alkaline ammonium citrate

(Petermann)

(6a) P2O5 soluble in mineral acids, of which at
least 75 % of the declared P2O5 content is
soluble in 2 % citric acid

(6b) P2O5 soluble in 2 % citric acid

(7) P2O5 soluble in mineral acids of which at
least 75 % of the declared P2O5 content is
soluble in alkaline ammonium citrate (Joulie)

(8) P2O5 soluble in mineral acids of which at
least 55 % of the declared P2O5 content is
soluble in 2 % formic acid

1. An NP fertiliser

from Thomas

free
phosphate,
partially

slag,
aluminium-calcium
calcined
phosphate,
rock
solubilised
phosphate and soft ground rock phosphate
must be declared in accordance with solu-
bilities (1), (2) or (3):
— when the water-soluble P2O5 does not
to 2 %, solubility (2) only shall

amount
be declared;

— when the water-soluble P2O5 is at

least
2 %, solubility (3) shall be declared, and
the water-soluble P2O5 content must be
indicated [solubility (1)].

The P2O5 content soluble in mineral acids only
must not exceed 2 %.

For this type 1, the test sample for determining
solubilities (2) and (3) shall be 1 g.

2 (a) A NP fertiliser containing soft ground rock
phosphate or partially solubilised rock
phosphate must be free from Thomas slag,
calcined phosphate and aluminium-calcium
phosphate.

It shall be declared in accordance with solubilities
(1), (3) and (4).

This type of fertiliser must contain:

— at least 2 % P2O5 soluble in mineral acids only

[solubility (4)];

— at least 5 % P2O5 soluble in water and neutral

ammonium citrate [solubility (3];

.

2
1
1
1
2
0
0
3

.

E
N

O

f
f
i
c
i
a
l

J
o
u
r
n
a
l

o
f

t
h
e

E
u
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o
p
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a
n
U
n
o
n

i

L

3
0
4
/
2
7

1

2

3

4

5

6

— at least 2,5 % water soluble P2O5 [solubility

(1)].

This type of fertiliser must be marketed under the
designation ‘NP fertiliser containing soft ground
rock phosphate’ or
containing
‘NP fertiliser
partially solubilised rock phosphate’.

For this type 2(a), the test sample for determining
solubility (3) shall be 3 g.

Particle size of the basic phosphatic ingredients:

Thomas slag

at least 75 % able to pass through a sieve with a mesh of 0,160 mm

Aluminium-calcium phosphate

at least 90 % able to pass through a sieve with a mesh of 0,160 mm

Calcined phosphate

at least 75 % able to pass through a sieve with a mesh of 0,160 mm

Soft ground rock phosphate

at least 90 % able to pass through a sieve with a mesh of 0,063 mm

Partially solubilised rock
phosphate

at least 90 % able to pass through a sieve with a mesh of 0,160 mm

2 (b) A NP

fertiliser

containing

aluminium-
calcium phosphate, must be free from
Thomas
soft
ground rock phosphate and partially solu-
bilised rock phosphate.

calcined phosphate,

slag,

It shall be declared in accordance with solubilities
(1) and (7), the latter applying after deduction of
the solubility in water.

This type of fertiliser must contain:

— at least 2 % water-soluble P2O5 [solubility (1)];
— at least 5 % P2O5 according to solubility (7).

This type of fertiliser must be marketed under the
designation ‘NP fertiliser containing aluminium-
calcium phosphate’.

3.

In the case of NP fertilisers containing only
the following types of phosphatic
one of
fertiliser: Thomas slag, calcined phosphate,
aluminium-calcium phosphate,
soft ground
the type designation must
rock phosphate,
be
the
indication
followed
phosphate ingredient.

by

an

of

The declaration of the solubility of the P2O5 must
be given in accordance with the following solu-
bilities:

— for fertilisers based on Thomas slag: solubility
Italy, Spain, Portugal, Greece),
(6a)
(6b)
Ireland,
Luxembourg, Netherlands, United Kingdom
and Austria);

(France,
(Germany, Belgium, Denmark,

L

3
0
4
/
2
8

E
N

O

f
f
i
c
i
a
l

J
o
u
r
n
a
l

o
f

t
h
e

E
u
r
o
p
e
a
n
U
n
o
n

i

.

2
1
1
1
2
0
0
3

.

1

2

3

4

5

6

— for fertilisers based on calcined phosphate:

solubility (5);

— for

fertilisers based on aluminium-calcium

phosphate: solubility (7);

— for

fertilisers based on soft ground rock

phosphate: solubility (8).

B.2. NP fertilisers (cont’d)

Type designation:

Data on method of production:

NP fertiliser containing crotonylidene diurea or isobutylidene diurea or urea formaldehyde (as appropriate)

Product obtained chemically without addition of organic nutrients of animal or vegetable origin and containing crotonylidene diurea or
isobutylidene diurea or urea formaldehyde

Minimum content of nutrients (percentage by weight):

B.2.2.

— Total: 18 % (N + P2O5);

— For each of the nutrients:

— 5 % N.

At least ¼ of the declared content of total nitrogen must derive from nitrogen form (5) or (6) or (7).

At least 3/5 of the declared nitrogen content (7) must be soluble in hot water,

— 5 % P2O5.

Forms, solubilities and nutrient content to be declared as specified in columns 4, 5 and 6
Particle size

Data for identification of the fertilisers
Other requirements

N

1

P2O5

2

K2O

3

N

4

P2O5

5

K2O

6

(1) Total nitrogen

(1) Water-soluble P2O5

(2) Nitric nitrogen

(2) P2O5 soluble in neutral ammonium citrate

(3) P2O5 soluble in neutral ammonium citrate

and in water

(3) Ammoniacal
nitrogen

(4) Ureic nitrogen

(5) Nitrogen

from
crotonylidene diurea

(6) Nitrogen

from
isobutylidene diurea

(7) Nitrogen from urea

formaldehyde

(1) Total nitrogen

(2) If any of the forms
to
of nitrogen (2)
(4) amounts to at
1 %
least
by
weight,
it must be
declared

(3) One of

the forms
of nitrogen (5)
to
(7) (as appropriate).
Nitrogen form (7)
must be declared
in
form of
nitrogen (8) and (9)

the

An NP fertiliser free of Thomas slag, calcined
phosphate,
phosphate,
aluminium-calcium
partially solubilised rock phosphate and rock
phosphate must be declared in accordance with
solubilities (1), (2) or (3):

— when the water-soluble P2O5 does not amount
to 2 %, solubility (2) only shall be declared;

— when the water-soluble P2O5 is at least 2 %,
solubility (3) shall be declared, and the water-
soluble P2O5 content must be indicated [solu-
bility (1)].

.

2
1
1
1
2
0
0
3

.

E
N

O

f
f
i
c
i
a
l

J
o
u
r
n
a
l

o
f

t
h
e

E
u
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a
n
U
n
o
n

i

L

3
0
4
/
2
9

1

2

3

4

5

6

(8) Nitrogen from urea
formaldehyde
that
is only soluble in
hot water

(9) Nitrogen from urea
that
soluble in cold

formaldehyde
is
water

The P2O5 content soluble in mineral acids only
must not exceed 2 %.

The test sample for determining solubilities (2)
and (3) shall be 1 g.

B.3. NK fertilisers

Type designation:

NK fertilisers.

Data on method of production:

B.3.1.

Product obtained chemically or by blending, without addition of organic nutrients of animal or vegetable origin.

Minimum content of nutrients (percentage by weight):

— Total: 18 % (N + K2O);

— For each of the nutrients: 3 % N, 5 % K2O.

Forms, solubilities and nutrient content to be declared as specified in columns 4, 5 and 6
Particle size

Data for identification of the fertilisers
Other requirements

N

1

(1) Total nitrogen

(2) Nitric nitrogen

(3) Ammoniacal
nitrogen

(4) Ureic nitrogen

(5) Cyanamide nitrogen

P2O5

2

K2O

3

N

4

P2O5

5

Water-soluble K2O

(1) Total nitrogen

(2) If any of the forms
of nitrogen (2)
to
(5) amounts to at
1 %
least
by
weight,
it must be
declared

K2O

6

(1) Water-soluble

potassium oxide

(2) The indication ‘low
is
in
linked
a
maximum content
of 2 % Cl

chloride’
to

(3) Chloride

content

may be declared

L

3
0
4
/
3
0

E
N

O

f
f
i
c
i
a
l

J
o
u
r
n
a
l

o
f

t
h
e

E
u
r
o
p
e
a
n
U
n
o
n

i

.

2
1
1
1
2
0
0
3

.

B.3. NK fertilisers (cont’d)

Type designation:

Data on method of production:

NK fertiliser containing crotonylidene diurea or isobutylidene diurea or urea formaldehyde (as appropriate).

Product obtained chemically without addition of organic nutrients of animal or vegetable origin and containing crotonylidene diurea or
isobutylidene diurea or urea formaldehyde.

Minimum content of nutrients (percentage by weight):

B.3.2.

— Total: 18 % (N + K2O);

— For each of the nutrients:

— 5 % N

At least ¼ of the declared content of total nitrogen must derive from nitrogen form (5) or (6) or (7).

At least 3/5 of the declared nitrogen content (7) must be soluble in hot water,

— 5 % K2O.

Forms, solubilities and nutrient content to be declared as specified in columns 4, 5 and 6
Particle size

Data for identification of the fertilisers
Other requirements

P2O5

2

K2O

3

N

4

P2O5

5

Water-soluble K2O

(1) Total nitrogen

(2) If any of the forms
to
of nitrogen (2)
(4) amounts to at
1 %
least
by
weight,
it must be
declared

(3) One of

the forms
of nitrogen (5)
to
(7) (as appropriate).
Nitrogen form (7)
must be declared
form of
in
nitrogen (8) and (9)

the

K2O

6

(1) Water-soluble

potassium oxide

(2) The indication ‘low
is
in
linked
a
maximum content
of 2 % Cl

chloride’
to

(3) Chloride

content

may be declared

N

1

(1) Total nitrogen

(2) Nitric nitrogen

(3) Ammoniacal
nitrogen

(4) Ureic nitrogen

(5) Nitrogen

from
crotonylidene diurea

(6) Nitrogen

from
isobutylidene diurea

(7) Nitrogen from urea

formaldehyde

(8) Nitrogen from urea
formaldehyde
that
is only soluble in
hot water

(9) Nitrogen from urea
that
soluble in cold

formaldehyde
is
water

.

2
1
1
1
2
0
0
3

.

E
N

O

f
f
i
c
i
a
l

J
o
u
r
n
a
l

o
f

t
h
e

E
u
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p
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a
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U
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o
n

i

L

3
0
4
/
3
1

B.4. PK fertilisers

Type designation:

Data on method of production:

Minimum content of nutrients (percentage by weight):

PK fertilisers.

Product obtained chemically or by blending, without addition of organic nutrients of animal or vegetable origin.

— Total: 18 % (P2O5 + K2O);
— For each of the nutrients: 5 % P2O5, 5 % K2O.

Forms, solubilities and nutrient content to be declared as specified in columns 4, 5 and 6
Particle size

Data for identification of the fertilisers
Other requirements

N

1

P2O5

2

K2O

3

N

4

P2O5

5

(1) Water-soluble P2O5
(2) P2O5 soluble in neutral ammonium citrate
(3) P2O5 soluble in neutral ammonium citrate

and in water

(4) P2O5 soluble in mineral acids only
(5) P2O5 soluble in alkaline ammonium citrate

(Petermann)

(6a) P2O5 soluble in mineral acids, of which at
least 75 % of the declared P2O5 content is
soluble in 2 % citric acid
(6b) P2O5 soluble in 2 % citric acid
(7) P2O5 soluble in mineral acids of which at
least 75 % of the declared P2O5 content is
soluble in alkaline ammonium citrate (Joulie)
(8) P2O5 soluble in mineral acids, of which at
least 55 % of the declared P2O5 content is
soluble in 2 % formic acid

Water soluble K2O

1. A PK fertiliser free from Thomas slag, calcined
phosphate,
aluminium-calcium phosphate,
partially solubilised rock phosphate and soft
ground rock phosphate must be declared in
accordance with solubilities (1), (2) or (3):
— when the water-soluble P2O5 does not
amount to 2 % solubility (2) only shall be
declared;

— when the water-soluble P2O5 is at least 2 %
solubility (3) shall be declared and the
be
water-soluble
indicated [solubility (1)].

content must

P2O5

The P2O5 content soluble in mineral acids only
must not exceed 2 %.

For this type 1, the test sample for determining
solubilities (2) and (3) shall be 1 g.

2 (a) A PK fertiliser containing soft ground rock
phosphate or partially solubilised rock
phosphate must be free from Thomas slag,
calcined phosphate and aluminium-calcium
phosphate.

It shall be declared in accordance with solubilities
(1), (3) and (4)

This type of fertiliser must contain:
— at least 2 % P2O5 soluble in mineral acids only

[solubility (4)];

— at least 5 % P2O5 soluble in water and neutral

ammonium citrate [solubility (3)];

K2O

6

(1) Water-soluble

potassium oxide

(2) The indication ‘low
is
in
linked
a
maximum content
of 2 % Cl

chloride’
to

(3) Chloride

content

may be declared

— at

least 2,5 % water-soluble P2O5 [solubility

(1)].

L

3
0
4
/
3
2

E
N

O

f
f
i
c
i
a
l

J
o
u
r
n
a
l

o
f

t
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e

E
u
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p
e
a
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U
n
o
n

i

.

2
1
1
1
2
0
0
3

.

1

2

3

4

5

6

This type of fertiliser must be marketed under the
designation ‘PK fertiliser containing soft ground
containing
‘PK fertiliser
rock phosphate’ or
partially solubilised rock phosphate’.

For this type 2(a), the test sample for determining
solubility (3) shall be 3 g

Particle size of the basic phosphatic ingredients:

2 (b) A PK fertiliser

Thomas slag

at least 75 % able to pass through a sieve with a mesh of 0,160 mm

Aluminium-calcium phosphate

at least 90 % able to pass through a sieve with a mesh of 0,160 mm

Calcined phosphate

at least 75 % able to pass through a sieve with a mesh of 0,160 mm

Soft ground rock phosphate

at least 90 % able to pass through a sieve with a mesh of 0,063 mm

Partially solubilised rock
phosphate

at least 90 % able to pass through a sieve with a mesh of 0,160 mm

containing

calcium phosphate must be
Thomas
partially solubilised rock phosphate.

aluminium-
from
free
and
calcined phosphate

slag,

It shall be declared in accordance with solubilities
(1) and (7), the latter applying after deduction of
the solubility in water.

This type of fertiliser must contain:

— at least 2 % water-soluble P2O5 [solubility (1)];
— at least 5 % P2O5 according to solubility (7).

This type of fertiliser must be marketed under the
designation ‘PK fertiliser containing aluminium-
calcium phosphate’.

3.

In the case of PK fertilisers containing only
one of
the following types of phosphatic
fertiliser: Thomas slag, calcined phosphate,
aluminium-calcium phosphate,
soft ground
the type designation must
rock phosphate,
be
the
indication
followed
phosphate ingredient.

by

an

of

The declaration of the solubility of the P2O5 must
be given in accordance with the following solu-
bilities:

— for fertilisers based on Thomas slag: solubility
Italy, Spain, Portugal, Greece),
(6a)
(6b)
Ireland,
Luxembourg, Netherlands, United Kingdom
and Austria);

(France,
(Germany, Belgium, Denmark,

— for fertilisers based on calcined phosphate:

solubility (5);

— for

fertilisers based on aluminium-calcium

phosphate: solubility (7);

— for

fertilisers based on soft ground rock

phosphate: solubility (8).

.

2
1
1
1
2
0
0
3

.

E
N

O

f
f
i
c
i
a
l

J
o
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n
a
l

o
f

t
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e

E
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U
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i

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3
3

C.

Inorganic fluid fertilisers

C.1. Straight fluid fertilisers

No

1

1

Type designation

Data on method of production and
essential ingredients

Minimum content of nutrients
(percentage by weight)
Data on the expression of nutrients
Other requirements

Other data or type designation

Nutrient content to be declared
Forms and solubilities of the nutrients
Other criteria

2

3

4

5

6

Nitrogen fertiliser solution

Product obtained chemically and by
dissolution in water, in a form stable
pressure, without
at
addition of
of
nutrients
animal or vegetable origin

atmospheric

organic

2

Urea
fertiliser solution

Ammonium

nitrate

Product obtained chemically and by
dissolution
containing
in water,
ammonium nitrate and urea

3

Calcium nitrate solution

Product
by
calcium nitrate in water

obtained

dissolving

15 % N
Nitrogen expressed as total nitrogen
or,
if there is only one form, nitric
nitrogen or ammoniacal nitrogen or
ureic nitrogen

Maximum biuret content:

ureic N × 0,026

26 % N
Nitrogen expressed as total nitrogen,
where the ureic nitrogen accounts
for about half of the nitrogen present

Maximum biuret content: 0,5 %

8 % N
Nitrogen expressed as nitrogen in
nitric form with a maximum 1 %
nitrogen as ammonia

Calcium expressed as water soluble
CaO

The type designation may be followed,
as
the
by
appropriate,
following indications:

one

of

— for foliar application;
— for making nutrient solutions;
— for ferti-irrigation.

4

Magnesium nitrate solution

Product obtained chemically and by
dissolving magnesium nitrate in water

6 % N
Nitrogen expressed as nitric nitrogen

9 % MgO
Magnesium expressed as water-soluble
magnesium oxide

Minimum pH: 4

Total nitrogen and, for any form that
amounts to not less than 1 %, nitric
nitrogen, ammoniacal nitrogen and/or
ureic nitrogen

If the biuret content is less than 0,2 %,
the words ‘low in biuret’ may be added

Total nitrogen

Nitric nitrogen, ammoniacal nitrogen
and ureic nitrogen

If the biuret content is less than 0,2 %,
the words ‘low in biuret’ may be added

Total nitrogen

Water soluble calcium oxide for the
uses stipulated in column 5

Optionally:

— nitrogen in nitric form;
— nitrogen as ammonia.

Nitric nitrogen

Water-soluble magnesium oxide

L

3
0
4
/
3
4

E
N

O

f
f
i
c
i
a
l

J
o
u
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n
a
l

o
f

t
h
e

E
u
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p
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a
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U
n
o
n

i

.

2
1
1
1
2
0
0
3

.

2

3

4

5

6

Calcium nitrate suspension

Product obtained by suspension of
calcium nitrate in water

8 % N
Nitrogen expressed as total nitrogen
or nitric and ammoniacal nitrogen
maximum content of
ammoniacal
nitrogen: 1,0 %

14 % CaO Calcium expressed as water
soluble CaO

The type designation may be followed
by one of the following indications:

Total nitrogen

Nitric nitrogen

— for foliar application;

— for making nutrient solutions and

Water soluble calcium oxide for the
uses stipulated in column 5

suspensions;

— for fertigation.

1

5

6

Nitrogen
with urea formaldehyde

fertiliser

solution

Product obtained chemically or by
dissolution in water of urea formal-
fertiliser
dehyde and a nitrogenous
from list A-1 in this
regulation,
excluding products 3(a), 3(b), and 5

18 % N expressed as total nitrogen

At least one third of the declared total
nitrogen content must derive from
urea formaldehyde

Maximum biuret
N + urea formaldehyde N) × 0,026

content:

(ureic

7

Nitrogen fertiliser
with urea formaldehyde

suspension

Product obtained chemically or by
suspension in water of urea formal-
fertiliser
dehyde and a nitrogenous
from list A-1 in this
regulation,
excluding products 3(a), 3(b), and 5

18 % N expressed as total nitrogen

At least one third of the declared total
nitrogen content must derive from
urea formaldehyde of which at least
three fifths has to be soluble in hot
water

Maximum biuret content: (ureic N +
urea formaldehyde N) × 0,026

Total nitrogen

For each form amounting to at least
1 %:

— Nitric nitrogen;

— Ammoniacal nitrogen;

— Ureic nitrogen.

Nitrogen from urea formaldehyde

Total nitrogen

For each form amounting to at least
1 %

— Nitric nitrogen;

— Ammoniacal nitrogen;

— Ureic nitrogen.

Nitrogen from urea formaldehyde

Nitrogen from urea formaldehyde that
is soluble in cold water

Nitrogen from urea formaldehyde that
is only soluble in hot water

.

2
1
1
1
2
0
0
3

.

E
N

O

f
f
i
c
i
a
l

J
o
u
r
n
a
l

o
f

t
h
e

E
u
r
o
p
e
a
n
U
n
o
n

i

L

3
0
4
/
3
5

C.2. Compound fluid fertilisers

Type designation:

Data on method of production:

NPK-fertiliser solution.

Product obtained chemically and by dissolution in water, in a form stable at atmospheric pressure, without addition of organic nutrients of
animal or vegetable origin.

C.2.1.

Minimum content of nutrients (percentage by weight) and other requirements: — Total: 15 %, (N + P2O5 + K2O);

— For each of the nutrients: 2 % N, 3 % P2O5, 3 % K2O;

— Maximum biuret content: ureic N × 0,026.

Forms, solubilities and nutrient content to be declared as specified in columns 4, 5 and 6
Particle size

Data for identification of the fertilisers
Other requirements

N

1

(1) Total nitrogen

(2) Nitric nitrogen

(3) Ammoniacal
nitrogen

(4) Ureic nitrogen

P2O5

2

K2O

3

N

4

P2O5

5

Water-soluble P2O5

Water-soluble K2O

(1) Total nitrogen

Water-soluble P2O5

(2) If any of the forms
of nitrogen (2)
to
(4) amounts to not
than 1 % by
less
it must be
weight,
declared

(3) If

the

biuret
content is less than
0,2 %,
the words
‘low in biuret’ may
be added

K2O

6

(1) Water-soluble

potassium oxide

(2) The words ‘low in
chloride’ may
be
used
only where
the Cl content does
not exceed 2 %

(3) The chloride content
may be declared

L

3
0
4
/
3
6

E
N

O

f
f
i
c
i
a
l

J
o
u
r
n
a
l

o
f

t
h
e

E
u
r
o
p
e
a
n
U
n
o
n

i

C.2. Compound fluid fertilisers (cont’d)

Type designation:

Data on method of production:

C.2.2.

NPK-fertiliser suspension.

Product in liquid form, in which the nutrients are derived from substances both in suspension in the water and in solution without addition
of organic nutrients of animal or vegetable origin.

Minimum content of nutrients (percentage by weight) and other requirements: — Total: 20 %, (N + P2O5 + K2O);

— For each of the nutrients: 3 % N, 4 % P2O5, 4 % K2O;
— Maximum biuret content: ureic N × 0,026.

.

2
1
1
1
2
0
0
3

.

Forms, solubilities and nutrient content to be declared as specified in columns 4, 5 and 6
Particle size

Data for identification of the fertilisers
Other requirements

N

1

P2O5

2

K2O

3

N

4

P2O5

5

K2O

6

(1) Total nitrogen

(1) Water-soluble P2O5

Water-soluble K2O

(1) Total nitrogen

(2) Nitric nitrogen

(2) P2O5 soluble in neutral ammonium citrate

(3) Ammoniacal
nitrogen

(4) Ureic nitrogen

(3) P2O5 soluble in neutral ammonium citrate

and water

(2) If any of the forms
of nitrogen 2 to 4
amounts to not less
1 %
than
by
weight,
it must be
declared

(3) If

the

biuret
content is less than
0,2 %,
the words
‘low in biuret’ may
be added

The fertilisers must not contain Thomas slag,
aluminium calcium phosphate, calcined phos-
phates, partially solubilised phosphates or rock
phosphates

(1) If the water-soluble P2O5 is less than 2 %,

only solubility 2 shall be declared

(2) If the water-soluble P2O5 is at least 2 %, solu-
bility 3 and the water-soluble P2O5 content
shall be declared

(1) Water-soluble

potassium oxide

(2) The words ‘low in
chloride’ may
be
used
only where
the Cl content does
not exceed 2%

(3) The chloride content
may be declared

C.2. Compound fluid fertilisers (cont’d)

Type designation:

Data on method of production:

NP-fertiliser solution.

Product obtained chemically and by dissolution in water, in a form stable at atmospheric pressure, without addition of organic nutrients of
animal or vegetable origin.

C.2.3.

Minimum content of nutrients (percentage by weight):

— Total: 18 %, (N + P2O5);

— For each of the nutrients: 3 % N, 5 % P2O5;

— Maximum biuret content: ureic N × 0,026.

Forms, solubilities and nutrient content to be declared as specified in columns 4, 5 and 6
Particle size

Data for identification of the fertilisers
Other requirements

N

1

P2O5

2

K2O

3

N

4

P2O5

5

K2O

6

(1) Total nitrogen

P2O5Water-soluble

(1) Total nitrogen

Water-soluble P2O5

(2) Nitric nitrogen

(3) Ammoniacal
nitrogen

(4) Ureic nitrogen

(2) If any of the forms
of nitrogen (2)
to
(4) amounts to not
than 1 % by
less
weight,
it must be
declared.

.

2
1
1
1
2
0
0
3

.

E
N

O

f
f
i
c
i
a
l

J
o
u
r
n
a
l

o
f

t
h
e

E
u
r
o
p
e
a
n
U
n
o
n

i

L

3
0
4
/
3
7

1

2

3

4

5

6

(3) If

the

biuret
content is less than
the words
0,2 %,
‘low in biuret’ may
be added

C.2. Compound fluid fertilisers (cont’d)

Type designation:

Data on method of production:

NP-fertiliser suspension.

Product in liquid form, in which the nutrients are derived from substances both in solution and in suspension in the water, without addition
of organic nutrients of animal or vegetable origin.

C.2.4.

Minimum content of nutrients (percentage by weight):

— Total: 18 %, (N + P2O5);

— For each of the nutrients: 3 % N, 5 % P2O5;

— Maximum biuret content: ureic N × 0,026.

Forms, solubilities and nutrient content to be declared as specified in columns 4, 5 and 6
Particle size

Data for identification of the fertilisers
Other requirements

N

1

P2O5

2

K2O

3

N

4

P2O5

5

K2O

6

(1) Total nitrogen

(1) Water-soluble P2O5

(2) Nitric nitrogen

(2) P2O5 soluble in neutral ammonium citrate

(3) Ammoniacal
nitrogen

(4) Ureic nitrogen

(3) P2O5 soluble in neutral ammonium citrate

and water

(1) Total nitrogen

(2) If any of the forms
of nitrogen (2)
to
(4) amounts to not
than 1 % by
less
weight,
it must be
declared.

(3) If

the

biuret
content is less than
0,2 %,
the words
‘low in biuret’ may
be added

(1) If the water-soluble P2O5 is less than 2 % only

solubility 2 shall be declared

(2) If the water-soluble P2O5 is at least 2 %, solu-
bility 3 will be declared and the water-soluble
P2O5 content must be stated.

The fertilisers may not contain Thomas slag,
aluminium calcium phosphate, calcined phos-
phates, partially solubilised phosphate or rock
phosphates

L

3
0
4
/
3
8

E
N

O

f
f
i
c
i
a
l

J
o
u
r
n
a
l

o
f

t
h
e

E
u
r
o
p
e
a
n
U
n
o
n

i

.

2
1
1
1
2
0
0
3

.

C.2. Compound fluid fertilisers (cont’d)

Type designation:

Data on method of production:

NK-fertiliser solution.

Product obtained chemically and by dissolution in water, in a form stable at atmospheric pressure, without addition of organic nutrients of
animal or vegetable origin.

C.2.5.

Minimum content of nutrients (percentage by weight):

— Total: 15 % (N + K2O);

— For each of the nutrients: 3 % N, 5 % K2O;

— Maximum biuret content: ureic N × 0,026.

Forms, solubilities and nutrient content to be declared as specified in columns 4, 5 and 6
Particle size

Data for identification of the fertilisers
Other requirements

N

1

(1) Total nitrogen

(2) Nitric nitrogen

(3) Ammoniacal
nitrogen

(4) Ureic nitrogen

P2O5

2

K2O

3

N

4

P2O5

5

Water-soluble K2O

(1) Total nitrogen

(2) If any of the forms
to
of nitrogen (2)
(4) amounts to not
than 1 % by
less
weight,
it must be
declared

(3) If

the

biuret
content is less than
0,2 %,
the words
‘low in biuret’ may
be added

K2O

6

(1) Water-soluble

potassium oxide

(2) The words ‘low in
chloride’ may
be
used
only where
the Cl content does
not exceed 2%

(3) The chloride content
may be declared

C.2. Compound fluid fertilisers (cont’d)

Type designation:

Data on method of production:

NK-fertiliser suspension.

Product in liquid form, in which the nutrients are derived from substances both in solution and in suspension in the water, without addition
of organic nutrients of animal or vegetable origin.

C.2.6.

Minimum content of nutrients (percentage by weight):

— Total: 18 % (N + K2O);

— For each of the nutrients: 3 % N, 5 % K2O;

— Maximum biuret content: ureic N × 0,026.

.

2
1
1
1
2
0
0
3

.

E
N

O

f
f
i
c
i
a
l

J
o
u
r
n
a
l

o
f

t
h
e

E
u
r
o
p
e
a
n
U
n
o
n

i

L

3
0
4
/
3
9

Forms, solubilities and nutrient content to be declared as specified in columns 4, 5 and 6
Particle size

Data for identification of the fertilisers
Other requirements

N

1

(1) Total nitrogen

(2) Nitric nitrogen

(3) Ammoniacal
nitrogen

(4) Ureic nitrogen

C.2. Compound fluid fertilisers (cont’d)

Type designation:

Data on method of production:

C.2.7.

P2O5

2

K2O

3

N

4

P2O5

5

Water-soluble K2O

(1) Total nitrogen

(2) If any of the forms
to
of nitrogen (2)
(4) amounts to not
than 1 % by
less
weight,
it must be
declared

(3) If

the

biuret
content is less than
0,2 %,
the words
‘low in biuret’ may
be added

K2O

6

(1) Water-soluble

potassium oxide

(2) The words ‘low in
chloride’ may
be
used
only where
the Cl content does
not exceed 2%

(3) The chloride content
may be declared

PK-fertiliser solution.

Product obtained chemically and by dissolution in water, without addition of organic nutrients of animal or vegetable origin.

Minimum content of nutrients (percentage by weight):

— Total: 18 % (P2O5 + K2O);

— For each of the nutrients: 5 % P2O5, 5 % K2O.

Forms, solubilities and nutrient content to be declared as specified in columns 4, 5 and 6
Particle size

Data for identification of the fertilisers
Other requirements

N

1

P2O5

2

K2O

3

N

4

P2O5

5

Water-soluble P2O5

Water-soluble K2O

Water-soluble P2O5

K2O

6

(1) Water-soluble

potassium oxide

(2) The words ‘low in
chloride’ may
be
used
only where
the Cl content does
not exceed 2%

(3) The chloride content
may be declared

L

3
0
4
/
4
0

E
N

O

f
f
i
c
i
a
l

J
o
u
r
n
a
l

o
f

t
h
e

E
u
r
o
p
e
a
n
U
n
o
n

i

.

2
1
1
1
2
0
0
3

.

C.2. Compound fluid fertilisers (cont’d)

Type designation:

Data on method of production:

C.2.8.

PK-fertiliser suspension.

Product in liquid form, in which the nutrients are derived from substances both in solution and in suspension in water, without addition of
organic nutrients of animal or vegetable origin.

Minimum content of nutrients (percentage by weight):

— Total: 18 % (P2O5 + K2O);

— For each of the nutrients: 5 % P2O5, 5 % K2O.

Forms, solubilities and nutrient content to be declared as specified in columns 4, 5 and 6
Particle size

Data for identification of the fertilisers
Other requirements

N

1

P2O5

2

K2O

3

N

4

P2O5

5

K2O

6

(1) Water-soluble P2O5

Water-soluble K2O

(2) P2O5 soluble in neutral ammonium citrate

(3) P2O5 soluble in neutral ammonium citrate

and water

(1) If the water-soluble P2O5 is less than 2 % only

solubility 2 will be declared

(1) Water-soluble

potassium oxide

(2) If the water-soluble P2O5 is at least 2 % solu-
bility 3 and the water-soluble P2O5 content
shall be declared

The fertilisers must not contain Thomas slag,
aluminium calcium phosphate, calcined phos-
phates, partially solubilised phosphates or rock
phosphates

(2) The words ‘low in
chloride’ may
be
used
only where
the Cl content does
not exceed 2%

(3) The chloride content
may be declared

.

2
1
1
1
2
0
0
3

.

E
N

O

f
f
i
c
i
a
l

J
o
u
r
n
a
l

o
f

t
h
e

E
u
r
o
p
e
a
n
U
n
o
n

i

L

3
0
4
/
4
1

D. Inorganic secondary nutrient fertilisers

No

1

1

Type designation

Data on method of production and
essential ingredients

Minimum content of nutrients
(percentage by weight)
Data on the expression of nutrients
Other requirements

Other data or type designation

Nutrient content to be declared
Forms and solubilities of the nutrients
Other criteria

2

3

4

5

6

Calcium sulphate

Product of natural or industrial origin
containing calcium sulphate at various
degrees of hydration

Usual trade names may be added

Total sulphur trioxide

Optional: total CaO

25 % CaO
35 % SO3
Calcium and sulphur expressed as
total CaO + SO3
Fineness of grind:

— at least 80 % to pass through a
sieve with a 2 mm mesh width,

— at least 99 % to pass through a
sieve with a 10 mm mesh width

2

Calcium chloride solution

Calcium chloride solution of industrial
origin

12 % CaO
Calcium expressed as water-soluble
CaO

3

4

Elemental sulphur

Comparatively
industrial product

refined

natural

or

98 % S (245 %: SO3)
Sulphur expressed as total SO3

Kieserite

Product of mineral origin containing
monohydrated magnesium sulphate
as main component

24 % MgO
45 % SO3
Magnesium and sulphur expressed as
water-soluble magnesium oxide and
sulphur trioxide

Calcium oxide

Optional: for plant spraying

Total sulphur trioxide

Usual trade names may be added

Water-soluble magnesium oxide

Optional: water-soluble sulphur trioxide

L

3
0
4
/
4
2

E
N

O

f
f
i
c
i
a
l

J
o
u
r
n
a
l

o
f

t
h
e

E
u
r
o
p
e
a
n
U
n
o
n

i

5

Magnesium sulphate

Product
magnesium
component

containing

sulphate

heptahydrated
main

as

15 % MgO
28 % SO3
Magnesium and sulphur expressed as
water-soluble magnesium oxide and
sulphur trioxide

Usual trade names may be added

Water-soluble magnesium oxide

Optional: water-soluble sulphur trioxide

5.1 Magnesium sulphate solution

Product obtained by dissolution in
water of magnesium sulphate of
industrial origin

5.2 Magnesium hydroxide

Product
having
as
magnesium hydroxide

obtained
its

chemically

and
ingredient

essential

5 % MgO
10 % SO3
Magnesium and sulphur expressed as
water-soluble magnesium oxide and
water-soluble sulphuric anhydride

60 % MgO
Particle size: at least 99 % able to pass
through a sieve with a mesh of
0,063 mm

Usual trade names may be added

Water-soluble magnesium oxide

Optional:
anhydride

water-soluble

sulphuric

Total magnesium oxide

.

2
1
1
1
2
0
0
3

.

2

3

4

5

6

1

5.3

Suspension
hydroxide

of magnesium

Product obtained by suspension of
type 5.2

24 % MgO

Total magnesium oxide

Magnesium oxide

6

Magnesium chloride solution

obtained

Product
magnesium chloride
origin

by

of

dissolving
industrial

13 % MgO
Magnesium expressed as magnesium
oxide

Maximum calcium content: 3 % CaO

E.

Inorganic micro-nutrient fertilisers

Explanatory note: The following notes are applicable to the whole of Part E.

Note 1: A chelating agent may be designated by means of its initials as set out in E.3.

Note 2:

If the product leaves no solid residue after being dissolved in water it may be described as ‘for dissolution’.

Note 3: Where a micro-nutrient is present in a chelated form, the pH range guaranteeing acceptable stability of the chelated fraction shall be stated.

E.1.

Fertilisers containing only one micro-nutrient

E.1.1. Boron

No

1

Type designation

Data on method of production and
essential ingredients

Minimum content of nutrients
(percentage by weight)
Data on the expression of nutrients
Other requirements

Other data on the type of designation

Nutrient content to be declared
Forms and solubilities of the nutrients
Other criteria

2

3

4

5

6

1a

Boric acid

1b

Sodium borate

1c

Calcium borate

Product obtained by the action of an
acid on a borate

Chemically
product
containing as its essential component
a sodium borate

obtained

Product obtained from colemanite or
pandermite containing as its essential
ingredient calcium borates

14 % water-soluble B

The usual trade names may be added Water-soluble boron (B)

10 % water-soluble B

The usual trade names may be added Water-soluble boron (B)

7 % total B

The usual trade names may be added Total boron (B)

Particle size: at
through a 0,063 mm sieve

least 98 % passing

1d

Boron ethanol amine

Product obtained by reacting a boric
acid with an ethanol amine

8 % water-soluble B

Water-soluble boron (B)

.

2
1
1
1
2
0
0
3

.

E
N

O

f
f
i
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a
l

J
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a
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U
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i

L

3
0
4
/
4
3

1

2

3

4

5

6

1e

Borated fertiliser in solution

Product obtained by dissolving types
1a and/or 1b and/or 1d

2 % water-soluble B

The designation must
include
names of the constituents present

the

Water-soluble boron (B)

1f

Borated fertiliser in suspension Product obtained by suspending types

2 % water-soluble B

1a and/or 1b and/or 1d in water

The designation must
include
names of the constituents present

the

Water-soluble boron (B)

E.1.2. Cobalt

No

1

Type designation

Data on method of production and
essential ingredients

Minimum content of nutrients
(percentage by weight)
Data on the expression of nutrients
Other requirements

Other data on the type of designation

Nutrient content to be declared
Forms and solubilities of the nutrients
Other criteria

2

3

4

5

6

2a

Cobalt salt

2b

Cobalt chelate

product
Chemically
containing a mineral salt of cobalt as
its essential ingredient

obtained

19 % water-soluble Co

The designation must
name of the mineral anion

include

the

Water-soluble cobalt (Co)

Water-soluble product obtained by
combining cobalt chemically with a
chelating agent

2 % water-soluble Co, at least 8/10 of
the declared value of which has been
chelated

Name of the chelating agent

Water-soluble cobalt (Co)

Chelated cobalt (Co)

2c

Cobalt fertiliser solution

Product obtained by dissolving types
2a and/or one of the type 2b in water

2 % water-soluble Co

The designation must include:

Water-soluble cobalt (Co)

(1) the

name(s)

of

the mineral

Chelated cobalt (Co) if present

anion(s);

(2) the name of any chelating agent if

present

L

3
0
4
/
4
4

E
N

O

f
f
i
c
i
a
l

J
o
u
r
n
a
l

o
f

t
h
e

E
u
r
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p
e
a
n
U
n
o
n

i

.

2
1
1
1
2
0
0
3

.

E.1.3. Copper

No

1

Type designation

Data on method of production and
essential ingredients

Minimum content of nutrients
(percentage by weight)
Data on the expression of nutrients
Other requirements

Other data on the type of designation

Nutrient content to be declared
Forms and solubilities of the nutrients
Other criteria

2

3

4

5

6

3a

Copper salt

3b

Copper oxide

3c

Copper hydroxide

3d

Copper chelate

Chemically
product
containing a mineral salt of copper
as its essential ingredient

obtained

20 % water-soluble Cu

The designation must
name of the mineral anion

include

the

Water-soluble copper (Cu)

Chemically
containing
copper
essential ingredient

obtained

oxide

product
its
as

70 % total Cu
Particle size: at
through a 0,063 mm sieve

least 98 % passing

Chemically
containing copper hydroxide as
essential ingredient

obtained

product
its

45 % total Cu
Particle size: at
through a 0,063 mm sieve

least 98 % passing

Total copper (Cu)

Total copper (Cu)

Water-soluble product obtained by
combining copper chemically with a
chelating agent

9 % water-soluble Cu, at least 8/10 of
the declared value of which has been
chelated

Name of the chelating agent

Water-soluble copper (Cu)

Chelated copper (Cu)

3e

Copper-based fertiliser

Product obtained by mixing types 3a
and/or 3b and/or 3c and/or a single
one of type 3d and, if required, filler
that is neither nutrient nor toxic

3f

Copper fertiliser solution

Product obtained by dissolving types
3a and/or one of the type 3d in water

5 % total Cu

The designation must include:

Total copper (Cu)

(1)

(2)

the
name(s)
components;

of

the

copper

the name of any chelating agent if
present

Water-soluble
this
copper
accounts for at least 1/4 of the total
copper

(Cu)

if

Chelated copper (Cu) if present

3 % water-soluble Cu

The designation must include:

Water-soluble copper (Cu)

(1)

(2)

name(s)

the
anion(s);

of

the mineral

Chelated copper (Cu) if present

the name of any chelating agent if
present

3g

Copper oxychloride

obtained

Chemically
product
oxychloride
copper
containing
[Cu2Cl(OH)3] as an essential ingredient

50 % total Cu
Particle size: at
through a 0,063 mm sieve

least 98 % passing

3h

Copper oxychloride suspension Product obtained by suspension of

17 % total Cu

type 3 g

Total copper (Cu)

Total copper (Cu)

.

2
1
1
1
2
0
0
3

.

E
N

O

f
f
i
c
i
a
l

J
o
u
r
n
a
l

o
f

t
h
e

E
u
r
o
p
e
a
n
U
n
o
n

i

L

3
0
4
/
4
5

E.1.4. Iron

No

1

Type designation

Data on method of production and
essential ingredients

Minimum content of nutrients
(percentage by weight)
Data on the expression of nutrients
Other requirements

Other data on the type of designation

Nutrient content to be declared
Forms and solubilities of the nutrients
Other criteria

2

3

4

5

6

4a

Iron salt

4b

Iron chelate

Chemically
containing a mineral
essential ingredient

obtained

product
iron salt as its

Water soluble product obtained by
chemical
iron with
chelating agents mentioned in the list
of Annex I chapter E.3

reaction

of

4c

Iron fertiliser solution

Product obtained by dissolving types
4a and/or one of the type 4b in water

12 % water-soluble Fe

The designation must
name of the mineral anion

include

the

Water-soluble iron (Fe)

5 % of water soluble iron, of which
the chelated fraction is at least 80 %

Name of the chelating agents

— Iron (Fe) water soluble

— Chelated fraction (EN 13366)

— Iron (Fe) chelated by each chelating
each fraction
as
agent
exceeds 2 % (EN 13368 part 1
and 2)

insofar

2 % water-soluble Fe

The designation must include:

Water-soluble iron (Fe)

(1)

(2)

name(s)

the
anion(s);

of

the mineral

Chelated iron (Fe) if present

the name of any chelating agent if
present

E.1.5. Manganese

No

1

Type designation

Data on method of production and
essential ingredients

Minimum content of nutrients
(percentage by weight)
Data on the expression of nutrients
Other requirements

Other data on the type of designation

Nutrient content to be declared
Forms and solubilities of the nutrients
Other criteria

2

3

4

5

6

5a

Manganese salt

5b Manganese chelate

5c

Manganese oxide

Chemically
product
containing a mineral manganese salt
(Mn II) as its essential ingredient

obtained

17 % water-soluble Mn

The designation must
name of the combined anion

include

the

Water-soluble manganese (Mn)

Water-soluble product obtained by
combining manganese
chemically
with a chelating agent

5 % water-soluble Mn, at least 8/10 of
the declared value of which has been
chelated

Chemically
obtained
containing manganese
essential ingredients

product
as

oxides

40 % total Mn

Particle size: at
through a 0,063 mm sieve

least 80 % passing

Name of the chelating agent

Water-soluble manganese (Mn)

Chelated manganese (Mn)

Total manganese (Mn)

L

3
0
4
/
4
6

E
N

O

f
f
i
c
i
a
l

J
o
u
r
n
a
l

o
f

t
h
e

E
u
r
o
p
e
a
n
U
n
o
n

i

.

2
1
1
1
2
0
0
3

.

1

2

3

4

5

6

5d Manganese-based fertiliser

Product obtained by mixing types 5a
and 5c

17 % total Mn

The designation must
the
name of the manganese components

include

Total manganese (Mn)

Water-soluble manganese (Mn)
this
accounts for at least 1/4 of the total
manganese

if

5e

Manganese-based
solution

fertiliser

Product obtained by dissolving types
5a and/or one of the type 5b in water

3 % water-soluble Mn

The designation must include:

Water-soluble manganese (Mn)

(1)

(2)

name(s)

the
anion(s);

of

the mineral

Chelated manganese (Mn) if present

the name of any chelating agent if
present

E.1.6. Molybdenum

No

1

Type designation

Data on method of production and
essential ingredients

Minimum content of nutrients
(percentage by weight)
Data on the expression of nutrients
Other requirements

Other data on the type of designation

Nutrient content to be declared
Forms and solubilities of the nutrients
Other criteria

2

3

4

5

6

6a

Sodium molybdate

Chemically
product
containing sodium molybdate as its
essential ingredient

obtained

35 % water-soluble Mo

6b

Ammonium molybdate

Chemically
product
containing ammonium molybdate as
its essential ingredient

obtained

50 % water-soluble Mo

6c

Molybdenum-based fertiliser

Product obtained by mixing types 6a
and 6b

35 % water-soluble Mo

6d

Molybdenum-based
solution

fertiliser

Product obtained by dissolving types
6a and/or one of the type 6b in water

3 % water-soluble Mo

Water-soluble molybdenum (Mo)

Water-soluble molybdenum (Mo)

Water-soluble molybdenum (Mo)

Water-soluble molybdenum (Mo)

The designation must
names
of
components

the

include
the
molybdenum

The designation must
name(s)
of
component(s)

the

the
include
molybdenum

.

2
1
1
1
2
0
0
3

.

E
N

O

f
f
i
c
i
a
l

J
o
u
r
n
a
l

o
f

t
h
e

E
u
r
o
p
e
a
n
U
n
o
n

i

L

3
0
4
/
4
7

E.1.7. Zinc

No

1

Type designation

Data on method of production and
essential ingredients

Minimum content of nutrients
(percentage by weight)
Data on the expression of nutrients
Other requirements

Other data on the type of designation

Nutrient content to be declared
Forms and solubilities of the nutrients
Other criteria

2

3

4

5

6

7a

Zinc salt

7b

Zinc chelate

7c

Zinc oxide

obtained

Chemically
having as its essential
mineral salt of zinc

and
product
ingredient a

15 % water-soluble Zn

The designation must
name of the mineral anion

include

the

Water-soluble zinc (Zn)

Water-soluble product obtained by
combining zinc chemically with a
chelating agent

5 % water-soluble Zn, at least 8/10 of
the declared content of which has
been chelated

obtained

Chemically
and
having as its essential ingredient zinc
oxide

product

70 % total Zn

Particle size: at
through a 0,063 mm sieve

least 80 % passing

Name of the chelating agent

Water-soluble zinc (Zn)

Chelated zinc (Zn)

Total zinc (Zn)

7d

Zinc-based fertiliser

Product obtained by mixing types 7a
and 7c

30 % total Zn

The designation must
the
name of the zinc components present

include

Total zinc (Zn)

Water-soluble zinc (Zn) if this accounts
for at least 1/4 of the total zinc (Zn)

7e

Zinc-based fertiliser solution

Product obtained by dissolving types
7a and/or one of type 7b in water

3 % water-soluble Zn

The designation must include:

Water-soluble zinc (Zn)

(1)

(2)

name(s)

the
anion(s);

of

the mineral

Chelated zinc (Zn) if present

the name of any chelating agent if
present.

L

3
0
4
/
4
8

E
N

O

f
f
i
c
i
a
l

J
o
u
r
n
a
l

o
f

t
h
e

E
u
r
o
p
e
a
n
U
n
o
n

i

.

2
1
1
1
2
0
0
3

.

21.11.2003

EN

Official Journal of the European Union

L 304/49

E.2. Minimum micro-nutrient content, percentage weight of fertilisers

E.2.1. Solid or fluid mixtures of micro-nutrient

Where the micro-nutrient is present in a form that is

exclusively mineral

chelated or complexed

For a micro-nutrient:

Boron (B)

Cobalt (Co)

Copper (Cu)

Iron (Fe)

Manganese (Mn)

Molybdenum (Mo)

Zinc (Zn)

0,2

0,02

0,5

2,0

0,5

0,02

0,5

0,2

0,02

0,1

0,3

0,1

—

0,1

Minimum total of micro-nutrient in a solid mixture: 5 % by mass of the fertiliser.

Minimum total of micro-nutrient in a fluid mixture: 2 % by mass of the fertiliser.

E.2.2. EC fertilisers containing primary and/or secondary nutrient with micro-nutrient applied to the soil

For crops or grassland

For horticultural use

Boron (B)

Cobalt (Co)

Copper (Cu)

Iron (Fe)

Manganese (Mn)

Molybdenum (Mo)

Zinc (Zn)

0,01

0,002

0,01

0,5

0,1

0,001

0,01

0,01

—

0,002

0,02

0,01

0,001

0,002

E.2.3. EC fertilisers containing primary and/or secondary nutrient with micro-nutrients for leaf sprays

Boron (B)

Cobalt (Co)

Copper (Cu)

Iron (Fe)

Manganese (Mn)

Molybdenum (Mo)

Zinc (Zn)

0,010

0,002

0,002

0,020

0,010

0,001

0,002

L 304/50

EN

Official Journal of the European Union

21.11.2003

E.3. List of authorised organic chelating and complexing agents for micro-nutrients

The following products are authorised provided they have complied with the requirements of Directive 67/548/EEC (1)
as amended.

E.3.1. Chelating agents (2)

Sodium, potassium or ammonium acid or salts of:

ethylenediaminetetraacetic acid

diethylenetriaminepentaacetic acid

[o,o]: ethylenediamine-di (o-hydroxyphenyl acetic) acid

[o,p]: ethylenediamine-N-(o-hydroxyphenylacetic)
acid)-N'-(p-hydroxyphenylacetic) acid

2-hydroxyethylethylenediaminetriacetic acid

[o,o]: ethylenediamine-di (o-hydroxy-o-methylphenylacetic) acid

[o,p]: ethylenediamine-di (o-hydroxy-p-methylphenylacetic) acid

[p,o]: ethylenediamine-di (p-hydroxy-o-methylphenylacetic) acid

[2,4]: ethylenediamine di-(2-hydroxy-4-carboxyphenylacetic) acid

[2,5]: ethylenediamine di-(2-carboxy-5-hydroxyphenylacetic) acid

[5,2]: ethylenediamine di-(5-carboxy-2-hydroxyphenylacetic) acid

E.3.2. Complexing agents:

List to be drawn up.

EDTA

DTPA

EDDHA

EDDHA

HEEDTA

EDDHMA

EDDHMA

EDDHMA

EDDCHA

EDDCHA

EDDCHA

C10H16O8N2

C14H23O10N3

C18H20O6N2

C18H20O6N2

C10H18O7N2

C20H24O6N2

C20H24O6N2

C20H24O6N2

C20H20O10N2

C20H20O10N2

C20H20O10N2

(1) OJ L 196, 16.8.1967, p. 1.
(2) The chelating agents are to be identified and quantified by European Standard EN 13368 part 1 and part 2, to the extent that this

standard covers the above agents.

21.11.2003

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Official Journal of the European Union

L 304/51

ANNEX II

TOLERANCES

The tolerances given in this Annex are negative values in percentage by mass.

The tolerance allowed in respect of the declared nutrient contents in the various types of EC fertiliser are as follows:

1.

Inorganic straight primary nutrient fertilisers absolute value in percentage by mass expressed as N, P2O5,
K2O, MgO, Cl

1.1. Nitrogenous fertilisers

calcium nitrate

calcium — magnesium nitrate

sodium nitrate

chile nitrate

calcium cyanamide

nitrogenous calcium cyanamide

ammonium sulphate

Ammonium nitrate or calcium ammonium nitrate:

— up to and including 32 %

— more than 32 %

ammonium sulphate-nitrate

magnesium sulphonitrate

magnesium ammonium nitrate

urea

calcium nitrate suspension

nitrogen fertiliser solution with urea formaldehyde

nitrogen fertiliser suspension with urea formaldehyde

urea-ammonium sulphate

nitrogen fertiliser solution

ammonium nitrate-urea solution

1.2. Phosphatic fertilisers

Thomas slag:

— declaration expressed as a range of 2 % by mass

— declaration expressed as a single number

Other phosphatic fertilisers

P2O5 solubility in:

— mineral acid

— formic acid

— neutral ammonium citrate

— alkaline ammonium citrate

— water

0,4

0,4

0,4

0,4

1,0

1,0

0,3

0,8

0,6

0,8

0,8

0,8

0,4

0,4

0,4

0,4

0,5

0,6

0,6

0,0

1,0

0,8

0,8

0,8

0,8

0,9

1,3

(number of fertiliser in Annex I)

(3, 6, 7)

(7)

(2a, 2b, 2c)

(4, 5, 6)

(2a, 2b, 3)

(2c)

L 304/52

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Official Journal of the European Union

21.11.2003

1.3. Potassic fertilisers

kainit

enriched kainit salt

muriate of potash:

— up to and including 55 %

— more than 55 %

potassium chloride containing magnesium salt

sulphate of potash

sulphate of potash containing magnesium salt

1.4. Other components

chloride

2.

Inorganic compound primary nutrient fertilisers

2.1. Nutrient elements

N

P2O5

K2O

2.2. Total negative deviations from the declared value

binary fertilisers

ternary fertilisers

3.

Secondary nutrients in fertilisers

1,5

1,0

1,0

0,5

1,5

0,5

1,5

0,2

1,1

1,1

1,1

1,5

1,9

The tolerances allowed in respect of the declared calcium, magnesium, sodium and sulphur contents shall be a
quarter of the declared contents of these nutrients up to a maximum of 0,9 % in absolute terms for CaO, MgO,
Na2O, and SO3, i.e. 0,64 for Ca, 0,55 for Mg, 0,67 for Na and 0,36 for S.

4. Micro-nutrients in fertilisers

The tolerance allowed in respect of the declared micro-nutrient content shall be:

— 0,4 % in absolute terms for a content of more than 2 %,

— one fifth of the declared value for a content not exceeding 2 %.

The tolerance allowed in respect of the declared content for the various forms of nitrogen or the declared
solubilities of phosphorus pentoxide is one-tenth of
the nutrient concerned with a
maximum of 2 % by mass, provided that the overall content of that nutrient remains within the limits specified
in Annex I and the tolerances specified above.

the overall content of

21.11.2003

EN

Official Journal of the European Union

L 304/53

ANNEX III

TECHNICAL PROVISIONS FOR AMMONIUM NITRATE FERTILISERS OF HIGH NITROGEN CONTENT

1.

Characteristics of and limits for straight ammonium nitrate fertilisers of high nitrogen content

1.1.

Porosity (oil retention)

The oil retention of the fertiliser, which must first have undergone two thermal cycles of a temperature ranging
from 25 to 50 °C and conforming with the provisions of part 2 of section 3. of this Annex, must not exceed 4 %
by mass.

1.2. Combustible ingredients

The percentage by mass of combustible material measured as carbon must not exceed 0,2 % for fertilisers having
a nitrogen content of at least 31,5 % by mass and must not exceed 0,4 % for fertilisers having a nitrogen content
of at least 28 % but less than 31,5 % by mass.

1.3.

pH

A solution of 10 g of fertiliser in 100 ml of water must have a pH of at least 4.5.

1.4.

Particle size analysis

Not more than 5 % by mass of the fertiliser must pass through a 1 mm mesh sieve and not more than 3 % by
mass must pass through a 0,5 mm mesh sieve.

1.5. Chlorine

The maximum chlorine content is set at 0,02 % by mass.

1.6. Heavy metals

Heavy metals should not be added deliberately, and any traces which are incidental to the production process
should not exceed the limit fixed by the Committee.

The copper content shall not be higher than 10 mg/kg.

No limits are specified for other heavy metals.

2.

Description of the test of resistance to detonation concerning ammonium nitrate fertilisers of high
nitrogen content

The test must be carried out on a representative sample of fertiliser. Before being tested for resistance to
detonation, the whole mass of the sample is to be thermally cycled five times complying with the provisions
of part 3 in section 3. of this Annex.

The fertiliser must be subjected to the test of resistance to detonation in a horizontal steel tube under the
following conditions:

— seamless steel tube,

— Tube length: 1 000 mm at least,

— Nominal external diameter: 114 mm at least,

— Nominal wall thickness: 5 mm at least,

— Booster: the type and mass of the booster chosen should be such as to maximise the detonation pressure

applied to the sample in order to determine its susceptibility to the transmission of detonation,

— Test temperature: 15-25 °C,

— Witness lead cylinders for detecting detonation: 50 mm diameter and 100 mm high

L 304/54

EN

Official Journal of the European Union

21.11.2003

— placed at 150 mm intervals and supporting the tube horizontally. The test is to be carried out twice. The test
is deemed conclusive if in both tests one or more of the supporting lead cylinders is crushed by less than 5 %.

3.

Methods of checking compliance with the limits specified in Annexes III-1 and III-2

M e t h o d 1

Methods for the application of thermal cycles

1.

Scope and field of application

This document defines the procedures for the application of thermal cycles prior to the execution of the oil
retention test for straight ammonium nitrate fertilisers of high nitrogen content and of the test on the
resistance to detonation for both, straight and compound ammonium nitrate fertiliser of high nitrogen
content.

The methods of the closed thermal cycles as described in this section are regarded as simulating sufficiently
the conditions to be taken into account within the scope of application of title II, chapter IV, however,
these methods may not necessarily simulate all conditions arising during transport and storage;

2.

Thermal cycles referred to in Annex III-1

2.1.

Field of application

This procedure is for thermal cycling prior to determining the oil retention of the fertiliser.

2.2.

Principle and definition

the sample from ambient

In an Erlenmeyer flask, heat
this
temperature for a period of two hours (phase at 50 °C). Thereupon cool the sample until a temperature
of 25 °C is achieved and maintain at that temperature for two hours (phase at 25 °C). The combination of
the successive phases at 50 °C and 25 °C forms one thermal cycle. After being subjected to two thermal
cycles, the test sample is held at a temperature of 20 ±3 °C for the determination of the oil retention value.

temperature to 50 °C and maintain at

2.3. Apparatus

Normal laboratory apparatus, in particular:

— water baths thermostated at 25 (± 1) and 50 (± 1) °C respectively,

— Erlenmeyer flasks with an individual capacity of 150 ml.

2.4.

Procedure

Put each test sample of 70 (± 5) grams into an Erlenmeyer flask which is then sealed with a stopper.

Move each flask every two hours from the 50 °C bath to the 25 °C bath and vice versa.

Maintain the water in each bath at constant temperature and keep in motion by rapid stirring to ensure the
water level comes above the level of the sample. Protect the stopper from condensation by a foam rubber
cap.

3.

Thermal cycles to be used for Annex III-2

3.1.

Field of application

This procedure is for thermal cycling prior to the execution of the detonability test.

3.2.

Principle and definition

In a watertight box heat the sample from ambient temperature to 50 °C and maintain at this temperature
for a period of one hour (phase at 50 °C). Thereupon cool the sample until a temperature of 25 °C is
achieved and maintain at that temperature for one hour (phase at 25 °C). The combination of the
successive phases at 50 °C and 25 °C forms one thermal cycle. After being subjected to the required
number of thermal cycles, the test sample is held at a temperature of 20 ±3 °C pending the execution of
the detonability test.

21.11.2003

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Official Journal of the European Union

L 304/55

3.3. Apparatus

— A water bath, thermostated in a temperature range of 20 to 51 °C with a minimum heating and
cooling rate of 10 °C/h, or two water baths, one thermostated at a temperature of 20 °C, the other at
51 °C. The water in the bath(s) is continuously stirred; the volume of the bath should be large enough
to guarantee ample circulation of the water.

— A stainless steel box, watertight all around and provided with a thermocouple in the centre. The outside
width of the box is 45 (± 2) mm and the wall thickness is 1,5 mm (see Figure 1). The height and
length of the box can be chosen to suit the dimensions of the water bath, e.g. length 600 mm, height
400 mm.

3.4.

Procedure

Place a quantity of fertilisers sufficient for a single detonation into the box and close the cover. Place the
box in the water bath. Heat the water to 51 °C and measure the temperature in the centre of the fertiliser.
One hour after the temperature at the centre has reached 50 °C cool the water. One hour after the
temperature at the centre has reached 25 °C heat the water to start the second cycle. In the case of
two water baths, transfer the box to the other bath after each heating/cooling period.

Figure 1

M e t h o d 2

Determination of oil retention

1.

Scope and field of application

This document defines the procedure for the determination of oil retention of straight ammonium nitrate
fertilisers of high nitrogen content.

The method is applicable to both prilled and granular fertilisers which do not contain oil-soluble materials.

L 304/56

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Official Journal of the European Union

21.11.2003

2.

Definition

Oil retention of a fertiliser: the quantity of oil retained by the fertiliser determined under the operating
conditions specified, and expressed as a percentage by mass.

3.

Principle

Total immersion of the test portion in gas oil for a specified period, followed by the draining away of
surplus oil under specified conditions. Measurement of the increase in mass of the test portion.

4.

Reagent

Gas oil

Viscosity max.: 5 mPas at 40 °C

Density: 0,8 to 0,85 g/ml at 20 °C

Sulphur content: £ 1,0 % (m/m)

Ash: £ 0,1 % (m/m)

5.

Apparatus

Ordinary laboratory apparatus, and:

5.1. Balance, capable of weighing to the nearest 0,01 gram.

5.2. Beakers, of capacity 500 ml.

5.3.

Funnel, of plastic materials, preferably with a cylindrical wall at the upper end, diameter approximately
200 mm.

5.4. Test sieve, aperture 0,5 mm, fitting into the funnel (5.3).

Note: The size of the funnel and sieve is such as to ensure that only a few granules lie one above another
and the oil is able to drain easily.

5.5.

Filter paper, rapid filtering grade, creped, soft, mass 150 g/m2.

5.6. Absorbent tissue (laboratory grade).

6.

Procedure

6.1. Two individual determinations are carried out in quick succession on separate portions of the same test

sample.

6.2. Remove particles smaller than 0,5 mm using the test sieve (5.4). Weigh to the nearest 0,01 gram
approximately 50 grams of the sample into the beaker (5.2). Add sufficient gas oil (section 4) to cover
the prills completely and stir carefully to ensure that the surfaces of all the prills are fully wetted. Cover the
beaker with a watch glass and leave to stand for one hour at 25 (± 2) °C.

6.3.

Filter the entire contents of the beaker through the funnel (5.3) containing the test sieve (5.4). Allow the
portion retained by the sieve to remain there for one hour so that most of the excess oil can drain away.

6.4.

Lay two sheets of filter paper (5.5) (about 500 × 500 mm) on top of each other on a smooth surface; fold
the four edges of both filter papers upwards to a width of about 40 mm to prevent the prills from rolling
away. Place two layers of absorbent tissue (5.6) in the centre of the filter papers. Pour the entire contents of
the sieve (5.4) over the absorbent tissues and spread the prills evenly with a soft, flat brush. After two
minutes lift one side of the tissues to transfer the prills to the filter papers beneath and spread them evenly
over these with the brush. Lay another sheet of filter paper, similarly with its edges turned upward, on the
sample and roll the prills between the filter papers with circular movements while exerting a little pressure.
Pause after every eight circular movements to lift the opposite edges of the filter papers and return to the
centre the prills that have rolled to the periphery. Keep to the following procedure: make four complete
circular movements, first clockwise and then anticlockwise. Then roll the prills back to the centre as
described above. This procedure to be carried out three times (24 circular movements, edges lifted
twice). Carefully insert a new sheet of filter paper between the bottom sheet and the one above it and
allow the prills to roll onto the new sheet by lifting the edges of the upper sheet. Cover the prills with a
new sheet of filter paper and repeat the same procedure as described above. Immediately after rolling, pour
the prills into a tared dish and reweigh to the nearest 0,01 gram to determine the mass of the quantity of
gas oil retained.

21.11.2003

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L 304/57

6.5. Repeating the rolling procedure and reweighing

If the quantity of gas oil retained in the portion is found to be greater than 2 grams, place the portion on a
fresh set of filter papers and repeat the rolling procedure, lifting the corners in accordance with section 6.4
(two times eight circular movements, lifting once). Then reweigh the portion.

7.

Expression of the results

7.1. Method of calculation and formula

The oil retention, from each determination (6.1) expressed as a percentage by mass of the sieved test
portion, is given by the equation:

Oil retention ¼

m2 (cid:1) m1
m1

(cid:2) 100

where:

m1 is the mass, in grams, of the sieved test portion (6.2),

m2 is the mass, in grams, of the test portion according to section 6.4 or 6.5 respectively as the result of the
last weighing.

Take as the result the arithmetic mean of the two individual determinations.

M e t h o d 3

Determination of the combustible ingredients

1.

Scope and field of application

This document defines the procedure for the determination of
ammonium nitrate fertilisers of high nitrogen content.

the combustible content of straight

2.

Principle

The carbon dioxide produced by inorganic fillers is removed in advance with an acid. The organic
compounds are oxidised by means of a chromic acid/sulphuric acid mixture. Carbon dioxide formed is
absorbed in a barium hydroxide solution. The precipitate is dissolved in a solution of hydrochloric acid and
measured by back-titration with sodium hydroxide solution.

3.

Reagents

3.1. Analytical-grade chromium (VI) trioxide Cr2O3;

3.2.

Sulphuric acid, 60 % by volume: pour 360 ml of water into a one-litre beaker and carefully add 640 ml of
sulphuric acid (density at 20 °C = 1.83 g/ml).

3.3.

Silver nitrate: 0,1 mol/l solution.

3.4.

Barium hydroxide

Weigh out 15 grams of barium hydroxide [Ba(OH)2. 8H2O], and dissolve completely in hot water. Allow
to cool and transfer to a one-litre flask. Fill up to the mark and mix. Filter through a pleated filter paper.

3.5. Hydrochloric acid: 0,1 mol/l standard solution.

3.6.

Sodium hydroxide: 0,1 mol/l standard solution.

3.7.

Bromophenol blue: solution of 0,4 grams per litre in water.

3.8.

Phenolphthalein: solution of 2 grams per litre in 60 % by volume ethanol.

3.9.

Soda lime: particle dimensions, about 1,0 to 1,5 mm.

3.10. Demineralised water, freshly boiled to remove carbon dioxide.

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4.

Apparatus

4.1.

Standard laboratory equipment, in particular:

— filter crucible with a plate of sintered glass and a capacity of 15 ml; plate diameter: 20 mm; total

height: 50 mm; porosity 4 (pore diameter from 5 to 15 µm),

— 600-ml beaker.

4.2.

Compressed nitrogen supply.

4.3. Apparatus made up of the following parts and assembled, if possible, by means of spherical ground joints

(see Figure 2).

4.3.1. Absorption tube A about 200 mm long and 30 mm in diameter filled with soda lime (3.9) kept in place

by fibreglass plugs.

4.3.2. 500-ml reaction flask B with side arm and a round bottom.

4.3.3. Vigreux fractionating column about 150 mm long (C').

4.3.4. Double-surface condenser C, 200 mm long.

4.3.5. Drechsel bottle D acting as a trap for any excess acid which may distil over.

4.3.6. Ice bath E to cool the Drechsel bottle.

4.3.7. Two absorption vessels F1 and F2, 32 to 35 mm in diameter, the gas distributor of which comprises a

10 mm disc of low-porosity sintered glass.

4.3.8. Suction pump and suction regulating device G comprising a T-shaped glass piece inserted into the circuit,
the free arm of which is connected to the fine capillary tube by a short rubber tube fitted with a screw
clamp.

Caution: The use of boiling chromic acid solution in an apparatus under reduced pressure is a hazardous
operation and requires appropriate precautions.

5.

Procedure

5.1.

Sample for analysis

Weigh approximately 10 grams of ammonium nitrate to the nearest 0,001 grams.

5.2.

Removal of carbonates

Place the sample for analysis in the reaction flask B. Add 100 ml of H2SO4(3.2). The prills dissolve in
about 10 minutes at ambient temperature. Assemble the apparatus as indicated in the diagram: connect
one end of the absorption tube (A) to the nitrogen source (4.2) via a non-return flow device containing a
pressure equivalent to 5 to 6 mm of mercury and the other end to the feed tube which enters the reaction
flask. Place the Vigreux fractionating column (C') and the condenser (C) with cooling water supply in
position. Adjust the nitrogen to provide a moderate flow through the solution, bring the solution to
boiling point and heat for two minutes. At the end of this time there should be no more effervescence.
If effervescence is seen, continue heating for 30 minutes. Allow solution to cool for at least 20 minutes
with the nitrogen flowing through it.

Complete assembly of the apparatus as indicated in the diagram by connecting the condenser tube to the
Drechsel bottle (D) and the bottle to the absorption vessels F1 and F2. The nitrogen must continue to pass
through the solution during the assembly operation. Rapidly introduce 50 ml of barium hydroxide
solution (3.4) into each of the absorption vessels (F1 and F2).

Bubble a stream of nitrogen through for about 10 minutes. The solution must remain clear in the
absorbers. If this does not happen, the carbonate removal process must be repeated.

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5.3. Oxidation and absorption

After withdrawing the nitrogen feed tube, rapidly introduce 20 grams of chromium trioxide (3.1) and 6 ml
of silver nitrate solution (3.3) via the side arm of the reaction flask (B). Connect the apparatus to the
suction pump and adjust the nitrogen flow so that a steady stream of gas bubbles passes through the
sintered-glass absorbers F1 and F2.

Heat the reaction flask (B) until the liquid boils and keep it boiling for one and a half hours (1). It may be
necessary to adjust the suction-regulating valve (G) to control the nitrogen flow since it is possible that the
barium carbonate precipitated during the test may block the sintered-glass discs. The operation is satis-
factory when the barium hydroxide solution in the absorber F2 remains clear. Otherwise repeat the test.
Stop heating and dismantle the apparatus. Wash each of the distributors (3.10) both inside and outside to
remove barium hydroxide and collect the washings in the corresponding absorber. Place the distributors
one after the other in a 600-ml beaker which will subsequently be used for the determination.

Rapidly filter under vacuum firstly the contents of absorber F2 and then of absorber F1 using the
sintered-glass crucible. Collect the precipitate by rinsing the absorbers with water (3.10) and wash the
crucible with 50 ml of the same water. Place the crucible in the 600-ml beaker and add about 100 ml of
boiled water (3.10). Introduce 50 ml of boiled water into each of the absorbers and pass nitrogen through
the distributors for five minutes. Combine the water with that from the beaker. Repeat the operation once
to ensure that the distributors are rinsed thoroughly.

5.4. Measurement of the carbonates originating from organic material

Add five drops of phenolphthalein (3.8) to the contents of the beaker. The solution becomes red in colour.
Add hydrochloric acid (3.5) drop by drop until the pink colour just disappears. Stir the solution well in the
crucible to check that the pink colour does not reappear. Add five drops of bromphenol blue (3.7) and
titrate with hydrochloric acid (3.5) until the solution turns yellow. Add a further 10 ml of hydrochloric
acid.

Heat the solution to boiling point and continue boiling for a maximum of one minute. Check carefully that
no precipitate remains in the liquid.

Allow to cool and back titrate with the sodium hydroxide solution (3.6).

6.

Blank test

Carry out a blank test following the same procedure and using the same quantities of all reagents.

7.

Expression of the results

The content of combustible ingredients (C), expressed as carbon, as a percentage by mass of the sample, is
given by the formula:

C % ¼ 0,06 (cid:2)

V1 (cid:1) V2
E

where:

E

= the mass in grams of the test portion,

V1 = the total volume in ml of 0,1 mol/l hydrochloric acid added after the change in colour of the

phenolphthalein,

V2 = the volume in ml of the 0,1 mol/l sodium hydroxide solution used for back titration.

(1) A reaction time of one and a half hours, is sufficient in the case of most of the organic substances in the presence of silver nitrate

catalyst.

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Figure 2

M e t h o d 4

Determination of the pH value

1.

Scope and field of application

This document defines the procedure for measuring the pH value of a solution of a straight ammonium
nitrate fertiliser of high nitrogen content.

2.

Principle

Measurement of the pH of an ammonium nitrate solution by means of a pH meter.

3. Reagents

Distilled or demineralised water, free from carbon dioxide.

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3.1. Buffer solution, pH 6,88 at 20 °C

Dissolve 3,40 ± 0,01 grams of potassium dihydrogen orthophosphate (KH2PO4) in approximately 400 ml of
water. Then dissolve 3,55 ± 0,01 grams of disodium hydrogen orthophosphate (Na2HPO4) in approximately
400 ml of water. Transfer the two solutions without loss into a 1 000-ml graduated flask, make up to the
mark and mix. Keep this solution in an airtight vessel.

3.2. Buffer solution, pH 4,00 at 20 °C

Dissolve 10,21 ± 0,01 grams of potassium hydrogen phthalate (KHC8O4H4) in water, transfer without loss
into a 1 000-ml graduated flask, make up to the mark and mix.

Keep this solution in an airtight vessel.

3.3. Commercially available pH standard solutions may be used.

4. Apparatus

pH meter, equipped with glass and calomel electrodes or equivalent, sensitivity 0,05 pH unit.

5.

Procedure

5.1. Calibration of the pH meter

Calibrate the pH meter (4) at a temperature of 20 (± 1) °C, using the buffer solutions (3.1), (3.2) or (3.3). Pass
a slow stream of nitrogen onto the surface of the solution and maintain this throughout the test.

5.2. Determination

Pour 100,0 ml of water onto 10 (± 0,01) grams of the sample in a 250 ml beaker. Remove the insolubles
by filtering, decanting or centrifuging the liquid. Measure the pH value of the clear solution at a temperature
of 20 (± 1) °C according to the same procedure as for the calibration of the meter.

6.

Expression of the results

Express the result in pH units, to the nearest 0,1 unit, and state the temperature used.

M e t h o d 5

Determination of the particle size

1.

Scope and field of application

This document defines the procedure for the test sieving of straight ammonium nitrate fertilisers of high
nitrogen content.

2.

Principle

The test sample is sieved on a nest of three sieves, either by hand or by mechanical means. The mass
retained on each sieve is recorded and the percentage of material passing the required sieves are calculated.

3. Apparatus

3.1. 200-mm-diameter woven-wire test sieves with apertures of 2,0 mm, 1,0 mm and 0,5 mm respectively of

standard ranges. One lid and one receiver for these sieves.

3.2. Balance to weigh to 0,1 gram.

3.3. Mechanical sieve shaker (if available) capable of imparting both vertical and horizontal motion to the test

sample.

4.

Procedure

4.1. The sample is divided representatively into portions of approximately 100 grams.

4.2. Weigh one of these portions to the nearest 0,1 gram.

4.3. Arrange the nest of sieves in ascending order; receiver, 0,5 mm, 1 mm, 2 mm and place the weighed test

portion on the top sieve. Fit the lid to the top of the nest of sieves.

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4.4. Shake by hand or machine,

imparting both a vertical and horizontal motion and if by hand, tapping
occasionally. Continue this process for 10 minutes or until the quantity passing through each sieve in
one minute is less than 0,1 gram.

4.5. Remove the sieves from the nest in turn and collect the material retained, brush gently from the reverse side

with a soft brush, if necessary.

4.6. Weigh the material retained on each sieve and that collected in the receiver, to the nearest 0,1 gram.

5.

Evaluation of the results

5.1. Convert the fraction masses to a percentage of the total of the fraction masses (not of the original charge).

Calculate the percentage in the receiver (i.e. < 0,5 mm): A %

Calculate the percentage retained on the 0,5 mm sieve: B %

Calculate the percentage passing 1,0 mm, i.e. (A + B) %

The sum of the fraction masses should be within 2 % of the initial mass taken.

5.2. At least two separate analyses should be carried out and the individual results for A should not differ by

more than 1,0 % absolute and for B by more than 1,5 % absolute. Repeat the test if this is not the case.

6.

Expression of the results

Report the mean of the two values obtained for A on the one hand and for A + B on the other.

M e t h o d 6

Determination of the chlorine content (as chloride ion)

1.

Scope and field of application

This document defines the procedure for the determination of the chlorine content (as chloride ion) of
straight ammonium nitrate fertilisers with a high nitrogen content.

2.

Principle

Chloride ions dissolved in water are determined by potentiometric titration with silver nitrate in an acidic
medium.

3. Reagents

Distilled or demineralised water, free from chloride ions.

3.1. Acetone AR.

3.2. Concentrated nitric acid (density at 20 °C = 1,40 g/ml)

3.3. Silver nitrate 0,1 mol/l standard solution. Store this solution in a brown glass bottle.

3.4. Silver nitrate 0,004 mol/l standard solution – prepare this solution at the time of use.

3.5. Potassium chloride 0,1 mol/l standard reference solution. Weigh, to the nearest 0,1 mg, 3,7276 grams of
analytical-grade potassium chloride, previously dried for one hour in an oven at 130 °C and cooled in a
desiccator to ambient temperature. Dissolve in a little water, transfer the solution without loss into a 500-ml
standard flask, dilute to the mark and mix.

3.6. Potassium chloride, 0,004 mol/l standard reference solution — prepare this solution at the time of use.

4. Apparatus

4.1. Potentiometer with silver indicating electrode and calomel reference electrode, sensitivity 2 mV, covering the

range – 500 to + 500 mV.

4.2. Bridge, containing a saturated potassium nitrate solution, connected to the calomel electrode (4.1), fitted at

the ends with porous plugs.

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4.3. Magnetic stirrer, with a Teflon-coated rod.

4.4. Microburette with fine-pointed tip, graduated in 0,01 ml divisions.

5.

Procedure

5.1. Standardisation of the silver nitrate solution

Take 5,00 ml and 10,00 ml of the standard reference potassium chloride solution (3.6) and place in two
low-form beakers of convenient capacity (for example 250 ml). Carry out the following titration of the
contents of each beaker.

Add 5 ml of the nitric acid solution (3.2), 120 ml of the acetone (3.1) and sufficient water to bring the total
volume to about 150 ml. Place the rod of the magnetic stirrer (4.3) in the beaker and set the stirrer in
motion. Immerse the silver electrode (4.1) and the free end of the bridge (4.2) in the solution. Connect the
electrodes to the potentiometer (4.1) and, after verifying the zero of the apparatus, note the value of the
starting potential.

Titrate, using the microburette (4.4), adding initially 4 or 9 ml respectively of the silver nitrate solution
corresponding to the standard reference potassium chloride solution used. Continue the addition in 0,1 ml
portions for the 0,004 mol/l solutions and in 0,05 ml portions for the 0,1 mol/l solutions. After each
addition, await the stabilisation of the potential.

Record the volumes added and the corresponding values of the potential in the first two columns of a table.

In a third column of the table, record the successive increments (∆1E) of the potential E. In a fourth column,
record the differences (∆2E) positive or negative, between the potential increments (∆1E). The end of the
titration corresponds to the addition of the 0,1 or 0,05 ml portion (V1) of the silver nitrate solution which
gives the maximum value of ∆1E.

In order to calculate the exact volume (Veq) of the silver nitrate solution corresponding to the end of the
reaction, use the formula:

where:

Veq ¼ V0 þ ðV1 (cid:2)

b
B

Þ

V0 is the total volume, in ml, of the silver nitrate solution immediately lower than the volume which gives
the maximum increment of ∆1E,

V1 is the volume, in ml, of the last portion of the silver nitrate solution added (0,1 or 0,05 ml),

b is the last positive value of ∆2E,

B is the sum of the absolute values of the last positive values of ∆2E and the first negative value of ∆2E (see
example in Table 1).

5.2. Blank test

Carry out a blank test and take account thereof when calculating the final result.

The result V4 of the blank test on the reagents is given, in ml, by the formula:

V4 ¼ 2V3 (cid:1) V2

where:

V2 is the value, in ml, of the exact volume (Veq) of the silver nitrate solution corresponding to the titration of
10 ml of the potassium chloride standard reference solution used,

V3 is the value, in ml, of the exact volume (Veq) of the silver nitrate solution corresponding to the titration of
5 ml of the potassium chloride standard reference solution used.

5.3. Check test

The blank test can at the same time serve as a check that the apparatus is functioning satisfactorily and that
the test procedure is being implemented correctly.

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5.4. Determination

Take a portion of sample in the range 10 to 20 grams and weigh to the nearest 0,01 gram. Transfer
quantitatively to a 250-ml beaker. Add 20 ml of water, 5 ml of nitric acid solution (3.2), 120 ml of acetone
(3.1) and sufficient water to bring the total volume to about 150 ml.

Place the rod of the magnetic stirrer (4.3) in the beaker, place the beaker on the stirrer and set the stirrer in
motion. Immerse the silver electrode (4.1) and the free end of the bridge (4.2) in the solution, connect the
electrodes to the potentiometer (4.1) and, after having verified the zero of the apparatus, note the value of
the starting potential.

Titrate with the silver nitrate solution, by additions from the microburette (4.4) in increments of 0,1 ml.
After each addition, await the stabilisation of the potential.

Continue the titration as specified in 5.1, starting from the fourth paragraph: ‘Record the volumes added and
the corresponding values of the potential in the first two columns of a table . . .’.

6.

Expression of the results

Express the result of the analysis as the percentage of chlorine contained in the sample as received for
analysis. Calculate the percentage of chlorine (Cl) content from the formula:

Cl % ¼

0,3545 (cid:2) T (cid:2) ðV5 (cid:1) V4Þ (cid:2) 100
m

where:

T is the concentration of silver nitrate solution used, in mol/l

V4 is the result, in ml, of the blank test (5.2),

V5 is the value, in ml, of Veq corresponding to the determination (5.4),

m is the mass, in grams, of the test portion.

Volume of the silver nitrate solution
V
(ml)

4,80

4,90

5,00

5,10

5,20

Veq ¼ 4,9 þ 0,1 (cid:2) 37

37 þ 49 ¼ 4,943

Table 1: Example

Potential
E
(mV)

176

211

283

306

319

∆1E

35

72

23

13

∆2E

+ 37

– 49

– 10

M e t h o d 7

Determination of copper

1.

Scope and field of application

This document defines the procedure for the determination of copper content of straight ammonium
nitrate fertilisers of high nitrogen content.

2.

Principle

The sample is dissolved in dilute hydrochloric acid and the copper is determined by atomic absorption
spectrophotometry.

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3.

Reagents

3.1. Hydrochloric acid (density at 20 °C = 1,18 g/ml).

3.2. Hydrochloric acid, 6 mol/l solution.

3.3. Hydrochloric acid 0,5 mol/l solution.

3.4. Ammonium nitrate.

3.5. Hydrogen peroxide, 30 % w/v

3.6.

Copper solution (1) (stock): weigh, to the nearest 0,001 gram, 1 gram of pure copper, dissolve in 25 ml
6 mol/l hydrochloric acid solution (3.2), add 5 ml of hydrogen peroxide (3.5) in portions and dilute to 1
litre with water. 1 ml of this solution contains 1 000 µg of copper (Cu).

3.6.1. Copper solution (dilute): dilute 10 ml of stock solution (3.6) to 100 ml with water and then dilute 10 ml
of the resulting solution, to 100 ml with water, 1 ml of the final dilution contains 10 µg of copper (Cu).

Prepare this solution at the time of use.

4.

Apparatus

Atomic absorption spectrophotometer with a copper lamp (324,8 nm).

5.

Procedure

5.1.

Preparation of the solution for analysis

Weigh, to the nearest 0,001 gram, 25 grams of the sample, place it in a 400-ml beaker, add carefully
20 ml of hydrochloric acid (3.1) (there may be a vigorous reaction due to carbon dioxide formation). Add
more hydrochloric acid, if necessary. When effervescence has stopped, evaporate to dryness on a steam
bath, stirring occasionally with a glass rod. Add 15 ml 6 mol/l hydrochloric acid solution (3.2) and
120 ml of water. Stir with the glass rod, which should be left in the beaker, and cover the beaker
with a watch glass. Boil the solution gently until dissolution is complete and then cool.

Transfer the solution quantitatively into a 250-ml graduated flask, by washing the beaker with 5 ml
6 mol/l hydrochloric acid (3.2), and twice with 5 ml of boiling water, make up to the mark with
0,5 mol/l hydrochloric acid (3.3) and mix carefully.

Filter through a copper-free filter paper (2), discarding the first 50 ml.

5.2.

Blank solution

Prepare a blank solution from which only the sample has been omitted and allow for this in the calculation
of the final results.

5.3. Determination

5.3.1. Preparation of sample and blank test solutions

Dilute the sample solution (5.1) and the blank test solution (5.2) with 0,5 mol/l hydrochloric acid solution
(3.3) to a concentration of copper within the optimal measuring range of the spectrophotometer. Normally
no dilution is needed.

5.3.2. Preparation of the calibration solutions

By diluting the standard solution (3.6.1) with 0,5 mol/l hydrochloric acid solution (3.3), prepare at least
five standard solutions corresponding to the optimal measuring range of the spectrophotometer (0 to
5,0 mg/l Cu). Before making up to the mark, add to every solution ammonium nitrate (3.4) to give
concentration of 100 mg per ml.

(1) Commercially available standard copper solution may be used.
(2) Whatman 541 or equivalent.

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5.4.

Measurement

Set up the spectrophotometer (4) at a wavelength of 324,8 nm. Use an oxidising air-acetylene flame.
Spray successively,
in triplicate, the calibration solution (5.3.2), the sample solution and the blank
solution (5.3.1), washing the instrument through with distilled water between each spraying. Plot the
calibration curve using the mean absorbances of every standard used as the ordinates and the corre-
sponding concentrations of copper in µg/ml as the abscissae.

Determine the concentration of copper in the final sample and blank solutions by reference to the
calibration curve.

6.

Expression of the results

Calculate the copper content of the sample taking into account the mass of the test sample, the dilutions
carried out in the course of the analysis and the value of the blank. Express the result as mg Cu/kg.

4.

Determination of resistance to detonation

4.1.

Scope and field of application

This document defines the procedure for the determination or resistance to detonation of ammonium nitrate
fertilisers of high nitrogen content.

4.2.

Principle

The test sample is confined in a steel tube and subjected to detonation shock from an explosive booster charge.
Propagation of the detonation is determined from the degree of crushing of lead cylinders on which the tube
rests horizontally during the test.

4.3.

Materials

4.3.1.

Plastic explosive containing 83 to 86 % penthrite

Density: 1 500 to 1 600 kg/m3

Detonation velocity: 7 300 to 7 700 m/s

Mass: 500 (± 1) gram.

4.3.2.

Seven lengths of flexible detonating cord with non-metallic sleeve

Filling mass: 11 to 13 g/m

Length of each cord: 400 (± 2) mm.

4.3.3.

Compressed pellet of secondary explosive, recessed to receive detonator

Explosive: hexogen/wax 95/5 or tetryl or similar secondary explosive, with or without added graphite.

Density: 1 500 to 1 600 kg/m3

Diameter: 19 to 21 mm

Height: 19 to 23 mm

Central recess to receive detonator: diameter 7 to 7,3 mm, depth 12 mm.

4.3.4.

Seamless steel tube as specified in ISO 65 — 1981 — Heavy Series, with nominal dimensions DN 100 (4'')

Outside diameter: 113,1 to 115,0 mm

Wall thickness: 5,0 to 6,5 mm

Length: 1 005 (± 2) mm.

4.3.5.

Bottom place

Material: steel of good weldable quality

Dimensions: 160 × 160 mm

Thickness: 5 to 6 mm

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4.3.6.

Six lead cylinders

Diameter: 50 (± 1) mm

Height: 100 to 101 mm

Materials: soft lead, at least 99,5 % purity.

4.3.7.

Steel block

Length: at least 1 000 mm

Width: at least 150 mm

Height: at least 150 mm

Mass: at least 300 kg if there is no firm base for the steel block.

4.3.8.

Plastic or cardboard cylinder for booster charge

Wall thickness: 1,5 to 2,5 mm

Diameter: 92 to 96 mm

Height: 64 to 67 mm

4.3.9.

Detonator (electric or non-electric) with initiation force 8 to 10

4.3.10. Wooden disc

Diameter: 92 to 96 mm. Diameter to be matched to the internal diameter of the plastic or cardboard cylinder
(4.3.8)

Thickness: 20 mm

4.3.11. Wooden rod of same dimensions as detonator (4.3.9)

4.3.12.

Dressmaking pins (maximum length 20 mm)

4.4.

Procedure

4.4.1.

Preparation of booster charge for insertion into steel tube

There are two methods of initiation of the explosive in the booster charge, depending on the availability of
equipment.

4.4.1.1.

Seven-point simultaneous initiation

The booster charge prepared for use is shown in Figure 1.

4.4.1.1.1. Drill holes in the wooden disc (4.3.10) parallel to the axis of the disc through the centre and through six
points symmetrically distributed around a concentric circle 55 mm in diameter. The diameter of the holes
must be 6 to 7 mm (see Section A-B in Figure 1), depending on the diameter of the detonating cord used
(4.3.2).

4.4.1.1.2. Cut seven lengths of flexible detonating cord (4.3.2) each 400 mm long, avoiding any loss of explosive at
each end by making a clean cut and immediately sealing the end with adhesive. Push each of the seven
lengths through the seven holes in the wooden disc (4.3.10) until their ends project a few centimetres on the
other side of the disc. Then insert a small dressmaking pin (4.3.12) transversally into the textile sleeve of each
length of cord 5 to 6 mm from the end and apply adhesive around the outside of the lengths of cord in a
band 2 cm wide adjacent to the pin. Finally, pull the long piece of each cord to bring the pin into contact
with the wooden disc.

4.4.1.1.3. Shape the plastic explosive (4.3.1) to form a cylinder 92 to 96 mm in diameter, depending on the diameter
of the cylinder (4.3.8). Stand this cylinder upright on a level surface and insert the shaped explosive. Then
insert the wooden disc (1) carrying the seven lengths of detonating cord into the top of the cylinder and press
it down onto the explosive. Adjust the height of the cylinder (64 to 67 mm) so that its top edge does not
extend beyond the level of the wood. Finally, fix the cylinder to the wooden disc for instance with staples or
small nails, around its entire circumference.

4.4.1.1.4. Group the free ends of the seven lengths of detonating cord around the circumference of the wooden rod
(4.3.11) so that their ends are all level in a plane perpendicular to the rod. Secure them in a bundle around
the rod by means of adhesive tape (2).

(1) The diameter of the disc must always correspond to the inside diameter of the cylinder.
(2) NB: When the six peripheral lengths of cord are taut after assembly, the central cord must remain slightly slack.

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4.4.1.2.

Central initiation by a compressed pellet

The booster charge prepared for use is shown in Figure 2.

4.4.1.2.1. Preparing a compressed pellet

Taking the necessary safety precautions, place 10 grams of a secondary explosive (4.3.3) in a mould with an
inside diameter of 19 to 21 mm and compress to the correct shape and density.

(The ratio of diameter: height should be roughly 1:1).

In the centre of the bottom of the mould there is a peg, 12 mm in height and 7,0 to 7,3 mm in diameter
(depending on the diameter of the detonator used), which forms a cylindrical recess in the compressed
cartridge for subsequent insertion of the detonator.

4.4.1.2.2. Preparing the booster charge

Place the explosive (4.3.1) into the cylinder (4.3.8) standing upright on a level surface, then press it down
with a wooden die to give the explosive a cylindrical shape with a central recess. Insert the compressed pellet
into this recess. Cover the cylindrically shaped explosive containing the compressed pellet with a wooden disc
(4.3.10) having a central hole 7,0 to 7,3 mm in diameter for insertion of a detonator. Fix the wooden disc
and the cylinder together with a cross of adhesive tape. Ensure that the hole drilled in the disc and the recess
in the compressed pellet are coaxial by inserting the wooden rod (4.3.11).

4.4.2.

Preparing steel tubes for the detonation tests

At one end of the steel tube (4.3.4), drill two diametrically opposed holes 4 mm in diameter perpendicularly
through the side wall at a distance of 4 mm from the edge.

Butt weld the bottom plate (4.3.5) to the opposite end of the tube, completely filling the right angle between
the bottom place and the wall of the tube with weld metal around the entire circumference of the tube.

4.4.3.

Filling and charging the steel tube

See Figures 1 and 2.

4.4.3.1.

The test sample, the steel tube and the booster charge must be conditioned to temperatures of 20 (± 5) °C. 16
to 18 kg of the test sample are needed for two detonation tests.

4.4.3.2.

Place the tube upright with its square bottom place resting on a firm, flat surface, preferably concrete. Fill the
tube to about one-third of its height with the test sample and drop it 10 cm vertically onto the floor five
times to compact the prills or granules as densely as possible in the tube. To accelerate compaction, vibrate
the tube by striking the side wall with a 750 to 1 000-gram hammer between drops for a total of 10 times.

Repeat this charging method with another portion of the test sample. Finally, a further addition shall be made
such that, after compaction by raising and dropping the tube 10 times and a total of 20 intermittent hammer
blows, the charge fills the tube to a distance of 70 mm from its orifice.

The filling height of the sample must be adjusted in the steel tube so that the booster charge (4.4.1.1 or
4.4.1.2) to be inserted later will be in close contact with the sample over its entire surface.

4.4.3.3.

Insert the booster charge into the tube so that it is in contact with the sample; the top surface of the wooden
disc must be 6 mm below the end of the tube. Ensure essential close contact between explosive and test
sample by adding or removing small quantities of sample. As shown in Figures 1 and 2, split pins should be
inserted through the holes near the open end of the tube and their legs opened flat against the tube.

4.4.4.

Positioning of the steel tube and lead cylinders (see figure 3)

4.4.4.1. Number the bases of the lead cylinders (4.3.6) 1 to 6. Make six marks 150 mm apart on the centre line of a
steel block (4.3.7) lying on a horizontal base, with the first mark at least 75 mm from the edge of the block.
Place a lead cylinder upright on each of these marks, with the base of each cylinder centred on its mark.

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4.4.4.2.

Lay the steel tube prepared according to 4.4.3 horizontally on the lead cylinders so that the axis of the tube is
parallel to the centre line of the steel block and the welded end of the tube extends 50 mm beyond lead
cylinder No 6. To prevent the tube from rolling, insert small wooden wedges between the tops of the lead
cylinders and the tube wall (one on each side) or place a cross of wood between the tube and the steel block.

Note: Make sure that the tube is in contact with all six lead cylinders; a slight curvature of the tube surface
can be compensated for by rotating the tube about its longitudinal axis; if any of the lead cylinders is too tall,
tap the cylinder in question carefully with a hammer until it is the required height.

4.4.5.

Preparation for detonation

4.4.5.1.

Set up the apparatus according to the 4.4.4 in a bunker or suitably prepared underground site (e.g. mine or
tunnel). Ensure that the temperature of the steel tube is kept at 20 (± 5) °C before detonation.

Note: Should such firing sites not be available, the work can, if necessary, be done in a concrete-lined pit
covered over with wooden beams. Detonation can cause steel fragments to be projected with high kinetic
energy, therefore, firing must be carried out at a suitable distance from dwellings or thoroughfares.

4.4.5.2.

If the booster charge with seven-point initiation is used, ensure that the detonation cords are stretched out as
described in the footnote to 4.4.1.1.4 and arranged as horizontally as possible.

4.4.5.3.

Finally, remove the wooden rod and replace with the detonator. Do not carry out firing until the danger zone
has been evacuated and the test personnel have taken cover.

4.4.5.4. Detonate the explosive.

4.4.6.

Allow sufficient time for the fumes (gaseous and sometimes toxic decomposition products such as nitrous
gases) to disperse, then collect the lead cylinders and measure their heights with a Vernier caliper

Record for each of the marked lead cylinders, the degree of crushing expressed as a percentage of the original
height of 100 mm. If the cylinders are crushed obliquely, record the highest and the lowest values and
calculate the average.

4.4.7.

A probe for continuous measurement of the detonation velocity can be used; the probe should be inserted
longitudinally to the axis of the tube or along its side wall

4.4.8.

Two detonation tests per sample are to be carried out

4.5.

Test report

Values for the following parameters are to be given in the test report for each of the detonation tests:

— the values actually measures for the outside diameter of the steel tube and for the wall thickness,

— the Brinell hardness of the steel tube,

— the temperature of the tube and the sample shortly before firing,

— the packing density (kg/m3) of the sample in the steel tube,

— the height of each lead cylinder after firing, specifying the corresponding cylinder number,

— method of initiation employed for the booster charge.

4.5.1.

Evaluation of test results

If, in each firing, the crushing of at least one lead cylinder is less than 5 %, the test shall be considered
conclusive and the sample in conformity with the requirements of Annex III.2.

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Figure 1

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Figure 2

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Figure 3

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ANNEX IV

METHODS OF SAMPLING AND ANALYSIS

A. METHOD OF SAMPLING FOR THE CONTROL OF FERTILISERS

INTRODUCTION

Correct sampling is a difficult operation which requires the greatest of care. The need to obtain a sufficiently represen-
tative sample for the official testing of fertilisers cannot, therefore, be stressed too much.

The sampling method described below must be applied with strict accuracy by specialists with experience of the
conventional sampling procedure.

1.

Purpose and scope

Samples intended for the official control of fertilisers, for quality and composition, shall be taken according
to the methods described below. Samples thus obtained shall be considered as representative of the sampled
portions.

Sampling officers

The samples shall be taken by specialist officers authorised for that purpose by the Member States.

Definitions

Sampled portion: A quantity of product constituting a unit, and having characteristics presumed to be
uniform.

Incremental sample: A quantity taken from one point in the sampled portion.

Aggregate sample: An aggregate of incremental samples taken from the same sampled portion.

Reduced sample: A representative part of the aggregate sample, obtained from the latter by a process of
reduction.

Final sample: A representative part of the reduced sample.

Apparatus

The sampling apparatus must be made of materials which cannot affect the characteristics of the products to
be sampled. Such apparatus may be officially approved by the Member States.

2.

3.

4.

4.1.

4.2.

Apparatus recommended for the sampling of solid fertilisers

4.2.1.

Manual sampling

4.2.1.1.

Flat-bottomed shovel with vertical sides.

4.2.1.2.

Sampling spear with a long split or compartments. The dimensions of the sampling spear must be appro-
priate to the characteristics of the sampled portion (depth of container, dimensions of sack, etc.) and to the
particle size of the fertiliser.

4.2.2.

Mechanical sampling

Approved mechanical apparatus may be used for the sampling of moving fertilisers.

4.2.3.

Divider

Apparatus designed to divide the sample into equal parts may be used for taking incremental samples and
for the preparation of reduced and final samples.

4.3.

Apparatus recommended for the sampling of fluid fertilisers

4.3.1.

Manual sampling

Open tube, probe, bottle or another appropriate equipment able to take samples at random from the
sampled portion.

4.3.2.

Mechanical sampling

Approved mechanical apparatus may be used for sampling of moving fluid fertilisers.

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5.

5.1.

Quantitative requirements

Sampled portion

The size of the sampled portion must be such that each of its constituent parts can be sampled.

5.2.

Incremental samples

5.2.1.

Loose solid fertilisers or fluid fertilisers in containers exceeding 100 kg

5.2.1.1.

Sampled portions not exceeding 2,5 tonnes:

Minimum number of incremental samples: seven

5.2.1.2.

Sampled portions exceeding 2,5 tonnes and up to 80 tonnes:

Minimum number of incremental samples:

ﬃp

20 times the number of tonnes
making up the sampled portion (1)

5.2.1.3.

Sampled portions exceeding 80 tonnes:

Minimum number of incremental samples: 40

5.2.2.

Packaged solid fertilisers or fluid fertilisers in containers (= packages each not exceeding 100 kg)

5.2.2.1.

Packages of more than 1 kg

5.2.2.1.1. Sampled portions of less than five packages:

Minimum number of packages to be sampled (2): all packages.

5.2.2.1.2. Sampled portions of five to 16 packages:

Minimum number of packages to be sampled (2): four.

5.2.2.1.3. Sampled portions of 17 to 400 packages:

Minimum number of packages to be sampled (2):

ﬃp

number of packages making up
the sampled portion (1)

5.2.2.1.4. Sampled portions exceeding 400 packages:

Minimum number of packages to be sampled (2): 20.

5.2.2.2.

Packages not exceeding 1 kg:

Minimum number of packages to be sampled (2): four.

5.3.

Aggregate sample

A single aggregate sample per sampled portion is required. The total mass of the incremental samples
making up the aggregate sample shall be not less than the following:

5.3.1.

Loose solid fertilisers or fluid fertilisers in containers exceeding 100 kg: 4 kg.

5.3.2.

Packaged solid fertilisers or fluid fertilisers in containers (= packages) each not exceeding 100 kg

5.3.2.1.

Packages of more than 1 kg: 4 kg

5.3.2.2.

Packages not exceeding 1 kg: mass of the contents of four original packages.

5.3.3.

Ammonium nitrate fertiliser sample for tests according to Annex III.2: 75 kg

(1) Where the number obtained is a fraction, it should be rounded up to the next whole number.
(2) For packages whose contents do not exceed 1 kg, an incremental sample shall be the contents of one original package.

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5.4.

Final samples

The aggregate sample gives the final samples on reduction when necessary. Analysis of at least one final
sample is required. The mass of the sample for analysis shall not be less than 500 g.

5.4.1.

Solid and fluid fertilisers

5.4.2.

Ammonium nitrate fertiliser sample for tests

The aggregate sample gives the final sample for tests on reduction when necessary.

5.4.2.1.

Minimum final sample mass for Annex III.1 tests: 1 kg

5.4.2.2.

Minimum final sample mass for Annex III.2 tests: 25 kg

6.

6.1.

Instructions for taking, preparing and packaging the samples

General

The samples must be taken and prepared as quickly as possible bearing in mind the precautions necessary to
ensure that they remain representative of the fertiliser sampled. Instruments and also surfaces and containers
intended to receive samples must be clean and dry.

In the case of fluid fertilisers, if possible the sampled portion should be mixed prior to sampling.

6.2.

Incremental samples

Incremental samples must be taken at random throughout the whole sampled portion and they must be of
approximately equal sizes.

6.2.1.

Loose solid fertilisers or fluid fertilisers in containers exceeding 100 kg

An imaginary division shall be made of the sampled portion into a number of approximately equal parts. A
number of parts corresponding to the number of incremental samples required in accordance with 5.2 shall
be selected at random and at least one sample taken from each of these parts. Where it is not possible to
comply with the requirements of 5.1 when sampling bulk fertilisers or fluid fertilisers in containers
exceeding 100 kg the sampling should be carried out when the sampled portion is being moved
(loading or unloading). In this case samples shall be taken from the randomly selected notional parts as
defined above while these are being moved.

6.2.2.

Packaged solid fertilisers or fluid fertilisers in containers (= packages) each not exceeding 100 kg

Having selected the required number of packages for sampling as indicated in 5.2, part of the contents of
each package shall be removed. Where necessary, the samples shall be taken after emptying the packages
separately.

6.3.

Preparation of aggregate sample

The incremental samples shall be mixed to form a single aggregate sample.

6.4.

Preparation of the final sample

The material in the aggregate sample shall be carefully mixed (1).

If necessary the aggregate sample should first be reduced to at least 2 kg (reduced sample) either by using a
mechanical divider or by the quartering method.

At least three final samples shall then be prepared, of approximately the same amount and conforming to
the quantitative requirements of 5.4. Each sample shall be put into an appropriate air tight container. All
necessary precautions shall be taken to avoid any change in the characteristics of the sample.

For the tests of Annex III, sections 1 and 2, the final samples shall be kept at a temperature between 0 °C
and 25 °C.

(1) Any lumps shall be broken up (if necessary by separating them out and returning them to the sample).

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7.

8.

9.

Packaging of final samples

The containers or packages shall be scaled and labelled (the total label must be incorporated in the seal) in
such a manner that they cannot be opened without damaging the seal.

Sampling record

A record must be kept of each sampling, permitting each sampled portion to be identified unambiguously.

Destination of samples

For each sample portion at least one final sample shall be sent as quickly as possible to an authorised
analytical laboratory or to the test institution, together with the information necessary for the analysis or the
test.

B. METHODS FOR THE ANALYSIS OF FERTILISERS

(See table of contents p. 2.)

L a b o r a t o r y e q u i p m e n t

General observations

In the descriptions of the methods, general laboratory equipment has not been precisely defined, except that the sizes of
flasks and pipettes are given. In all cases laboratory apparatus must be well cleaned, particularly when small quantities of
elements are to be determined.

C o n t r o l

t e s t s

Before analysis it is necessary to ensure that all apparatus functions well and that the analytical technique is carried out
correctly, using where appropriate chemical compounds of known composition (e.g. ammonium sulphate, mono
potassium phosphate, etc.). Nevertheless, the results from analysed fertilisers can indicate wrong chemical composition
if the analytical technique is not rigorously followed. On the other hand, a certain number of determinations are
empirical and are relative to products of complex chemical composition. It is recommended that where available,
laboratories should make use of standard reference fertilisers of well defined composition.

General provisions relating to methods of analysing fertilisers

1. R e a g e n t s

Unless otherwise specified in the method of analysis, all of the reagents must be analysis-pur (a.p.). Where micro-
nutrients are to be analysed the purity of the reagents must be checked by means of a blank test. Depending upon
the result obtained, it might be necessary to conduct a further purification.

2. W a t e r

Where dissolution, dilution, rinsing or washing operations referred to in the methods of analysis do not specify the
nature of solvents or diluents the use of water is implied. Normally, the water will have to be demineralised or
distilled. In these specific instances, as mentioned in the method of analysis, that water will have to be subjected to
specific purification processes.

3. L a b o r a t o r y e q u i p m e n t

In view of the equipment normally used in inspection laboratories, the apparatus described in the methods of
analysis is restricted to special instruments and apparatus or to such demanded by any specific requirements. This
equipment must be perfectly clean, above all where small quantities are to be determined. The laboratory will have to
ensure the accuracy of any graduated glassware used by referring to appropriate metrological standards.

M e t h o d 1

Preparation of the sample for analysis

1.

Scope

This document defines the procedure for the preparation of the sample for analysis, taken from the final
sample.

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2.

Principle

The preparation of a final sample received at the laboratory is a series of operations, usually sieving, grinding
and mixing, carried out in such a way that:

— on the one hand, the smallest amount weighed out laid down by the methods of analysis is represen-

tative of the laboratory sample,

— on the other hand, the fineness of the fertiliser cannot have been changed by the preparation to the

extent that its solubility in the various extraction reagents is appreciably affected.

3.

Apparatus

Sample divider (optional).

Sieves with apertus of 0,2 and 0,5 mm.

250-ml flasks, stoppered.

Porcelain pestle and mortar or grinder.

4.

Choice of treatment to be used

Preliminary remark

If the product is suitable, only a representative part of the final sample need be kept.

4.1.

Final samples which must not be ground

Calcium nitrate, calcium magnesium nitrate, sodium nitrate, Chile nitrate, calcium cyanamide, nitrogenous
calcium cyanamide, ammonium sulphate, ammonium nitrates of over 30 % N, urea, basic slag, natural
phosphate rendered partially soluble, precipitated dihydrated dicalcium phosphate, calcined phosphate,
aluminium calcium phosphate, soft ground rock phosphate.

4.2.

Final samples which must be divided and part of which must be ground

These are products in respect of which certain determinations are carried out without previous grinding
(fineness of grinding for example) and other determinations after grinding. They include all compound
fertilisers containing the following phosphate ingredients: basic slag, aluminium calcium phosphate,
calcined phosphate, soft ground rock phosphate and natural phosphate rendered partially soluble. To that
end, divide the final sample into two parts, which are as identical as possible, using a sample divider or by
quartering.

4.3.

Final samples in respect of which all determinations are carried out on a ground product

Only a representative part of the final sample need be ground. These are all the other fertilisers on the list
which are not to be found under 4.1 and 4.2.

5.

Method

The part of the final sample referred to under 4.2 and 4.3 is sieved rapidly through a sieve with apertures of
0,5 mm. The residue is ground roughly so as to obtain a product in which there is a minimum of fine
particles, and it is then sieved. The grinding must be done in conditions such that the substance is not
appreciably heated. The operation is repeated as many times as is necessary until there is no residue, and it
must be effected as quickly as possible in order to prevent any gain or loss of constituents (water, ammonia).
The whole ground and sieved product is placed in a clean flask which can be stoppered.

Before any weighing is carried out for the analysis, the whole sample must be thoroughly mixed.

6.

Special cases

(a) Fertilisers comprising a blend of several categories of crystals

In this case, separation frequently occurs. It is therefore absolutely essential to crush and pass the sample
through a sieve with apertures of 0,200 mm. For example: mixtures of ammonium phosphate and
potassium nitrate. The grinding of the whole of the final sample is recommended in the case of these
products.

(b) Residue which is difficult to grind and does not contain fertilising substances

Weigh the residue and take account of its mass when calculating the final result.

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(c) Products which decompose on heating

Grinding must be carried out in such a way as to avoid any heating. It is preferable in this case to use a
mortar for grinding. For example: compound fertilisers containing calcium cyanamide and urea.

(d) Products which are abnormally moist or made into a paste by grinding

To ensure homogeneity, a sieve is to be chosen which has the smallest apertures compatible with the
destruction of lumps by hand or with the pestle. This may be the case of mixtures, certain ingredients of
which contain water of crystallisation.

M e t h o d s 2

Nitrogen

M e t h o d 2.1

Determination of ammoniacal nitrogen

1.

2.

Scope

This document defines the procedure for the determination of the ammoniacal nitrogen.

Field of application

All nitrogenous fertilisers, including compound fertilisers, in which nitrogen is found exclusively either in the
form of ammonium salts, or ammonium salts together with nitrates.

It is not applicable to fertilisers containing urea, cyanamide or other organic nitrogenous compounds.

3.

Principle

Displacement of ammonia by means of an excess of sodium hydroxide; distillation; determining the yield of
ammonia in a given volume of a standard sulphuric acid and titration of the excess acid by means of a
standard solution of sodium or potassium hydroxide.

4.

Reagents

Distilled or demineralised water, free from carbon dioxide and all nitrogenous compounds.

4.1.

Diluted hydrochloric acid: one volume of HCl (d20 = 1,18 g/ml) plus one volume of water

4.2.

4.3.

4.4.

4.5.

4.6.

4.7.

4.8.

4.9.

Sulphuric acid: 0,1 mol/l

9
>>=

Sodium or potassium hydroxide solution, carbonate
free: 0,1 mol/l

>>;

for variant a.

Sulphuric acid: 0,2 mol/l

9
>>=

Sodium or potassium hydroxide solution, carbonate
free: 0,2 mol/l

>>;

Sulphuric acid: 0,5 mol/l

9
>>=

Sodium or potassium hydroxide solution, carbonate
free: 0,5 mol/l

>>;

for variant b (see note 2).

for variant c (see note 2).

Sodium hydroxide, approximately 30 % NaOH (d20 = 1,33 g/ml), ammonia free

Indicator solutions

4.9.1.

Mixed indicator

Solution A: Dissolve 1 g of methyl red in 37 ml of sodium hydroxide solution 0,1 mol/l and make up to
one litre with water.

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Solution B: Dissolve 1 g of methylene blue in water and make up to one litre.

Mix one volume of A with two volumes of B.

This indicator is violet in acid solution, grey in neutral solution and green in alkaline solution. Use 0,5 ml
(10 drops) of this indicator solution.

4.9.2.

Methyl red indicator solution

Dissolve 0,1 g of methyl red in 50 ml of 95 % ethanol. Make up to 100 ml with water and filter if
necessary. This indicator may be used (four to five drops) instead of the preceding one.

4.10.

Anti-bump granules of pumice stone, washed in hydrochloric acid and calcined

4.11.

Ammonium sulphate for analysis

5.

5.1.

5.2.

5.3.

5.4.

6.

7.

7.1.

Apparatus

Distillation apparatus consisting of a round-bottomed flask of suitable capacity connected to a condenser by
means of a splash head

N o t e 1

The different types of equipment approved and recommended for this determination are reproduced,
showing all the features of construction, in Figures 1, 2, 3 and 4.

Pipettes of 10, 20, 25, 50, 100 and 200 ml

A 500-ml graduated flask

Rotary shaker (35 to 40 turns per minute)

Preparation of the sample

See Method 1.

Method of analysis

Preparation of the solution

Carry out a solubility test on the sample in water at room temperature and in the proportion of 2 % (W/V).
Weigh to 0,001 g, according to the indications in Table 1, a quantity of 5 or 7 or 10 g of the prepared
sample and place it in a 500-ml graduated flask. According to the result of the solubility test, proceed as
follows:

(a) Products completely soluble in water

Add to the flask the quantity of water needed to dissolve the sample; shake, and when completely
dissolved, make up the volume and mix thoroughly.

(b) Products not completely soluble in water

Add to the flask 50 ml of water and then 20 ml of hydrochloric acid (4.1). Shake. Leave undisturbed
until the evolution of carbon dioxide has ceased. Add 400 ml of water and shake for half an hour with
the rotary shaker (5.4). Make up the volume with water, mix and filter through a dry filter into a dry
receptacle.

7.2.

Analysis of the solution

According to the variant chosen, place in the receiving flask a measured quantity of standard sulphuric acid
as indicated in Table 1. Add the appropriate quantity of the chosen indicator solution (4.9.1 or 4.9.2) and, if
necessary, water in order to obtain a volume of at least 50 ml. The end of the extension tube of the
condenser must be below the surface of the solution.

Transfer by precision pipette, according to the details given in the table, an aliquot portion (1) of the clear
solution, into the distilling flask of the apparatus. Add water in order to obtain a total volume of about
350 ml, and several grains of pumice in order to control the boiling.

(1) The quantity of ammoniacal nitrogen contained in the aliquot part taken according to Table 1 will be approximately:

— 0,05 g for variant a,
— 0,10 g for variant b,
— 0,20 g for variant c.

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Assemble the distillation apparatus, and taking care to avoid any loss of ammonia, add to the contents of the
distillation flask 10 ml of concentrated sodium hydroxide solution (4.8) or 20 ml of the reagent in the cases
where one has used 20 ml hydrochloric acid (4.1) in order to dissolve the test sample. Gradually warm the
flask, to avoid boiling vigorously. When boiling commences, distil at the rate of about 100 ml in 10 to 15
minutes; the total volume of distillate should be about 250 ml (1). When no more ammonia is likely to be
evolved, lower the receiving flask so that the tip of the condenser extension is above the surface of the
liquid.

Test the subsequent distillate by means of an appropriate reagent to ensure that all the ammonia is
completely distilled. Wash the condenser extension with a little water and titrate the surplus acid with
the standard solution of sodium or potassium hydroxide prescribed for the variant adopted (see note 2).

N o t e 2

Standard solutions of different strengths may be used for the back titration provided that the volumes used
for the titration do not, as far as possible, exceed 40 to 45 ml.

7.3.

Blank

Make a blank test under the same conditions and refer to this in the calculation of the final result.

7.4.

Control test

8.

9.

Before carrying out analyses, check that the apparatus is working properly and that the correct application
of the method is used, using an aliquot part of a freshly prepared solution of ammonium sulphate (4.11)
containing the maximum quantity of nitrogen prescribed for the chosen variant.

Expression of the result

Express the result of the analysis as the percentage of ammoniacal nitrogen in the fertiliser as received for
analysis.

Annexes

As specified in Note 1 in 5.1 ‘Apparatus’, Figures 1, 2, 3 and 4 refer to construction features of the different
types of equipment used in this document.

Table 1

Determination of the ammoniacal nitrogen and of the ammoniacal and nitrate nitrogen in fertilisers

Table of the weighing, dilution and calculation to be carried out for each of the variants a, b and c of
the method

Variant a

Approximate maximum quantity of nitrogen to be distilled: 50 mg.

Sulphuric acid 0,1 mol/l to be placed in the receiving flask: 50 ml.

Back titration with NaOH or KOH 0,1 mol/l.

Declaration
(% N)

Amount to be
weighed
(g)

Dilution
(ml)

Solution of sample
to be distilled
(ml)

Expression of the result (a)
(% N = (50 — A) F)

0-5

5-10

10-15

15-20

20-40

10

10

7

5

7

500

500

500

500

500

50

25

25

25

10

(50 — A) × 0,14

(50 — A) × 0,28

(50 — A) × 0,40

(50 — A) × 0,56

(50 — A) × 1,00

(a) For the purposes of the formula for expression of the result:

— 50 or 35 = millilitres of standard solution of sulphuric acid to be placed in the receiving flask;
— A = millilitres of sodium or potassium hydroxide used for the back titration;
— F = factor comprising the amount weighed, the dilution, the aliquot part of solution of the sample to be distilled and

the volumetric equivalent.

(1) The condenser must be regulated so that a continuous flow of condensate is ensured. The distillation should be completed in 30 to

40 minutes.

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Variant b

Approximate maximum quantity of nitrogen to be distilled: 100 mg.

Sulphuric acid 0,2 mol/l to be placed in the receiving flask: 50 ml.

Back titration with NaOH or KOH 0,2 mol/l.

Declaration
(% N)

Amount to be
weighed
(g)

Dilution
(ml)

Solution of sample
to be distilled
(ml)

Expression of the result (a)
(% N = (50 — A) F)

0-5

5-10

10-15

15-20

20-40

10

10

7

5

7

500

500

500

500

500

100

50

50

50

20

(50 — A) × 0,14

(50 — A) × 0,28

(50 — A) × 0,40

(50 — A) × 0,56

(50 — A) × 1,00

(a) For the purposes of the formula for expression of the result:

— 50 or 35 = millilitres of standard solution of sulphuric acid to be placed in the receiving flask;

— A = millilitres of sodium or potassium hydroxide used for the back titration;

— F = factor comprising the amount weighed, the dilution, the aliquot part of solution of the sample to be distilled and

the volumetric equivalent.

Variant c

Approximate maximum quantity of nitrogen to be distilled: 200 mg.

Sulphuric acid 0,5 mol/l to be placed in the receiving flask: 35 ml.

Back titration with NaOH or KOH 0,5 mol/l.

Declaration
(% N)

Amount to be
weighed
(g)

Dilution
(ml)

Solution of sample
to be distilled
(ml)

Expression of the result (a)
(% N = (35 — A) F)

0-5

5-10

10-15

15-20

20-40

10

10

7

5

5

500

500

500

500

500

200

100

100

100

50

(35 — A) × 0,175

(35 — A) × 0,350

(35 — A) × 0,500

(35 — A) × 0,700

(35 — A) × 1,400

(a) For the purposes of the formula for expression of the result:

— 50 or 35 = millilitres of standard solution of sulphuric acid to be placed in the receiving flask;
— A = millilitres of sodium or potassium hydroxide used for the back titration;
— F = factor comprising the amount weighed, the dilution, the aliquot part of solution of the sample to be distilled and

the volumetric equivalent.

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Figure 1

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Figure 2

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Figure 3

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Figure 4

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Key to Figures 1, 2, 3 and 4

Figure 1

(a) A round-bottomed, long-necked flask of 1 000 ml capacity.

(b) Distillation tube with a splash head, connected to the condenser by means of a spherical joint (No 18) (the spherical

joint for the connection to the condenser may be replaced by an appropriate rubber connection).

(c) Funnel with a teflon tap for the addition of sodium hydroxide (the tap may likewise be replaced by a rubber

connection with a clip).

(d) A six-bulb condenser with spherical joint (No 18) at the entrance, and joined at the issue to a glass extension tube
by means of a small rubber connection (when the connection to the distillation tube is effected by means of a rubber
tube, the spherical joint may be replaced by a suitable rubber bung).

(e) A 500-ml flask in which the distillate is collected.

The equipment is made of borosilicate glass.

Figure 2

(a) A round-bottomed, short-necked flask of 1 000 ml capacity with a spherical joint (No 35).

(b) Distillation tube with a splash head, equipped with a spherical joint (No 35) at the entrance and a spherical joint (No

18) at the issue, connected at the side to a funnel with a teflon tap for the addition of sodium hydroxide.

(c) A six-bulb condenser with a spherical joint (No 18) at the entrance and joined at the issue to a glass extension tube

by means of a small rubber connection.

(d) A 500-ml flask in which the distillate is collected.

The equipment is made of borosilicate glass.

Figure 3

(a) A round-bottomed, long-necked flask of 750 or 1 000 ml capacity with a bell mouth.

(b) Distillation tube with a splash head and a spherical joint (No 18) at the issue.

(c) An elbow tube with a spherical joint (No 18) at the entrance, and a drip cone (the connection to the distillation tube

may be effected by means of a rubber tube instead of a spherical joint).

(d) A six-bulb condenser joined at the issue to a glass extension tube by means of a small rubber connection.

(e) A 500-ml flask in which the distillate is collected.

The equipment is made of borosilicate glass.

Figure 4

(a) A round-bottomed, long-necked flask of 1 000 ml capacity with a bell mouth.

(b) Distillation tube with a splash head and a spherical joint (No 18), at the issue, connected at the side to a funnel with
a teflon tap for the addition of sodium hydroxide (a suitable rubber bung may be used instead of the spherical joint;
the tap may be replaced by a rubber connection with an appropriate clip).

(c) A six-bulb condenser with a spherical joint (No 18) at the entrance, joined at the issue, by a rubber connection, to a
glass extension tube (when the connection to the distillation tube is effected by means of a rubber tube, the spherical
joint may be replaced by a suitable rubber bung).

(d) A 500-ml flask for the collection of the distillate.

The equipment is made of borosilicate glass.

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M e t h o d s 2.2

Determination of nitric and ammoniacal nitrogen

M e t h o d s 2.2.1

1.

2.

3.

Determination of nitric and ammoniacal nitrogen according to Ulsch

Scope

This document defines the procedure for the determination of nitrate and ammoniacal nitrogen with
reduction according to Ulsch.

Field of application

All nitrogenous fertilisers, including compound fertilisers, in which nitrogen is found exclusively in nitrate
form, or in ammoniacal and nitrate form.

Principle

Reduction of nitrates and nitrites to ammonia by means of metallic iron in an acid medium, and
displacement of the ammonia thus formed by the addition of an excess of sodium hydroxide: distillation
of the ammonia, and determination of the yield of ammonia in a known volume of standard sulphuric acid
solution. Titration of the excess sulphuric acid by means of a standard solution of sodium or potassium
hydroxide.

4.

Reagents

Distilled or demineralised water, free from carbon dioxide and all nitrogenous compounds.

Dilute hydrochloric acid: one volume of HCl (d20 = 1,18 g/ml) plus one volume of water

Sulphuric acid: 0,1 mol/l

Sodium or potassium hydroxide solution, carbonate free: 0,1 mol/l

Sulphuric acid solution, approximately 30 % H2SO4 (W/V), ammonia free

Powdered iron reduced in hydrogen (the prescribed quantity of iron must be able to reduce at least 0,05 g
of nitrate nitrogen)

Sodium hydroxide solution, approximately 30 % NaOH (d20 = 1,33 g/ml), ammonia free

Indicator solutions

4.1.

4.2.

4.3.

4.4.

4.5.

4.6.

4.7.

4.7.1.

Mixed indicator

Solution A: Dissolve 1 g of methyl red in 37 ml of 0,1 mol/l sodium hydroxide solution and make up to
one litre with water.

Solution B: Dissolve 1 g of methylene blue in water and make up to one litre.

Mix one volume of A with two volumes of B.

This indicator is violet in acid solution, grey in neutral solution and green in alkaline solution. Use 0,5 ml
(10 drops).

4.7.2.

Methyl red indicator solution

Dissolve 0,1 g of methyl red in 50 ml of 95 % ethanol. Make up to 100 ml with water and filter if
necessary.

4.8.

4.9.

5.

This indicator may be used (four to five drops) instead of the preceding one.

Anti-bump granules of pumice stone, washed in hydrochloric acid and calcined

Sodium nitrate for analysis

Apparatus

See Method 2.1 ‘Determination of ammoniacal nitrogen’.

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6.

Preparation of the sample

See Method 1 ‘Preparation of the sample’.

7.

7.1.

Method of analysis

Preparation of the solution

See Method 2.1 ‘Determination of ammoniacal nitrogen’.

7.2.

Procedure

Place in the receiving flask an exactly measured quantity of 50 ml of standard sulphuric acid as indicated in
Table 1 of Method 2.1 (variant a) and add the appropriate quantity of indicator solution 4.7.1 or 4.7.2. The
end of the extension tube of the condenser must be below the surface of the standard acid in the receiving
flask.

Using a precision pipette, transfer an aliquot part of the clear solution as indicated in Table 1 of Method 2.1
(variant a) and place it in the distilling flask of the apparatus. Add 350 ml of water, 20 ml of 30 %
sulphuric acid solution (4.4) stir, and add 5 g of reduced iron (4.5). Wash the neck of the flask with
several millilitres of water, and place in the neck of the flask a small, long-stemmed funnel. Heat in a boiling
water bath for an hour and then wash the stem of the funnel with a few millilitres of water.

Taking care to avoid any loss of ammonia, add to the contents of the distilling flask 50 ml of concentrated
sodium hydroxide solution (4.6), or in the cases where 20 ml of hydrochloric acid (1 + 1) (4.1) has been
used to dissolve the sample, add 60 ml of concentrated sodium hydroxide solution (4.6). Assemble the
distillation apparatus. Distil the ammonia according to the procedure given in Method 2.1.

7.3.

Blank test

Carry out a blank test (omitting the sample) under the same conditions and refer to this in the calculation of
the final result.

7.4.

Control test

Before analysis, check that the apparatus is working properly and that the correct application of the method
is used by using an aliquot part of a freshly prepared solution of sodium nitrate (4.9) containing 0,045 to
0,050 g of nitrogen.

8.

Expression of the result

Express the result of analysis as a percentage of nitrate nitrogen or combined ammoniacal and nitrate
nitrogen contained in the fertiliser as received for analysis.

M e t h o d 2.2.2

Determination of nitric and ammoniacal nitrogen according to Arnd

Scope

This document defines the procedure for the determination of nitric and ammoniacal nitrogen with
reduction according to Arnd (modified for each of the variants a, b and c).

Field of application

See Method 2.2.1.

Principle

1.

2.

3.

Reduction of nitrates and nitrites to ammonia in a neutral aqueous solution by means of a metallic alloy
composed of 60 % Cu and 40 % Mg (Arnd's alloy) in the presence of magnesium chloride (MgCl2).

Distillation of the ammonia, and determination of the yield in a known volume of standard sulphuric acid
solution. Titration of the excess acid by means of a standard solution of sodium or potassium hydroxide.

4.

Reagents

Distilled or demineralised water, free from carbon dioxide and all nitrogenous compounds.

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4.1.

4.2.

4.3.

4.4.

4.5.

4.6.

4.7.

4.8.

4.9.

Dilute hydrochloric acid: one volume of HCl (d = 1,18) plus one volume of water

Sulphuric acid: 0,1 mol/l

Sodium or potassium hydroxide solution, carbonate
free: 0,1 mol/l

Sulphuric acid: 0,2 mol/l

Sodium or potassium hydroxide solution, carbonate
free: 0,2 mol/l

Sulphuric acid: 0,5 mol/l

Sodium or potassium hydroxide solution, carbonate
free: 0,5 mol/l

9
>>>=
>>>;

9
>>>=
>>>;

9
>>>=
>>>;

for variant a.

for variant b (see note 2, Method
2.1).

for variant c (see note 2, Method
2.1).

Sodium hydroxide solution: approximately 2 mol/l

Arnd's alloy for analysis: powdered so as to pass through a sieve with apertures less than 1 mm square

4.10.

20 % magnesium chloride solution

Dissolve 200 g of magnesium chloride (MgCl2. 6H2O) in approximately 600 to 700 ml of water in a
one-litre, flat-bottomed flask. To prevent frothing, add 15 g of magnesium sulphate (MgSO4. 7H2O).

After dissolution add 2 g of magnesium oxide and a few anti-bump granules of pumice stone, and
concentrate the suspension to 200 ml by boiling,
thus expelling any trace of ammonia from the
reagents. Cool, make up the volume to one litre and filter.

4.11.

Indicator solutions

4.11.1.

Mixed indicator

Solution A: Dissolve 1 g of methyl red in 37 ml of 0,1 mol/l sodium hydroxide solution and make up to
one litre with water.

Solution B: Dissolve 1 g of methylene blue in water and make up to one litre.

Mix one volume of A with two volumes of B.

This indicator is violet in acid solution, grey in neutral solution and green in alkaline solution. Use 0,5 ml
(10 drops).

4.11.2.

Methyl red indicator solution

Dissolve 0,1 g of methyl red in 50 ml of 95 % ethanol. Make up to 100 ml with water and filter if
necessary. This indicator may be used (four or five drops) instead of the preceding one.

4.11.3.

Congo red indicator solution

Dissolve 3 g of Congo red in one litre of warm water and filter if necessary after cooling. This indicator may
be used, instead of the two described above, in the neutralisation of acid extracts before distillation, using
0,5 ml per 100 ml of liquid to be neutralised.

4.12.

Anti-bump granules of pumice stone washed in hydrochloric acid and calcined

4.13.

Sodium nitrate for analysis

5.

6.

Apparatus

See Method 2.1 ‘Determination of ammoniacal nitrogen’.

Preparation of the sample

See Method 1.

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7.

7.1.

Method of analysis

Preparation of the solution for analysis

See Method 2.1 ‘Determination of ammoniacal nitrogen’.

7.2.

Analysis of the solution

According to the chosen variant, place in the receiving flask the exactly measured quantity of standard
sulphuric acid as indicated in Table 1 of Method 2.1. Add the appropriate quantity of chosen indicator
solution (4.11.1 or 4.11.2) and finally, sufficient water to give a volume of at least 50 ml. The end of the
extension tube of the condenser must be below the surface of the solution.

Using a precision pipette, take, according to Table 1, an adequate aliquot of the clear solution. Place it in the
distillation flask.

Add sufficient water to obtain a total volume of about 350 ml (see note 1), 10 g of Arnd's alloy (4.9),
50 ml of magnesium chloride solution (4.10) and a few fragments of pumice stone (4.12). Rapidly connect
the flask to the distillation apparatus. Heat gently for about 30 minutes. Then increase the heating to distil
the ammonia. Continue the distillation for about an hour. After this time, the residue in the flask ought to
have a syrupy consistency. When the distillation has finished, titrate the quantity of excess acid in the
receiving task according to the procedure in Method 2.1.

N o t e 1

When the sample solution is acid (addition of 20 ml of HCl (4.1) to dissolve the sample) the aliquot part
taken for analysis is neutralised in the following way: to the distillation flask containing the taken aliquot
part add about 250 ml of water, the necessary quantity of one of the indicators (4.11.1, 4.11.2, 4.11.3) and
shake carefully.

Neutralise with 2 mol/l sodium hydroxide solution (4.8) and acidify again with a drop of hydrochloric acid
(4.1). Then proceed as indicated in 7.2 (second line).

7.3.

Blank test

Carry out a blank test (omitting the sample) under the same conditions and refer to this in the calculation of
the final result.

7.4.

Control test

Before analysis, check that the apparatus is working properly and that the correct technique is applied using
a freshly prepared solution of sodium nitrate (4.13) containing 0,050 to 0,150 g of nitrate nitrogen
depending on the variant chosen.

8.

Expression of the result

See Method 2.2.1.

1.

2.

3.

M e t h o d 2.2.3

Determination of nitric and ammoniacal nitrogen according to Devarda

Scope

This document defines the procedure for the determination of nitrate and ammoniacal nitrogen with
reduction according to Devarda (modified for each of the variants a, b and c).

Field of application

See Method 2.2.1.

Principle

Reduction of nitrates and nitrites to ammonia in a strongly alkaline solution by means of a metallic alloy
composed of 45 % Al, 5 % Zn and 50 % Cu (Devarda alloy). Distillation of the ammonia and determination
of the yield in a known volume of standard sulphuric acid; titration of the excess sulphuric acid by means of
a standard solution of sodium or potassium hydroxide.

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4.

Reagents

Distilled or demineralised water, free from carbon dioxide and all nitrogenous compounds.

4.1.

Dilute hydrochloric acid: one volume of HCl (d = 1,18) plus one volume of water

4.2.

4.3.

4.4.

4.5.

4.6.

4.7.

4.8.

Sulphuric acid: 0,1 mol/l

Sodium or potassium hydroxide solution, carbonate
free: 0,1 mol/l

Sulphuric acid: 0,2 mol/l

Sodium or potassium hydroxide solution, carbonate
free: 0,2 mol/l

Sulphuric acid: 0,5 mol/l

Sodium or potassium hydroxide solution, carbonate
free: 0,5 mol/l

Devarda alloy for analysis

9
>>>=
>>>;

9
>>>=
>>>;

9
>>>=
>>>;

for variant a.

for variant b (see note 2, Method
2.1).

for variant c (see note 2, Method
2.1).

Powdered so that 90 to 100 % will pass through a sieve with apertures less than 0,25 mm square, 50 to
75 % will pass through a sieve with apertures of less than 0,075 mm square.

Pre-packed bottles containing a maximum of 100 g are recommended.

4.9.

Sodium hydroxide solution, approximately 30 % NaOH (d20 = 1,33 g/ml), ammonia free

4.10.

Indicator solutions

4.10.1.

Mixed indicator

Solution A: Dissolve 1 g of methyl red in 37 ml of 0,1 mol/l sodium hydroxide solution and make up to
one litre with water.

Solution B: Dissolve 1 g of methylene blue in water and make up to one litre.

Mix one volume of A with two volumes of B.

This indicator is violet in acid solution, grey in neutral solution and green in alkaline solution. Use 0,5 ml
(10 drops).

4.10.2.

Methyl red indicator

Dissolve 0,1 g of methyl red in 50 ml of 95 % ethanol. Make up to 100 ml with water and filter if
necessary.

This indicator (four or five drops) may be used instead of the preceding one.

4.11.

Ethanol, 95 to 96 %

4.12.

Sodium nitrate for analysis

5.

Apparatus

See Method 2.1.

5.1.

5.2.

5.3.

Distillation apparatus consisting of a round-bottomed flask of suitable capacity, connected to a condenser by
a distilling tube with a splash head, equipped, in addition, with a bubble trap on the receiving flask to
prevent any loss of ammonia.

The type of apparatus approved for this determination is reproduced, showing all
construction, in Figure 5.

the features of

Pipettes of 10, 20, 25, 50, 100 and 200 ml

A 500-ml graduated flask

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5.4.

Rotary shaker (35 to 40 turns a minute)

6.

Preparation of the sample

7.

7.1.

See Method 1.

Procedure

Preparation of the solution for analysis

See Method 2.1 ‘Determination of ammoniacal nitrogen’.

7.2.

Analysis of the solution

The quantity of nitric nitrogen present in the aliquot part of the solution must not exceed the maximum
quantity expressed in Table 1.

According to the variant chosen, place in the receiving flask an exactly measured quantity of standard
sulphuric acid as indicated in Table 1. Add the appropriate quantity of the chosen indicator solution (4.10.1
or 4.10.2) and finally, sufficient water to give a volume of 50 ml. The end of the extension tube of the
condenser must be underneath the surface of the solution. Fill the bubble trap with distilled water.

Using a precision pipette, take an aliquot part as indicated in Table 1 of Method 2.1. Place it in the
distillation flask.

Add sufficient water to the distillation flask to obtain a volume of 250 to 300 ml, 5 ml ethanol (4.11) and
4 g Devarda's alloy (4.8) (See note 2).

Taking the necessary precautions to avoid loss of ammonia, add to the flask about 30 ml of 30 % sodium
hydroxide solution (4.9) and finally, in the case of acid soluble samples an additional quantity sufficient to
neutralise the quantity of hydrochloric acid (4.1) present in the aliquot part taken for the analysis. Connect
the distillation flask to the apparatus, ensuring the tightness of connections. Carefully shake the flask to mix
the contents.

Warm gently, so that the release of hydrogen decreases appreciably over about half an hour and the liquid
will boil. Continue the distillation, increasing the heat so that at least 200 ml liquid distils in about 30
minutes (do not prolong the distillation beyond 45 minutes).

When the distillation is complete, disconnect the receiving flask from the apparatus, carefully wash the
extension tube and bubble trap, collecting the rinsings in the titration flask. Titrate the excess acid according
to the procedure in Method 2.1.

N o t e 2

In the presence of calcium salts such as calcium nitrate and calcium ammonium nitrate, it is necessary to
add before distillation for each gram of sample present in the aliquot, 0,700 g sodium phosphate (Na2HPO4.
2H2O) to prevent the formation of Ca(OH)2.

7.3.

Blank test

Carry out a blank test (omitting the sample) under the same conditions and refer to this in the calculation of
the final results.

7.4.

Control test

Before carrying out the analysis, check that
the correct
application of the method is used, using an aliquot of a freshly prepared solution of sodium nitrate
(4.12) containing, according to the variant chosen, 0,050 to 0,150 g of nitrate nitrogen.

the apparatus is working properly and that

8.

Expression of the result

See Method 2.2.1.

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Figure 5

Key to Figure 5

(a) A 750-ml (1 000 ml) round-bottomed, long-necked flask with a bell mouth.

(b) Distillation tube with a splash head and a No 18 spherical joint at the issue.

(c) Elbow tube with a No 18 spherical joint at the entrance, and a drip cone at the issue (a suitable rubber connection

may be used instead of the spherical joint).

(d) A six-bulb condenser with an extension tube mounted on a rubber bung holding a bubble trap.

(e) A 750-ml receiving flask.

(f) A bubble trap to prevent loss of ammonia.

The equipment is made of borosilicate glass.

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M e t h o d 2.3

Determination of total nitrogen

M e t h o d 2.3.1

Determination of the total nitrogen in calcium cyanamide nitrate free

Scope

This document defines the procedure for the determination of total nitrogen in nitrate free, calcium
cyanamide.

Field of application

Exclusively to calcium cyanamide (nitrate free).

Principle

After Kjeldahl digestion, the ammoniacal nitrogen formed is displaced by sodium hydroxide, collected and
estimated in a standard solution of sulphuric acid.

Reagents

Distilled or demineralised water, free from carbon dioxide and all nitrogenous compounds.

Dilute sulphuric acid (d20 = 1,54 g/ml): one volume of sulphuric acid (d20 = 1,84 g/ml) plus one volume of
water

Potassium sulphate for analysis

Copper oxide (CuO): 0,3 to 0,4 g for each estimation, or an equivalent quantity of copper sulphate
pentahydrate (CuSO4. 5H2O), from 0,95 to 1,25 g for each estimation

Sodium hydroxide solution, approximately 30 % NaOH (d20 = 1,33 g/ml), ammonia free

Sulphuric acid: 0,1 mol/l

9
>>=

Sodium or potassium hydroxide solution, carbonate
free: 0,1 mol/l

>>;

Sulphuric acid: 0,2 mol/l

9
>>=

Sodium or potassium hydroxide solution, carbonate
free: 0,2 mol/l

>>;

for variant a (see Method 2.1).

for variant b (see note 2, Method
2.1).

1.

2.

3.

4.

4.1.

4.2.

4.3.

4.4.

4.5.

4.6.

4.7.

4.8.

4.9.

Sulphuric acid: 0,5 mol/l

9
>>=

4.10.

Sodium or potassium hydroxide solution, carbonate
free: 0,5 mol/l

>>;

for variant c (see note 2, Method
2.1).

4.11.

Indicator solutions

4.11.1.

Mixed indicator

Solution A: Dissolve 1 g of methyl red in 37 ml of 0,1 mol/l sodium hydroxide solution and make up to
one litre with water.

Solution B: Dissolve 1 g of methylene blue in water and make up to one litre.

Mix one volume of A with two volumes of B.

This indicator is violet in acid solution, grey in neutral solution and green in alkaline solution. Use 0,5 ml
(10 drops).

4.11.2.

Methyl red indicator

Dissolve 0,1 g of methyl red in 50 ml of 95 % ethanol and make up to 100 ml with water. Filter if
necessary. This indicator (four or five drops) may be used instead of the preceding one.

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4.12.

Anti-bump granules of pumice stone, washed in hydrochloric acid and calcined

4.13.

Potassium thiocyanate for analysis

5.

5.1.

5.2.

5.3.

5.4.

6.

7.

7.1.

Apparatus

Distilling apparatus, see Method 2.1 ‘Determination of ammoniacal nitrogen’

A long-necked Kjeldahl flask of suitable capacity

Pipettes of 50, 100 and 200 ml

A 250-ml graduated flask

Preparation of the sample

See Method 1.

Procedure

Preparation of the solution for analysis

Weigh, to the nearest 0,001 g, 1 g of the sample and place it in the Kjeldahl flask. Add 50 ml of diluted
sulphuric acid (4.1), 10 to 15 g of potassium sulphate (4.2), and the prescribed catalyst (4.3). Heat slowly to
drive off the water, boil gently for two hours, allow to cool, and dilute with 100 to 150 ml of water. Cool
again, transfer quantitatively the suspension to a graduated 250-ml flask, make up the volume with water,
shake, and filter through a dry filter into a dry flask.

7.2.

Analysis of the solution

With a pipette, transfer, according to the variant chosen (see Method 2.1), 50, 100 or 200 ml of the
solution thus obtained, and distil the ammonia as described in Method 2.1, adding sufficient NaOH solution
(4.4) to ensure a considerable excess.

7.3.

Blank test

Carry out a blank test (omitting the sample) under the same conditions and refer to this in the calculation of
the final result.

7.4.

Control test

Before carrying out the analysis, check that
the correct
application of the method is used, using an aliquot part of a standard solution of potassium thiocyanate
(4.13), approximating to the concentration of nitrogen in the sample.

the apparatus is working properly and that

8.

Expression of the result

Express the result as the percentage of nitrogen (N) contained in the fertiliser as received for analysis.

Variant a: % N = (50 — A) × 0,7

Variant b: % N = (50 — A) × 0,7

Variant c: % N = (35 — A) × 0,875

Determination of total nitrogen in calcium cyanamide containing nitrates

M e t h o d 2.3.2

1.

2.

Scope

This document defines the procedure for the determination of total nitrogen in calcium cyanamide.

Field of application

The method is applicable to calcium cyanamide containing nitrates.

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3.

Principle

The direct application of Kjeldahl's Method cannot be applied to calcium cyanamides containing nitrates. For
this reason the nitrate nitrogen is reduced to ammonia with metallic iron and stannous chloride before
Kjeldahl digestion.

4.

Reagents

Distilled or demineralised water, free from carbon dioxide and all nitrogenous compounds.

4.1.

4.2.

4.3.

4.4.

4.5.

4.6.

4.7.

4.8.

4.9.

Sulphuric acid (d20 = 1,84 g/ml)

Powdered iron reduced in hydrogen

Potassium sulphate, finely pulverised, for analysis

Sulphuric acid: 0,1 mol/l

9
>>=

Sodium or potassium hydroxide standard solution,
carbonate free: 0,1 mol/l

>>;

Sulphuric acid: 0,2 mol/l

9
>>=

Sodium or potassium hydroxide standard solution,
carbonate free: 0,2 mol/l

>>;

Sulphuric acid: 0,5 mol/l

9
>>=

Sodium or potassium hydroxide standard solution,
carbonate free: 0,5 mol/l

>>;

4.10.

Indicator solutions

4.10.1.

Mixed indicator

for variant a (see Method 2.1).

for variant b (see note 2, Method
2.1).

for variant c (see note 2, Method
2.1).

Solution A: Dissolve 1 g of methyl red in 37 ml of 0,1 mol/l sodium hydroxide solution and make up to
one litre with water.

Solution B: Dissolve 1 g of methylene blue in water and make up to one litre.

Mix one volume of A with two volumes of B.

This indicator is violet in acid solution, grey in neutral solution and green in alkaline solution. Take 0,5 ml
(10 drops) of this indicator solution.

4.10.2.

Methyl red indicator

Dissolve 0,1 g of methyl red in 50 ml of 95 % ethanol, make up to 100 ml with water and filter if
necessary. This indicator (four or five drops) may be used instead of the preceding one.

4.11.

Solution of stannous chloride

Dissolve 120 g of SnCl2. 2H2O in 400 ml of concentrated hydrochlorine acid (d20 = 1,18 g/ml) and make
up to one litre with water. The solution must be completely clear and prepared immediately before use. It is
essential to check the reducing power of the stannous chloride.

N o t e

Dissolve 0,5 g of SnCl2. 2H2O in 2 ml of concentrated hydrochloric acid (d20 = 1,18 g/ml) and make up to
50 ml with water. Then add 5 g of Rochelle salt (potassium sodium tartrate) and a sufficient quantity of
sodium bicarbonate for analysis for the solution to show an alkaline reaction to a litmus paper test.

Titrate with 0,1 mol/l iodine solution in the presence of a starch solution as an indicator.

1 ml of iodine solution 0,1 mol/l corresponds to 0,01128 g of SnCl2. 2H2O.

At least 80 % of the total tin present in the solution thus prepared must be in a bivalent form. For the
titration at least 35 ml of 0,1 mol/l iodine solution should be used.

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4.12.

Solution of sodium hydroxide containing about 30 % NaOH (d20 = 1,33 g/ml), ammonia free

4.13.

Standard nitrate-ammoniacal solution

Weigh out 2,5 g of potassium nitrate for analysis and 10,16 g of ammonium sulphate for analysis and
place them in a 250-ml graduated flask. Dissolve in water and make up to 250 ml. 1 ml of this solution
contains 0,01 g of nitrogen.

4.14.

Pumice stone anti-bump granules, washed in hydrochloric acid and calcined

5.

6.

7.

7.1.

Apparatus

See Method 2.3.1.

Preparation of the sample

See Method 1.

Procedure

Preparation of the solution

Weigh, to the nearest 0,001 g, 1 g of the sample and place it in the Kjeldahl flask. Add 0,5 g of powdered
iron (4.2) and 50 ml of the stannous chloride solution (4.11), stir and leave standing for half an hour.
During the time it is left standing, stir again after 10 and 20 minutes. Then add 10 g of potassium sulphate
(4.3) and 30 ml of sulphuric acid (4.1). Boil and carry on the process for an hour after the appearance of
white fumes. Leave to cool and dilute with 100 to 150 ml of water. Transfer the suspension quantitatively
into a 250-ml graduated flask, cool and make up the volume with water, stir and filter through a dry filter
into a dry container. Instead of then siphoning off the suspension in order to apply the variant a, b or c,
used in Method 2.1, the ammoniacal nitrogen in this solution may also be distilled directly, after adding
sufficient sodium hydroxide to ensure a large surplus (4.12).

7.2.

Analysis of the solution

With a pipette, transfer, according to the variant a, b or c, used in Method 2.1, 50, 100 or 200 ml of the
solution thus obtained. Distil the ammonia according to the process described in Method 2.1, taking care to
add to the distillation flask sufficient sodium hydroxide solution (4.12) to ensure a large excess.

7.3.

Blank test

Carry out a blank test (omitting the sample) under the same conditions and refer to this in the calculation of
the final result.

7.4.

Control test

Before carrying out the analysis, check that
the correct
application of the method is used with a standard solution (4.13) containing quantities of ammoniacal
and nitrate nitrogen comparable to the quantities of cyanamide and nitrate nitrogen contained in nitrated
calcium cyanamide.

the apparatus is working properly and that

For this purpose place 20 ml of the standard solution (4.13) in the Kjeldahl flask.

Carry out the analysis according to the method described in 7.1 and 7.2.

8.

Expression of the result

The result of the analysis must be expressed as the percentage of total nitrogen (N) contained in the fertiliser
as received for analysis.

Variant a: % N = (50 — A) × 0,7

Variant b: % N = (50 — A) × 0,7

Variant c: % N = (35 — A) × 0,875

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M e t h o d 2.3.3

Determination of total nitrogen in urea

1.

2.

3.

Scope

This document defines the procedure for the determination of total nitrogen in urea.

Field of application

This method is applied exclusively to urea fertilisers which are nitrate free.

Principle

Urea is transformed quantitatively into ammonia by boiling in the presence of sulphuric acid. The ammonia
thus obtained is distilled from an alkaline medium, the distillate being collected in an excess of standard
sulphuric acid. The excess acid is titrated by means of a standard alkaline solution.

4.

Reagents

4.1.

4.2.

4.3.

4.4.

4.5.

4.6.

4.7.

4.8.

Distilled or demineralised water, free from carbon dioxide and all nitrogenous compounds.

Sulphuric acid, concentrated (d20 = 1,84 g/ml)

Sodium hydroxide solution, approximately 30 % NaOH (d20 = 1,33 g/ml), ammonia free

Sulphuric acid: 0,1 mol/l

9
>>=

Sodium or potassium hydroxide solution, carbonate
free: 0,1 mol/l

>>;

Sulphuric acid: 0,2 mol/l

9
>>=

Sodium or potassium hydroxide solution, carbonate
free: 0,2 mol/l

>>;

Sulphuric acid: 0,5 mol/l

9
>>=

Sodium or potassium hydroxide solution, carbonate
free: 0,5 mol/l

>>;

for variant a (see Method 2.1).

for variant b (see note 2, Method
2.1).

for variant c (see note 2, Method
2.1).

4.9.

Indicator solutions

4.9.1.

Mixed indicator

Solution A: Dissolve 1 g of methyl red in 37 ml of 0,1 mol/l sodium hydroxide solution and make up to
one litre with water.

Solution B: Dissolve 1 g of methylene blue in water and make up to one litre.

Mix one volume of A with two volumes of B.

This indicator is violet in acid solution, grey in neutral solution and green in alkaline solution. Use 0,5 ml
(10 drops).

4.9.2.

Methyl red indicator solution

Dissolve 0,1 g of methyl red in 50 ml of 95 % ethanol and make up to 100 ml with water. Filter if
necessary. This indicator (four or five drops) may be used instead of the preceding one.

Anti-bump granules of pumice stone, washed in hydrochloric acid and calcined

Urea for analysis

Apparatus

Distillation apparatus, see Method 2.1 ‘Determination of ammoniacal nitrogen’

A 500-ml graduated flask

Pipettes of 25, 50 and 100 ml

4.10.

4.11.

5.

5.1.

5.2.

5.3.

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6.

Preparation of the sample

See Method 1.

Procedure

Preparation of the solution

7.

7.1.

Weigh, to the nearest 0,001 g, 2,5 g of the prepared sample, place it in a 300-ml Kjeldahl flask and
moisten with 20 ml water. Stir in 20 ml of concentrated sulphuric acid (4.1) and add a few glass beads to
prevent bumping. To prevent splashing, place a long-stemmed glass funnel in the neck of the flask. Heat,
slowly at first, then increase the heat until white fumes are observed (30 to 40 minutes).

Cool and dilute with 100 to 150 ml water. Quantitatively transfer to a 500-ml volumetric flask, discarding
any sediment. Allow to cool to room temperature. Make up the volume with water, mix and, if necessary,
filter through a dry filter into a dry receptacle.

7.2.

Analysis of the solution

With a precision pipette, transfer 25, 50 or 100 ml of the solution thus obtained into the distillation flask,
according to the variant chosen (see Method 2.1). Distil the ammonia as described in Method 2.1, adding
sufficient NaOH (d20 = 1,33 g/ml) (4.2) to the distilling flask to ensure a considerable excess.

7.3.

Blank test

Carry out a blank test (omitting the sample) under the same conditions and refer to this in the calculation of
the final result.

7.4.

Control test

Before carrying out the analysis, check that
the correct
application of the Method is used, using an aliquot part of a freshly prepared solution of urea (4.11).

the apparatus is working properly and that

8.

Expression of the result

Express the result as the percentage of nitrogen (N) contained in the fertiliser as received for analysis.

Variant a: % N = (50 — A) × 1,12

Variant b: % N = (50 — A) × 1,12

Variant c: % N = (35 — A) × 1,40

M e t h o d 2.4

Determination of cyanamide nitrogen

Scope

This document defines the procedure for the determination of cyanamide nitrogen.

Field of application

Calcium cyanamide and calcium cyanamide/nitrate mixtures.

Principle

Cyanamide nitrogen is precipitated as a silver complex and estimated in the precipitate by Kjeldahl's method.

Reagents

Distilled or demineralised water, free from carbon dioxide and all nitrogenous compounds.

1.

2.

3.

4.

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4.1.

4.2.

4.3.

4.4.

4.5.

4.6.

4.7.

4.8.

4.9.

Glacial acetic acid

Ammonia solution containing 10 % of ammonia gas by mass (d20 = 0,96 g/ml)

Ammoniacal silver solution, according to Tollens

Mix 500 ml of 10 % silver nitrate (AgNO3) solution in water with 500 ml of 10 % ammonia (4.2).

Do not expose unnecessarily to light, heat or air. The solution normally keeps for years. As long as the
solution remains clear, the reagent is of good quality.

Concentrated sulphuric acid (d20 = 1,84 g/ml)

Potassium sulphate for analysis

Copper oxide (CuO), 0,3 to 0,4 g for each estimation, or an equivalent quantity of copper sulphate
pentahydrate (CuSO4. 5H2O) from 0,95 to 1,25 g for each estimation

Sodium hydroxide solution, approximately 30 % NaOH (d20 = 1,33 g/ml), ammonia free

Sulphuric acid: 0,1 mol/l

Sodium or potassium hydroxide solution: 0,1 mol/l

4.10.

Indicator solutions

4.10.1.

Mixed indicator

Solution A: Dissolve 1 g of methyl red in 37 ml of 0,1 mol/l sodium hydroxide solution and make up to
one litre with water.

Solution B: Dissolve 1 g of methylene blue in water and make up to one litre.

Mix one volume of A with two volumes of B.

This indicator is violet in acid solution, grey in neutral solution and green in alkaline solution. Use 0,5 ml
(10 drops).

4.10.2.

Methyl red indicator solution

Dissolve 0,1 g of methyl red in 50 ml of 95 % ethanol and make up to 100 ml with water. Filter if
necessary. This indicator (four to five drops) may be used instead of the preceding one.

4.11.

Anti-bump granules of pumice stone, washed in hydrochloric acid and calcined

4.12.

Potassium thiocyanate for analysis

5.

5.1.

5.2.

5.3.

5.4.

5.5.

6.

7.

7.1.

Apparatus

Distillation apparatus, see Method 2.1 ‘Determination of ammoniacal nitrogen’

A 500-ml graduated flask (e.g. Stohmann)

A long-necked Kjeldahl flask of suitable capacity (300 to 500 ml)

A 50-ml pipette

A rotary shaker (35 to 40 turns per minute)

Preparation

See Method 1.

Procedure

Safety precaution

When using any ammoniacal silver solution safety goggles must be worn. As soon as a thin membrane
forms on the surface of the liquid, an explosion may be produced by agitation and the greatest caution is
essential.

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7.2.

Preparation of the solution for analysis

Weigh, to the nearest 0,001 g, 2,5 g of the sample and place it in a small glass mortar. Grind the sample
three times with water, pouring off the water after each grinding into a 500-ml graduated Stohmann flask
(5.2). Transfer quantitatively the sample into the 500-ml graduated Stohmann flask, washing the mortar,
pestle and funnel with water. Make up with water to approximately 400 ml. Add 15 ml of acetic acid (4.1).
Shake on the rotary shaker (5.5) for two hours.

Make up to 500 ml with water, mix and filter.

The analysis must be carried out as quickly as possible.

7.3.

Analysis of the solution

Transfer 50 ml of the filtrate, into a 250-ml beaker.

Add ammonia solution (4.2) until slightly alkaline and add 30 ml of warm ammoniacal silver nitrate (4.3) in
order to precipitate the yellow silver complex of the cyanamide.

Leave overnight, filter and wash the precipitate with cold water until it is completely free of ammonia.

Place the filter and the precipitate, still moist, in a Kjeldahl flask, add 10 to 15 g of potassium sulphate (4.5),
the catalyst (4.6), in the prescribed proportion, then 50 ml of water and 25 ml of concentrated sulphuric
acid (4.4).

Warm the flask slowly, while shaking it gently until the contents come to the boil. Increase the heat, boil
until the contents of the flask become colourless or pale green.

Continue boiling for one hour, then leave to cool.

Transfer the liquid quantitatively from the Kjeldahl flask to the distilling flask, add a few anti-bump granules
of pumice stone (4.11) and make up with water to a total volume of approximately 350 ml. Mix and cool.

Distil the ammonia according to Method 2.1, variant a, adding sufficient NaOH solution (4.7) to ensure the
presence of a considerable excess.

7.4.

Blank test

Carry out a blank test (omitting the sample) under the same conditions and refer to this in the calculation of
the final result.

7.5.

Control test

Before carrying out the analysis, check that
the correct
application of the method is used using an aliquot part of a standard solution of potassium thiocyanate
(4.12) corresponding to 0,05 g of nitrogen.

the apparatus is working properly and that

8.

Expression of the result

Express the result as the percentage of cyanamide nitrogen contained in the fertiliser as received for analysis.

% N ¼ ð50 (cid:1) AÞ (cid:2) 0,56

M e t h o d 2.5

Spectrophotometric determination of biuret in urea

Scope

This document defines the procedure for the determination of biuret in urea.

Field of application

The method is applied exclusively to urea.

1.

2.

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3.

Principle

In an alkaline medium, in the presence of potassium sodium tartrate, biuret and bivalent copper from a
violet cupric compound. The absorbance of the solution is measured at a wave length of about 546 nm
(nanometer).

4.

Reagents

Distilled or demineralised water, free from carbon dioxide and ammonia. The quality of this water is
particularly important in this determination.

4.1.

4.2.

4.3.

4.4.

Methanol

Sulphuric acid solution, about 0,1 mol/l

Sodium hydroxide solution, about 0,1 mol/l

Alkaline solution of potassium sodium tartrate

In a graduated one-litre flask, dissolve 40 g of sodium hydroxide in 500 ml of water and leave to cool. Add
50 g of potassium sodium tartrate (NaKC4H4O6. 4H2O). Make up to the mark. Leave standing 24 hours
before use.

4.5.

Solution of copper sulphate

In a graduated one-litre flask, dissolve 15 g of copper sulphate pentahydrate (CuSO4. 5H2O) in 500 ml of
water. Make up to the mark.

4.6.

Freshly prepared biuret standard solution

In a 250-ml graduated flask, dissolve 0,250 g of pure biuret (1) in water. Make up to 250 ml. 1 ml of this
solution contains 0,001 g of biuret.

4.7.

Indicator solution

In a graduated 100-ml flask, dissolve 0,1 g of methyl red in 50 ml of 95 % ethanol, make up to 100 ml
with water. Filter if any insolubles remain.

Apparatus

Spectrometer or photometer with filters of a sensitivity and precision to permit measures of less than 0,5 %
T to be reproduced (2).

Graduated flasks of 100, 250 and 1 000 ml

Graduated pipettes of 2, 5, 10, 20, 25 and 50 ml or a 25 ml burette, graduated to 0,05 ml

A 250-ml beaker

Preparation of the sample

See Method 1.

Procedure

Preparation of the calibration curve

5.

5.1.

5.2.

5.3.

5.4.

6.

7.

7.1.

Transfer 0, 2, 5, 10, 20, 25 and 50 ml of aliquots of biuret standard solution (4.6) into a series of seven
graduated 100-ml flasks. Make up the volumes to about 50 ml with water, add one drop of indicator (4.7)
and neutralise, if necessary, with sulphuric acid 0,1 mol/l (4.2). Stir in 20 ml of the alkaline tartrate solution
(4.4) then 20 ml of the copper sulphate solution (4.5).

N o t e

These solutions (4.4 and 4.5) must be measured in with two precision burettes or better still with pipettes.

Make up to 100 ml with distilled water, mix and leave standing for 15 minutes at 30 (± 2) °C.

(1) Biuret can be purified beforehand by washing with an ammoniacal solution (10 %), then with acetone and drying in a vacuum.
(2) See point 9 ‘Appendix’.

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With the ‘0’ biuret standard solution as reference, measure the absorbance of each solution at a wavelength
of about 546 nm using cells of a suitable path length.

Plot the calibration curve, using the absorbances as the ordinates and the corresponding quantities of biuret,
in milligrams, as the abscissae.

7.2.

Preparation of the solution to be analysed

Weigh, to the nearest 0,001 g, 10 g of the prepared sample; dissolve in about 150 ml of water in a 250-ml
graduated flask, and make up to the mark. Filter if necessary.

R e m a r k 1

If the sample for analysis contains more than 0,015 g of ammoniacal nitrogen, dissolve it, in a 250-ml
beaker, in 50 ml of methanol (4.1). Reduce by evaporation to a volume of about 25 ml. Transfer quanti-
tatively to a graduated 250-ml flask. Make up to the mark with water. Filter, if necessary, through a dry
fluted filter into a dry container.

R e m a r k 2

Elimination of the opalescence: if any colloid substance is present, difficulties may arise during filtering. The
solution intended for analysis is in that case prepared as follows: dissolve the sample for analysis in 150 ml
of water, add 2 ml of 1 mol/l hydrochloric acid, and filter the solution through two flat very fine filters into
a graduated 250-ml flask. Wash the filters with water and make up to volume. Continue the process
according to the method described in 7.3 ‘Determination’.

7.3.

Determination

According to the presumed biuret content, transfer 25 or 50 ml from the solution mentioned in 7.2 with a
pipette, place this quantity in a 100-ml graduated flask and neutralise if necessary with a 0,1 mol/l reagent
(4.2 or 4.3) as required, using methyl red as an indicator and add, with the same accuracy as that used when
drawing up a calibration curve, 20 ml of the alkaline solution of potassium sodium tartrate (4.4) and 20 ml
of the copper solution (4.5). Make up to volume, mix thoroughly and leave standing for 15 minutes at 30 (±
2) °C.

Then carry out the photometric measurements and calculate the quantity of biuret present in the urea.

8.

Expression of the result

% biuret ¼

C (cid:2) 2,5
V

Where

‘C’ is the mass, in milligrams, of biuret, read from the calibration graph,

‘V’ the volume of the aliquot:

9.

Appendix

‘Jo’ being the intensity of the beam of monochromatic rays (of a determinate wavelength) before it passes
through a transparent body, and ‘J’ being the intensity of this beam after the passage, then:

T ¼

O ¼

J
Jo
Jo
J

E ¼ log O

k ¼ E
s

K ¼ E

C (cid:2) S

— factor of transmission:

— opacity:

— absorbance:

— absorbance per unit of optical run:

— coefficient of specific absorbance:

where

s = thickness of the layer in centimetres.

c = concentration in milligrams per litre.

k = specific factor for each substance in the Lambert-Beer law.

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M e t h o d s 2.6

Determination of different forms of nitrogen in the same sample

M e t h o d 2.6.1

Determination of different forms of nitrogen in the same sample in fertilisers containing nitrogen as nitric,
ammoniacal, urea and cyanamide nitrogen

1.

2.

3.

3.1.

Scope

This document defines the procedure for the determination of any one form of nitrogen in the presence of
any other form.

Field of application

Any fertiliser provided for in Annex I containing nitrogen in various forms.

Principle

Total soluble and insoluble nitrogen

According to the list of standard fertilisers (Annex I), this determination is applicable to products containing
calcium cyanamide.

3.1.1.

In the absence of nitrates, the test sample is mineralised by direct Kjeldahl digestion

3.1.2.

In the presence of nitrates, the test sample is mineralised by Kjeldahl digestion after reduction with the aid of
metallic iron and stannous chloride

In both cases, the ammonia is determined according to Method 2.1.

N o t e

If analysis shows an insoluble nitrogen content of more than 0,5 %, one concludes that the fertiliser contains
other forms of insoluble nitrogen not included in the list in Annex I.

3.2.

Forms of soluble nitrogen

The following are determined from different aliquots taken from the same solution of the sample:

3.2.1.

total soluble nitrogen:

3.2.1.1.

in the absence of nitrates, by direct Kjeldahl digestion,

3.2.1.2.

in the presence of nitrates, by Kjeldahl digestion on an aliquot part taken from the solution after reduction
according to Ulsch, the ammonia being determined in both cases, as described in Method 2.1;

3.2.2.

total soluble nitrogen with the exception of nitrate nitrogen by Kjeldahl digestion after elimination in an acid
medium of nitrate nitrogen with ferrous sulphate, the ammonia being determined as described in Method
2.1;

3.2.3.

nitrate nitrogen by difference:

3.2.3.1.

in the absence of calcium cyanamide, between 3.2.1.2 and 3.2.2 or between total soluble nitrogen (3.2.1.2)
and the sum of ammoniacal nitrogen and ureic organic nitrogen (3.2.4 + 3.2.5),

3.2.3.2.

in the presence of calcium cyanamide, between 3.2.1.2 and 3.2.2 or between 3.2.1.2 and the sum of 3.2.4 +
3.2.5 + 3.2.6;

3.2.4.

ammoniacal nitrogen:

3.2.4.1.

solely in the presence of ammoniacal nitrogen and ammoniacal plus nitrate nitrogen, by applying Method 1,

3.2.4.2.

in the presence of urea nitrogen and/or cyanamide nitrogen by cold distillation after making slightly alkaline,
the ammonia being absorbed in a standard solution of sulphuric acid and determined as described in Method
2.1;

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3.2.5.

urea nitrogen:

3.2.5.1.

by conversion using urease, into ammonia which is titrated with a standard solution of hydrochloric acid,

or

3.2.5.2.

by gravimetry with xanthydrol: the co-precipitated biuret can be counted with urea nitrogen without great
error, its content remaining generally low in absolute value in compound fertilisers,

or

3.2.5.3.

by difference according to the following table:

Case

Nitrate nitrogen

Ammoniacal
nitrogen

Cyanamidic
nitrogen

Difference

1

2

3

4

Absent

Present

Absent

Present

Present

Present

Present

Present

Present

Present

Absent

Absent

(3.2.1.1) — (3.2.4.2 + 3.2.6)

(3.2.2) — (3.2.4.2 + 3.2.6)

(3.2.1.1) — (3.2.4.2)

(3.2.2) — (3.2.4.2)

3.2.6.

cyanamide nitrogen, by precipitation as a silver compound, the nitrogen being estimated in the precipitate
by the Kjeldahl method

4.

Reagents

4.1.

4.2.

4.3.

4.4.

4.5.

4.6.

4.7.

4.8.

4.9.

Distilled or demineralised water.

Potassium sulphate for analysis

Iron powder, reduced with hydrogen (the prescribed quantity of iron must be able to reduce at least 50 mg
of nitrate nitrogen)

Potassium thiocyanate for analysis

Potassium nitrate for analysis

Ammonium sulphate for analysis

Urea for analysis

Dilute sulphuric acid 1: 1 by volume: one volume of sulphuric acid (d20 = 1,84 g/ml) in one volume of water

Standard solution of sulphuric acid: 0,2 mol/l

Concentrated sodium hydroxide solution. Aqueous solution at about 30 % (W/V) of NaOH, free from
ammonia

4.10.

Standard solution of sodium or potassium hydroxide: 0,2 mol/l, free from carbonates

4.11.

Stannous chloride solution

Dissolve 120 g of SnCl2. 2H2O in 400 ml of concentrated hydrochloric acid (d20 = 1,18 g/ml) and make
up to one litre with water. The solution must be perfectly clear and prepared immediately before its use.

N o t e

It is essential to check the reducing power of stannous chloride: dissolve 0,5 g of SnCl2. 2H2O in 2 ml of
concentrated hydrochloric acid (d20 = 1,18 g/ml) and make up to 50 ml with water. Then add 5 g of
Rochelle salt (potassium sodium tartrate), then a sufficient quantity of sodium bicarbonate for the solution to
be alkaline to litmus paper.

Titrate with a 0,1 mol/l iodine solution in the presence of a starch solution as an indicator.

1 ml of 0,1 mol/l iodine solution corresponds to 0,01128 g of SnCl2. 2H2O.

At least 80 % of the total tin present in the solution thus prepared must be in bivalent form. For the titration
at least 35 ml of 0,1 mol/l iodine solution must therefore be used.

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4.12.

4.13.

Sulphuric acid (d20 = 1,84 g/ml)

Dilute hydrochloric acid: one volume of hydrochloric acid (d20 = 1,18 g/ml) plus one volume of water

4.14.

Acetic acid: 96 to 100 %

4.15.

4.16.

Sulphuric acid solution containing about 30 % of H2SO4 (W/V)

Ferrous sulphate: crystalline, FeSO4. 7H2O

4.17.

Standard sulphuric acid solution: 0,1 mol/l

4.18.

Octyl alcohol

4.19.

Saturated solution of potassium carbonate

4.20.

Standard solution of sodium or potassium hydroxide: 0,1 mol/l (free from carbonates)

4.21.

Saturated solution of barium hydroxide

4.22.

Sodium carbonate solution: at 10 % (W/V)

4.23.

Hydrochloric acid: 2 mol/l

4.24.

Standard solution of hydrochloric acid: 0,1 mol/l

4.25.

Urease solution

Suspend 0,5 g of active urease in 100 ml of distilled water. Using hydrochloric acid 0,1 mol/l (4.24), adjust
the pH to 5,4, measured by a pH meter.

4.26.

Xanthydrol

Solution at 5 % in ethanol or methanol (4.31) (do not use products giving a high proportion of insoluble
matter). The solution may be kept for three months in a well-stoppered bottle, away from the light.

4.27.

Copper oxide (CuO): 0,3 to 0,4 g per estimation or an equivalent quantity of copper sulphate pentahydrate
(CuSO4. 5H2O) of 0,95 to 1,25 g per estimation

4.28.

Anti-bump granules washed in hydrochloric acid and calcined

4.29.

Indicator solutions

4.29.1.

Solution A: Dissolve 1 g of methyl red in 37 ml of sodium hydroxide solution 0,1 mol/l and make up to
one litre with water.

Solution B: Dissolve 1 g of methylene blue in water and make up to one litre.

Mix one volume of A with two volumes of B.

This indicator is violet in acid solution, grey in neutral solution and green in alkaline solution. Use 0,5 ml
(10 drops) of this indicator solution.

4.29.2.

Methyl red indicator solution

Dissolve 0,1 g of methyl red in 50 ml of 95 % ethanol. Make up to 100 ml with water and filter if
necessary. This indicator (four or five drops) can be used instead of the previous one.

4.30.

Indicator papers

Litmus bromothymol blue (or other papers sensitive to pH 6 to 8).

4.31.

Ethanol or methanol: solution 95 %

5.

5.1.

Apparatus

Distillation apparatus

See Method 2.1.

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5.2.

Apparatus for the estimation of ammoniacal nitrogen according to analytical technique 7.2.5.3 (see Figure 6)

The apparatus is made up of a specially shaped receptacle with a ground glass neck, with a side neck, a
connecting tube with a splash head and a perpendicular tube for the introduction of air. The tubes can be
connected to the receptacle by means of a simple perforated rubber bung. It is important to give a suitable
shape to the end of the tubes introducing air, since the bubbles of gas must be perfectly distributed
throughout the solutions contained in the receptacle and the absorber. The best arrangement consists of
small mushroom-shaped pieces with an external diameter of 20 mm and six openings of 1 mm around the
periphery.

5.3.

Apparatus for the estimation of urea nitrogen according to the urease technique (7.2.6.1)

It consists of a 300 ml Erlenmeyer flask, with a separating funnel and a small absorber (see Figure 7).

5.4.

5.5.

5.6.

5.7.

Rotary shaker (35 to 40 turns per minute)

A pH meter

Adjustable oven

Glassware:

pipettes of 2, 5, 10, 20, 25, 50 and 100 ml,

long-necked Kjeldahl flasks of 300 and 500 ml,

graduated flasks of 100, 250, 500 and 1 000 ml,

crucibles of sintered glass, pore diameter, 5 to 15 µ,

mortars.

6.

Preparation of the sample

See Method 1.

7.

7.1.

Analytical technique

Total soluble and insoluble nitrogen

7.1.1.

In the absence of nitrates

7.1.1.1.

Digestion

Weigh out, to an accuracy of 0,001 g, a quantity of the sample containing 100 mg of nitrogen at the most.
Place it in the flask of the distillation apparatus (5.1). Add 10 to 15 g of potassium sulphate (4.1), the
catalyst (4.27), and a few anti-bump granules (4.28). Then add 50 ml of dilute sulphuric acid (4.7), and mix
thoroughly. First heat gently mixing from time to time, until foam no longer forms. Then heat so that the
liquid boils regularly and keep it boiling for one hour after the solution has become clear, preventing any
organic matter from sticking to the sides of the flask. Allow to cool. Carefully add about 350 ml of water,
with mixing. Ensure that the dissolution is as complete as possible. Allow to cool and connect the flask to
the distillation apparatus (5.1).

7.1.1.2.

Distillation of ammonia

Transfer with a precision pipette,
into the receiver of the apparatus, 50 ml of a standard solution of
sulphuric acid 0,2 mol/l (4.8). Add the indicator (4.29.1 or 4.29.2). Ensure that the tip of the condenser
is at least 1 cm below the level of the solution.

the concentrated sodium hydroxide solution (4.9)

Taking the necessary precautions to avoid any loss of ammonia, carefully add to the distillation flasks
enough of
to make the liquid strongly alkaline
(120 ml
is generally sufficient; check by adding a few drops of phenolphthalein. At the end of the
distillation the solution in the flask must still be clearly alkaline). Adjust the heating of the flask so as to
distil 150 ml in half an hour. Test with indicator paper (4.30) that the distillation has been completed. If it
has not, distil a further 50 ml and repeat the test until the supplementary distillate reacts neutrally to the
indicator paper (4.30). Then lower the receiver, distil a few millilitres more and rinse the tip of the
condenser. Titrate the excess of acid with a standard solution of potassium or sodium hydroxide
0,2 mol/l (4.10) until the indicator changes colour.

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7.1.1.3.

Blank test

Carry out a blank test (omitting the sample) under the same conditions and take account of it when
calculating the final result.

7.1.1.4.

Expression of the result

where

% N ¼

ða (cid:1) AÞ (cid:2) 0,28
M

a = ml of standard solution of sodium or potassium hydroxide 0,2 mol/l, used for the blank, carried out by
pipetting into the receiver of the apparatus (5.1), 50 ml of standard solution of sulphuric acid
0,2 mol/l (4.8),

A = ml of standard solution of sodium or potassium hydroxide 0,2 mol/l, used for the analysis,

M = mass of the test sample, in grams.

7.1.2.

In the presence of nitrate

7.1.2.1.

Test sample

Mass out, to an accuracy of 0,001 g, a quantity of the sample containing not more than 40 mg of nitrate
nitrogen.

7.1.2.2.

Reduction of the nitrate

Mix the test sample in a small mortar with 50 ml of water. Transfer with the minimum amount of distilled
water into a 500-ml Kjeldahl flask. Add 5 g of reduced iron (4.2) and 50 ml of stannous chloride solution
(4.11). Shake and leave it to stand for half an hour. During the time it is standing, stir again after 10 and 20
minutes.

7.1.2.3.

Kjeldahl digestion

Add 30 ml of sulphuric acid (4.12), 5 g of potassium sulphate (4.1), the prescribed quantity of catalyst
(4.27) and some anti-bump granules (4.28). Heat gently with the flask slightly tilted. Increase the heat slowly
and shake the solution frequently to keep the mixture suspended: the liquid darkens and then clears with the
formation of a yellow-green anhydrous iron sulphate suspension. Then continue heating for one hour after
obtaining a clear solution, maintaining it at simmering point. Leave to cool. Cautiously take the contents of
the flask up in a little water and add little by little 100 ml of water. Mix and transfer the contents of the
flask into a 500-ml graduated flask. Make up the volume with water. Mix. Filter through a dry filter into a
dry receptacle.

7.1.2.4.

Analysis of the solution

Transfer by pipette,
into the flask of the distillation apparatus (5.1), an aliquot containing 100 mg of
nitrogen at the most. Dilute to about 350 ml with distilled water, add a few anti-bump granules (4.28),
connect the flask to the distillation apparatus and continue the estimation as described in 7.1.1.2.

7.1.2.5.

Blank test

See 7.1.1.3.

7.1.2.6.

Expression of the result

where

% N ¼

ða (cid:1) AÞ (cid:2) 0,28
M

a = ml of standard solution of sodium or potassium hydroxide 0,2 mol/l, used for the blank, carried out by
pipetting into the receiver of the apparatus (5.1), 50 ml of standard solution of sulphuric acid
0,2 mol/l (4.8),

A = ml of standard solution of sodium or potassium hydroxide 0,2 mol/l, used for the analysis,

M = mass of the sample, expressed in grams, present in the aliquot part taken in 7.1.2.4.

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7.2.

Forms of soluble nitrogen

7.2.1.

Preparation of the solution to be analysed

Mass out, to an accuracy of 1 mg, 10 g of the sample and place it in a 500-ml graduated flask.

7.2.1.1.

In the case of fertilisers not containing cyanamide nitrogen

Add to the flask 50 ml of water and then 20 ml of dilute hydrochloric acid (4.13). Shake and leave it to
stand until the evolution of carbon dioxide ceases. Then add 400 ml of water and shake for half an hour on
the rotary shaker (5.4). Make up to the volume with water, mix and filter through a dry filter into a dry
receptacle.

7.2.1.2.

In the case of fertilisers containing cyanamide nitrogen

Add to the flask 400 ml of water and a few drops of methyl red (4.29.2). If necessary make the solution
acid by using acetic acid (4.14). Add 15 ml of acetic acid (4.14). Shake on the rotary shaker for two hours
(5.4). If necessary, reacidify the solution during the operation, using acetic acid (4.14). Make up to the
volume with water, mix, filter immediately through a dry filter into a dry receptacle and immediately
estimate the cyanamide nitrogen.

In both cases, estimate the various soluble forms of nitrogen the same day the solution is made up, starting
with the cyanamide nitrogen and urea nitrogen if they are present.

7.2.2.

Total soluble nitrogen

7.2.2.1.

In the absence of nitrate

Pipette into a 300-ml Kjeldahl flask, an aliquot of the filtrate (7.2.1.1 or 7.2.1.2), containing 100 mg of
nitrogen at the most. Add 15 ml of concentrated sulphuric acid (4.12), 0,4 g of copper oxide or 1,25 g of
copper sulphate (4.27) and a few anti-bump granules (4.28). First heat gently to begin the digestion and then
at a higher temperature until the liquid become colourless or slightly greenish and white fumes are clearly
apparent. After cooling, quantitatively transfer the solution into the distillation flask, dilute to about 500 ml
with water, and add a few anti-bump granules (4.28). Connect the flask to the distillation apparatus (5.1) and
continue the determination as described in 7.1.1.2.

7.2.2.2.

In the presence of nitrate

Transfer with a precision pipette into a 500-ml Erlenmeyer, an aliquot of the filtrate (7.2.1.1 or 7.2.1.2)
containing not more than 40 mg of nitrate nitrogen. At this stage of the analysis the total quantity of
nitrogen is not important. Add 10 ml of sulphuric acid at 30 % (4.15), 5 g of reduced iron (4.2), and
immediately cover the Erlenmeyer with a watch glass. Heat gently until the reaction is steady but not
vigorous. At this juncture stop the heating and allow the flask to stand for at least three hours at
ambient temperature. With water, quantitatively transfer the liquid into a 250-ml graduated flask, leaving
behind the undissolved iron — make up to the mark with the water. Mix thoroughly, and transfer by
precision pipette into a 300-ml Kjeldahl flask, an aliquot containing 100 mg of nitrogen at the most. Add
15 ml of concentrated sulphuric acid (4.12), 0,4 g of copper oxide or 1,25 g of copper sulphate (4.27) and
some anti-bump granules (4.28). First heat gently to begin the digestion and then at a higher temperature
until the liquid becomes colourless or slightly greenish and white fumes are clearly apparent. After cooling,
quantitatively transfer the solution into the distillation flask, dilute to approximately 500 ml with water and
add some anti-bump granules (4.28). Connect the flask to the distillation apparatus (5.1) and continue the
determination as described in 7.1.1.2.

7.2.2.3.

Blank test

See 7.1.1.3.

7.2.2.4.

Expression of the result

where

% N ¼

ða (cid:1) AÞ (cid:2) 0,28
M

a = ml of standard solution of sodium or potassium hydroxide 0,2 mol/l, used for the blank, carried out by
pipetting into the receiver of the apparatus (5.1), 50 ml of standard solution of sulphuric acid 0,2
mol/l (4.8),

A = ml of standard solution of sodium or potassium hydroxide 0,2 mol/l, used for the analysis,

M = mass of the sample, expressed in grams, present in the aliquot part taken in 7.2.2.1 or 7.2.2.2.

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7.2.3.

Total soluble nitrogen with the exception of nitrate nitrogen

Transfer with a precision pipette into a 300-ml Kjeldahl flask, an aliquot sample of the filtrate (7.2.1.1 or
7.2.1.2) containing not more than 50 mg of nitrogen to be determined. Dilute to 100 ml with water, add
5 g of ferrous sulphate (4.16), 20 ml of concentrated sulphuric acid (4.12) and some anti-bump granules
(4.28). First heat gently and then increase the heat until white fumes appear. Continue the digestion for 15
minutes. Stop the heating, introduce copper oxide (4.27) as a catalyst and keep it at a temperature such that
white fumes are emitted for a further 10 to 15 minutes. After cooling, quantitatively transfer the contents to
the Kjeldahl flask into the distillation flask of the apparatus (5.1). Dilute to approximately 500 ml with
water and add a few anti-bump granules (4.28). Connect the flask to the distillation apparatus and continue
the determination as described in 7.1.1.2.

7.2.3.1.

Blank test

See 7.1.1.3.

7.2.3.2.

Expression of the result

where

% N ¼

ða (cid:1) AÞ (cid:2) 0,28
M

a = ml of standard solution of sodium or potassium hydroxide 0,2 mol/l, used for the blank, carried out by
pipetting into the receiver of the apparatus (5.1), 50 ml of standard solution of sulphuric acid 0,2
mol/l (4.8),

A = ml of standard solution of sodium or potassium hydroxide 0,2 mol/l, used for the analysis,

M = mass of the sample, expressed in grams, present in the aliquot part taken for the estimation.

7.2.4.

Nitrate nitrogen

7.2.4.1.

In the absence of calcium cyanamide

Is obtained by the difference between the results obtained in 7.2.2.4 and 7.2.3.2 and/or the result obtained
in 7.2.2.4 and the sum of the results obtained in (7.2.5.2 or 7.2.5.5) and (7.2.6.3 or 7.2.6.5 or 7.2.6.6).

7.2.4.2.

In the presence of calcium cyanamide

Is obtained by the difference between the results obtained in 7.2.2.4 and 7.2.3.2 and between the result
obtained in 7.2.2.4 and the sum of the results obtained in (7.2.5.5), (7.2.6.3 or 7.2.6.5 or 7.2.6.6) and
(7.2.7).

7.2.5.

Ammoniacal nitrogen

7.2.5.1.

Solely in the presence of ammoniacal nitrogen and ammoniacal plus nitrate nitrogen

Transfer with a precision pipette into the flask of the distillation apparatus (5.1), an aliquot sample of the
filtrate (7.2.1.1) containing 100 mg of ammoniacal nitrogen at the most. Add water to obtain a total
volume of about 350 ml and some anti-bump granules (4.28) to facilitate boiling. Connect the flask to
the distillation apparatus, add 20 ml of sodium hydroxide solution (4.9) and distil as described in 7.1.1.2.

7.2.5.2.

Expression of the result

where

% N ðammoniacalÞ ¼

ða (cid:1) AÞ (cid:2) 0,28
M

a = ml of standard solution of sodium or potassium hydroxide 0,2 mol/l, used for the blank, carried out by
pipetting into the receiver of the apparatus (5.1), 50 ml of standard solution of sulphuric acid 0,2
mol/l (4.8),

A = ml of standard solution of sodium or potassium hydroxide 0,2 mol/l, used for the analysis,

M = mass of the sample, expressed in grams, present in the aliquot part taken for the estimation.

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7.2.5.3.

In the presence of urea and/or cyanamide nitrogen

Transfer with a precision pipette, into the dry flask of the apparatus (5.2), an aliquot sample of the filtrate
(7.2.1.1 or 7.2.1.2) containing 20 mg of ammoniacal nitrogen at the most. Then assemble the apparatus.
Pipette, into the 300-ml Erlenmeyer, 50 ml of the standard sulphuric acid solution 0,1 mol/l (4.17) and
enough distilled water for the level of the liquid to be approximately 5 cm above the opening of the delivery
tube. Introduce, through the side neck of the reaction flask, distilled water so as to make up the volume to
about 50 ml. Mix. To avoid foaming during aeration, add a few drops of octyl alcohol (4.18). Then make
the solution alkaline by using 50 ml of saturated potassium carbonate solution (4.19) and immediately
begin to expel the ammonia thus liberated from the cold suspension. The strong current of air necessary to
that end (flow of approximately three litres per minute) is purified beforehand by passing it through washing
flasks containing dilute sulphuric acid and dilute sodium hydroxide. Instead of using pressurised air, it is also
possible to work in a vacuum (water pump) provided that the inflow tube is connected in a sufficiently
airtight manner to the receptacle used to recover the ammonia. The elimination of the ammonia is generally
complete after three hours. It is nevertheless wise to make sure of that by changing the receiving flask.
When the operation is finished, separate the flask from the apparatus, rinse the tip of the tube and the sides
of the flask with a little distilled water. Titrate the excess of acid with a standard solution of sodium
hydroxide 0,1 mol/l (4.20) until the indicator turns grey (4.29.1).

7.2.5.4.

Blank test

See 7.1.1.3.

7.2.5.5.

Expression of the result

where

% N ðammoniacalÞ ¼

ða (cid:1) AÞ (cid:2) 0,14
M

a = ml of standard solution of sodium or potassium hydroxide 0,1 mol/l, used for the blank, carried out by
pipetting into the 300-ml Erlenmeyer of the apparatus (5.2), 50 ml of standard solution of sulphuric
acid 0,1 mol/l (4.17),

A = ml of standard solution of sodium or potassium hydroxide 0,1 mol/l, used for the analysis,

M = mass of the sample, expressed in grams, present in the aliquot part taken for the analysis.

7.2.6.

Urea nitrogen

7.2.6.1.

Urease method

Transfer with a precision pipette, into a 500-ml graduated flask, an aliquot of the filtrate (7.2.1.1 or 7.2.1.2)
containing not more than 250 mg of urea nitrogen. To precipitate the phosphates add some saturated
barium hydroxide solution (4.21) until no further precipitation occurs. Then eliminate the excess of barium
ions (and any dissolved calcium ions) with the aid of the sodium carbonate solution at 10 % (4.22).

Leave it to settle and check whether total precipitation has occurred. Make up to the mark, mix and filter
through a pleated filter. Pipette 50 ml of the filtrate into the 300-ml Erlenmeyer of the apparatus (5.3).
Acidify the filtrate with hydrochloric acid 2 mol/l (4.23) until a pH of 3,0 measured by the pH meter is
obtained (5.5). Then raise the pH to 5,4 with sodium hydroxide 0,1 mol/l (4.20).

To avoid losses of ammonia during decomposition by the urease, close the Erlenmeyer with a stopper
provided with a separating funnel and a small bubble trap containing exactly 2 ml of a standard solution of
hydrochloric acid 0,1 mol/l (4.24). Introduce through the separating funnel 20 ml of urease solution (4.25),
and leave it to stand for one hour at 20 to 25 °C. Then pipette 25 ml of the standard solution of hydro-
chloric acid 0,1 mol/l (4.24) into the separating funnel, allow it to run through into the solution and then
rinse with a little water. In the same way quantitatively transfer the contents of the protective receptacle into
the solution contained in the Erlenmeyer. Titrate the excess of acid with the standard solution of sodium
hydroxide 0,1 mol/l (4.20), until a pH of 5,4 is obtained, measured by the pH meter.

7.2.6.2.

Blank test

See 7.1.1.3.

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7.2.6.3.

Expression of the result

where

% N ðureaÞ ¼

ða (cid:1) AÞ (cid:2) 0,14
M

a = ml of standard solution of sodium or potassium hydroxide 0,1 mol/l, used for the blank, carried out

exactly in the same conditions as the analysis,

A = ml of standard solution of sodium or potassium hydroxide 0,1 mol/l, used for the analysis,

M = mass of the sample, expressed in grams, present in the aliquot part taken for the analysis.

R e m a r k

(1) After precipitation by the solutions of barium hydroxide and sodium carbonate, make up to the mark,

filter and neutralise as rapidly as possible.

(2) The titration test may also be carried out with the indicator (4.29.2), but the end point is then more

difficult to observe.

7.2.6.4.

Gravimetric method with xanthydrol

Transfer with a precision pipette,
into a 250-ml beaker, an aliquot of the filtrate (7.2.1.1 or 7.2.1.2)
containing not more than 20 mg of urea. Add 40 ml of acetic acid (4.14). Stir with a glass rod for one
minute, leave any precipitate to settle for five minutes. Filter on a flat bed into a 100-ml beaker, wash with
several millilitres of acetic acid (4.14), then add to the filtrate drop by drop, 10 ml of xanthydrol (4.26),
stirring continuously with a glass rod. Leave it to settle until the precipitate appears, at that juncture, stir
again for one or two minutes. Leave it to stand for one and a half hours. Filter through a glass filtering
crucible, which has been previously dried and weighed, pressing it down slightly; wash three times with
5 ml of ethanol (4.31) without trying to eliminate all the acetic acid. Place it in the oven and keep it at a
temperature of 130 °C for an hour (do not go above 145 °C). Leave it to cool in a desiccator and weigh.

7.2.6.5.

Expression of the result

% urea N þ biuret ¼

6,67 (cid:2) m1
M2

where

m1 = mass of the precipitate obtained, in grams,

M2 = mass of the sample, expressed in grams, present in the aliquot part taken for the estimation.

Correct for a blank. Biuret may, generally speaking, be measured with the urea nitrogen without any great
error, since its content remains small in absolute value in compound fertilisers.

7.2.6.6.

Method by difference

Urea nitrogen may also be calculated according to the following table:

Case

Nitrate N

Ammoniacal N Cyanamide N

Urea N

1

2

3

4

Absent

Present

Absent

Present

Present

Present

Present

Present

Present

Present

Absent

Absent

(7.2.2.4) — (7.2.5.5 + 7.2.7)

(7.2.3.2) — (7.2.5.5 + 7.2.7)

(7.2.2.4) — (7.2.5.5)

(7.2.3.2) — (7.2.5.5)

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7.2.7.

Cyanamide nitrogen

Take one aliquot part of the filtrate (7.2.1.2), containing 10 to 30 mg of cyanamide nitrogen and place it in
a 250-ml beaker. Continue the analysis according to Method 2.4.

8.

8.1.

8.2.

Verification of the results

In certain cases, a difference may be found between the total nitrogen obtained directly from a weighed out
sample (7.1) and total soluble nitrogen (7.2.2). Nevertheless, the difference should not be greater than 0,5 %.
If this is not the case, the fertiliser contains forms of insoluble nitrogen not contained in the list in Annex I.

Before each analysis, check that the apparatus is working properly and that the correct application of the
method is used, with a standard solution including the various forms of nitrogen in proportions similar to
those of the test sample. This standard solution is prepared from standard solutions of potassium thiocyanate
(4.3), potassium nitrate (4.4), ammonium sulphate (4.5) and urea (4.6).

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Figure 6

Apparatus for the estimation of ammoniacal nitrogen (7.2.5.3)

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Figure 7

Apparatus for the estimation of urea nitrogen (7.2.6.1)

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Determination of different forms of nitrogen in fertilisers containing nitrogen only as nitric, ammoniacal and
urea nitrogen

M e t h o d 2.6.2

1.

2.

3.

Object

The purpose of the present document is to specify a simplified method for the determination of different
forms of nitrogen in fertilisers containing nitrogen only as nitric, ammoniacal and urea nitrogen.

Field of application

The present method can be used for all fertilisers mentioned in Annex I which contain exclusively nitric,
ammoniacal or urea nitrogen.

Principle

The following determinations are made on different portions of a single sample solution:

3.1.

Total soluble nitrogen:

3.1.1.

in the absence of nitrates, by direct Kjeldahl digestion of the solution,

3.1.2.

in the presence of nitrates, by Kjeldahl digestion of a portion of the solution after reduction by the Ulsch
method; ammonia is determined in both cases as described in Method 2.1;

3.2.

3.3.

3.4.

total soluble nitrogen except nitric nitrogen, by Kjeldahl digestion after elimination of nitric nitrogen in acid
medium by means of ferrous sulphate; ammonia is determined as described in Method 2.1;

nitric nitrogen, by the difference between 3.1.2 and 3.2 or between total soluble nitrogen (3.1.2) and the
sum of ammoniacal and urea nitrogen (3.4 + 3.5);

ammoniacal nitrogen, by cold distillation after slight alkalinisation; the ammonia is obtained in a solution of
sulphuric acid and determined as in Method 2.1;

3.5.

urea nitrogen, either:

3.5.1.

3.5.2.

by transformation using urease, into ammonia, which is determined by titration with a standard solution of
hydrochloric acid,

by gravimetry using xanhydrol: co-precipitated biuret can be taken with urea nitrogen with little error; its
level is usually of small absolute value in compound fertilisers,

3.5.3.

by difference, following the table:

Case

1

2

Nitrate nitrogen

Ammoniacal nitrogen

Difference

Absent

Present

Present

Present

(3.1.1) — (3.4)

(3.2) — (3.4)

4.

Reagents

4.1.

4.2.

4.3.

4.4.

4.5.

4.6.

4.7.

Distilled or demineralised water.

Potassium sulphate for analysis

Iron for analysis, hydrogen reduced (the specified amount of iron must be able to reduce at least 50 mg of
nitrate nitric N)

Potassium nitrate for analysis

Ammonium sulphate for analysis

Urea for analysis

Sulphuric acid solution: 0,2 mol/l

Concentrated sodium hydroxide solution: approximately 30 % (W/V) aqueous solution of NaOH, free of
ammonia

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4.8.

4.9.

Sodium or potassium hydroxide solution: 0,2 mol/l, free of carbonates

Sulphuric acid density (d20 = 1,84 g/ml)

4.10.

Dilute hydrochloric acid: one volume of hydrochloric acid (d20 = 1,18 g/ml) plus one volume of water

4.11.

Acetic acid: 96 to 100 %

4.12.

4.13.

Sulphuric acid solution containing approximately 30 % H2SO4 (W/V), free of ammonia

Ferrous sulphate: crystalline, FeSO4. 7H2O

4.14.

Titrated sulphuric acid solution: 0,1 mol/l

4.15.

Octyl alcohol

4.16.

Saturated potassium carbonate solution

4.17.

Sodium or potassium hydroxide: 0,1 mol/l

4.18.

Saturated barium hydroxide solution

4.19.

Sodium carbonate solution: 10 % (W/V)

4.20.

Hydrochloric acid: 2 mol/l

4.21.

Hydrochloric acid solution: 0,1 mol/l

4.22.

Urease solution

Make a suspension of 0,5 g of active urease in 100 ml of distilled water, using 0,1 mol/l hydrochloric acid
(4.21), adjust the pH to 5,4, measured with pH meter.

4.23.

Xanthydrol

5 % solution in ethanol or methanol (4.28) (do not use products giving a high proportion of insoluble
material); the solution can be kept for three months in a carefully stoppered bottle in darkness.

4.24.

Catalyst

Copper oxide (CuO): 0,3 to 0,4 g per determination, or an equivalent amount of copper sulphate
pentahydrate (CuSO4. 5H2O) of 0,95 to 1,25 g determination.

4.25.

Pumice stone granules washed with hydrochloric acid and calcined

4.26.

Indicator solutions

4.26.1.

Mixed indicator

Solution A: Dissolve 1 g of methyl red in 37 ml of 0,1 mol/l sodium hydroxide solution and make up to
one litre with water.

Solution B: Dissolve 1 g of methylene blue in water and make up to one litre.

Mix one volume of A with two volumes of B.

This indicator is violet in acid solution, grey in neutral solution and green in alkaline solution. Use 0,5 ml
(10 drops) of this indicator.

4.26.2.

Methyl red indicator solution

Dissolve 0,1 g of methyl red in 50 ml of 95 % ethanol. Make up to 100 ml with water and filter if
necessary. Four or five drops of this indicator can be used instead of the previous one.

4.27.

Indicator papers

Litmus, bromothymol blue (or other papers sensitive to pH 6 to 8).

4.28.

Ethanol or methanol: 95 % (W/V)

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5.

5.1.

Apparatus

Distillation apparatus

See Method 2.1.

5.2.

Apparatus for determination of ammoniacal nitrogen (7.5.1)

See Method 2.6.1 and Figure 6.

5.3.

Apparatus for determination of urea nitrogen by the urease technique (7.6.1)

See Method 2.6.1 and Figure 7.

Rotary shaker (35 to 40 turns per minute)

A pH meter

Glassware:

5.4.

5.5.

5.6.

precision pipettes of 2, 5, 10, 20, 25, 50 and 100 ml,

long-necked Kjeldahl flasks of 300 and 500 ml,

graduated flasks of 100, 250, 500 and 1 000 ml,

crucibles of sintered glass, pore diameter, 5 to 15 µm,

mortar.

6.

Preparation of the sample

See Method 1.

Methods

Preparation of solution for analysis

7.

7.1.

Weigh out, to an accuracy of 1 mg, 10 g of sample, and transfer to a 500-ml graduated flask. Add 50 ml
water and then 20 ml dilute hydrochloric acid (4.10). Shake. Allow to rest until any CO2 release comes to
an end. Add 400 ml of water; shake for half an hour (5.4); make up to volume with water, homogenise,
filter on a dry filter into a dry container.

7.2.

Total nitrogen

7.2.1.

In absence of nitrates

Pipette into a 300-ml Kjeldahl flask a portion of the filtrate (7.1), containing a maximum of 100 mg N. Add
15 ml of concentrated sulphuric acid (4.9), 0,4 g of copper oxide or 1,25 g of copper sulphate (4.24), and
a few glass beads to control boiling. Heat moderately at first in order to initiate the reaction, then more
strongly until the liquid becomes colourless or slightly greenish and white fumes unmistakably appear. After
cooling, transfer the solution into the distillation flask, dilute to approximately 500 ml with water and add a
few granules of pumice stone (4.25). Connect the flask to the distillation apparatus (5.1) and carry out the
determination as described in 7.1.1.2, Method 2.6.1.

7.2.2.

In the presence of nitrates

Pipette into 500-ml Erlenmeyer a portion of the filtrate (7.1) containing not more than 40 mg of nitric N.
At this stage of the analysis, the total quantity of N is unimportant. Add 10 ml of 30 % sulphuric acid
(4.12), 5 g of reduced iron (4.2), and immediately cover the Erlenmeyer with a watch glass. Heat gently until
the reaction becomes strong but not violent. Stop heating and leave for at least three hours at ambient
temperature. Transfer the liquid quantitatively to a 250-ml graduated flask, ignoring undissolved iron. Make
up to the mark with water. Homogenise carefully. Pipette a portion containing a maximum of 100 mg N
into a 300-ml Kjeldahl flask. Add 15 ml of concentrated sulphuric acid (4.9), 0,4 g of copper oxide or
1,25 g of copper sulphate (4.24), and some glass beads for the control of boiling. Heat moderately at first in
order to initiate the reaction, then more strongly until the liquid becomes colourless or slightly greenish and
white fumes unmistakably appear. After cooling, transfer the solution quantitatively to the distillation flask,
dilute to approximately 500 ml with water, and add a few granules of pumice stone (4.25). Connect the
flask to the distillation apparatus (5.1) and continue the determination as described in 7.1.1.2, Method 2.6.1.

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7.2.3.

Blank test

Carry out a blank test (omitting the sample) under the same conditions, and use the result in calculating the
final result.

7.2.4.

Expression of the result

where

% N ðtotalÞ ¼

ða (cid:1) AÞ (cid:2) 0,28
M

a = ml of titrated 0,2 mol/l sodium or potassium hydroxide solution (4.8), used in the blank test, carried
out by placing 50 ml of titrated 0,2 mol/l sulphuric acid solution into the receiver of the apparatus
(4.6),

A = ml of titrated 0,2 mol/l sodium or potassium hydroxide solution (4.8), used for the analysis,

M = mass of the test sample, in grams, present in the aliquot (7.2.1 or 7.2.2).

7.3.

Total nitrogen excluding nitric N

7.3.1.

Analysis

Pipette into a 300-ml Kjeldahl flask an aliquot of filtrate (7.1) containing not more than 50 mg N to be
determined. Dilute to 100 ml with water, add 5 g of ferrous sulphate (4.13), 20 ml of concentrated
sulphuric acid (4.9), and a few glass beads to control boiling. Heat moderately at
then more
strongly until white fumes appear. Continue the reaction for 15 minutes. Stop heating, introduce 0,4 g
of copper oxide or 1,25 g of copper sulphate (4.24) as catalyst. Resume heating and maintain production of
white fumes for 10 to 15 minutes. After cooling, transfer the contents of the Kjeldahl flask quantitatively to
the distillation flask (5.1). Dilute to approximately 500 ml with water, and add a few granules of pumice
stone (4.25). Connect the flask to the distillation apparatus and continue the determination as in 7.1.1.2,
Method 2.6.1.

first,

7.3.2.

Blank test

See 7.2.3.

7.3.3.

Expression of the result

where

% N ðtotalÞ ¼

ða (cid:1) AÞ (cid:2) 0,28
M

a = ml of titrated 0,2 mol/l sodium or potassium hydroxide solution (4.8), used in the blank test, carried
out by pipetting 50 ml of titrated 0,2 mol/l sulphuric acid solution (4.6) into the receiver of the
apparatus,

A = ml of titrated 0,2 mol/l sodium or potassium hydroxide solution, used for the analysis,

M = mass of the sample, expressed in grams, present in the aliquot used in the determination.

7.4.

Nitric nitrogen

Is obtained by the difference between:

7.2.4 — (7.5.3 + 7.6.3)

or

7.2.4 — (7.5.3 + 7.6.5)

or

7.2.4 — (7.5.3 + 7.6.6)

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7.5.

Ammoniacal nitrogen

7.5.1.

Analysis

Pipette into the dry flask of the apparatus (5.2) a portion of filtrate (7.1) containing a maximum of 20 mg
of ammoniacal N. Connect up the apparatus. Pipette into the 300-ml Erlenmeyer exactly 50 ml of titrated
0,1 mol/l sulphuric acid solution (4.14) and an amount of distilled water so that the level of the liquid is
approximately 5 cm above the opening of the intake tube. Introduce through the side neck of the reaction
flask, distilled water so as to bring the volume to approximately 50 ml. Shake. In order to avoid the
formation of froth on the introduction of the gaseous flow, add several drops of octyl alcohol (4.15).
Add 50 ml of saturated potassium carbonate solution (4.16), and immediately begin to expel
the
ammonia thus released from the cold suspension. The intense air flow required for this purpose (flow
rate of approximately three litres per minute) is previously purified by passage through washing flasks
containing dilute sulphuric acid and dilute sodium hydroxide.
Instead of using air under pressure, a
vacuum may be used (water suction pump) provided that the connections between the apparatus are air
tight.

The elimination of ammonia is generally completed after three hours.

However, it is desirable to make certain of this by changing the Erlenmeyer. When the process is finished,
separate the Erlenmeyer from the apparatus, rinse the end of the intake tube and the Erlenmeyer walls with a
little distilled water, and titrate the excess acid against a standard 0,1 mol/l sodium hydroxide solution (4.17).

7.5.2.

Blank test

See 7.2.3.

7.5.3.

Expression of the result

where

% N ðammoniacalÞ ¼

ða (cid:1) AÞ (cid:2) 0,14
M

a = ml of titrated 0,1 mol/l sodium or potassium hydroxide solution (4.17), used in the blank test, carried
out by pipetting into the 300-ml Erlenmeyer of the apparatus (5.2) 50 ml of titrated 0,1 mol/l
sulphuric acid solution (4.14),

A = ml of titrated 0,1 mol/l sodium or potassium hydroxide solution, used for the analysis (4.17),

M = mass of the sample, expressed in grams, present in the aliquot used for the analysis.

7.6.

Urea nitrogen

7.6.1.

Urease method

Pipette into a 500-ml graduated flask a portion of filtrate (7.1) containing not more than 250 mg of urea
nitrogen. To precipitate phosphates, add a suitable quantity of saturated barium hydroxide solution (4.18)
until further addition does not cause the production of more precipitate. Eliminate excess barium ions (and
any dissolved calcium ions) by means of 10 % sodium carbonate solution (4.19). Allow to settle and check
whether precipitation is complete. Make up to the mark, homogenise, and filter through a folder filter.
Pipette 50 ml of filtrate into the 300-ml Erlenmeyer of the apparatus (5.3). Acidify with 2 mol/l hydro-
chloric acid (4.20) to pH 3,0, measured by means of pH meter. Raise the pH to 5,4 by means of 0,1 mol/l
sodium hydroxide (4.17). To avoid ammonia losses when hydrolysis by urease occurs, close the Erlenmeyer
by means of a stopper attached to a dropping funnel and a small protective container holding exactly 2 ml
of 0,1 mol/l hydrochloric acid solution (4.21). By way of the dropping funnel, introduce 20 ml of urease
solution (4.22). Leave for one hour at 20 to 25 °C. Pipette 25 ml of the standard 0,1 mol/l hydrochloric
acid solution (4.21) into the dropping funnel, allow to run into the solution, then rinse with a little water.
Also transfer quantitatively the contents of the protective container to the solution held in the Erlenmeyer.
Titrate the excess acid using the standard 0,1 mol/l sodium hydroxide solution (4.17), until a pH of 5,4 is
obtained, measured on the pH meter.

R e m a r k s

1. After precipitation by the barium hydroxide and sodium carbonate solutions, make up to the mark, filter,

and neutralise as quickly as possible.

2. The titration may also be assessed using the indicator (4.26), although the change of colour is more

difficult to observe.

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7.6.2.

Blank test

See 7.2.3.

7.6.3.

Expression of the result

where

% N ðureaÞ ¼

ða (cid:1) AÞ (cid:2) 0,14
M

a = ml of titrated 0,1 mol/l sodium or potassium hydroxide solution (4.17), used in the blank test, carried

out in exactly the same conditions as the analysis,

A = ml of titrated 0,1 mol/l sodium or potassium hydroxide solution (4.17), used in the analysis,

M = sample mass, expressed in grams, present in the aliquot used for the analysis.

7.6.4.

Gravimetric method with xanthydrol

Pipette into a 100-ml beaker a portion of filtrate (7.1) containing not more than 20 mg of urea. Add 40 ml
of acetic acid (4.11). Stir with a glass rod for one minute. Allow any precipitate to settle for five minutes.
Filter, wash with a few millilitres of acetic acid (4.11). Add 10 ml of xanthydrol to the filtrate drop by drop
(4.23), stirring continually with a glass rod. Leave it to settle until the precipitate appears, and at that
juncture stir again for one to two minutes. Leave for one and a half hours. Filter on a glass filtration crucible,
previously dried and weigh, using a slight reduction of pressure; wash three times with 5 ml of ethanol
(4.28), without aiming to eliminate all the acetic acid. Transfer to oven and maintain at 130 °C for one hour
(do not exceed 145 °C). Allow to cool in a desiccator and weigh.

7.6.5.

Expression of the result

% N ðureaÞ ¼

6,67 (cid:2) m
M

where

m = mass of the precipitate obtained, in grams,

M = mass of the sample, in grams, present in the aliquot used in the determination.

Make the corrections for the blank. Biuret can generally be taken with urea nitrogen without large error, its
level being of small absolute value in compound fertilisers.

7.6.6.

Difference method

Urea N can also be calculated as indicated in the following table:

Case

1

2

Nitric N

Absent

Present

Ammoniacal N

Urea N

Present

Present

(7.2.4) — (7.5.3)

(7.3.3) — (7.5.3)

8.

Verification of the result

Before each analysis, check the functioning of the apparatus and the correct application of the methods used
with a standard solution containing the different forms of nitrogen in proportions similar to those in the
sample. This standard solution is prepared from titrated solutions of potassium nitrate (4.3), ammonium
sulphate (4.4) and urea (4.5).

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M e t h o d s 3

Phosphorus

M e t h o d s 3.1

Extractions

M e t h o d 3.1.1

Extraction of phosphorus soluble in mineral acids

Scope

This document describes the procedure for the determination of phosphorus soluble in mineral acids.

Field of application

Applicable exclusively to the phosphate fertilisers listed in Annex I.

Principle

Extraction of the phosphorus in the fertiliser with a mixture of nitric acid and sulphuric acid.

Reagents

Distilled or demineralised water.

Sulphuric acid (d20 = 1,84 g/ml).

Nitric acid (d20 = 1,40 g/ml).

Equipment

Standard laboratory equipment.

A Kjeldahl flask, with a capacity of at least 500 ml, or a 250-ml round-bottomed flask with a glass tube
forming a reflux condenser.

1.

2.

3.

4.

4.1.

4.2.

5.

5.1.

5.2.

A 500-ml graduated flask.

6.

Preparation of the sample

See Method 1.

7.

7.1.

Procedure

Sample

Weigh, to the nearest 0,001 g, 2,5 g of the prepared sample and place it in a dry Kjeldahl flask.

7.2.

Extraction

Add 15 ml of water and stir so as to suspend the substance. Add 20 ml of nitric acid (4.2) and carefully
add 30 ml of sulphuric acid (4.1).

When the initial violent reaction has ceased, slowly bring the contents of the flask to boiling and boil for 30
minutes. Allow to cool and then carefully add with mixing about 150 ml of water. Continue boiling for 15
minutes.

Cool completely and transfer the liquid quantitatively to a 500-ml graduated flask. Make up to volume, mix
and filter through a dry pleated filter, free from phosphates, discarding the first portion of the filtrate.

7.3.

Determination

The determination of the phosphorus will be carried out by Method 3.2 on an aliquot part of the solution
thus obtained.

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1.

2.

3.

4.

4.1.

M e t h o d 3.1.2

Extraction of the phosphorus soluble in 2 % formic acid (20 g per litre)

Scope

This document defines the procedure for the determination of phosphorus soluble in 2 % formic acid (20 g
per litre).

Field of application

Soft natural phosphates exclusively.

Principle

To differentiate between hard natural phosphates and soft natural phosphates, phosphorus soluble in formic
acid is extracted under specific conditions.

Reagents

Formic acid, 2 % (20 g per litre)

N o t e

Make 82 ml of formic acid (concentration 98 to 100 %; d20 = 1,22 g/ml) up to five litres with distilled
water.

5.

Apparatus

Standard laboratory equipment.

5.1.

5.2.

6.

7.

7.1.

A 500-ml graduated flask (e.g. Stohmann)

Rotary shaker (35 to 40 turns per minute)

Preparation of the sample

See Method 1.

Procedure

Sample

Weigh, to the nearest 0,001 g, 5 g of the prepared sample and place it in a dry 500-ml graduated
Stohmann flask (5.1) with a wide neck.

7.2.

Extraction

it is
While continuously rotating the flask by hand, add the 2 % formic acid at 20 (± 1) °C (4.1) until
approximately 1 cm below the graduation mark and make up to the volume. Close the flask with a rubber
stopper and shake for 30 minutes at 20 (± 2) °C on a rotary shaker (5.2).

Filter the solution through a dry pleated filter, free from phosphates, into a dry glass receptacle. Discard the
first portion of the filtrate.

7.3.

Determination

Determine the phosphorus according to Method 3.2 in an aliquot part of the completely clear filtrate.

M e t h o d 3.1.3

Extraction of phosphorus soluble in 2 % citric acid (20 g per litre)

1.

Scope

This document defines the procedure for the determination of phosphorus soluble in 2 % citric acid (20 g
per litre).

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2.

3.

4.

Field of application

Only applicable to types of Basic slag (see Annex I A).

Principle

Extraction of phosphorus from the fertiliser with a 2 % citric acid solution (20 g per litre)
conditions.

in given

Reagents

Distilled or demineralised water.

4.1.

2 % citric acid solution (20 g per litre), prepared from crystallised, citric acid (C6H8O7.H2O)

N o t e

Verify the concentration of this citric acid solution by titrating 10 ml of the latter with a sodium hydroxide
standard solution 0,1 mol/l, using phenolphtalein as an indicator.

If the solution is correct 28,55 ml of the standard solution should be used.

5.

5.1.

6.

7.

7.1.

Apparatus

Rotary shaker (35 to 40 turns per minute)

Preparation of the sample

The analysis is carried out on the product as received after carefully mixing the original sample to ensure it
is homogeneous. See Method 1.

Procedure

Sample

Weigh, to the nearest 0,001 g, 5 g of the prepared sample and place it in a dry flask with a sufficiently
wide neck, with a capacity of 600 ml, allowing the liquid to be shaken thoroughly.

7.2.

Extraction

Add 500 (± 1) ml of the citric acid solution at 20 (± 1) °C. When adding the first millilitres of the reagent
shake vigorously by hand to stop the formation of lumps and to prevent the substance sticking to the sides.
Close the flask with a rubber stopper and shake it in the rotary shaker (5.1) for exactly 30 minutes at a
temperature of 20 (± 2) °C.

Filter immediately through a dry pleated filter, free of phosphates, into a dry glass receiver and discard the
first 20 ml of the filtrate. Continue the filtering until a sufficient quantity of filtrate is obtained to carry out
the phosphorus determination.

7.3.

Determination

The determination of the phosphorus extract will be carried out according to Method 3.2 on an aliquot part
of the solution thus obtained.

M e t h o d 3.1.4

Extraction of phosphorus which is soluble in neutral ammonium citrate

1.

2.

3.

Scope

This document defines the procedure for the determination of phosphorus soluble in neutral ammonium
citrate.

Field of application

All fertilisers in respect of which solubility in neutral ammonium citrate is laid down (see Annex I).

Principle

Extraction of phosphorus at a temperature of 65 °C using a neutral ammonium citrate solution (pH 7,0)
under specific conditions.

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4.

Reagent

Distilled or demineralised water.

4.1.

Neutral ammonium citrate solution (pH 7,0)

This solution must contain per litre 185 g of crystallised citric acid and must have a specific gravity of 1,09
at 20 °C and a pH of 7,0.

The reagent is prepared as follows:

Dissolve 370 g of crystalline citric acid (C6H8O7.H2O)
in about 1,5 litres of water and make an
approximately neutral solution by adding 345 ml of ammonium hydroxide solution (28 to 29 % of
NH3). If the NH3 concentration is lower than 28 % add a correspondingly larger quantity of ammonium
hydroxide solution and dilute the citric acid in correspondingly smaller quantities of water.

Cool and make exactly neutral by keeping the electrodes of a pH meter immersed in the solution. Add the
ammonia, at 28 to 29 % of NH3, drop by drop, stirring continuously (with a mechanical stirrer) until
obtaining exactly a pH of 7,0 at a temperature of 20 °C. At this point make up the volume to two
litres and test the pH again. Keep the reagent in a closed container and check the pH at regular intervals.

5.

5.1.

5.2.

5.3.

5.4.

5.5.

6.

7.

7.1.

Apparatus

A two-litre beaker

A pH meter

A 200 or 250-ml Erlenmeyer flask

500-ml graduated flasks and a 2,000-ml graduated flask

Water bath which can be set thermostatically at 65 °C, equipped with a suitable stirrer (see Figure 8)

Preparation of the sample

See Method 1.

Procedure

Sample

Transfer 1 or 3 g of the fertiliser to be analysed (see Annex I A and B to the Regulation) into a 200 or
250-ml Erlenmeyer flask containing 100 ml of ammonium citrate solution previously heated to 65 °C.

7.2.

Analysis of the solution

Stopper the Erlenmeyer flask and shake in order to suspend the fertiliser without forming lumps. Remove
the stopper for an instant in order to balance the pressure and close the Erlenmeyer flask again. Place the
flask in a water bath set to maintain the contents of the flask at exactly 65 °C and connect it to the stirrer
(see Figure 8). During stirring, the level of the suspension in the flask must stay constantly below the level of
the water in the water bath (1). Mechanical stirring will be regulated so as to ensure complete suspension.

After stirring for exactly one hour, remove the Erlenmeyer flask from the water bath.

Cool immediately under running water to ambient temperature and, immediately, quantitatively transfer the
contents from the Erlenmeyer flask into a graduated 500-ml flask with a jet of water (wash bottle). Make up
the volume with water. Mix thoroughly. Filter through a dry pleated filter (medium speed phosphate free)
into a dry container, discarding the first part of the filtrate (about 50 ml).

About 100 ml of clear filtrate will then be collected.

7.3.

Determination

Determine the phosphorus of the extract thus obtained according to Method 3.2.

(1) If no mechanical stirrer is available, the flask may be shaken by hand every five minutes.

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Figure 8

M e t h o d s 3.1.5

Extraction by alkaline ammonium citrate

M e t h o d 3.1.5.1

Extraction of soluble phosphorus according to Petermann at 65 °C

1.

2.

3.

4.

Scope

This document defines the procedure for the determination of soluble phosphorus in alkaline ammonium
citrate.

Field of application

Exclusively to precipitated dihydrated dicalcium phosphate (CaHPO4.2H2O).

Principle

Extraction of phosphorus at a temperature of 65 °C with an alkaline solution of ammonium citrate
(Petermann) under specified conditions.

Reagents

Distilled water, or demineralised water having the same characteristics as distilled water.

4.1.

Petermann's solution.

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4.2.

Characteristics

Citric acid (C6H8O7.H2O): 173 g per litre.

Ammonia: 42 g per litre of ammoniacal nitrogen.

pH between 9,4 and 9,7.

Preparation from diammonium citrate

Dissolve 931 g of diammonium citrate (molecular mass 226,19) in about 3 500 ml of water, in a five-litre
standard flask. Stand in a bath of running water, mix and cool and add in small amounts ammonia. For
example, for d20 = 906 g/ml corresponding to a level of 20,81 % by mass of ammoniacal nitrogen, it is
necessary to use 502 ml of ammonia solution. Adjust the temperature to 20 °C, make up to volume with
distilled water. Mix.

Preparation from citric acid and ammonia

Dissolve 865 g of citric acid monohydrate in about 2 500 ml of distilled water in a container of about
five-litres capacity. Place the container in an ice bath, and add in small amounts, shaking constantly,
ammonia solution using a funnel,
the stem of which is immersed in the citric acid solution. For
example, for d20 = 906 g/ml corresponding to a level of 20,81 % by mass of ammoniacal nitrogen, it is
necessary to add 1 114 ml of ammonia solution. Adjust the temperature to 20 °C, transfer to a five-litre
standard flask, make up to the mark with distilled water and mix.

Check the ammoniacal nitrogen content as follows

Transfer 25 ml of the solution into a 250-ml standard flask and make up to volume with distilled water.
Mix. Determine the ammoniacal content on 25 ml of this solution following Method 2.1. If the solution is
correct, one must use 15 ml of 0,5 N mol/l H2SO4.

If the strength of ammoniacal nitrogen is greater than 42 g per litre, NH3 can be expelled by a stream of
inert gas or by moderate heating to bring back the pH to 9,7. Carry out a second determination.

If the strength of ammoniacal nitrogen is less than 42 g per litre, it will be necessary to add a mass M of
ammonia solution:

M ¼ ð42 (cid:1) n (cid:2) 2,8Þ (cid:2)

500
20,81

g

or a volume V ¼

M
0,906

at 20 °C.

If V is less than 25 ml, add it directly to the five-litre flask with a mass of V × 0,173 g powdered citric acid.

If V is greater than 25 ml, it will be convenient to make a new litre of reagent in the following way.

Weigh 173 g of citric acid. Dissolve it in 500 ml of water. And, taking the precautions indicated, add not
more than 225 + V × 1 206 ml of ammonia solution which was used to prepare the five litres of reagent.
Make up to volume with water. Mix.

Mix this litre with the 4 975 ml previously prepared.

5.

5.1.

Apparatus

Water bath which can be maintained at a temperature of 65 (± 1) °C

5.2.

A 500-ml graduated flask (e.g. Stohmann)

6.

Preparation of the sample

See Method 1.

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7.

7.1.

Procedure

Sample

Weigh, to the nearest 0,001 g, 1 g of the prepared sample and transfer to the 500-ml graduated flask (5.2).

7.2.

Extraction

Add 200 ml of alkaline ammonium citrate solution (4.1). Stopper the flask and shake vigorously by hand to
avoid the formation of lumps and to prevent any adherence of the substance to the sides.

Place the flask in the water bath set at 65 °C and shake every five minutes during the first half an hour.
After each shaking, raise the stopper to equilibrate the pressure. The level of water in the water bath ought
to be above the level of solution in the flask. Allow the flask to remain in the water bath a further hour at
65 °C and shake every 10 minutes. Remove the flask, cool to a temperature of about 20 °C, make up to a
volume of 500 ml with water. Mix and filter through a dry fluted filter paper, free from phosphates,
rejecting the first portion of filtrate.

7.3.

Determination

The determination of phosphate extracted will be carried out by Method 3.2 on an aliquot part of the
solution thus obtained.

Extraction of the soluble phosphorus according to Petermann at ambient temperature

M e t h o d 3.1.5.2

Scope

This document defines the procedure for the determination of phosphorus soluble in cold alkaline
ammonium citrate.

Field of application

Disintegrated phosphates exclusively.

Principle

Extraction of phosphorus at a temperature about 20 °C with an alkaline solution of ammonium citrate
(Petermann's solution) in specific conditions.

Reagent

See Method 3.1.5.1.

Apparatus

Standard laboratory equipment, and a 250-ml graduated flask (e.g. Stohmann)

Rotary shaker (35 to 40 turns per minute)

Preparation of the sample

See Method 1.

Procedure

Sample

1.

2.

3.

4.

5.

5.1.

5.2.

6.

7.

7.1.

Weigh, to the nearest 0,001 g, 2,5 g of the prepared sample and place it in a 250-ml graduated flask (5.1).

7.2.

Extraction

Add a little of Petermann's solution at 20 °C, shake very hard in order to stop the formation of lumps and
to prevent any of the substance adhering to the side of the flask. Make up to the graduation mark with
Petermann's solution and close the flask with a rubber stopper.

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Shake for two hours in the rotary shaker (5.2). Filter immediately through a dry pleated filter, free from
phosphate, into a dry container, discarding the first portion of the filtrate.

7.3.

Determination

The phosphorus determination will be carried out by Method 3.2 on an aliquot part of the solution thus
obtained.

Extraction of the phosphorus soluble in Joulie's alkaline ammonium citrate

M e t h o d 3.1.5.3

Scope

This document defines the procedure for the determination of phosphorus soluble in Joulie's alkaline
ammonium citrate.

Field of application

All the straight and compound phosphate fertilisers, in which the phosphate occurs in an alumino-calcic
form.

Principle

Extraction by shaking vigorously with an alkaline solution of ammonium citrate of defined specification (and
where appropriate in the presence of oxine) at about 20 °C.

Reagents

Destilled or demineralised water.

1.

2.

3.

4.

4.1.

Joulie's alkaline solution of ammonium citrate.

This solution contains 400 g of citric acid and 153 g of NH3 per litre. Its free ammonia content is
approximately 55 g per litre. It can be prepared by one of the methods described below.

4.1.1.

In a one-litre graduated flask, dissolve 400 g of citric acid (C6H8O7.H2O) in approximately 600 ml of
ammonia (d20 = 0,925 g/ml i.e. 200 g of NH3 per litre). The citric acid is added successively in quantities of
50 to 80 g maintaining the temperature below 50 °C. Make up the volume to one litre with ammonia.

4.1.2.

In a one-litre graduated flask, dissolve 432 g of dibasic ammonium citrate (C6H14N2O7) in 300 ml of water.
Add 440 ml of ammonia (d20 = 0,925 g/ml). Make the volume up to one litre with water.

N o t e

Verification of the total ammonia content.

Take a 10-ml sample of the citrate solution and place it in a 250-ml flask. Make up the volume with distilled
water. Determine the ammoniacal nitrogen content on 25 ml of this solution according to Method 2.1.

1 ml of H2SO4 0,5 mol/l = 0,008516 g of NH3

In these conditions, the reagent is considered to be correct when the number of millilitres found upon
titration lies between 17,7 and 18 ml.

If this is not so add 4,25 ml of ammonia (d20 = 0,925 g/l) per 0,1 ml below 18 ml

indicated above.

Powdered 8-hydroxyquinoline (oxine)

Apparatus

Standard laboratory equipment and small mortar in glass or porcelain with pestle

500-ml graduated flasks

A 1 000-ml graduated flask

Rotary shaker (35 to 40 turns per minute)

4.2.

5.

5.1.

5.2.

5.3.

5.4.

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6.

Preparation of the sample

See Method 1.

7.

7.1.

Procedure

Sample

Weigh, to the nearest 0,0005 g, 1 g of the prepared sample and place in a small mortar. Add about 10
drops of citrate (4.1) to moisten it and break it up very carefully with the pestle.

7.2.

Extraction

Add 20 ml of ammonium citrate (4.1) and mix to a paste, leave it to settle for about one minute.

Decant the liquid into a 500-ml graduated flask, straining off particles which might have escaped the
preceding moist disintegration. Add 20 ml of citrate solution (4.1) to the residue, grind as above and
decant the liquid into the graduated flask. Repeat the process four times, so that by the end of the fifth
time all the product can be poured into the flask. The total quantity of citrate used for these processes must
be approximately 100 ml.

Rinse the pestle and mortar above the graduated flask with 40 ml of distilled water.

The stoppered flask is shaken for three hours on the rotary shaker (5.4).

Leave the flask standing for 15 to 16 hours, shake it again under same conditions for three hours. The
temperature during the whole process is kept at 20 (± 2) °C.

Make up to the graduation mark with distilled water. Filter through a dry filter, discard the first portion of
the filtrate and collect the clear filtrate in a dry flask.

7.3.

Determination

The estimation of the extracted phosphorus will be carried out according to Method 3.2 on an aliquot part
of the solution thus obtained.

8.

Appendix

The use of oxine makes it possible to apply this Method to fertilisers containing magnesium. This use is
recommended when the ratio of magnesium and phosphoric anhydride contents is higher than 0,03
(Mg/P2O5 > 0,03). If this is the case, add 3 g of oxine to the moistened sample for analysis. The use of
oxine in the absence of magnesium is not, moreover, likely to interfere subsequently with the determination.
In the known absence of magnesium it is, however, possible not to use oxine.

M e t h o d 3.1.6

Extraction of water soluble phosphorus

Scope

This document defines the procedure for the determination of water soluble phosphorus.

Field of application

All fertilisers, including compound fertilisers, where water soluble phosphorus is to be determined.

Principle

Extraction in water by shaking under specific conditions.

Reagent

Distilled or demineralised water.

Apparatus

A 500-ml graduated flask (e.g. Stohmann)

1.

2.

3.

4.

5.

5.1.

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5.2.

6.

7.

7.1.

Rotary shaker (35 to 40 turns per minute)

Preparation of the sample

See Method 1.

Procedure

Sample

Weigh, to the nearest 0,001 g, 5 g of the prepared sample and place it in a 500-ml graduated flask (5.1).

7.2.

Extraction

Add to the flask 450 ml of water, the temperature of which must be between 20 and 25 °C.

Shake in the rotary shaker (5.2) for 30 minutes.

Then make up to the mark with water, mix thoroughly by shaking and filter through a dry pleated filter, free
of phosphate, into a dry container.

7.3.

Determination

The estimation of phosphorus will be carried out on an aliquot part of the solution thus obtained by Method
3.2.

M e t h o d 3.2

Determination of extracted phosphorus

(Gravimetric Method Using Quinoline Phosphomolybdate)

1.

2.

3.

Scope

This document defines the procedure for the determination of phosphorus in the extracts from fertilisers.

Field of application

The Method is applicable to all extracts of fertilisers (1) for the determination of the different forms of
phosphorus.

Principle

After possible hydrolysis of the different forms of phosphorus other than orthophosphates, the orthophos-
phated ions are precipitated in an acid medium in the form of quinoline phosphomolybdate.

After filtering and washing, the precipitate is dried at 250 °C and weighed.

In the abovementioned conditions no interfering action is exerted by the compounds likely to be found in
the solution (mineral and organic acids, ammonium ions, soluble silicates, etc.) if a reagent based on sodium
molybdate or ammonium molybdate is used in the precipitation.

4.

Reagents

Distilled or demineralised water.

Concentrated nitric acid (d20 = 1,40 g/ml)

Preparation of reagent

4.1.

4.2.

4.2.1.

Preparation of the reagent based on sodium molybdate

Solution A: Dissolve 70 g of sodium molybdate dihydrate in 100 ml of distilled water.

Solution B: Dissolve 60 g of citric acid monhydrate in 100 ml of distilled water and add 85 ml concen-
trated nitric acid (4.1).

Solution C: Stir solution A into solution B to obtain solution C.

(1) Phosphorus soluble in mineral acids, water soluble phosphorus, phosphorus soluble in solutions of ammonium citrate, phosphorus

soluble in 2 % citric acid and phosphorus soluble in 2 % formic acid.

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Solution D: To 50 ml of distilled water, add 35 ml of concentrated nitric acid (4.1), then 5 ml of freshly
distilled quinoline. Add this solution to solution C, mix thoroughly and leave standing overnight in the dark.
After this make up to 500 ml with distilled water, mix again, and filter through a sintered glass funnel (5.6).

4.2.2.

Preparation of the reagent based on ammonium molybdate

Solution A: In 300 ml of distilled water, dissolve 100 g of ammonium molybdate while heating gently and
stirring from time to time.

Solution B: Dissolve 120 g of citric acid monohydrate in 200 ml of distilled water, add 170 ml of concen-
trated nitric acid (4.1).

Solution C: Add 10 ml of freshly distilled quinoline to 70 ml of concentrated nitric acid (4.1).

Solution D: Slowly pour, stirring well, solution A into solution B. After thoroughly mixing add solution C to
this mixture and make up to one litre. Leave standing for two days in a dark place and filter through a
sintered glass funnel (5.6).

The Reagents 4.2.1 and 4.2.2 can be used in the same way; both must be kept in the dark in stoppered
polyethylene bottles.

Apparatus

Standard laboratory equipment and a 500-ml Erlenmeyer flask with a wide neck

Graduated pipettes of 10, 25 and 50 ml

Filter crucible with porosity of 5 to 20 µm

Buchner flask

Drying oven regulated at 250 (+ 10) °C

Sintered glass funnel with porosity of 5 to 20 µm

Procedure

Treatment of the solution

5.

5.1.

5.2.

5.3.

5.4.

5.5.

5.6.

6.

6.1.

With a pipette, take an aliquot part of fertiliser extract (see Table 2) containing about 0,01 g of P2O5 and
put it in a 500-ml Erlenmeyer flask. Add 15 ml of concentrated nitric acid (1) (4.1) and dilute with water to
about 100 ml.

Table 2

Determining the aliquot parts of the phosphate solutions

% P2O5 in the
fertiliser

% P in the fertiliser

Sample for
analysis
(g)

Dilution
(to ml)

Sample
(ml)

Dilution
(to ml)

Sample to be
precipitated
(ml)

Quinoline phospho-
molybdate conversion factor
(F), in % P2O5

Quinoline phospho-
molybdate conversion factor
(F'), in % P

5-10

2.2-4.4

10-25

4.4-11.0

+ 25

+ 11

8
<

:
8
<

:
8
<

:

1

5

1

5

1

5

500

500

500

500

500

500

—

—

—

50

—

50

—

—

—

500

—

500

50

10

25

50

10

25

32,074

32,074

64,148

64,148

160,370

128,296

13,984

13,984

27,968

27,968

69,921

55,937

(1) 21 ml when the solution to be precipitated contains more than 15 ml of citrate solution (neutral citrate, Petermann or Joulie alkaline

citrate).

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6.2.

Hydrolysis

the presence of metaphosphates, pyrophosphates or polyphosphates is suspected in the solution,

If
hydrolysis is carried out as follows.

Bring the contents of the Erlenmeyer flask to the boil slowly and keep at this temperature until hydrolysis is
completed (this usually takes one hour). Care must be taken to avoid losses by splashing and excessive
evaporation which could reduce the initial volume by more than half, by fitting a reflux condenser. After
Hydrolysis make up to the initial volume with distilled water.

6.3.

Weighing the crucible

Dry the filter crucible (5.3) for at least 15 minutes in the drying oven set at 250 (± 10) °C. Weigh it after it
has been cooled in a desiccator.

6.4.

Precipitation

The acid solution contained in the Erlenmeyer flask is heated until it begins to boil then precipitation of the
quinoline phosphomolybdate is started by adding 40 ml of the precipitating reagent (reagent 4.2.1 or
4.2.2) (1) drop by drop, stirring continuously. Place the Erlenmeyer flask in a steam bath, leave it there
for 15 minutes, shaking it from time to time. The solution can be filtered immediately or after it has cooled
down.

6.5.

Filtering and washing

Filter the solution under vacuum by decantation. Wash the precipitate in the Erlenmeyer flask with 30 ml of
water. Decant and filter the solution. Repeat this process five times. Quantitatively transfer the rest of the
precipitate into the crucible washing it with water. Wash four times with 20 ml of water, allowing the liquid
to drain from the crucible before each addition. Dry the precipitate thoroughly.

6.6.

Drying and weighing

Wipe the outside of the crucible with a filter paper. Place this crucible in a drying oven and keep it there
until its mass remains constant, at a temperature of 250 °C (5.5) (usually 15 minutes); leave it to cool in the
desiccator at ambient temperature and weigh rapidly.

6.7.

Blank test

For each series of determinations, carry out a blank test using only the reagents and solvents in the
proportions used in the extraction (citrate solution, etc.) and allow for them in the calculation of the
final result.

6.8.

Verification

Carry out the determination using an aliquot part of a potassium dihydrogen phosphate solution containing
0,01 g of P2O5.

7.

Expression of the result

If the samples for analysis and dilutions shown in Table 2 are used, the following formula applies:

% P in the fertiliser ¼ ðA (cid:1) aÞ F0

% P2O5 in the fertiliser ¼ ðA (cid:1) aÞ F

or

where

A = mass, in grams, of the quinoline phosphomolybdate,

a = mass, in grams, of the quinoline phosphomolybdate obtained in the blank test,

F and F' = factors given in the last two columns of Table 2.

(1) To precipitate phosphate solutions containing more than 15 ml of citrate solution (neutral, Petermann or Joulie) which have been

acidified with 21 ml of concentrated nitric acid (see footnote to 6.1) use 80 ml of the precipitating reagent.

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With samples for analysis and dilutions which differ from those of Table 2, the following formula applies:

% P in the fertiliser ¼

ðA (cid:1) aÞ (cid:2) f 0 (cid:2) D (cid:2) 100
M

% P2O5 in the fertiliser ¼

ðA (cid:1) aÞ (cid:2) f (cid:2) D (cid:2) 100
M

or

where

f and f' = conversion factors of quinoline phosphomolybdate

P = 0,013984 (f'),

into P2O5 = 0,032074,

(f) or

into

D = dilution factor,

M = mass, in grams, of the sample analysed.

M e t h o d 4

Potassium

M e t h o d 4.1

Determination of the water soluble potassium content

Scope

This document defines the procedure for the determination of water soluble potassium.

Field of application

All the potassium fertilisers listed in Annex I.

Principle

1.

2.

3.

The potassium in the sample to be analysed is dissolved in water. After eliminating or fixing the substances
which might interfere with the quantitative determination, the potassium is precipitated in a slightly alkaline
medium in the form of potassium tetraphenylborate.

4.

Reagents

Distilled or demineralised water.

4.1.

Formaldehyde

Clear formaldehyde solution at 25 to 35 %.

4.2.

4.3.

Potassium chloride for analysis

Sodium hydroxide solution: 10 mol/l

Care should be taken to ensure that only potassium free sodium hydroxide is used.

4.4.

Indicator solution

Dissolve 0,5 g of phenolphthalein in ethanol at 90 % and make the volume up to 100 ml.

4.5.

EDTA solution

Dissolve 4 g of the dihydrated disodium salt of ethylenediaminetetraacetic acid in water in a 100-ml
graduated flask. Make up the volume and mix.

Store the reagent in a plastic container.

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4.6.

STPB solution

Dissolve 32,5 g of sodium tetraphenylborate in 480 ml of water add 2 ml of the sodium hydroxide
solution (4.3) and 20 ml of a magnesium chloride solution (100 g of MgCl2. 6H2O per litre).

Stir for 15 minutes and filter through a fine, ashless filter.

Store this reagent in a plastic container.

4.7.

Liquid for washing

Dilute 20 ml of the STPB solution (4.6) to 1 000 ml with water.

4.8.

Bromine water

Saturated bromine solution in water.

5.

5.1.

5.2.

5.3.

5.4.

5.5.

6.

Apparatus

1 000-ml graduated flasks

A 250-ml beaker

Filter crucibles with a porosity of 5 to 20 µ

Oven regulated at 120 (± 10) °C

Desiccator

Preparation of the sample

See Method 1.

In the case of potassium salts the sample must be ground fine enough in order that a representative sample
is obtained for analysis. For these products Method 1 (6) (a) must be used.

7.

7.1.

Procedure

Sample

Weigh, to the nearest 0,001 g, 10 g of the prepared sample (5 g for potassium salts containing more than
50 % of potassium oxide). Place this test sample in a 600-ml beaker with approximately 400 ml of water.

Bring to the boil and allow it to boil for 30 minutes. Cool, transfer quantitatively into a 1 000 ml graduated
flask, make up the volume, mix and filter into a dry receiver. Discard the first 50 ml of the filtrate (see 7.6,
note on procedure).

7.2.

Preparation of the aliquot part for precipitation

Transfer by pipette an aliquot part of the filtrate containing 25 to 50 mg of potassium (see Table 3) and
place it in a 250-ml beaker. If required make up to 50 ml with water.

To remove any interference, add 10 ml of the EDTA solution (4.5), several drops of the phenolphtalein
solution (4.4) and stir in, drop by drop, sodium hydroxide solution (4.3) until it turns red, then finally add a
few more drops of sodium hydroxide to ensure an excess (usually 1 ml of sodium hydroxide is sufficient to
neutralise the sample and ensure an excess).

To eliminate most of the ammonia (see 7.6 (b), note on procedure) boil gently for 15 minutes.

If necessary add water to make the volume up to 60 ml.

Bring the solution to the boil, remove the beaker from the heat and add 10 ml of formaldehyde (4.1). Add
several drops of phenolphtalein and, if necessary, some more sodium hydroxide, until a distinct red colour
appears. Cover the beaker with a watch glass and place it on a steam bath for 15 minutes.

7.3.

Weighing the crucible

Dry the filter crucible (see 5 ‘Apparatus’) to constant mass (about 15 minutes) in the oven at 120 °C (5.4).

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Allow the crucible to cool in a desiccator and then weigh it.

7.4.

Precipitation

Remove the beaker from the steam bath, stir in drop by drop 10 ml of the STPB solution (4.6). This
addition takes about two minutes. Wait for at least 10 minutes before filtering.

7.5.

Filtering and washing

Filter under vacuum into the weighed crucible, rinse the beaker with the liquid for washing (4.7), wash the
precipitate three times with the liquid for washing (60 ml in all of the liquid for washing) and twice with 5
to 10 ml of water.

Dry the precipitate thoroughly.

7.6.

Drying and weighing

Wipe the outside of the crucible with a filter paper. Place the crucible with its contents in the oven for one
and a half hours at a temperature of 120 °C. Allow the crucible to cool
in a desiccator to ambient
temperature and weigh rapidly.

N o t e o n p r o c e d u r e

(a) If the filtrate is dark in colour, transfer by pipette, an aliquot part containing at the most 100 mg of K2O
and place in a 100-ml graduated flask, add bromine water and bring to the boil to eliminate any surplus
bromine. After cooling make up the volume, filter and quantitatively determine the potassium in an
aliquot part of the filtrate.

(b) Where there is little or no ammoniacal nitrogen present, there is no need to boil for 15 minutes.

7.7.

Aliquot parts to be taken as samples and conversion factors

Table 3

For Method 4

% K2O in the
fertiliser

% K in the
fertiliser

5-10

4,2-8,3

10-20

8,3-16,6

20-50

16,6-41,5

more than
50

more than
41,5

Sample for
analysis
(g)

Sample of the
extract solution
for the dilution
(ml)

Dilution
(to ml)

Aliquot part
to be taken as
a sample for
precipitation
(ml)

10

10

10

5

(cid:2)±±±±±½±±±±±¼
(cid:2)±±±±±±±±½±±±±±±±±¼

—

—

either —
or 50

either —

or 50

—

—

250

—

250

50

25

10
50

10

50

Conversion
factor

(F)

% K2 O
gTPBK

26,280

52,560

131,400
131,400

Conversion
factor
F' % K
gTPBK

21,812

43,624

109,060
109,060

262,800

218,120

262,800

218,120

7.8.

Blank test

For each series of determinations, carry out a blank test using only the reagents in the proportions used in
the analysis and allow for this when calculating the final result.

7.9.

Control test

In order to obtain a control for the method of analysis, carry out a determination on an aliquot part of an
aqueous solution of potassium chloride, containing at the most 40 mg of K2O.

8.

Expression of the result

If one uses the samples for analysis and the dilutions shown in Table 3, the formula to apply is the
following:

% K2O in the fertiliser ¼ ðA (cid:1) aÞ F

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or

where

% K in the fertiliser ¼ ðA (cid:1) aÞ F0

A = mass, in grams, of the precipitate from the sample,

a = mass, in grams, of the precipitate from the blank,

F and F' = factors (see Table 3).

With samples and dilutions which differ from those shown in Table 3, use the following formula:

K2O in the fertiliser ¼

ðA (cid:1) aÞ (cid:2) f (cid:2) D (cid:2) 100
M

K in the fertiliser ¼

ðA (cid:1) aÞ (cid:2) f 0 (cid:2) D (cid:2) 100
M

or

where

f = conversion factor, KTPB into K2O = 0,1314,

f' = conversion factor, KTPB into K = 0,109,

D = dilution factor,

M = mass, in grams, of sample for analysis.

No item

1.

2.

3.

M e t h o d 5

M e t h o d 6

Chlorine

M e t h o d 6.1

Determination of chlorides in the absence of organic material

Scope

This document defines the procedure for the determination of chloride, in the absence of organic material.

Field of application

All fertilisers which are free from organic material.

Principle

The chlorides, dissolved in water, are precipitated in an acid medium by an excess of standard solution of
silver nitrate. The excess is titrated with a solution of ammonium thiocyanate in the presence of ferric
ammonium sulphate (Volhard's method).

4.

Reagents

Distilled or demineralised water, free from chlorides.

4.1.

4.2.

Nitrobenzene or diethyl ether

Nitric acid: 10 mol/l

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4.3.

Indicator solution

Dissolve 40 g of ferric ammonium sulphate Fe2(SO4)3. (NH4)2SO4. 24H2O, in water and make up to one
litre.

4.4.

Silver nitrate standard solution: 0,1 mol/l

Preparation

Since this salt is hygroscopic and cannot be dried without risk of decomposition, it is advisable to weigh out
approximately 9 g, dissolve in water and make up the volume to one litre. Adjust to 0,1 mol/l strength by
titration of AgNO3 0,1 mol/l.

5.

5.1.

5.2.

5.3.

5.4.

6.

7.

7.1.

Apparatus

Rotary shaker (35 to 40 turns per minute)

Burettes

A 500-ml graduated flask

Conical (Erlenmeyer) flask of 250 ml

Preparation of the sample

See Method 1.

Procedure

Sample and preparation of the solution

Place 5 g of the sample, weighed out to nearest 0,001 g, in a 500-ml graduated flask and add 450 ml of
water. Mix for half an hour on the shaker (5.1); make up to 500 ml with distilled water; mix and filter into
a beaker.

7.2.

Determination

Take an aliquot part of the filtrate containing not more than 0,150 g of chloride. For example 25 ml
(0,25 g), 50 ml (0,5 g) or 100 ml (1 g). If the sample taken is smaller than 50 ml it is necessary to make
up the volume to 50 ml with distilled water.

Add 5 ml of nitric acid 10 mol/l (4.2), 20 ml of indicator solution (4.3), and two drops of ammonium
thiocyanate standard solution (a sample of this latter reagent is taken with a burette adjusted to zero for this
purpose).

With a burette then add silver nitrate standard solution (4.4) until there is an excess of 2 to 5 ml. Add 5 ml
of nitrobenzene or 5 ml of diethyl ether (4.1) and shake well to agglomerate the precipitate. Titrate the
excess silver nitrate with ammonium thiocyanate 0,1 mol/l (4.5) until a red-brown colour appears which
remains after the flask has been shaken slightly.

N o t e

Nitrobenzene or diethyl ether (but above all nitrobenzene) prevents the silver chloride from reacting with
thiocyanate ions. Thus a clear colour change is obtained.

7.3.

Blank test

Carry out a blank test (omitting the sample) under the same conditions and allow for it when calculating the
final result.

7.4.

Control test

Before carrying out the estimations check the accuracy of the Method by using an aliquot part of a freshly
prepared solution of potassium chloride, such that this part contains a known quantity in the order of
100 mg of chloride.

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8.

Expression of the result

Express the result of the analysis as a percentage of chloride contained in the sample as it has been received
for analysis.

Calculate the percentage of chloride (Cl) with the formula:

% chloride ¼ 0,003546 (cid:2)

ðVz (cid:1) VczÞ (cid:1) ðVa (cid:1) VcaÞ (cid:2) 100
M

where

Vz

= number of millilitres of silver nitrate 0,1 mol/l,

Vcz = number of millilitres of silver nitrate 0,1 mol/l, used in the blank test,

Va

= number of millilitres of ammonium thiocyanate 0,1 mol/l,

Vca = number of millilitres of ammonium thiocyanate 0,1 mol/l, used in the blank test,

M = mass, in grams, of the sample taken (7.2).

M e t h o d s 7

Fineness of grinding

M e t h o d 7.1

Determination of fineness of grinding

(dry procedure)

1.

2.

3.

4.

4.1.

4.2.

Scope

This document defines the dry procedure, for the determination of the fineness of grinding.

Field of application

All EC type fertilisers in which requirements are given of fineness of grinding using 0,630 and 0,160 mm
sieves.

Principle

By mechanical sieve shaking, the quantities of product with a granule size greater than 0,630 mm and those
with a granule size between 0,160 and 0,630 mm are determined, and the percentage of fineness of
grinding is calculated.

Apparatus

Mechanical sieve shaker

Sieves with apertures of 0,160 and 0,630 mm respectively of standard ranges (20 cm diameter and 5 cm
high)

5.

Procedure

Weigh, to the nearest 0,05 g, 50 g of the substance. Assemble the two sieves and the collecting container
on the shaker (4.1), the sieve with the larger apertures being placed on top. Place the sample for analysis on
the top. Sieve for 10 minutes and remove the part collected on the bottom. Start the apparatus up again and
after one minute check that the amount collected on the bottom during this time is not more than 250 mg.
Repeat the process (for one minute each time) until the amount collected is less than 250 mg. Weigh the
residual material on both sieves separately.

6.

Expression of the result

% fineness of the sample shown by the sieve, with 0,630 mm apertures ¼ ð50 (cid:1) M1Þ (cid:2) 2

% fineness of the sample shown by the sieve, with 0,160 mm apertures ¼ ½50 (cid:1) ðM1 þ M2Þ(cid:3) (cid:2) 2

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where

M1 = mass, in grams, of residue on the sieve, with 0,630 mm apertures,

M2 = mass, in grams, of residue on the sieve, with 0,160 mm apertures.

The reject from the sieve, with 0,630 mm apertures having been already eliminated.

The results of these calculations are rounded up to the nearest unit.

M e t h o d 7.2

Determination of the fineness of grinding of soft natural phosphates

Scope

This Method is for determining the fineness of grinding of soft natural phosphates.

Field of application

Soft natural phosphates.

Principle

For samples of fine particle size, agglomeration may occur thus making dry sieving difficult. For this reason,
wet sieving is normally used.

Reagents

Sodium hexametaphosphate solution: 1 %.

Apparatus

Sieves with apertures of 0,063 and 0,125 mm respectively of standard ranges (diameter 20 cm and height
5 cm); collecting containers

Glass funnel of 20 cm diameter mounted on a stand

250-ml beakers

Drying oven

Method of analysis

Sampling

1.

2.

3.

4.

5.

5.1.

5.2.

5.3.

5.4.

6.

6.1.

Weigh, to the nearest 0,05 g, 50 g of the substance. Wash both sides of the sieve with water and place the
sieve with 0,125 mm apertures above the 0,063 mm sieve.

6.2.

Procedure

Place the sample for analysis on the top sieve. Sieve under a small jet of cold water (tap water can be used)
until the water is practically clear when it passes through. Care should be taken to ensure that the flow of
water is such that the lower sieve never fills with water.

When the residue on the top sieve seems to remain more or less constant, remove this sieve, and place, in
the meanwhile on a collecting container.

Continue the wet sieving through the lower sieve for a few minutes, until the water passing through is
nearly clear.

Replace the 0,125 mm sieve over the 0,063 mm sieve. Transfer any deposit from the collecting container
to the top sieve and begin sieving again under a small jet of water until this water becomes almost clear
once more.

Quantitatively transfer each of the residues into a different beaker by means of the funnel. Suspend each
residue by filling the beakers with water. Leave to stand for about one minute, decant, as much water as
possible.

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Place the beakers in the drying oven at 150 °C for two hours.

Allow them to cool, detach the residues with a brush and weigh them.

7.

Expression of the result

The results of the calculations are rounded up to the nearest unit.

% fineness shown by the residue left on the 0,125 mm sieve ¼ ð50 (cid:1) M1Þ (cid:2) 2

% fineness shown by the residue left on the 0,063„mm sieve ¼ ½50 (cid:1) ðM1 þ M2Þ(cid:3) (cid:2) 2

where

M1 = mass, in grams, of the residue on the 0,125 mm sieve,

M2 = mass, in grams, of the residue on the 0,063 mm sieve.

8.

Remarks

If the presence of lumps is observed after sieving the analysis should be carried out again in the following
way.

Slowly pour 50 g of the sample into a one-litre flask containing 500 ml of the sodium hexametaphosphate
solution stirring continuously. Stopper the flask and shake vigorously by hand to break up the lumps.
Transfer the whole suspension into the top sieve and wash the flask thoroughly. Continue the analysis as
described in 6.2.

M e t h o d s 8

Secondary nutrients

M e t h o d 8.1

Extraction of total calcium, total magnesium, total sodium and total sulphur in the form of sulphates

1.

Scope

This document defines the procedure for extracting total calcium, total magnesium and total sodium, and for
extracting the total sulphur present in the form of sulphates, so that the same extract may be used for the
determination of each nutrient required.

Field of application

This Method applies to EC fertilisers, for which a declaration of the total calcium, total magnesium, total
sodium, and total sulphur in the form of sulphates is provided for in this Regulation.

Principle

Solubilisation by boiling in dilute hydrochloric acid.

Reagents

Diluted hydrochloric acid

One volume of hydrochloric acid (d20 = 1,18 g/ml) plus one volume of water.

Apparatus

Electric hot plate with adjustable temperature.

Preparation of the sample

See Method 1.

2.

3.

4.

4.1.

5.

6.

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7.

7.1.

Procedure

Test sample

Calcium, magnesium, sodium and sulphur in the form of sulphates are extracted from a test sample of five
grams weighed to within one milligram.

However, when the fertiliser contains more than 15 % of sulphur (S) i.e. 37,5 % SO3, and more than 18,8 %
of calcium (Ca) i.e. 26,3 % CaO, the extraction of calcium and sulphur is carried out on a test sample of one
gram, weighed to within one milligram. Place the test sample in a 600 millilitre beaker.

7.2.

Preparation of the solution

Add approximately 400 millilitres of water and, taking care when the sample contains a significant quantity
of carbonates, 50 millilitres of dilute hydrochloric acid (4.1) a small amount at a time. Bring to the boil and
maintain for 30 minutes. Allow to cool, stirring occasionally. Decant quantitatively into a 500 millilitre
graduated flask. Make up to volume with water, and mix. Pass through a dry filter into a dry container,
discarding the initial portion. The extract must be completely transparent. Stopper if the filtrate is not used
immediately.

1.

2.

3.

4.

4.1.

4.2.

4.3.

4.4.

5.

6.

7.

7.1.

M e t h o d 8.2

Extraction of total sulphur present in various forms

Scope

This document defines the procedure for extracting the total sulphur contained in fertilisers in elemental
form and/or in other chemical combinations.

Field of application

This Method applies to EC fertilisers for which a declaration of the total sulphur present in various forms
(elemental, thiosulphate, sulphite, sulphate) is provided for in this Regulation.

Principle

Elemental sulphur is converted in an alkaline medium into polysulphides and thiosulphate; these, together
with any sulphites which may be present, are then oxidised with hydrogen peroxide. The various forms of
sulphur are thus converted into sulphate which is determined by precipitation of barium sulphate (Method
8.9).

Reagents

Diluted hydrochloric acid:

One volume of hydrochloric acid (d = 1,18) plus one volume of water.

Sodium hydroxide solution, NaOH, 30 % minimum (d = 1,33)

Hydrogen peroxide solution, 30 % w/w

Aqueous solution of barium chloride BaCl2, 2H2O, 122 grams per litre

Apparatus

Electric hot plate with adjustable temperature.

Preparation of the sample

See Method 1.

Procedure

Test sample

Weigh out to within one milligram a quantity of fertiliser containing between 80 and 350 milligrams of
sulphur (S) or 200 and 875 milligrams of SO3.

As a rule (where S < 15 %), weigh out 2,5 grams. Place the test sample in a 400 millilitre beaker.

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7.2.

Oxidation

Add 20 millilitres of sodium hydroxide solution (4.2) and 20 millilitres of water. Cover with a watch glass.
Boil for five minutes on the hot plate (5.1). Remove from the hot plate. Using a jet of hot water, collect the
sulphur sticking to the sides of the beaker and boil for 20 minutes. Leave to cool.

Add 2 millilitres increments of hydrogen peroxide (4.3) until no reaction is observed. Six to eight ml of
hydrogen peroxide will be necessary. Allow oxidation to continue for one hour, then bring to the boil for
half an hour. Leave to cool.

7.3.

Preparation of the solution to be analysed

Add approximately 50 millilitres of water and 50 millilitres of the hydrochloric acid solution (4.1).

— If the level of sulphur (S) is less than 5 %:

filter into a 600 millilitre beaker. Wash the residue on the filter several times with cold water. After
washing, check for the absence of sulphate in the last drops of the filtrate using a barium chloride
solution (4.4). The filtrate must be perfectly clear. Sulphate is determined on the whole of the filtrate in
accordance with Method 8.9.

— If the level of sulphur (S) is at above 5 %:

transfer quantitatively into a 250 millilitre volumetric flask, make up to volume with water and mix.
Filter through a dry filter into a dry container; the filtrate must be completely clear. Stopper if the
solution is not to be used immediately. Determine sulphates on an aliquot of this solution by precipi-
tation in the form of barium sulphate (Method 8.9).

M e t h o d 8.3

Extraction of water-soluble calcium, magnesium, sodium and sulphur
(in the form of sulphates)

Scope

This document defines the procedure for extracting water-soluble calcium, magnesium, sodium and sulphur
(in the form of sulphates), so that the same extract can be used to determine each nutrient required.

Field of application

This Method applies solely to fertilisers for which a declaration of the water soluble calcium, magnesium,
sodium and sulphur (in the form of sulphates) is provided for in Annex I.

Principle

The nutrients are solubilised in boiling water.

Reagents

Distilled or demineralised water of equivalent quality.

Apparatus

Electric hot plate with adjustable temperature.

Preparation of the sample

See Method 1.

1.

2.

3.

4.

5.

6.

7.

7.1.

Procedure

Test sample

(a) Where fertilisers contain no sulphur or where they contain, at the same time, no more than 3 % of the
sulphur (S) i.e. 7,5 % SO3 and no more than 4 % of calcium (Ca) i.e. 5,6 % CaO, weigh out five grams of
fertiliser to within one milligram.

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(b) Where fertilisers contain more than 3 % of sulphur (S) and more than 4 % of calcium (Ca), weigh out

one gram of fertiliser to within one milligram.

Place the test sample in a 600 millilitre beaker.

7.2.

Preparation of the solution

Add approximately 400 millilitres of water and boil for 30 minutes. Allow to cool, stirring occasionally, and
decant quantitatively into a 500 millilitre graduated flask. Make up to volume with water and mix.

Filter through a dry filter into a dry container. Discard the initial portions of the filtrate. The filtrate must be
completely transparent.

Stopper if the solution is not to be used immediately.

Extraction of water-soluble sulphur where the sulphur is in various forms

M e t h o d 8.4

Scope

This document defines the procedure for extracting the water-soluble sulphur contained in fertilisers in
various forms.

Field of application

This Method applies to fertilisers for which a declaration of the water-soluble sulphur trioxide is provided for
in Annex I.

Principle

The sulphur is dissolved in cold water and converted into sulphate by oxidation with hydrogen peroxide in
an alkaline medium.

Reagents

Diluted hydrochloric acid

One volume of hydrochloric acid (d20 = 1,18 g/ml) plus one volume of water.

Sodium hydroxide solution containing at least 30 % NaOH (d20 = 1,33 g/ml)

Hydrogen peroxide solution, 30 % w/w

Apparatus

500 millilitre graduated Stohmann flask

Rotary shaker, 30 to 40 turns per minute

Electric hot plate with adjustable temperature

Preparation of the sample

See Method 1.

Procedure

Test sample

(a) Where fertilisers contain a maximum of 3 % of sulphur (S) i.e. 7,5 % SO3, together with a maximum of

4 % of calcium (Ca) i.e. 5,6 % CaO, weigh out 5 grams of fertiliser to within one milligram.

(b) Where fertilisers contain more than 3 % of sulphur (S) and more than 4 % of calcium (Ca), weigh out

one gram of fertiliser to within one milligram.

Place the test sample in a 500 millilitre flask (5.1).

1.

2.

3.

4.

4.1.

4.2.

4.3.

5.

5.1.

5.2.

5.3.

6.

7.

7.1.

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7.2.

Preparation of the solution

Add approximately 400 millilitres of water. Stopper. Shake (5.2) for 30 minutes. Make up to volume with
water and mix. Pass through a dry filter into a dry container. Stopper if the solution is not to be used
immediately.

7.3.

Oxidation of the aliquot portion to be analysed

Take an aliquot portion of the extraction solution not exceeding 50 millilitres and, if possible, containing
between 20 and 100 milligrams of sulphur (S).

Make up the volume to 50 millilitres with water, if necessary. Add three millilitres of sodium hydroxide
solution (4.2) and two millilitres of hydrogen peroxide solution (4.3). Cover with a watch glass and boil
gently for one hour on the hot plate (5.3). Keep adding one millilitre increments of hydrogen peroxide
solution for as long as the reaction continues (maximum quantity five millilitres).

Then leave to cool. Remove the watch glass and wash the underside into the beaker. Add approximately 20
millilitres of dilute hydrochloric acid (4.1). Make up to approximately 300 millilitres with water.

Determine the content of sulphates on the whole of the oxidised solution in accordance with Method 8.9.

M e t h o d 8.5

Extraction and determination of elemental sulphur

Warning

This Method of analysis involves the use of carbon disulphide (CS2). Special safety measures must therefore be taken, in
particular with regard to:

— the storage of CS2,

— protective equipment for staff,

— occupational hygiene,

— prevention of fires and explosions,

— disposal of the reagent.

This Method requires a highly skilled staff and a suitably equipped laboratory.

1.

2.

3.

4.

5.

5.1.

5.2.

5.3.

5.4.

Scope

This defines the procedure for extracting and determining the elemental sulphur contained in fertilisers.

Field of application

This Method applies to EC fertilisers for which a declaration of the total sulphur in elemental form is
provided for in Annex I.

Principle

After the removal of soluble compounds, elemental sulphur is extracted by using carbon disulphide, followed
by gravimetric determination of the sulphur extracted.

Reagents

Carbon disulphide.

Apparatus

100 millilitre extraction flask with ground glass stopper

Soxhlet apparatus, with the appropriate filter elements

Vacuum rotary evaporator

Electric oven, fan assisted, set at 90 (± 2) °C

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5.5.

5.6.

6.

7.

7.1.

Porcelain petri dishes, five to seven centimetres in diameter, not exceeding five centimetres in height

Electric hot plate with adjustable temperature

Preparation of the sample

See Method 1.

Procedure

Test sample

Weigh out five to ten grams of the sample to an accuracy of one milligram and place in the thimble of the
Soxhlet apparatus (5.2).

7.2.

Extraction of the sulphur

Wash thoroughly the contents with hot water to remove all soluble compounds. Dry in the oven at 90 °C
(5.4) for at least one hour. Place the filter in the Soxhlet apparatus (5.2).

Place a few glass beads in the flask of the apparatus (5.1) and weigh (P0), then add 50 millilitres of carbon
disulphide (4.1).

Connect the apparatus and leave the elemental sulphur to be extracted for six hours. Switch off the heat and,
after cooling, disconnect the flask. Connect the flask to the rotary evaporator (5.3) and evaporate until the
contents of the flask have solidified in a spongy mass.

Dry the flask in the oven at 90 °C (5.4) (generally one hour is necessary) until a constant mass is obtained
(P1).

7.3.

Determination of the purity of the elemental sulphur

Certain substances may have been extracted by the carbon disulphide at the same time as the elemental
sulphur. The purity of the elemental sulphur is determined as follows:

homogenise the contents of the flask as thoroughly as possible, and remove two or three grams, weighed to
an accuracy of one milligram (n). Place in the Petri dish (5.5). Weigh dish and contents together (P2). Place
on the hot plate (5.6) set at a temperature not exceeding 220 °C so as not to cause combustion of the
sulphur. Continue sublimation for three or four hours until a constant mass is obtained (P3).

N o t e

For some fertilisers, it may not be necessary to determine how pure the sulphur is. In this case, omit step
7.2.

8.

Expression of results

The percentage elemental sulphur (S) content of the fertiliser is as follows:

Impure S (%) of the fertiliser ¼

Purity of sulphur extracted (%) ¼

P1(cid:1)P0

m (cid:2) 100

P2(cid:1)P1
n

(cid:2) 100

Pure S (%) of the fertiliser ¼

ðP1(cid:1)P0ÞðP2 (cid:1) P3Þ
m (cid:2) n

(cid:2) 100

Where

m = the mass of the test sample of fertiliser in grams,

P0 = the mass of the Soxhlet flask in grams,

P1 = the mass of the Soxhlet flask and the impure sulphur after drying,

n = the mass of the impure sulphur to be purified in grams,

P2 = the mass of the Petri dish,

P3 = the mass of the Petri dish after sublimation of the sulphur in grams.

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

M e t h o d 8.6

1.

2.

3.

Scope

This document defines the procedure for determining the calcium in fertiliser extracts.

Field of application

This Method applies to EC fertilisers for which a declaration of the total and/or water-soluble calcium is
provided for in Annex I.

Principle

Precipitation of the calcium contained in an aliquot of the extraction solution in the form of an oxalate,
which is determined by titration using potassium permanganate.

4.

4.1.

Reagents

Diluted hydrochloric acid

One volume of hydrochloric acid (d20 = 1,18 g/ml) and one volume of water.

4.2.

1:10 dilute sulphuric acid

One volume of sulphuric acid (d20 = 1,84 g/ml) in ten volumes of water.

4.3.

1:1 dilute ammonia solution

One volume of ammonia (d20 = 0,88 g/ml) and one volume of water.

4.4.

4.5.

4.6.

4.7.

4.8.

4.9.

5.

5.1.

5.2.

6.

Saturated solution of ammonia oxalate [(NH4)2C2O4 H2O] at ambient temperature (approximately 40 grams
per litre)

Citric acid solution, 30 % (m/v)

Ammonium chloride solution, 5 % (m/v)

Solution of bromothymol blue in ethanol, at 95 %, 0,1 % (m/v)

Solution of bromocresol green in ethanol, at 95 %, 0,04 % (m/v)

Standard solution of potassium permanganate, 0,02 mol/l

Apparatus

Filter crucible with 5 to 20 µ porosity sintered glass

Hot water bath

Preparation of the aliquot to be analysed

Using a pipette, take an aliquot portion of the extraction solution obtained by Method 8.1 or 8.3, containing
between 15 and 50 milligrams of Ca (= 21 to 70 milligrams of CaO). Let the volume of this aliquot be v2.
Pour into a 400 millilitre beaker. If necessary, neutralise (turning of indicator (4.7) from green to blue) with
a few drops of the ammonia solution (4.3).

Add one millilitre of the citric acid solution (4.5) and five millilitres of ammonium chloride solution (4.6).

7.

Precipitation of the calcium oxalate

Add approximately 100 millilitres of water. Bring to the boil, add eight to ten drops of indicator solution
(4.8) and, slowly, 50 millilitres of a hot ammonium oxalate solution (4.4). If a precipitate forms, dissolve by
adding a few drops of hydrochloric acid (4.1). Neutralise very slowly with ammonia solution (4.3) while
stirring continuously to a pH of 4,4 to 4,6 (turning of indicator (4.8) from green to blue). Place the beaker in
a boiling hot water bath (5.2) for approximately 30 minutes.

Remove the beaker from the bath, leave standing for an hour and filter into the crucible (5.1).

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8.

Titration of the oxalate precipitate

Wash the beaker and crucible until the excess ammonium oxalate has been completely removed (this can be
checked by the absence of chloride in the washing water). Place the crucible in the 400 millilitre beaker and
dissolve the precipitate with 50 millilitres of hot sulphuric acid (4.2). Add water to the beaker in order to
obtain a volume of approximately 100 millilitres. Bring to a temperature of 70 to 80 °C and titrate drop by
drop with a permanganate solution (4.9) until the pink colour lasts for a minute. Let this volume be n.

9.

Expression of results

The calcium (Ca) content of the fertiliser is as follows:

Ca ð%Þ ¼ n (cid:2) 0,2004 (cid:2)

t
0,02

(cid:2)

v1
v2 (cid:2) m

Where

n = the number of millilitres of permanganate used,

m = the mass of the test sample in grams,

v2 = the aliquot volume in millilitres,

v1 = the volume of the extraction solution in millilitres,

t

= the concentration of the permanganate solution in moles per litre.

CaO (%) = Ca (%) × 1,400

M e t h o d 8.7

Determination of magnesium by atomic absorption spectrometry

1.

2.

Scope

This document defines the procedure for determining the magnesium in fertiliser extracts.

Field of application

This Method applies to EC fertiliser extracts obtained by methods 8.1 and 8.3, for which a declaration of the
total magnesium and/or water soluble magnesium is required, with the exception of the following fertilisers
listed in Annex I D relating to secondary nutrients:

— type 4 (kieserite),

— type 5 (magnesium sulphate) and type 5.1 (magnesium sulphate solution),

— and with the exception of the following fertiliser listed in Annex I A 3 relating to potassic fertilisers:

— type 7 (kieserite with potassium sulphate)

— to which Method 8.8 applies.

The Method set out below applies to all fertiliser extracts containing elements in quantities that might
interfere with the complexometric determination of magnesium.

3.

Principle

Determination of magnesium by atomic absorption spectrometry after appropriate dilution of the extract.

4.

4.1.

4.2.

Reagents

Hydrochloric acid, 1 mol/l solution

Hydrochloric acid, 0,5 mol/l solution

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4.3.

4.3.1.

4.3.2.

Standard solution of magnesium, 1,00 milligrams per millilitre

Dissolve 1,013 grams of magnesium sulphate (MgSO4, 7H2O) in the 0,5 mol/l hydrochloric acid solution
(4.2)

Weigh out 1,658 grams of magnesium oxide (MgO), previously calcined to remove all traces of carbonation.
Place in a beaker with 100 millilitres of water and 120 millilitres of 1 mol/l hydrochloric acid (4.1). When it
has dissolved, decant quantitatively into a 1 000 millilitre graduated flask. Make up the volume by adding
and mix

or

4.3.3.

Commercial standard solution

The laboratory is responsible for testing such solutions.

4.4.

Strontium chloride solution

Dissolve 75 grams of strontium chloride (SrCl2 6H2O) in a hydrochloric acid solution (4.2) and make up to
500 millilitres with the same acid solution.

5.

Apparatus

Spectrometer fitted for atomic absorption, with a magnesium lamp, set at 285,2 nm.

Air-acetylene flame.

6.

Preparation of the sample

See Methods 8.1 and 8.3.

7.

7.1.

7.2.

7.3.

Procedure

If the fertiliser has a declared magnesium (Mg) content of more than 6 % (i.e. 10 % as MgO), take 25
millilitres (V1) of the extraction solution (6). Transfer into a 100 millilitre graduated flask, and make up to
volume with water and mix. The dilution factor is D1 = 100/V1

Using a pipette, take 10 millilitres of the extraction solution (6) or the solution (7.1). Transfer into a 200
millilitre graduated flask. Make up to volume with the 0,5 mol/l hydrochloric acid solution (4.2) and mix.
The dilution factor is 200/10

Dilute this solution (7.2) with the 0,5 mol/l hydrochloric acid solution (4.2) so as to obtain a concentration
in the optimum working field of the spectrometer (5.1). V2 is the volume of the sample in 100 millilitres.
The dilution factor is D2 = 100/V2

The final solution should contain 10 % v/v of the strontium chloride solution (4.4).

7.4.

Preparation of blank solution

Prepare a blank solution by repeating the whole procedure from the extraction (Method 8.1 or 8.3), omitting
only the test sample of fertiliser.

7.5.

Preparation of calibration solutions

By diluting the standard solution (4.3) with the 0,5 mol/l hydrochloric acid, prepared at least five calibration
solutions of increasing concentration within the optimum measuring range of the apparatus (5.1).

These solutions should contain 10 % v/v of the strontium chloride solution (4.4).

7.6.

Measurement

Set up the spectrometer (5.1) at a wavelength of 285,2 nm.

Spray, successively, the calibration solutions (7.5), the sample solution (7.3) and the blank solution (7.4),
washing the instrument through with the solution to be measured next. Repeat this operation three times.
Plot the calibration curve using the mean absorbancies of each of the calibrations (7.5) as the ordinates and
the corresponding concentration of magnesium in µg/ml as the abscissae. Determine the concentration of
magnesium in the sample (7.3), Xs and blank (7.4), Xb, by reference to the calibration curve.

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8.

Expression of results

Calculate the amount of magnesium (Mg) or magnesium oxide (MgO) in the sample by reference to the
calibration solutions and taking into consideration the blank.

The percentage of magnesium (Mg) in the fertiliser is equal to:

Mg ð%Þ ¼

ðXs (cid:1) XbÞ D1ð200=10Þ D2 500,100
1000:1000 M

Where

Xs = the concentration of the solution to be analysed recorded on the calibration curve, in µg/ml.

Xb = the concentration of the blank solution as recorded on the calibration curve, in µg/ml.

D1 = the dilution factor when the solution is diluted (7.1).

— It is equal to four if 25 millilitres are taken.

— It is equal to one when the solution is not diluted.

— D2 = the dilution factor is 7.3.

— M = the mass of the test sample at the time of extraction.

— MgO (%) = Mg (%)/0,6

M e t h o d 8.8

Determination of magnesium by complexometry

1.

2.

Scope

This document defines the procedure for the determination of magnesium in fertiliser extracts.

Field of application

This Method applies to the following EC fertiliser extracts for which the determination of total magnesium
and/or water-soluble magnesium is provided for:

— fertilisers listed in Annex I: straight nitrogenous fertilisers, type 1b + 1c (calcium magnesium nitrate),
type 7 (magnesium sulphonitrate), type 8 (nitrogenous fertilisers with magnesium) and straight potassic
fertilisers,
type 6
type 2 (enriched kainite),
(potassium sulphate containing magnesium salt),

type 4 (potassium chloride containing magnesium),

— fertilisers listed in the Annex I D relating to secondary nutrients.

3.

Principle

The magnesium is solubilised by methods 8.1 and/or 8.3. First titration: with EDTA of Ca and Mg in the
presence of Eriochrome black-T. Second titration: with EDTA of Ca in the presence of calcein or of calcon
carbonic acid. Determination of magnesium by difference.

4.

4.1.

4.1.1.

Reagents

Standard 0,05 mol/l solution of magnesium:

Dissolve 1,232 grams of magnesium sulphate (MgSO4 7H2O) in the 0,5 mol/l hydrochloric acid solution
(4.11) and make up to 100 millilitres with the same acid

or

4.1.2.

Weigh out 2,016 grams of magnesium oxide, previously calcined to remove all traces of carbonation. Place
it in a beaker with 100 millilitres of water

Stir in approximately 120 millilitres of approximately 1 mol/l hydrochloric acid (4.12).

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After dissolution, transfer quantitatively into a graduated 1 000 millilitre flask. Make up to volume and mix.

One millilitre of these solutions should contain 1,216 milligrams of Mg (= 2,016 milligrams of MgO).

The laboratory is responsible for testing the strength of this standard solution.

4.2.

0,05 molar solution of EDTA

out

18,61

grams

Weigh
ethylenediaminetetraacetic
(C10H14N2Na2O8,2H2O), place it in a 1 000 millilitre beaker and dissolve in 600 to 800 millilitres of
water. Transfer the solution quantitatively into a graduated 1 000 millilitre flask. Make up the volume
and mix. Check this solution with the standard solution (4.1) by taking a sample of 20 millilitres of the
latter and by titration according to the analytical procedure described at (7.2).

disodium salt

dihydrated

the

of

of

One millilitre of the EDTA solution should correspond to 1,216 milligrams of Mg (= 2,016 milligrams of
MgO) and to 2,004 milligrams of Ca (= 2,804 milligrams CaO) (see remarks 10,1 and 10,6).

4.3.

0,05 molar standard solution of calcium

Weigh out 5,004 grams of dry calcium carbonate. Place it in a beaker with 100 millilitres of water.
Progressively stir in 120 millilitres of approximately 1 mol/l hydrochloric acid (4.12).

Bring to the boil in order to drive off the carbon dioxide, cool, transfer quantitatively into a graduated
one-litre flask, make up the volume with water and mix. Check this solution against the EDTA solution (4.2)
following analytical procedure (7.3). One millilitre of this solution should contain 2,004 milligrams of Ca
(= 2,804 milligrams of CaO) and should correspond to one millilitre of the 0,05 molar EDTA solution (4.2).

4.4.

Calcein indicator

Carefully mix in a mortar one gram of calcein with 100 grams of sodium chloride. Use 10 milligrams of this
mixture. The indicator changes from green to orange. Titration must be carried out until an orange is
obtained which is free from green tinges.

4.5.

Calcon carbonic acid indicator

Dissolve 400 milligrams of calcon carbonic acid in 100 millilitres of methanol. This solution may only be
kept for approximately four weeks. Use three drops of this solution. The indicator changes from red to blue.
Titration must be carried out until a blue is obtained which is free from red tinges.

4.6.

Eriochrome black-T indicator

Dissolve 300 milligrams of Eriochrome black-T in a mixture of 25 millilitres of propanol-1 and 15 millilitres
of triethanolamine. This solution may only be kept for approximately four weeks. Use three drops of this
solution. This indicator turns from red to blue and titration must be carried out until a blue is obtained
which is free from red tinges. It changes colour only when magnesium is present. If necessary add one
millilitre of the standard solution (4.1).

When both calcium and magnesium are present the EDTA first forms a complex with the calcium and then
with the magnesium. In that case two elements are determined concurrently.

4.7.

Potassium cyanide solution

Aqueous solution of KCN at 2 %. (Do not pipette by mouth and see 10.7).

4.8.

Solution of potassium hydroxide and potassium cyanide

Dissolve 280 grams of KOH and 66 grams of KCN in water, make up the volume to one litre and mix.

4.9.

pH 10,5 buffer solution

In a 500 millilitre graduated flask, dissolve 33 grams of ammonium chloride in 200 millilitres of water, add
250 millilitres of ammonia (d20 = 0,91 g/ml) make up the volume with water and mix. Test the pH of the
solution regularly.

4.10.

Diluted hydrochloric acid: one volume of hydrochloric acid (d20 = 1,18 g/ml) plus one volume of water

4.11.

Hydrochloric acid solution approximately 0,5 mol/l

4.12.

Hydrochloric acid solution approximately 1 mol/l

4.13.

Sodium hydroxide solution 5 mol/l

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5.

5.1.

5.2.

6.

Apparatus

Magnetic or mechanical stirrer

pH meter

Control test

Carry out a determination on aliquot parts of solutions (4.1 and 4.3) such that the Ca/Mg ratio is
approximately equal to that of the solution to be analysed. To this end take (a) millilitres of Mg standard
solution (4.3) and (b-a) millilitres of standard solution (4.1) (a) and (b) are the numbers of millilitre EDTA
solution used in the two titrations performed on the solution to be analysed. This procedure is correct only
if the solutions of EDTA, calcium and magnesium are exactly equivalent. If this is not the case, it is necessary
to make corrections.

7.

Preparation of the solution to be analysed

See methods 8.1 and 8.3.

8.

8.1.

Determination

Aliquot samples to be taken

The aliquot part will as far as possible contain between 9 and 18 milligrams of magnesium (= 15 to 30
milligrams of MgO).

8.2.

Titration in the presence of Eriochrome black-T

Pipette an aliquot part (8.1) of the solution to be analysed into a 400 millilitre beaker. Neutralise the surplus
acid with the 5 mol/l sodium hydroxide solution (4.12) using the pH meter. Dilute with water to
approximately 100 millilitres. Add 5 millilitres of the buffer solution (4.9). The pH measured by the
meter must be 10,5 ± 0,1. Add 2 millilitres of the potassium cyanide solution (4.7) and three drops of
the Eriochrome black-T indicator (4.6). Titrate with the EDTA solution (4.2). Stirring gently with the stirrer
(5.1) (see 10,2, 10,3 and 10,4). Let ‘b’ be the number of millilitres of 0,05 mol/l EDTA solution.

8.3.

Titration in the presence of calcein or of calcon carbonic acid

Pipette an aliquot part of the solution to be analysed equal to that taken from the above titration and place it
in a 400 millilitre beaker. Neutralise the surplus acid with the 5 mol/l sodium hydroxide solution (4.13)
using the pH meter. Dilute with water to about 100 millilitres. Add 10 millilitres of the KOH/KCN solution
(4.8) and the indicator (4.4 or 4.5). Stirring gently with the stirrer (5.1) titrate with the EDTA solution (4.2)
(see 10,2, 10,3 and 10,4). Let ‘a’ be the number of millilitres of 0,05 mol/l EDTA solution.

9.

Expression of the results

For the EC fertilisers to which the Method is applicable (5 grams of fertiliser in 500 millilitres of extract), the
percentage content of the fertiliser is:

MgO (%) in the fertiliser ¼

Mg (%) in the fertiliser ¼

ðb (cid:1) aÞ (cid:2) T
M

ðb (cid:1) aÞ (cid:2) T0
M

Where

a = the number of millilitres of 0,05 mol/l EDTA solution used for the titration in the presence of calcein

or calcon carbonic acid,

b = the number of millilitres of 0,05 mol/l EDTA solution used for the titration in the presence of

Eriochrome black-T,

M = the mass of the sample present in the aliquot part taken (in grams),

T = 0,2016 × mol/l of the EDTA solution/0,05 (see 4.2),

T' = 0,1216 × mol/l of the EDTA solution/0,05 (see 4.2).

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10.

10.1.

10.2.

10.3.

10.4.

10.5.

10.6.

10.7.

1.

2.

3.

4.

4.1.

4.2.

4.3.

5.

5.1.

5.2.

5.3.

5.4.

Remarks

The stoichiometric EDTA-metal ratio in the complexometric analyses is always 1:1 whatever the valency of
the metal and in spite of the fact that EDTA is quadrivalent. The EDTA titration solution and the standard
solutions will therefore be molar and not normal

Complexometric indicators are often sensitive to air. The solution may lose colour during titration. In this
case, one or two drops of indicator must be added. This is true particularly in the case of eriochrome black
and calcon carbonic acid

The metal-indicator complexes are often relatively stable and it may take some time for the colour to
change. The last drops of EDTA must therefore be added slowly and a drop of 0,05 mol/l solution of
magnesium (4.1) or calcium (4.3) added to ensure that the colour change has not already taken place. This is
particularly true in the case of the eriochrome-magnesium complex

The turning of the indicator must be observed not vertically, but horizontally across the solution and the
beaker must be placed against a white background in a well-lit position. The turning of the indicator may
also be observed easily by placing the beaker on frosted glass lit moderately from below (25 watt lamp)

This analysis requires a certain amount of experience. The task will involve, inter alia, observing the colour
changes of standard solutions 4.1 and 4.3. It is recommended that the determinations be carried out by the
same laboratory chemist

If an EDTA solution of guaranteed strength is used (Titrisol, Normex, for example) this may simplify the
control of the equivalence of standard solutions 4.1, 4.2 and 4.3

The solutions containing potassium cyanide must not be poured down the sink until the cyanide has been
converted into a harmless compound, for example, by oxidization with sodium hypochlorite following
alkalisation

M e t h o d 8.9

Determination of sulphates

Scope

This document defines the procedure for determining the sulphur present in fertiliser extracts in the form of
sulphates.

Field of application

This Method applies to the determination of sulphates present in the extractions performed in methods 8.1,
8.2, 8.3 and 8.4.

Principle

Gravimetric determination as barium sulphate.

Reagents

Diluted hydrochloric acid

One volume of hydrochloric acid (d20 = 1,18 g/ml) and one volume of water.

Barium chloride solution BaCl22H2O:122 grams per litre

Silver nitrate solution: 5 grams per litre

Apparatus

Porcelain crucibles

Hot water bath

Drying oven set at 105 °C (± 1) °C

Electric oven set at 800 °C (± 50) °C

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6.

6.1.

Procedure

Sampling of the solution

Pipette an aliquot part of one of the extraction solutions indicated at 2 containing between 20 and 100
milligrams of S or 50 and 250 milligrams of SO3.

Place this aliquot in a beaker of suitable capacity. Add 20 millilitres of dilute hydrochloric acid (4.1). Make
up to about 300 millilitres with water.

6.2.

Preparation of the precipitate

Bring the solution to the boil. Add, drop by drop, about 20 millilitres of the barium chloride solution (4.2)
while stirring the solution vigorously. Boil for a few minutes.

Place the beaker, covered with a watch glass, in a boiling hot water bath (5.2) for an hour. Then leave
standing hot (about 60 °C) until the supernatant liquor is clear. Decant the clear solution through a slow
filtration ash-free filter. Wash the precipitate several times with hot water. Continue to wash the precipitate
on the filter until the filtrate is chloride free. This can be checked by using silver nitrate solution (4.3).

6.3.

Incineration and weighing of the precipitate

Place the filter paper and precipitate in a porcelain crucible (5.1) previously weighed to the nearest 0,1
milligrams. Dry in the oven (5.3) and ash at approximately 800 °C for half an hour (5.4). Allow to cool in a
desiccator and weigh to within 0,1 milligrams.

7.

Expression of the results

One milligram of barium sulphate corresponds to 0,137 milligrams of S or to 0,343 milligrams of SO3.

The percentage S content of the fertiliser is as follows:

S ð%Þ ¼ w (cid:2) 0,0137 (cid:2)

v1
v2 (cid:2) m

SO3ð%Þ ¼ S ð%Þ (cid:2) 2,5

Where

w = the mass of the barium sulphate precipitate in milligrams,

v1 = the volume of the extraction solution in millilitres,

v2 = the aliquot volume in millilitres,

m = the mass of the test sample in grams.

M e t h o d 8.10

Determination of the sodium extracted

Scope

This document defines the procedure for determining the sodium in fertiliser extracts.

Field of application

This Method applies to EC fertilisers for which a declaration of the sodium is provided for in Annex I.

1.

2.

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3.

Principle

Following suitable dilution of the extract obtained via Method 8.1 and/or 8.3, the sodium content of the
solution is determined by flame-emission spectrometry.

4.

4.1.

4.2.

4.3.

4.4.

4.5.

Reagents

Diluted hydrochloric acid

One volume of hydrochloric acid for analysis (d20 = 1,18 g/ml) plus one volume of water.

Aluminium nitrate Al(NO3)3.9H2O

Caesium chloride, CsCl

Anhydrous sodium chloride, NaCl

Caesium chloride and aluminium nitrate solution

Dissolve in water 50 grams of caesium chloride (4.3) and 250 grams of aluminium nitrate (4.2) in a 1 000
millilitre graduated flask. Make up to volume with water and mix.

4.6.

Standard sodium solution of one milligram/millilitre of Na

Dissolve in water 2,542 grams of sodium chloride (4.4) in a 1 000 millilitre graduated flask. Add 10
millilitres of hydrochloric acid (4.1). Make up to volume with water and mix.

5.

Apparatus

6.

6.1.

6.2.

Spectrometer equipped for flame emission, set at 589,3 nm.

Calibration solutions

Place 10 millilitres of standard solution (4.6) in a 250 millilitre graduated flask. Make up to volume and mix.
Concentration of solution: 40 µg/ml of Na

Place 0, 5, 10, 15, 20, 25 millilitres of the intermediate solution (6.1) in 100 millilitre graduated flasks. Add
10 millilitres of the solution (4.5). Make up to volume and mix. Concentration of solutions: 0, 2, 4, 6, 8,
10 µg/ml of Na

7.

Preparation of solutions to be measured

Depending upon the expected sodium content of the extraction solution as in Method 8.1 or 8.3 (five grams
of fertiliser in 500 millilitres), carry out the dilutions in accordance with the following table:

Na2O (%)

Na (%)

Sample (ml) (v2)

Dilution to ml
(v3)

Sample (ml) (v4) Dilution to ml

Intermediate dilution

Final dilution

3-5

5-10

10-20

20-38

2,2-3,7

3,7-7,4

7,4-15

15-28

10

10

10

5

50

100

100

100

10

10

5

5

100

100

100

100

Degree
of dilution

50

100

200

400

Make up the intermediate dilution with water. For the final dilution add ten millilitres of the solution (4.5) to
the 100 millilitre graduated flask.

For a test sample of one gram multiply the volume of the final dilution (v4) by five.

8.

Determination

Prepare the spectrometer (5.1) for the measurements at 589,3 nm. Calibrate the instrument by measuring
the response of the calibration solutions (6.2). Then adjust the sensitivity of the instrument to use its entire
scale when the most concentrated calibration solution is used. Then measure the response of the sample
solution to be analysed (7). Repeat this operation three times.

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9.

Calculation of results

Draw a calibration curve by plotting the average response for each calibration solution along the ordinate
and the corresponding concentrations, expressed in µg per millilitre on the abscissa. Determine from this the
sodium concentration of the test solution. Calculate the quantity of sodium from the standard solutions
taking account of the levels of dilution. Express the results as a percentage of the sample.

The percentage sodium (Na) content of the fertiliser is as follows:

Na % ¼ x:

v3
v4

v1
v2

10(cid:1)2
m

Na2O ð%Þ ¼ Na ð%Þ (cid:2) 1,348

Where

x = the concentration of the solution introduced into the spectrometer in µg/ml,

v1 = the volume of the extraction solution in millilitres,

v2 = the aliquot volume in the intermediate dilution in millilitres,

v3 = the volume of intermediate dilution in millilitres,

v4 = the aliquot volume in ml of the final dilution (to 100 millilitres),

m = the mass of the test sample in grams.

M e t h o d s 9

Micro-nutrients at a concentration of less than or equal to 10 %

M e t h o d 9.1

Extraction of total micro-nutrients

1.

Scope

This Method defines the procedure for extracting the following micro-nutrients: total boron, total cobalt,
total copper, total iron, total manganese, total molybdenum and total zinc. The aim is to carry out the
minimum number of extractions, making use wherever possible of the same extract to determine the total
level of each of the micro-nutrients listed above.

2.

Field of application

This procedure concerns EC fertilisers covered by Annex I E containing one or more of the following
micro-nutrients: boron, cobalt, copper,
iron, manganese, molybdenum and zinc. It is applicable to each
micro-nutrient the declared content of which is less than or equal to 10 %.

3.

Principle

Dissolution in boiling dilute hydrochloric acid.

N o t e

The extraction is empirical and may not be quantitative depending on the product or the other constituents
of the fertiliser. In particular,
in the case of certain manganese oxides, the quantity extracted may be
substantially smaller than the total quantity of manganese which the product contains. It is the responsibility
of the fertiliser manufacturers to ensure that the declared content actually corresponds to the quantity
extracted under the conditions pertaining to the method.

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4.

4.1.

4.2.

5.

Reagents

Dilute hydrochloric acid (HCl) solution, about 6 mol/l

Mix 1 volume of hydrochloric acid (d20 = 1,18 g/ml) with 1 volume of water.

Concentrated ammonia solution (NH4OH, d20 = 0,9 g/ml)

Apparatus

Electric hotplate with variable temperature control.

N o t e

Where the boron content of an extract is to be determined, do not use borosilicate glassware. As the Method
involves boiling, teflon or silica is preferable. Rinse the glassware thoroughly if it has been washed in
detergents containing borates.

6.

Preparation of the sample

See Method 1.

7.

7.1.

Procedure

Test sample

Take a quantity of fertiliser weighing between 2 and 10 g depending on the declared content of element in
the product. The following table shall be used to obtain a final solution which, after appropriate dilution,
will be within the measuring range for each method. Samples should be weighed to within 1 mg.

Declared content of micro-nutrient in the fertiliser (%)

< 0,01

0,01-< 5

‡ 5-10

Mass of test sample (g)

Mass of element in the sample (mg)

Volume of extract V (ml)

Concentration of element in extract (mg/l)

Place the sample in a 250 ml beaker.

7.2.

Preparation of the solution

10

1

250

4

5

2

0,5-250

100-200

500

500

1-500

200-400

If necessary moisten the sample with a little water, add 10 ml of dilute hydrochloric acid (4.1) per gram of
fertiliser carefully, in small amounts, then add about 50 ml of water. Cover the beaker with a watch glass
and mix. Bring to the boil on the hotplate and boil for 30 minutes. Allow to cool, stirring occasionally.
Transfer quantitatively to a 250 or 500 ml volumetric flask (see Table). Make up to volume with water and
mix thoroughly. Filter through a dry filter into a dry container. Discard the first portion. The extract must be
perfectly clear.

It is recommended that the determination be carried out without delay on aliquot portions of the clear
filtrate, if not the containers should be stoppered.

R e m a r k

Extracts in which the boron content has to be determined: Adjust the pH to between 4 and 6 with
concentrated ammonia (4.2).

8.

Determination

The determination of each micro-nutrient is to be carried out on the aliquot portions indicated in the
Method for each individual micro-nutrient.

If necessary, remove organic chelating or complexing substances from an aliquot portion of the extract by
using Method 9.3. In the case of determination by atomic absorption spectrometry, such removal may not
be necessary.

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M e t h o d 9.2

Extraction of water-soluble micro-nutrients

1.

Scope

This Method defines the procedure for extracting water-soluble forms of the following micro-nutrients:
boron, cobalt, copper,
iron, manganese, molybdenum and zinc. The aim is to carry out the minimum
number of extractions, making use wherever possible of the same extract to determine the level of each
of the micro-nutrients listed above.

2.

Field of application

This procedure concerns EC fertilisers covered by Annex I containing one or more of the following micro-
nutrients: boron, cobalt, copper, iron, manganese, molybdenum and zinc. It is applicable to each micro-
nutrient the declared content of which is less than or equal to 10 %.

3.

Principle

The micro-nutrients are extracted by shaking the fertiliser in water at 20 °C (± 2) °C.

N o t e

The extraction is empirical and may or may not be quantitative.

Reagents

Dilute hydrochloric acid (HCl) solution, about 6 mol/l

Mix 1 volume of hydrochloric acid (d20 = 1,18 g/ml) with 1 volume of water.

Apparatus

Rotary shaker set at about 35 to 40 rpm

pH-meter

N o t e

4.

4.1.

5.

5.1.

5.2.

Where the boron content of the extract is to be determined, do not use borosilicate glassware. Teflon or
silica is preferable for this extraction. Rinse the glassware thoroughly if it has been washed in detergents
containing borates.

6.

Preparation of the sample

See Method 1.

7.

7.1.

Procedure

Test sample

Take a quantity of fertiliser weighing between 2 and 10 g depending on the declared content of the element
in the product. The following table shall be used to obtain a final solution which, after appropriate dilution,
will be within the measuring range for each method. The samples should be weighed to within 1 mg.

Declared content of micro-nutrient in the fertiliser (%)

< 0,01

0,01-< 5

‡ 5-10

Mass of test sample (g)

Mass of element in the sample (mg)

Volume of extract V (ml)

Concentration of element in extract (mg/l)

10

1

250

4

5

2

0,5-250

100-200

500

500

1-500

200-400

Place the sample in a 250 or 500 ml flask (according to the Table).

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7.2.

Preparation of the solution

Add about 200 ml of water to the 250 ml flask or 400 ml of water to the 500 ml flask.

Stopper the flask well. Shake vigorously by hand to disperse the sample, then place the flask on the shaker
and shake for 30 minutes.

Make up to volume with water and mix thoroughly.

7.3.

Preparation of the test solution

Filter immediately into a clean, dry flask. Stopper the flask. Carry out the determination immediately after
filtering.

N o t e

If the filtrate gradually becomes cloudy, make another extraction following 7.1 and 7.2 in a flask of volume
Ve. Filter into a calibrated flask of volume W which has previously been dried and has received 5,00 ml of
dilute hydrochloric acid (4.1). Stop the filtration at the exact moment when the calibration mark is reached.
Mix thoroughly.

Under these conditions the value of V in the expression of results is:

V ¼ Ve (cid:2) W = ðW (cid:1) 5Þ

The dilutions in the expression of results depend on this value of V.

8.

Determination

The determination of each micro-nutrient is carried out on the aliquot portions indicated in the Method for
each individual micro-nutrient.

If necessary, remove organic chelating or complexing substances from an aliquot portion by using Method
9.3. In the case of determination by atomic absorption spectrometry, such removal may not be necessary.

M e t h o d 9.3

Removal of organic compounds from fertiliser extracts

1.

2.

Scope

This Method defines a procedure for removing organic compounds from fertiliser extracts.

Field of application

This procedure is applicable to analysing samples of fertilisers extracted by Methods 9.1 and 9.2 for which a
declaration of total and/or water-soluble element is required by Annex I E to this Regulation.

N o t e

The presence of small quantities of organic matter usually does not affect determination by means of atomic
absorption spectrometry.

3.

Principle

The organic compounds in an aliquot portion of the extract are oxidised with hydrogen peroxide.

4.

4.1.

Reagents

Dilute hydrochloric acid (HCl) solution, about 0,5 mol/l

Mix 1 volume of hydrochloric acid (d20 = 1,18 g/ml) with 20 volumes of water.

4.2.

Hydrogen peroxide solution (30 % H2O2, d20 = 1,11 g/ml), free from micro-nutrients

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5.

6.

Apparatus

Electric hotplate with variable temperature control.

Procedure

Take 25 ml of the extract solution obtained by Method 9.1 or Method 9.2 and place in a 100 ml beaker. In
the case of Method 9.2, add 5 ml of the dilute hydrochloric acid solution (4.1). Then add 5 ml of the
hydrogen peroxide solution (4.2). Cover with a watch glass. Allow oxidation to occur at room temperature
for about one hour, then bring gradually to boiling and boil for half an hour. If necessary, add a further
5 ml of the hydrogen peroxide to the solution once it has cooled. Then boil to remove the excess hydrogen
peroxide. Allow to cool and transfer quantitatively to a 50 ml volumetric flask and make up to volume.
Filter where necessary.

Account should be taken of this dilution when taking aliquot portions and calculating the percentage of
micro-nutrient in the product.

Determination of micro-nutrients in fertiliser extracts by atomic absorption spectrometry
(general procedure)

M e t h o d 9.4

1.

Scope

This document defines a general procedure for determining the levels of certain micro-nutrients in fertiliser
extracts by atomic absorption spectrometry.

2.

Field of application

This procedure is applicable to analysing samples of fertilisers extracted by Methods 9.1 and 9.2 for which a
declaration of total and/or water-soluble element is required by Annex I E to this Regulation.

Adaptations of this procedure for the various micro-nutrients are detailed in the methods defined specifically
for each element.

N o t e

In most cases the presence of small quantities of organic matter will not affect determinations by atomic
absorption spectrometry.

3.

Principle

After the extract has been treated where necessary to reduce or eliminate interfering chemical species, the
extract is diluted so that its concentration is in the optimum range of the spectrometer at a wave-length
suitable for the micro-nutrient to be determined.

4.

4.1.

Reagents

Dilute hydrochloric acid solution (HCl), about 6 mol/l:

Mix one volume of hydrochloric acid (d20 = 1,18 g/ml) with one volume of water.

4.2.

Dilute hydrochloric acid solution (HCl), about 0,5 mol/l:

Mix one volume of hydrochloric acid (d20 = 1,18 g/ml) with 20 volumes of water.

4.3.

Lanthanum salt solutions (10 g of La per litre)

This reagent is used for determinations of cobalt, iron, manganese and zinc. It can be prepared either:

(a) with lanthanum oxide dissolved in hydrochloric acid (4.1). Place 11,73 g of lanthanum oxide (La2O3) in
150 ml of water in a one litre volumetric flask and add 120 ml of 6 mol/l hydrochloric acid (4.1).
Allow to dissolve and then make up to 1 litre with water and mix thoroughly. This solution is
approximately 0,5 mol/l in hydrochloric acid

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(b) or with solutions of lanthanum chloride, sulphate or nitrate. Dissolve 26,7 g of lanthanum chloride
heptahydrate (LaCl3 7H2O) or 31,2 g of lanthanum nitrate hexahydrate [La(NO3)3 6H2O] or 26,2 g of
lanthanum sulphate nonahydrate [La2(SO4)3 9H2O] in 150 ml of water, then add 85 ml of 6 mol/l
hydrochloric acid (4.1). Allow to dissolve and then make up to 1 litre with water. Mix thoroughly. This
solution is approximately 0,5 mol/l in hydrochloric acid.

4.4.

Calibration solutions

For the preparation of these, see the individual determination Method for each micro-nutrient.

5.

Apparatus

Atomic absorption spectrometer fitted with sources emitting radiation characteristic of the micro-nutrients
to be determined.

The analyst must follow the manufacturer's instructions and be familiar with the apparatus. The apparatus
must allow background correction so that it can be used whenever necessary (Co and Zn). The gases to be
used are air and acetylene.

6.

6.1.

Preparation of the solution to be analysed

Preparation of extract solutions of the micro-nutrients to be determined.

See Methods 9.1 and/or 9.2 and, if appropriate, 9.3.

6.2.

Treatment of the test solution

Dilute an aliquot portion of the extract obtained by Method 9.1, 9.2 or 9.3 with water and/or hydrochloric
acid (4.1) or (4.2) so as to obtain, in the final solution for measurement, a concentration of the element to
be determined that is appropriate to the calibration range used (7.2) and a hydrochloric acid concentration
of at least 0,5 mol/l and not more than 2,5 mol/l. This operation may require one or more successive
dilutions.

Take an aliquot portion of the final solution obtained by dilution of the extract, let (a) be its volume in ml,
and pour into a 100 ml volumetric flask. When determining the cobalt, iron, manganese or zinc content,
add 10 ml of the lanthanum salt solution (4.3). Make up to volume with the 0,5 mol/l hydrochloric acid
solution (4.2) and mix thoroughly. This is the final solution for measurement. Let D be the dilution factor.

7.

7.1.

Procedure

Preparation of a blank solution

Prepare a blank solution by repeating the whole procedure from the extraction stage, omitting only the test
sample of fertiliser.

7.2.

Preparation of calibration solutions

From the working calibration solution prepared using the Method given for each individual micro-nutrient,
prepare in 100 ml volumetric flasks a series of at least five calibration solutions of increasing concentration
within the optimum measuring range of the spectrometer. If necessary, adjust the concentration of hydro-
chloric acid to bring it as close as possible to that of the diluted test solution (6.2). For determining cobalt,
iron, manganese or zinc, add 10 ml of the same lanthanum salt solution (4.3) as used in 6.2. Make up to
volume with the 0,5 mol/l hydrochloric acid solution (4.2) and mix thoroughly.

7.3.

Determination

Prepare the spectrometer (5) for the determination and adjust to the wavelength given in the Method for the
individual micro-nutrient concerned.

Spray three times in succession the calibration solutions (7.2), the test solution (6.2) and the blank solution
(7.1), noting each result and flushing the instrument with distilled water between individual sprayings.

Construct the calibration curve by plotting the average spectrometer reading for each calibration solution
(7.2) along the ordinate and the corresponding concentration of the element, expressed in µg/ml, along the
abscissa.

From this curve, determine the concentrations of the relevant micro-nutrient in the test solution xs (6.2) and
in the blank solution xb(7.1), expressing these concentrations in µg per ml.

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8.

Expression of results

The percentage of micro-nutrient (E) in the fertiliser is equal to:

E ð%Þ ¼ ½ðxs (cid:1) xbÞ (cid:2) V (cid:2) D(cid:3) = ðM (cid:2) 104Þ

If Method 9.3 has been used:

E ð%Þ ¼ ½ðxs (cid:1) xbÞ (cid:2) V (cid:2) 2D(cid:3) = ðM (cid:2) 104Þ

Where

E is the amount of the micro-nutrient determined, expressed as a percentage of the fertiliser;

xs is the concentration of the test solution (6.2), in µg/ml;

xb is the concentration of the blank solution (7.1), in µg/ml;

V is the volume of the extract obtained by Method 9.1 or 9.2, in ml;

D is the factor corresponding to the dilution carried out in 6.2;

M is the mass of the test sample taken in accordance with Method 9.1 or 9.2, in grams.

Calculation of dilution factor D:

If (a1), (a2), (a3),.,.,., (ai) and (a) are the aliquot portions and (v1), (v2), (v3),.,.,., (vi) and (100) are the volumes
in ml corresponding to their respective dilutions, the dilution factor D will be equal to:

D ¼ ðv1=a1Þ (cid:2) ðv2=a2Þ (cid:2) ðv3=a3Þ (cid:2) : (cid:2) : (cid:2) : (cid:2) ðvi=aiÞ (cid:2) ð100=aÞ

Determination of boron in fertiliser extracts by means of spectrometry with azomethine-H

M e t h o d 9.5

1.

2.

3.

Scope

This Method describes a procedure for determining boron in fertiliser extracts.

Field of application

This procedure is applicable to analysing samples of fertilisers extracted by Methods 9.1 and 9.2 for which a
declaration of total and/or water-soluble boron is required by Annex I to this Regulation.

Principle

In an azomethine-H solution, borate ions form a yellow complex the concentration of which is determined
by molecular absorption spectrometry at 410 nm. Interfering ions are masked with EDTA.

4.

4.1.

Reagents

EDTA buffer solution

Place in a 500 ml volumetric flask containing 300 ml of water:

— 75 g of ammonium acetate (NH4OOCCH3);

— 10 g of disodium salt of ethylene diamine tetraacetic acid (Na2EDTA);

— 40 ml of acetic acid (CH3COOH, d20 = 1,05 g/ml).

Make up to volume with water and mix thoroughly. The pH of the solution, checked by means of a glass
electrode, must be 4,8 ± 0,1.

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4.2.

Azomethine-H solution

Place in a 200 ml volumetric flask

— 10 ml of the buffer solution (4.1);

— 400 mg of azomethine-H (C17H12NNaO8S2);

— 2 g of absorbic acid (C6H8O6);

— Make up to volume and mix thoroughly. Do not prepare large quantities of this reagent as it is stable for

only a few days.

4.3.

Boron calibration solutions

4.3.1.

Boron stock solution (100 µg/ml)

Dissolve 0,5719 g of boric acid (H2BO3) in water in a 1 000 ml volumetric flask. Make up to volume with
water and mix thoroughly. Transfer to a plastic bottle for storage in a refrigerator.

4.3.2.

Boron working solution (10 µg/ml)

Place 50 ml of stock solution (4.3.1) in a 500 ml volumetric flask. Make up to volume with water and mix
thoroughly.

5.

Apparatus

Spectrometer fitted for molecular absorption with cells having a 10 mm optical path and set to a wave-
length of 410 nm.

6.

6.1.

Preparation of the solution to be analysed

Preparation of the boron solution

See Methods 9.1 and/or 9.2 and, if appropriate, 9.3.

6.2.

Preparation of the test solution

Dilute an aliquot portion of extract (6.1) to obtain a boron concentration as specified in 7.2. Two successive
dilutions may be necessary. Let D be the dilution factor.

6.3.

Preparation of the correction solution

If the test solution (6.2) is coloured, prepare a corresponding correction solution by placing in a plastic flask
5 ml of test solution (6.2), 5 ml of EDTA buffer solution (4.1) and 5 ml of water and mix thoroughly.

7.

7.1.

Procedure

Preparation of the blank solution

Prepare a blank solution by repeating the whole procedure from the extraction stage, omitting only the test
sample of fertiliser.

7.2.

Preparation of the calibration solutions

Transfer 0, 5, 10, 15, 20 and 25 ml of the working calibration solution (4.3.3) to a series of 100 ml
volumetric flasks. Make up to 100 ml with water and mix thoroughly. These solutions contain between 0
and 2,5 µg/ml of boron.

7.3.

Colour development

Transfer 5 ml of the calibration solutions (7.2), test solutions (6.2) and blank (7.1) to a series of plastic
flasks. Add 5 ml of the EDTA buffer solution (4.1). Add 5 ml of the azomethine-H solution (4.2).

Mix thoroughly and allow the colour to develop in the dark for 21/2 to three hours.

7.4.

Determination

Measure the absorbance of the solutions obtained at 7.3 and if appropriate the correction solution (6.3)
against water at a wavelength of 410 nm. Rinse the cells with water before each new reading.

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8.

Expression of results

Plot a calibration curve of the concentration of the calibration solutions (7.2) along the abscissa and the
absorbance given by the spectrometer (7.4) along the ordinate.

Read off the calibration curve the concentration of boron in the blank (7.1), the concentration of boron in
the test solution (6.2) and, if the test solution is coloured, the corrected concentration of the test solution. To
calculate the latter, subtract the absorbance of the correction solution (6.3) from the absorbance of the test
solution (6.2) and determine the corrected concentration of the test solution. Note the concentration of the
test solution (6.2), with or without correction, X(xs) and of the blank (xb).

The percentage of boron in the fertiliser is given by:

B % ¼ ½ðxs (cid:1) xbÞ (cid:2) V (cid:2) D(cid:3)=ðM (cid:2) 104Þ

If Method 9.3 is used:

where

B % ¼ ½ðxs (cid:1) xbÞ (cid:2) V (cid:2) 2D(cid:3)=ðM (cid:2) 104Þ

B is the quantity of boron expressed as a percentage of the fertiliser;

xs is the concentration (µg/ml) in the test solution (6.2), with or without correction;

xb is the concentration (µg/ml) in the blank (7.1);

V is the volume in ml of extract obtained in accordance with Method 9.1 or 9.2;

D is the factor corresponding to the dilution carried out in 6.2;

M is the mass in grams of the test sample taken in accordance with Method 9.1 or 9.2.

Calculation of the dilution factor D: if (a1) and (a2) are successive aliquot portions and (v1) and (v2) are the
volumes corresponding to their respective dilutions, the dilution factor D is given by:

D ¼ ðv1=a1Þ (cid:2) ðv2=a2Þ

M e t h o d 9.6

1.

2.

3.

4.

4.1.

Determination of cobalt in fertiliser extracts by atomic absorption spectrometry

Scope

This Method describes a procedure for determining cobalt in fertiliser extracts.

Field of application

This Procedure is applicable to analysing samples of fertilisers extracted by Methods 9.1 and 9.2 for which a
declaration of total and/or water-soluble cobalt is required by Annex I E of this Regulation.

Principle

After suitable treatment and dilution of the extracts, the cobalt content is determined by atomic absorption
spectrometry.

Reagents

Hydrochloric acid solution, about 6 mol/l

See Method 9.4 (4.1).

4.2.

Hydrochloric acid solution, about 0,5 mol/l

See Method 9.4 (4.2).

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4.3.

Lanthanum salt solutions (10 g of La per litre)

See Method 9.4 (4.3).

4.4.

Cobalt calibration solutions

4.4.1.

Cobalt stock solution (1 000 µg/ml)

In a 250 ml beaker, weigh to the nearest 0,1 mg, 1 g of cobalt, add 25 ml of 6 mol/l hydrochloric acid
(4.1) and heat on a hotplate until the cobalt is completely dissolved. When cool, transfer quantitatively to a
1 000 ml volumetric flask. Make up to volume with water and mix thoroughly.

4.4.2.

Cobalt working solution (100 µg/ml)

Place 10 ml of the stock solution (4.4.1) in a 100 ml volumetric flask. Make up to volume with 0,5 mol/l
hydrochloric acid solution (4.2) and mix thoroughly.

5.

Apparatus

Atomic absorption spectrometer: see Method 9.4 (5). The instrument must be equipped with a source of rays
characteristic of cobalt (240,7 nm). The spectrometer must allow background correction to be made.

6.

6.1.

Preparation of the solution to be analysed

Cobalt extract solution

See Methods 9.1 and/or 9.2 and, if appropriate, 9.3.

6.2.

Preparation of the test solution

See Method 9.4 (6.2). The test solution must contain 10 % (v/v) of a lanthanum salt solution (4.3).

7.

7.1.

Procedure

Preparation of blank solution

See Method 9.4 (7.1). The blank must contain 10 % (v/v) of the lanthanum salt solution used in 6.2.

7.2.

Preparation of calibration solutions

See Method 9.4 (7.2).

For an optimum determination range of 0 to 5 µg/ml of cobalt, place 0, 0,5, 1, 2, 3, 4 and 5 ml respectively
of working solution (4.4.2) in a series of 100 ml volumetric flasks. If necessary adjust the hydrochloric acid
concentration as closely as possible to that of the test solution. Add to each flask 10 ml of the lanthanum
salt solution used in 6.2. Make up to 100 ml with 0,5 mol/l hydrochloric acid solution (4.2) and mix
thoroughly. These solutions contain 0, 0,5, 1, 2, 3, 4 and 5 µg/ml respectively of cobalt.

7.3.

Determination

See Method 9.4 (7.3). Prepare the spectrometer (5) for measurement at a wavelength of 240,7 nm.

8.

Expression of results

See Method 9.4 (8).

The percentage of cobalt in the fertiliser is given by:

Co % ¼ ½ðxs (cid:1) xbÞ (cid:2) V (cid:2) D(cid:3) = ðM (cid:2) 104Þ

If Method 9.3 is used:

where

Co % ¼ ½ðxs (cid:1) xbÞ (cid:2) V (cid:2) 2D(cid:3) = ðM (cid:2) 104Þ

Co is the quantity of cobalt expressed as a percentage of the fertiliser;

xs is the concentration in µg/ml of the test solution (6.2);

xb is the concentration in µg/ml of the blank solution (7.1);

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V is the volume in ml of extract obtained in accordance with Method 9.1 or 9.2;

D is the factor corresponding to the dilution carried out in 6.2;

M is the mass in grams of the test sample taken in accordance with Method 9.1 or 9.2.

Calculation of the dilution factor D: if (a1), (a2), (a3),.,.,., (ai) and (a) are aliquot portions and (v1), (v2),
(v3),.,.,., (vi) and (100) are the volumes in ml corresponding to their respective dilutions, the dilution factor
D is given by:

D ¼ ðv1=a1Þ (cid:2) ðv2=a2Þ (cid:2) ðv3=a3Þ (cid:2) : (cid:2) : (cid:2) : (cid:2) : (cid:2) ðvi=aiÞ (cid:2) ð100=aÞ

Determination of copper in fertiliser extracts by atomic absorption spectrometry

M e t h o d 9.7

Scope

This Method describes a procedure for determining copper in fertiliser extracts.

Field of application

This procedure is applicable to analysing samples of fertilisers extracted by Methods 9.1 and 9.2 for which a
declaration of total and/or water-soluble copper is required by Annex I E to this Regulation.

Principle

After suitable treatment and dilution of the extracts, the copper content is determined by atomic absorption
spectrometry.

Reagents

Hydrochloric acid solution, about 6 mol/l

See Method 9.4 (4.1).

1.

2.

3.

4.

4.1.

4.2.

Hydrochloric acid solution, about 0,5 mol/l

See Method 9.4 (4.2).

4.3.

4.4.

Hydrogen peroxide solution (30 % H2O2, d20 = 1,11 g/ml), free from micro-nutrients

Copper calibration solutions

4.4.1.

Copper stock solution (1 000 µg/ml)

In a 250 ml beaker, weigh to the nearest 0,1 mg, 1 g of copper, add 25 ml of 6 mol/l hydrochloric acid
(4.1), add 5 ml hydrogen peroxide solution (4.3) and heat on a hotplate until the copper is completely
dissolved. Transfer quantitatively to a 1 000 ml volumetric flask. Make up to volume with water and mix
thoroughly.

4.4.2.

Copper working solution (100 µg/ml)

Place 20 ml of the stock solution (4.4.1) in a 200 ml volumetric flask. Make up to volume with 0,5 mol/l
hydrochloric acid solution (4.2) and mix thoroughly.

5.

Apparatus

Spectrometer equipped for atomic absorption: see Method 9.4 (5). The instrument must be fitted with a
source of rays characteristics of copper (324,8 nm).

6.

6.1.

Preparation of the solution to be analysed

Copper extract solution

See Methods 9.1 and/or 9.2 and, if appropriate, 9.3.

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6.2.

Preparation of the test solution

7.

7.1.

See Method 9.4 (6.2).

Procedure

Preparation of blank solution

See Method 9.4 (7.1).

7.2.

Preparation of calibration solutions

See Method 9.4 (7.2).

For an optimum determination range of 0 to 5 µg/ml of copper, place 0, 0,5, 1, 2, 3, 4 and 5 ml
respectively of working solution (4.4.2) in a series of 100 ml volumetric flasks. If necessary adjust the
hydrochloric acid concentration as closely as possible to that of the test solution (6.2). Make up to 100 ml
with 0,5 mol/l hydrochloric acid solution (4.2) and mix thoroughly. These solutions contain 0, 0,5, 1, 2, 3, 4
and 5 µg/ml respectively of copper.

7.3.

Determination

See Method 9.4 (7.3). Prepare the spectrometer (5) for measurement at a wavelength of 324,8 nm.

8.

Expression of results

See Method 9.4 (8).

The percentage of copper in the fertiliser is given by:

Cu % ¼ ½ðxs (cid:1) xbÞ (cid:2) V (cid:2) D(cid:3) = ðM (cid:2) 104Þ

If Method 9.3 is used:

where

Cu % ¼ ½ðxs (cid:1) xbÞ (cid:2) V (cid:2) 2D(cid:3) = ðM (cid:2) 104Þ

Cu is the quantity of copper expressed as a percentage of the fertiliser;

xs is the concentration in µg/ml of the test solution (6.2);

xb is the concentration in µg/ml of the blank solution (7.1);

V is the volume in ml of extract obtained in accordance with Method 9.1 or 9.2;

D is the factor corresponding to the dilution carried out in 6.2;

M is the mass in grams of the test sample taken in accordance with Method 9.1 or 9.2.

Calculation of the dilution factor D: if (a1), (a2), (a3),.,.,., (ai) and (a) are aliquot portions and (v1), (v2),
(v3),.,.,., (vi) and (100) are the volumes in ml corresponding to their respective dilutions, the dilution factor
D is given by:

D ¼ ðv1=a1Þ (cid:2) ðv2=a2Þ (cid:2) ðv3=a3Þ (cid:2) : (cid:2) : (cid:2) : (cid:2) : (cid:2) ðvi=aiÞ (cid:2) ð100=aÞ

Determination of iron in fertiliser extracts by atomic absorption spectrometry

M e t h o d 9.8

1.

2.

Scope

This Method describes a procedure for determining iron in fertiliser extracts.

Field of application

This procedure is applicable to analysing samples of fertilisers extracted by Methods 9.1 and 9.2 for which a
declaration of total and/or water-soluble iron is required by Annex 1E of this Regulation.

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3.

Principle

After suitable treatment and dilution of the extracts, the iron content is determined by atomic absorption
spectrometry.

4.

4.1.

Reagents

Hydrochloric acid solution, about 6 mol/l

See Method 9.4 (4.1).

4.2.

Hydrochloric acid solution, about 0,5 mol/l

See Method 9.4 (4.2).

4.3.

4.4.

Hydrogen peroxide solution (30 % H2O2, d20 = 1,11 g/ml), free from micro-nutrients

Lanthanum salt solutions (10 g of La per litre)

See Method 9.4 (4.3).

4.5.

Iron calibration solutions

4.5.1.

Iron stock solution (1 000 µg/ml)

In a 500 ml beaker, weigh to the nearest 0,1 mg, 1 g of iron wire, add 200 ml of 6 mol/l hydrochloric
acid (4.1) and 15 ml of hydrogen peroxide solution (4.3). Heat on a hotplate until the iron is completely
dissolved. When cool, transfer quantitatively to a 1 000 ml volumetric flask. Make up to volume with water
and mix thoroughly.

4.5.2.

Iron working solution (100 µg/ml)

Place 20 ml of the stock solution (4.5.1) in a 200 ml volumetric flask. Make up to volume with 0,5 mol/l
hydrochloric acid solution (4.2) and mix thoroughly.

5.

Apparatus

Atomic absorption spectrometer: see Method 9.4 (5). The instrument must be fitted with a source of rays
characteristic of iron (248,3 nm).

6.

6.1.

Preparation of the solution to be analysed

Iron extract solution

See Methods 9.1 and/or 9.2 and, if appropriate, 9.3.

6.2.

Preparation of the test solution

See Method 9.4 (6.2). The test solution must contain 10 % (v/v) of a lanthanum salt solution.

7.

7.1.

Procedure

Preparation of blank solution

See Method 9.4 (7.1). The test solution must contain 10 % (v/v) of the lanthanum salt solution used in 6.2.

7.2.

Preparation of calibration solutions

See Method 9.4 (7.2).

For an optimum determination range of 0 to 10 µg/ml of iron, place 0, 2, 4, 6, 8 and 10 ml respectively of
working solution (4.5.2) in a series of 100 ml volumetric flasks. If necessary adjust the hydrochloric acid
concentration as closely as possible to that of the test solution. Add 10 ml of the lanthanum salt solution
used in 6.2. Make up to volume with 0,5 mol/l hydrochloric acid solution (4.2) and mix thoroughly. These
solutions contain 0, 2, 4, 6, 8 and 10 µg/ml respectively of iron.

7.3.

Determination

See Method 9.4 (7.3). Prepare the spectrometer (5) for measurement at a wavelength of 248,3 nm.

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8.

Expression of results

See Method 9.4 (8).

The percentage of iron in the fertiliser is given by:

Fe % ¼ ½ðxs (cid:1) xbÞ (cid:2) V (cid:2) D(cid:3)=ðM (cid:2) 104Þ

If Method 9.3 is used:

where

Fe % ¼ ½ðxs (cid:1) xbÞ (cid:2) V (cid:2) 2D(cid:3)=ðM (cid:2) 104Þ

Fe is the quantity of iron expressed as a percentage of the fertiliser;

xs is the concentration in µg/ml of the test solution (6.2);

xb is the concentration in µg/ml of the blank solution (7.1);

V is the volume in ml of extract obtained in accordance with Method 9.1 or 9.2;

D is the factor corresponding to the dilution carried out in 6.2;

M is the mass in grams of the test sample taken in accordance with Method 9.1 or 9.2.

Calculation of the dilution factor D: if (a1), (a2), (a3),.,.,., (ai) and (a) are aliquot portions and (v1), (v2),
(v3),.,.,., (vi) and (100) are the volumes in ml corresponding to their respective dilutions, the dilution factor
D is given by:

D ¼ ðv1=a1Þ (cid:2) ðv2=a2Þ (cid:2) ðv3=a3Þ (cid:2) : (cid:2) : (cid:2) : (cid:2) : (cid:2) ðvi=aiÞ (cid:2) ð100=aÞ

M e t h o d 9.9

Determination of manganese in fertiliser extracts by atomic absorption spectrometry

Scope

This Method describes a procedure for determining manganese in fertiliser extracts.

Field of application

This procedure is applicable to analysing samples of fertilisers extracted by Methods 9.1 and 9.2 for which a
declaration of total and/or water-soluble manganese is required by Annex I E of this Regulation.

Principle

After suitable treatment and dilution of the extracts, the manganese level is determined by atomic absorption
spectrometry.

Reagents

Hydrochloric acid solution, about 6 mol/l

See Method 9.4 (4.1).

1.

2.

3.

4.

4.1.

4.2.

Hydrochloric acid solution, about 0,5 mol/l

See Method 9.4 (4.2).

4.3.

Lanthanum salt solutions (10 g of La per litre)

See Method 9.4 (4.3).

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4.4.

Manganese calibration solutions

4.4.1.

Manganese stock solution (1 000 µg/ml)

In a 250 ml beaker, weigh to the nearest 0,1 mg, 1 g of manganese, add 25 ml of 6 mol/l hydrochloric
acid (4.1). Heat on a hotplate until the manganese is completely dissolved. When cool, transfer quantitatively
to a 1 000 ml volumetric flask. Make up to volume with water and mix thoroughly.

4.4.2.

Manganese working solution (100 µg/ml)

Dilute 20 ml of the stock solution (4.4.1) in the 0,5 mol/l hydrochloric acid solution (4.2) in a 200 ml
volumetric flask. Make up to volume with 0,5 mol/l hydrochloric acid solution (4.2) and mix thoroughly.

5.

Apparatus

Atomic absorption spectrometer: see Method 9.4 (5). The instrument must be fitted with a source of lines
characteristic of manganese (279,6 nm).

6.

6.1.

Preparation of the solution to be analysed

Manganese extract solution

See Methods 9.1 and/or 9.2 and, if appropriate, 9.3.

6.2.

Preparation of the test solution

See Method 9.4 (6.2). The test solution must contain 10 % by volume of lanthanum salt solution (4.3).

7.

7.1.

Procedure

Preparation of blank solution

See Method 9.4 (7.1). The test solution must contain 10 % by volume of the lanthanum salt solution used in
6.2.

7.2.

Preparation of calibration solutions

See Method 9.4 (7.2).

For an optimum determination range of 0 to 5 µg/ml of manganese, place 0, 0,5, 1, 2, 3, 4 and 5 ml
respectively of working solution (4.4.2) in a series of 100 ml volumetric flasks. Where necessary adjust the
hydrochloric acid concentration to bring it as close as possible to that of the test solution. To each flask, add
10 ml of the lanthanum salt solution used in 6.2. Make up to 100 ml with 0,5 mol/l hydrochloric acid
solution (4.2) and mix thoroughly. These solutions contain 0, 0,5, 1, 2, 3, 4 and 5 µg/ml respectively of
manganese.

7.3.

Determination

See Method 9.4 (7.3). Prepare the spectrometer (5) for measurement at a wavelength of 279,6 nm.

8.

Expression of results

See Method 9.4 (8).

The percentage of manganese in the fertiliser is as follows:

Mn % ¼ ½ðxs (cid:1) xbÞ (cid:2) V (cid:2) D(cid:3)=ðM (cid:2) 104Þ

If Method 9.3 is used:

where

Mn % ¼ ½ðxs (cid:1) xbÞ (cid:2) V (cid:2) 2D(cid:3)=ðM (cid:2) 104Þ

Mn is the quantity of manganese expressed as a percentage of the fertiliser;

xs is the concentration in µg/ml of the test solution (6.2);

xb is the concentration in µg/ml of the blank solution (7.1);

V is the volume in ml of extract obtained in accordance with Method 9.1 or 9.2;

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D is the factor corresponding to the dilution carried out in 6.2;

M is the mass in grams of the test sample taken in accordance with Method 9.1 or 9.2.

Calculation of the dilution factor D: if (a1), (a2), (a3),.,.,., (ai) and (a) are aliquot portions and (v1), (v2),
(v3),.,.,., (vi) and (100) are the volumes in ml corresponding to their respective dilutions, the dilution factor
D will be equal to:

D ¼ ðv1=a1Þ (cid:2) ðv2=a2Þ (cid:2) ðv3=a3Þ (cid:2) : (cid:2) : (cid:2) : (cid:2) : (cid:2) ðvi=aiÞ (cid:2) ð100=aÞ

Determination of molybdenum in fertiliser extracts by spectrometry of a complex with ammonium
thiocyanate

M e t h o d 9.10

1.

2.

3.

4.

4.1.

Scope

This Method describes a procedure for determining molybdenum in fertiliser extracts.

Field of application

This procedure is applicable to analysing samples of fertilisers extracted by Methods 9.1 and 9.2 for which a
declaration of total and/or water-soluble molybdenum is required by Annex I E to this Regulation.

Principle

Molybdenum (V) forms a complex [MoO(SCN)5]—in an acid medium with SCN- ions.

The complex is extracted with n-butyl acetate. Interfering ions such as those of iron remain in the aqueous
phase. The yellow-orange colour is determined by molecular absorption sectrometry at 470 nm.

Reagents

Dilute hydrochloric acid solution (HCl), about 6 mol/l

See Method 9.4 (4.1).

4.2.

Copper solution (70 mg/l) in 1,5 mol/l hydrochloric acid

Dissolve 275 mg of copper sulphate (CuSO4 5H2O) weighed to within 0,1 mg in 250 ml of the 6 mol/l
hydrochloric acid solution (4.1) in a 1 000 ml volumetric flask. Make up to volume with water and mix
thoroughly.

4.3.

Ascorbic acid solution (50 g/l)

Dissolve 50 g of ascorbic acid (C6H8O6) in water in a 1 000 ml volumetric flask. Make up to volume with
water, mix thoroughly and keep in a refrigerator.

4.4.

4.5.

n-butyl acetate

Ammonium thiocyanate solution, 0,2 mol/l

Dissolve 15,224 g of NH4SCN in water in a 1 000 ml volumetric flask. Make up to volume with water; mix
thoroughly and store in a dark-coloured bottle.

4.6.

Stannous chloride solution (50 g/l) in 2 mol/l hydrochloric acid

This solution must be perfectly clear and prepared immediately before use. Very pure stannous chloride must
be used otherwise the solution will not be clear.

To prepare 100 ml of solution, dissolve 5 g of (SnCl22H2O) in 35 ml of 6 mol/l HCl solution (4.1). Add
10 ml of the copper solution (4.2). Make up to volume with water and mix thoroughly.

4.7.

Molybdenum calibration solutions

4.7.1.

Molybdenum stock solution (500 µg/ml)

Dissolve 0,920 g of ammonium molybdate [(NH4)6Mo7O24 4H2O] weighed to within 0,1 mg in the 6 mol/l
hydrochloric acid (4.1) in a 1 000 ml volumetric flask. Make up to volume with that solution and mix
thoroughly.

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4.7.2.

Molybdenum intermediate solution (25 µg/ml)

Place 25 ml of the stock solution (4.7.1) in a 500 ml volumetric flask. Make up to volume with 6 mol/l
hydrochloric acid (4.1) and mix thoroughly.

4.7.3.

Molybdenum working solution (2,5 µg/ml)

Place 10 ml of the intermediate solution (4.7.2) in a 100 ml volumetric flask. Make up to volume with
6 mol/l hydrochloric acid (4.1) and mix thoroughly.

Apparatus

Spectrometer fitted for molecular absorption with cuvettes having a 20 mm optical path and set to a
wavelength of 470 nm

200 or 250 ml separating funnels

Preparation of the solution to be analysed

Molybdenum extract solution

See Methods 9.1 and/or 9.2 and, if appropriate, 9.3.

5.

5.1.

5.2.

6.

6.1.

6.2.

Preparation of the test solution

Dilute an aliquot portion of the extract (6.1) with 6 mol/l hydrochloric acid solution (4.1) so as to obtain an
appropriate molybdenum concentration. Let D be the dilution factor.

Take an aliquot portion (a) from the extract solution containing 1 to 12 µg molybdenum and place it in the
separating funnel (5.2). Make up to 50 ml with the 6 mol/l hydrochloric acid solution (4.1).

7.

7.1.

Procedure

Preparation of the blank solution

Prepare a blank solution by repeating the whole procedure from the extraction stage, omitting only the test
sample of fertiliser.

7.2.

Preparation of the series of calibration solutions

Prepare a series of at least six calibration solutions of increasing concentration corresponding to the
optimum response range of the spectrometer.

For the interval 0-12,5 µg molybdenum, place 0, 1, 2, 3, 4 and 5 ml respectively of working solution (4.7.3)
in the separating funnels (5.2). Make up to 50 ml with 6 mol/l hydrochloric acid (4.1). The funnels contain
respectively 0, 2,5, 5, 7,5, 10 and 12,5 µg molybdenum.

7.3.

Development and separation of the complex

To each separating funnel (6.2, 7.1 and 7.2), add in the following order:

— 10 ml of the copper solution (4.2)

— 20 ml of the ascorbic acid solution (4.3);

mix thoroughly and wait for two or three minutes. Then add:

— 10 ml of n-butyl acetate (4.4), using a precision pipette

— 20 ml of the thiocyanate solution (4.5).

Shake for one minute to extract the complex in the organic phase; allow to precipitate; after the separation
of the two phases, draw off the entire aqueous phase and discard it; then wash the organic phase with:

— 10 ml of the stannous chloride solution (4.6).

Shake for one minute. Allow to precipitate and draw off the entire aqueous phase. Collect the organic phase
in a test tube; this will make it possible to collect the drops of water in suspension.

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7.4.

Determination

Measure the absorbencies of the solutions obtained at 7.3 at a wavelength of 470 nm using the 0 µg/ml
molybdenum calibration solution (7.2) as a reference.

8.

Expression of results

Construct the calibration curve by plotting the corresponding masses of molybdenum in the calibration
solutions (7.2) expressed in µg along the abscissa and the corresponding values of the absorbencies (7.4)
given by the spectrometer reading along the ordinate.

From this curve determine the mass of molybdenum in the test solution (6.2) and the blank solution (7.1).
These masses are designated (xs) and (xb) respectively.

The percentage of molybdenum in the fertiliser is:

Mo % ¼ ½ðxs (cid:1) xbÞ (cid:2) V=a (cid:2) D(cid:3)=ðM (cid:2) 104Þ

If Method 9.3 is used:

where

Mo % ¼ ½ðxs (cid:1) xbÞ (cid:2) V=a (cid:2) 2D(cid:3)=ðM (cid:2) 104Þ

Mo is the quantity of molybdenum expressed as a percentage of the fertiliser;

a is the volume in ml of the aliquot taken from the last dilute solution (6.2);

xs is the Mo mass in µg in the test solution (6.2);

xb is the Mo mass in µg in the blank solution (7.1) the volume of which corresponds to the volume (a) of
the aliquot of the test solution (6.2);

V is the volume in ml of extract solution obtained in accordance with Method 9.1 or 9.2;

D is the factor corresponding to the dilution performed in 6.2;

M is the mass in grams of the test sample taken in accordance with Method 9.1 or 9.2.

Calculation of the dilution factor D: where (a1), (a2) are successive aliquot portions and (v1), (v2) are the
volumes corresponding to their respective dilutions, the dilution factor D will be:

D ¼ ðv1=a1Þ (cid:2) ðv2=a2Þ

M e t h o d 9.11

1.

2.

3.

4.

4.1.

Determination of zinc in fertiliser extracts by atomic absorption spectrometry

Scope

This Method describes a procedure for determining zinc in fertiliser extracts.

Field of application

This procedure is applicable to analysing samples of fertilisers extracted by Methods 9.1 and 9.2 for which a
declaration of total and/or water-soluble zinc is required by Annex I E to this Regulation.

Principle

After suitable treatment and dilution of the extracts, the zinc level
spectrometry.

is determined by atomic absorption

Reagents

Hydrochloric acid solution, about 6 mol/l

See Method 9.4 (4.1).

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4.2.

Hydrochloric acid solution, about 0,5 mol/l

See Method 9.4 (4.2).

4.3.

Lanthanum salt solutions (10 g of La per litre)

See Method 9.4 (4.3).

4.4.

Zinc calibration solutions

4.4.1.

Zinc stock solution (1 000 µg/ml)

In a 1 000 ml volumetric flask, dissolve 1 g of zinc powder or flakes weighed to within 0,1 mg in 25 ml
of 6 mol/l hydrochloric acid (4.1). When completely dissolved, make up to volume with water and mix
thoroughly.

4.4.2.

Zinc working solution (100 µg/ml)

In a 200 ml volumetric flask, dilute 20 ml of the stock solution (4.4.1) in 0,5 mol/l hydrochloric acid
solution (4.2). Make up to volume with the 0,5 mol/l hydrochloric acid solution (4.2) and mix thoroughly.

5.

Apparatus

Atomic absorption spectrometer: see Method 9.4 (5). The instrument must be fitted with a source of lines
characteristic of zinc (213,8 nm), the spectrometer must allow background correction to be made.

6.

6.1.

Preparation of the solution to be analysed

Zinc extract solution

See Methods 9.1 and/or 9.2 and, if appropriate, 9.3.

6.2.

Preparation of the test solution

See Method 9.4 (6.2). The test solution must contain 10 % by volume of lanthanum salt solution (4.3).

7.

7.1.

Procedure

Preparation of blank solution

See Method 9.4 (7.1). The test solution must contain 10 % by volume of the lanthanum salt solution used in
6.2.

7.2.

Preparation of calibration solutions

See Method 9.4 (7.2).

For an optimum interval of 0 to 5 µg/ml of zinc, place 0, 0,5, 1, 2, 3, 4 and 5 ml respectively of working
solution (4.4.2)
in a series of 100 ml volumetric flasks. Where necessary adjust the hydrochloric acid
concentration to bring it as close as possible to that of the test solution. To each flask, add 10 ml of
the lanthanum salt solution used in 6.2. Make up to 100 ml with 0,5 mol/l hydrochloric acid solution (4.2)
and mix thoroughly. These solutions contain 0, 0,5, 1, 2, 3, 4 and 5 µg/ml respectively of zinc.

7.3.

Determination

See Method 9.4 (7.3). Prepare the spectrometer (5) for measurement at a wavelength of 213,8 nm.

8.

Expression of results

See Method 9.4 (8).

The percentage of zinc in the fertiliser is as follows:

Zn % ¼ ½ðxs (cid:1) xbÞ (cid:2) V (cid:2) D(cid:3)=ðM (cid:2) 104Þ

If Method 9.3 is used:

Zn % ¼ ½ðxs (cid:1) xbÞ (cid:2) V (cid:2) 2D(cid:3)=ðM (cid:2) 104Þ

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where

Zn is the quantity of zinc expressed as a percentage of the fertiliser;

xs is the concentration in µg/ml of the test solution (6.2);

xb is the concentration in µg/ml of the blank solution (7.1);

V is the volume in ml of extract obtained in accordance with Method 9.1 or 9.2;

D is the factor corresponding to the dilution carried out in 6.2;

M is the mass in grams of the test sample taken in accordance with Method 9.1 or 9.2.

Calculation of the dilution factor D: if (a1), (a2), (a3),.,.,., (ai) and (a) are aliquot portions and (v1), (v2),
(v3),.,.,., (vi) and (100) are the volumes in ml corresponding to their respective dilutions, the dilution factor
D will be equal to:

D ¼ ðv1=a1Þ (cid:2) ðv2=a2Þ (cid:2) ðv3=a3Þ (cid:2) : (cid:2) : (cid:2) : (cid:2) : (cid:2) ðvi=aiÞ (cid:2) ð100=aÞ

M e t h o d s 1 0

Micro-nutrients at a concentration greater than 10 %

M e t h o d 10.1

Extraction of total micro-nutrients

1.

Scope

This Method defines the procedure for extracting the following micro-nutrients: total boron, total cobalt,
total copper, total iron, total manganese, total molybdenum and total zinc. The aim is to carry out the
minimum number of extractions, making use wherever possible of the same extract to determine the total
level of each of the micro-nutrients listed above.

2.

Field of application

This procedure concerns Community fertilisers covered by Annex I E to this Regulation containing one or
more of the following micro-nutrients: boron, cobalt, copper, iron, manganese, molybdenum and zinc. It is
applicable to each micro-nutrient the declared content of which is more than 10 %.

3.

Principle

Dissolution in boiling dilute hydrochloric acid.

N o t e

The extraction is empirical and may not be quantitative depending on the product or the other constituents
of the fertiliser. In particular,
in the case of certain manganese oxides, the quantity extracted may be
substantially smaller than the total quantity of manganese which the product contains. It is the responsibility
of the fertiliser manufacturers to ensure that the declared content actually corresponds to the quantity
extracted under the conditions pertaining to the method.

4.

4.1.

4.2.

5.

5.1.

Reagents

Dilute hydrochloric acid (HCl) solution, about 6 mol/l

Mix 1 volume of hydrochloric acid (d20 = 1,18 g/ml) with 1 volume of water.

Concentrated ammonia solution (NH4OH, d20 = 0,9 g/ml)

Apparatus

Electric hotplate with variable temperature control

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5.2.

pH meter

N o t e

Where the boron content of an extract is to be determined, do not use borosilicate glassware. As the Method
involves boiling, teflon or silica is preferable. Rinse the glassware thoroughly if it has been washed in
detergents containing borates.

6.

Preparation of the sample

See Method 1.

7.

7.1.

Procedure

Test sample

Take a quantity of fertiliser weighing 1 or 2 g depending on the declared content of element in the product.
The following table shall be used to obtain a final solution which, after appropriate dilution, will be within
the measuring range for each method. Samples should be weighed to within 1 mg.

Declared content of micro-nutrient in the fertiliser (%)

Mass of test sample (g)

Mass of element in the sample (mg)

Volume of extract V (ml)

> 10 < 25

2

> 200 < 500

500

Concentration of element in extract (mg/l)

> 400 < 1 000

‡ 25

1

‡ 250

500

‡ 500

Place the sample in a 250 ml beaker.

7.2.

Preparation of the solution

If necessary moisten the sample with a little water, add 10 ml of dilute hydrochloric acid (4.1) per gram of
fertiliser carefully, in small amounts, then add about 50 ml of water. Cover the beaker with a watch glass
and mix. Bring to the boil on the hotplate and boil for 30 minutes. Allow to cool, stirring occasionally.
Transfer quantitatively to a 500 ml volumetric flask. Make up to volume with water and mix thoroughly.
Filter through a dry filter into a dry container. Discard the first portion. The extract must be perfectly clear.

It is recommended that the determination be carried out without delay on aliquot portions of the clear
filtrate, if not the containers should be stoppered.

N o t e

Extracts in which the boron content has to be determined: Adjust the pH to between 4 and 6 with
concentrated ammonia (4.2).

8.

Determination

The determination of each micro-nutrient is to be carried out on the aliquot portions indicated in the
Method for each individual micro-nutrient.

Methods 10.5, 10.6, 10.7, 10.9 and 10.10 cannot be used to determine elements present in a chelated or
complexed form. In such cases Method 10.3 must be used prior to the determination.

In the case of determination by AAS (Methods 10.8 and 10.11) such treatment may not be necessary.

M e t h o d 10.2

Extraction of water-soluble micro-nutrients

1.

Scope

This Method defines the procedure for extracting water-soluble forms of the following micro-nutrients:
boron, cobalt, copper,
iron, manganese, molybdenum and zinc. The aim is to carry out the minimum
number of extractions, making use wherever possible of the same extract to determine the level of each
of the micro-nutrients listed above.

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2.

Field of application

This Procedure concerns Community fertilisers covered by Annex I E to this Regulation containing one or
more of the following micro-nutrients: boron, cobalt, copper, iron, manganese, molybdenum and zinc. It is
applicable to each micro-nutrient the declared content of which is more than 10 %.

3.

Principle

The micro-nutrients are extracted by shaking the fertiliser in water at 20 °C (± 2) °C.

N o t e

The extraction is empirical and may or may not be quantitative.

Reagents

Dilute hydrochloric acid (HCl) solution, about 6 mol/l

Mix 1 volume of hydrochloric acid (d20 = 1,18 g/ml) with 1 volume of water.

Apparatus

Rotary shaker set at about 35 to 40 rpm

N o t e

4.

4.1.

5.

5.1.

Where the boron content of the extract is to be determined, do not use borosilicate glassware. Teflon or
silica is preferable for this extraction. Rinse the glassware thoroughly if it has been washed in detergents
containing borates.

6.

Preparation of the sample

See Method 1.

7.

7.1.

Procedure

Test sample

Take a quantity of fertiliser weighing 1 or 2 g depending on the declared content of the product. The
following table shall be used to obtain a final solution which, after appropriate dilution, will be within the
measuring range for each method. The samples should be weighed to within 1 mg.

Declared content of micro-nutrient in the fertiliser (%)

Mass of test sample (g)

Mass of element in the sample (mg)

Volume of extract V (ml)

> 10 < 25

2

> 200 < 500

500

Concentration of element in extract (mg/l)

> 400 < 1 000

‡ 25

1

‡ 250

500

‡ 500

Place the sample in a 500 ml flask.

7.2.

Preparation of the solution

Add about 400 ml of water.

Stopper the flask well. Shake vigorously by hand to disperse the sample, then place the flask on the shaker
and shake for 30 minutes.

Make up to volume with water and mix thoroughly.

7.3.

Preparation of the test solution

Filter immediately into a clean, dry flask. Stopper the flask. Carry out the determination immediately after
filtering.

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N o t e

If the filtrate gradually becomes cloudy, make another extraction following 7.1 and 7.2 in a flask of volume
Ve. Filter into a calibrated flask of volume W which has previously been dried and has received 5 ml of
dilute hydrochloric acid (4.1). Stop the filtration at the exact moment when the calibration mark is reached.
Mix thoroughly.

Under these conditions the value of V in the expression of results is:

V ¼ Ve (cid:2) W=ðW (cid:1) 5Þ

The dilutions in the expression of results depend on this value of V.

8.

Determination

The determination of each micro-nutrient is carried out on the aliquot portions indicated in the Method for
each individual micro-nutrient.

Methods 10.5, 10.6, 10.7, 10.9 and 10.10 cannot be used to determine elements present in a chelated or
complexed form. In such cases Method 10.3 must be used prior to the determination.

In the case of determination by AAS (Methods 10.8 and 10.11) such treatment may not be necessary.

M e t h o d 10.3

Removal of organic compounds from fertiliser extracts

1.

2.

Scope

This Method defines a procedure for removing organic compounds from fertiliser extracts.

Field of application

This procedure is applicable to analysing samples of fertilisers extracted by Methods 10.1 and 10.2 for which
a declaration of total and/or water-soluble element is required by Annex I E to this Regulation.

N o t e

The presence of small quantities of organic matter usually does not affect determination by means of atomic
absorption spectrometry.

3.

Principle

The organic compounds in an aliquot portion of the extract are oxidised with hydrogen peroxide.

4.

4.1.

Reagents

Dilute hydrochloric acid (HCl) solution, about 0,5 mol/l

Mix 1 volume of hydrochloric acid (d20 = 1,18 g/ml) with 20 volumes of water.

4.2.

Hydrogen peroxide solution (30 % H2O2, d20 = 1,11 g/ml), free from micro-nutrients

5.

6.

Apparatus

Electric hotplate with variable temperature control.

Procedure

Take 25 ml of the extract solution obtained by Method 10.1 or Method 10.2 and place in a 100 ml beaker.
In the case of Method 10.2, add 5 ml of the dilute hydrochloric acid solution (4.1). Then add 5 ml of the
hydrogen peroxide solution (4.2). Cover with a watch glass. Allow oxidation to occur at room temperature
for about one hour, then bring gradually to boiling and boil for half an hour. If necessary, add a further
5 ml of the hydrogen peroxide to the solution once it has cooled. Then boil to remove the excess hydrogen
peroxide. Allow to cool and transfer quantitatively to a 50 ml volumetric flask and make up to volume.
Filter where necessary.

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Account should be taken of this dilution when taking aliquot portions and calculating the percentage of
micro-nutrient in the product.

Determination of micro-nutrients in fertiliser extracts by atomic absorption spectrometry
(general procedure)

M e t h o d 10.4

1.

Scope

This document defines a general procedure for determining the levels of iron and zinc in fertiliser extracts by
atomic absorption spectrometry.

2.

Field of application

This procedure is applicable to analysing samples of fertilisers extracted by Methods 10.1 and 10.2 for which
a declaration of total and/or water-soluble iron or zinc is required by Annex I E to this Regulation.

Adaptations of this procedure for the various micro-nutrients are detailed in the methods defined specifically
for each element.

N o t e

In most cases the presence of small quantities of organic matter will not affect determinations by atomic
absorption spectrometry.

3.

Principle

After the extract has been treated where necessary to reduce or eliminate interfering chemical species, the
extract is diluted so that its concentration is in the optimum range of the spectrometer at a wavelength
suitable for the micro-nutrient to be determined.

4.

4.1.

Reagents

Dilute hydrochloric acid solution (HCl), about 6 mol/l

Mix one volume of hydrochloric acid (d20 = 1,18 g/ml) with one volume of water.

4.2.

Dilute hydrochloric acid solution (HCl), about 0,5 mol/l

Mix one volume of hydrochloric acid (d20 = 1,18 g/ml) with 20 volumes of water.

4.3.

Lanthanum salt solutions (10 g of La per litre)

This reagent is used for determinations of iron and zinc. It can be prepared either:

(a) with lanthanum oxide dissolved in hydrochloric acid (4.1). Place 11,73 g of lanthanum oxide (La2O3) in
150 ml of water in a one litre volumetric flask and add 120 ml of 6 mol/l hydrochloric acid (4.1).
Allow to dissolve and then make up to 1 litre with water and mix thoroughly. This solution is
approximately 0,5 mol/l in hydrochloric acid; or

(b) with solutions of

lanthanum chloride
lanthanum chloride, sulphate or nitrate. Dissolve 26,7 g of
heptahydrate (LaCl3 7H2O) or 31,2 g of lanthanum nitrate hexahydrate [La(NO3)3 6H2O] or 26,2 g
of lanthanum sulphate nonahydrate [La2(SO4)3 9H2O] in 150 ml of water, then add 85 ml of 6 mol/l
hydrochloric acid (4.1). Allow to dissolve and then make up to 1 litre with water. Mix thoroughly. This
solution is approximately 0,5 mol/l in hydrochloric acid.

4.4.

Calibration solutions

For the preparation of these, see the individual determination Method for each micro-nutrient.

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5.

Apparatus

Atomic absorption spectrometer fitted with sources emitting radiation characteristic of the micro-nutrients
to be determined.

The analyst must follow the manufacturer's instructions and be familiar with the apparatus. The apparatus
must allow background correction so that it can be used whenever necessary (e.g. Zn). The gases to be used
are air and acetylene.

6.

6.1.

Preparation of the solution to be analysed

Preparation of extract solutions containing the elements to be determined

See Methods 10.1 and/or 10.2 and, if appropriate, 10.3.

6.2.

Treatment of the test solution

Dilute an aliquot portion of the extract obtained by Method 10.1, 10.2 or 10.3 with water and/or hydro-
chloric acid (4.1) or (4.2) so as to obtain, in the final solution for measurement, a concentration of the
element to be determined that is appropriate to the calibration range used (7.2) and a hydrochloric acid
concentration of at least 0,5 mol/l and not more than 2,5 mol/l. This operation may require one or more
successive dilutions.

The final solution has to be obtained by placing an aliquot portion of the diluted extract in a 100 ml
volumetric flask. Let the volume of this aliquot portion be (a) ml. Add 10 ml of the lanthanum salt solution
(4.3). Make up to volume with the 0,5 mol/l hydrochloric acid solution (4.2) and mix thoroughly. Let D be
the dilution factor.

7.

7.1.

Procedure

Preparation of a blank solution

Prepare a blank solution by repeating the whole procedure from the extraction stage, omitting only the test
sample of fertiliser.

7.2.

Preparation of calibration solutions

From the working calibration solution prepared using the Method given for each individual micro-nutrient,
prepare in 100 ml volumetric flasks a series of at least five calibration solutions of increasing concentration
within the optimum measuring range of the spectrometer. If necessary, adjust the concentration of hydro-
chloric acid to bring it as close as possible to that of the diluted test solution (6.2). When determining iron
or zinc, add 10 ml of the same lanthanum salt solution (4.3) as used in 6.2. Make up to volume with the
0,5 mol/l hydrochloric acid solution (4.2) and mix thoroughly.

7.3.

Determination

Prepare the spectrometer (5) for the determination and adjust to the wavelength given in the Method for the
individual micro-nutrient concerned.

Spray three times in succession the calibration solutions (7.2), the test solution (6.2) and the blank solution
(7.1), noting each result and flushing the instrument with distilled water between individual sprayings.

Construct the calibration curve by plotting the average spectrometer reading for each calibration solution
(7.2) along the ordinate and the corresponding concentration of the element, expressed in µg/ml, along the
abscissa.

From this curve, determine the concentrations of the relevant micro-nutrient in the test solution xs (6.2) and
in the blank solution xb(7.1), expressing these concentrations in µg per ml.

8.

Expression of results

The percentage of micro-nutrient (E) in the fertiliser is given by:

E ð%Þ ¼ ½ðxs (cid:1) xbÞ (cid:2) V (cid:2) D(cid:3) = ðM (cid:2) 104Þ

If Method 10.3 has been used:

E ð%Þ ¼ ½ðxs (cid:1) xbÞ (cid:2) V (cid:2) 2D(cid:3)=ðM (cid:2) 104Þ

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Where

E is the amount of the micro-nutrient determined, expressed as a percentage of the fertiliser;

xs is the concentration of the test solution (6.2), in µg/ml;

xb is the concentration of the blank solution (7.1), in µg/ml;

V is the volume of the extract obtained by Method 10.1 or 10.2, in ml;

D is the factor corresponding to the dilution carried out in 6.2;

M is the mass of the test sample taken in accordance with Method 10.1 or 10.2, in grams.

Calculation of dilution factor D:

If (a1), (a2), (a3),.,.,., (ai) and (a) are the aliquot portions and (v1), (v2), (v3),.,.,., (vi) and (100) are the volumes
in ml corresponding to their respective dilutions, the dilution factor D will be equal to:

D ¼ ðv1=a1Þ (cid:2) ðv2=a2Þ (cid:2) ðv3=a3Þ (cid:2) : (cid:2) : (cid:2) : (cid:2) ðvi=aiÞ (cid:2) ð100=aÞ

1.

2.

3.

Determination of boron in fertiliser extracts by means of acidimetric titration

M e t h o d 10.5

Scope

This Method defines a procedure for determining the boron content of fertiliser extracts.

Field of application

This procedure is applicable to extracts from samples of fertilisers obtained by Methods 10.1 or Method 10.2
and for which a declaration of total and/or water-soluble boron is required by Annex I E to this Regulation.

Principle

A mannitoboric complex is formed by the following reaction of the borate with mannitol:

C6H8 ðOHÞ6 þ H3BO3 C6H15O8B þ H2O

The complex is titrated with sodium hydroxide solution to a pH of 6,3.

4.

4.1.

Reagents

Methyl red indicator solution

Dissolve 0,1 g of methyl red (C15H15N3O2) in 50 ml of ethanol (95 % in a 100 ml volumetric flask). Make
up the volume to 100 ml with water. Mix thoroughly.

4.2.

Diluted hydrochloric acid solution, about 0,5 mol

Mix 1 volume of hydrochloric acid HCl (d20 = 1,18 g/ml) with 20 volumes of water.

4.3.

Sodium hydroxide solution, about 0,5 mol/l

Must be free of carbon dioxide. Dissolve 20 g of sodium hydroxide (NaOH) in pellet form in a 1 litre
volumetric flask containing about 800 ml of boiled water. When the solution has cooled, make up to
1 000 ml with boiled water and mix thoroughly.

4.4.

Standard sodium hydroxide solution, about 0,025 mol/l

Must be free of carbon dioxide. Dilute the 0,5 mol/l sodium hydroxide solution (4.3) 20 times with boiled
water and mix thoroughly. The value of the solution expressed as boron (B) is to be determined (see
Paragraph 9).

4.5.

Boron calibration solution (100 µg/ml B)

Dissolve 0,5719 g of boric acid (H3BO3), weighed to the nearest 0,1 mg, in water in a 1,000 ml volumetric
flask. Make up to volume with water and mix thoroughly. Transfer to a plastic bottle for storage in a
refrigerator.

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4.6.

4.7.

5.

5.1.

5.2.

5.3.

6.

6.1.

7.

7.1.

8.

9.

D-mannitol (C6H14O6) powder

Sodium chloride (NaCl)

Apparatus

pH meter with glass electrode

Magnetic stirrer

400 ml beaker with teflon rod

Preparation of the solution to be analysed

Preparation of the boron solution

See Methods 10.1, 10.2 and, where appropriate, 10.3.

Procedure

Test

Place in a 400 ml beaker (5.3) an aliquot (a) of the extract (6.1) containing 2 to 4 mg B. Add 150 ml of
water.

Add several drops of the methyl red indicator solution (4.1).

In the case of extraction with Method 10.2, acidify by adding 0,5 mol/l hydrochloric acid (4.2) up to the
point of change of the indicator solution, then add a further 0,5 ml of 0,5 mol/l hydrochloric acid (4.2).

After adding 3 g of sodium chloride (4.7), bring to boiling to drive off the carbon dioxide. Allow to cool.
Place the beaker on the magnetic stirrer (5.2) and insert the precalibrated pH meter electrodes (5.1).

Adjust the pH to exactly 6,3, first with the 0,5 mol/l sodium hydroxide solution (4.3), then with the
0,025 mol/l solution (4.4).

Add 20 g of D-mannitol (4.6), dissolve completely and mix thoroughly. Titrate with the 0,025 mol/l sodium
hydroxide solution (4.4) to pH 6,3 (at least 1 minute stability). Let X1 be the volume required.

Blank solution

Prepare a blank solution by repeating the whole procedure from the preparation of solution stage, omitting
only the fertiliser. Let X0 be the volume required.

Boron (B) value of the sodium hydroxide solution (4.4)

Pipette 20 ml (2,0 mg B) of the calibration solution (4.5), into a 400 ml beaker and add several drops of
methyl red indicator solution (4.1). Add 3 g of sodium chloride (4.7) and the hydrochloric acid solution
(4.2) up to the point of change of the indicator solution (4.1).

Make up the volume to about 150 ml and bring gradually to the boil so as to eliminate carbon dioxide.
Allow to cool. Place the beaker on the magnetic stirrer (5.2), and insert the precalibrated pH meter
electrodes (5.1). Adjust the pH to exactly 6,3, first with the 0,5 mol/l sodium hydroxide solution (4.3),
then with the 0,025 mol/l solution (4.4).

Add 20 g of D-mannitol (4.6), dissolve completely and mix thoroughly. Titrate with the 0,025 mol/l sodium
hydroxide solution (4.4) to pH 6,3 (at least 1 minute stability). Let V1 be the volume required.

Prepare a blank solution in the same way, substituting 20 ml of water for the calibration solution. Let V0 be
the volume required.

The boron value (F) in mg/ml of the standard NaOH solution (4.4) is as follows:

F (in mg/ml) ¼ 2 = ðV1 (cid:1) V0Þ

1 ml of exactly 0,025 mol/l sodium hydroxide solution corresponds to 0,27025 mg B.

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10.

Expression of results

The percentage of boron in the fertiliser is given by:

B ð%Þ ¼

ðX1 (cid:1) X0Þ (cid:2) F (cid:2) V
10 (cid:2) a (cid:2) M

where

B (%) is the percentage of boron in the fertiliser;

X1 is the volume, in ml, of the 0,025 mol/l sodium hydroxide solution (4.4); needed for the test solution;

X0 is the volume, in ml, of the 0,025 mol/l sodium hydroxide solution (4.4); needed for the blank solution;

F is the boron (B) value, in mg/ml, of the 0,025 mol/l sodium hydroxide solution mol/l (4.4);

V is the volume, in ml, of the extract solution obtained in accordance with Method 10.1 or 10.2;

a is the volume, in ml, of the aliquot (7.1) taken from the extract solution (6.1);

M is the mass, in grams, of the test sample taken in accordance with Method 10.1 or 10.2.

Determination of cobalt in fertiliser extracts by the gravimetric method with 1-nitroso-2-naphthol

M e t h o d 10.6

Scope

This document defines a procedure for determining cobalt in fertiliser extracts.

Field of application

This procedure is applicable to extracts from samples of fertilisers obtained by Method 10.1 or Method 10.2
for which a declaration of cobalt content is required by Annex I E to this Regulation.

Principle

Cobalt III combines with 1-nitroso-2-naphthol to give a red precipitate Co(C10H6ONO)3, 2H2O. After the
cobalt present in the extract has been brought to the cobalt III state, the cobalt is precipitated in an acetic
acid medium by a solution of 1-nitroso-2-naphthol. After filtration, the precipitate is washed and dried to
constant mass and then weighed as Co(C10H6ONO)3, 2H2O.

Reagents

Hydrogen peroxide solution (H2O2, d20 = 1,11 g/ml) 30 %

Sodium hydroxide solution, about 2 mol/l

Dissolve 8 g of sodium hydroxide in pellet form in 100 ml of water.

1.

2.

3.

4.

4.1.

4.2.

4.3.

Diluted hydrochloric acid solution, about 6 mol/l

Mix one volume of hydrochloric acid (d20 = 1,18 g/ml) with 1 volume of water.

4.4.

4.5.

4.6.

Acetic acid (99,7 % CH3CO2H) (d20 = 1,05 g/ml)

Acetic acid solution (1:2), about 6 mol/l

Mix one volume of acetic acid (4.4) with 2 volumes of water.

Solution of 1-nitroso-2-naphthol in 100 ml of acetic acid (4.4). Add 100 ml of lukewarm water. Mix
thoroughly. Filter at once. The solution obtained must be used immediately

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5.

5.1.

5.2.

6.

6.1.

Apparatus

Filter crucible P 16/ISO 4 793, porosity 4, capacity 30 or 50 ml

Drying oven at 130 (± 2) °C

Preparation of the solution to be analysed

Preparation of the cobalt solution

See Methods 10.1 or 10.2.

6.2.

Preparation of the solution to be analysed

Place an aliquot of the extract containing not more than 20 mg Co in a 400 ml beaker. If the extract is
obtained according to Method 10.2, acidify with five drops of hydrochloric acid (4.3). Add about 10 ml of
the hydrogen peroxide solution (4.1). Allow the oxidant to act in the cold state for 15 minutes, then make
up to about 100 ml with water. Cover the beaker with a watch glass. Bring the solution to boiling point and
allow to boil for about 10 minutes. Cool. Make alkaline with the sodium hydroxide solution (4.2) drop by
drop until black cobalt hydroxide begins to precipitate.

7.

Procedure

Add 10 ml of acetic acid (4.4) and make up the solution with water to about 200 ml. Heat until boiling.
Using a burette, add 20 ml of the 1-nitroso-2-naphthol solution (4.6) drop by drop, stirring constantly.
Complete by vigorous stirring to make the precipitate coagulate.

Filter through a previously weighed filter crucible (5.1), taking care not to clog up the crucible. With this in
mind, ensure that liquid is left above the precipitate throughout the filtration process.

Wash the beaker with dilute acetic acid (4.5) to remove all the precipitate, wash the precipitate on the filter
with dilute acetic acid (4.5) and then three times with hot water.

Dry in a drying oven (5.2) at 130 (± 2) °C until constant mass is achieved.

8.

Expression of the results

1 mg of Co (C10H6ONO)3, 2H2O precipitate corresponds to 0,096381 mg Co.

The percentage of Cobalt (Co) in the fertiliser is given by:

Co ð%Þ ¼ X (cid:2) 0,0096381 (cid:2)

V (cid:2) D
a (cid:2) M

where

X is the mass in mg of the precipitate;

V is the volume in ml of the extract solution obtained in accordance with Method 10.1 or Method 10.2;

a is the volume in ml of the aliquot taken from the last dilution;

D is the dilution factor of this aliquot;

M is the mass in g of the test sample.

M e t h o d 10.7

Determination of copper in fertiliser extracts by the titrimetric method

1.

Scope

This document defines a procedure for determining copper in fertiliser extracts.

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2.

3.

4.

4.1.

4.2.

4.3.

Field of application

This procedure is applicable to extracts from samples of fertilisers obtained by Method 10.1 or Method 10.2
for which a declaration of copper content is required by Annex IE to this Regulation.

Principle

The cupric ions are reduced in an acidic medium with potassium iodide:

2Cuþþ þ 4I ﬁ 2CuI þ I2

The iodine released in this way is titrated with a standard sodium thiosulphate solution in the presence of
starch as an indicator in accordance with:

I2 þ 2Na2S2O3 ﬁ 2NaI þ Na2S4O6

Reagents

Nitric acid (HNO3, d20 = 1,40 g/ml)

Urea [(NH2)2 C = 0]

Ammonium bifluoride (NH4HF2) solution 10 % w/v

Keep the solution in a plastic container.

4.4.

Ammonium hydroxide solution (1 + 1)

Mix 1 volume of ammonia (NH4OH, d20 = 0,9 g/ml) with 1 volume of water.

4.5.

Sodium thiosulphate standard solution

Dissolve 7,812 g of sodium thiosulphate pentahydrate (Na2S2O35H2O) with water in a 1 litre volumetric
flask. This solution must be prepared so that 1 ml = 2 mg Cu. For stabilisation, add several drops of
chloroform. The solution must be kept in a glass container and protected from direct light.

4.6.

4.7.

Potassium iodide (KI)

Potassium thiocyanate (KSCN) solution (25 % w/v)

Keep this solution in a plastic flask.

4.8.

Starch solution (about 0,5 %)

Place 2,5 g of starch in a 600 ml beaker. Add about 500 ml of water. Boil while stirring. Cool to ambient
temperature. The solution has a short preservation period. Its preservation can be extended by adding about
10 mg of mercury iodide.

5.

Preparation of the solution to be analysed

Preparation of the copper solution

See Methods 10.1 and 10.2.

6.

6.1.

Procedure

Preparation of the solution of titration

Place an aliquot portion of the solution containing not less than 20-40 mg Cu in a 500 ml Erlenmeyer
flask.

Drive off any excess oxygen present by boiling briefly. Make up to a volume of about 100 ml water. Add
5 ml of nitric acid (4.1), bring to boiling and allow to boil for about half a minute.

Remove the Erlenmeyer flask from the heating apparatus, add about 3 g of urea (4.2) and resume boiling
for about half a minute.

Remove from the heating apparatus and add 200 ml of cold water. Where necessary, cool the contents of
the Erlenmeyer flask to ambient temperature.

Gradually add ammonia hydroxide solution (4.4) until the solution becomes blue, then add 1 ml in excess.

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Add 50 ml of ammonium bifluoride solution (4.3) and mix.

Add 10 g of potassium iodide (4.6) and dissolve.

6.2.

Titration of the solution

Place the Erlenmeyer flask on a magnetic stirrer. Insert the rod into the Erlenmeyer flask and adjust the
stirrer to the desired speed.

Using a burette, add standard sodium thiosulphate solution (4.5) until the brown colour of the iodine
released from the solution becomes less intense.

Add 10 ml of the starch solution (4.8).

Continue to titrate with the sodium thiosulphate solution (4.5) until the purple colour has almost disap-
peared.

Add 20 ml of the potassium thiocyanate solution (4.7) and continue titration until the violet blue colour has
completely disappeared.

Note the volume for thiosulphate solution employed.

7.

Expression of results

1 ml of standard sodium thiosulphate solution (4.5) corresponds to 2 mg Cu.

The percentage of copper in the fertiliser is given by:

Cu ð%Þ ¼ X

V
a (cid:2) M (cid:2) 5

where

X is the volume in ml of the sodium thiosulphate solution used;

V is the volume in ml of the extract solution in accordance with Methods 10.1 and 10.2;

a is the volume in ml of the aliquot portion;

M is the mass in g of the test sample treated in accordance with Methods 10.1 and 10.2.

Determination of iron in fertiliser extracts by atomic absorption spectrometry

M e t h o d 10.8

Scope

This Method describes a procedure for determining iron in fertiliser extracts.

Field of application

This procedure is applicable to extracts from samples of fertilisers obtained by Methods 10.1 and 10.2 for
which a declaration of total and/or water-soluble iron is required by Annex I E to this Regulation.

Principle

After suitable treatment and dilution of the extract, the iron content is determined by atomic absorption
spectrometry.

Reagents

Hydrochloric acid solution, about 6 mol/l

See Method 10.4 (4.1).

1.

2.

3.

4.

4.1.

4.2.

Hydrochloric acid solution, about 0,5 mol/l

See Method 10.4 (4.2).

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4.3.

4.4.

Hydrogen peroxide solution (30 % H2O2, d20 = 1,11 g/ml) free from micro-nutrients

Lanthanum salt solutions (10 g of La per litre)

See Method 10.4 (4.3).

4.5.

Iron calibration solution

4.5.1.

Iron stock solution (1 000 µg/ml)

In a 500 ml beaker, weigh to the nearest 0,1 mg, 1 g of pure iron wire, add 200 ml of 6 mol/l hydro-
chloric acid (4.1) and 15 ml of hydrogen peroxide solution (4.3). Heat on a hotplate until the iron is
completely dissolved. When cool, transfer quantitatively to a 1 000 ml volumetric flask. Make up to volume
with water and mix thoroughly.

4.5.2.

Iron working solution (100 µg/ml)

Place 20 ml of the stock solution (4.5.1) in a 200 ml volumetric flask. Make up to volume with the
0,5 mol/l hydrochloric acid solution (4.2) and mix thoroughly.

5.

Apparatus

Atomic absorption spectrometer: see Method 10.4 (5). The instrument must be fitted with a source of
emitted radiation characteristic of iron (248,3 nm).

6.

6.1.

Preparation of the solution to be analysed

Iron extract solution

See Methods 10.1 and/or 10.2 and, if appropriate, 10.3.

6.2.

Preparation of the test solution

See Method 10.4 (6.2). The test solution must contain 10 % (v/v) of a lanthanum salt solution.

7.

7.1.

Procedure

Preparation of blank solution

See Method 10.4 (7.1). The blank solution must contain 10 % (v/v) of the lanthanum salt solution used in
6.2.

7.2.

Preparation of calibration solutions

See Method 10.4 (7.2).

For an optimum determination range of 0 to 10 µg/ml of iron, place 0, 2, 4, 6, 8 and 10 ml respectively of
working solution (4.5.2) in a series of 100 ml volumetric flasks. If necessary adjust the hydrochloric acid
concentration as closely as possible to that of the test solution. Add 10 ml of the lanthanum salt solution
used in 6.2. Make up to volume with 0,5 mol/l hydrochloric acid solution (4.2) and mix thoroughly. These
solutions contain 0, 2, 4, 6, 8 and 10 µg/ml respectively of iron.

7.3.

Determination

See Method 10.4 (7.3). Prepare the spectrometer (5) for measurement at a wavelength of 248,3 nm.

8.

Expression of results

See Method 10.4 (8).

The percentage of iron in the fertiliser is given by:

Fe ð%Þ ¼ ½ðxs (cid:1) xbÞ (cid:2) V (cid:2) D(cid:3) = ðM (cid:2) 104Þ

If Method 10.3 is used:

Fe ð%Þ ¼ ½ðxs (cid:1) xbÞ (cid:2) V (cid:2) 2D(cid:3) = ðM (cid:2) 104Þ

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Where

Fe is the quantity of iron expressed as a percentage of the fertiliser;

xs is the concentration in µg/ml of the test solution (6.2);

xb is the concentration in µg/ml of the blank solution (7.1);

V is the volume in ml of extract obtained in accordance with Method 10.1 or 10.2;

D is the factor of dilution carried out in 6.2;

M is the mass in grams of the test sample taken in accordance with Method 10.1 or 10.2.

Calculation of the dilution factor D: if (a1), (a2), (a3), . . ., (ai) and (a) are aliquot portions and (v1), (v2), (v3),
. . ., (vi) and (100) are the volumes in ml corresponding to their respective dilutions, the dilution factor D is
given by:

D ¼ ðv1=a1Þ (cid:2) ðv2=a2Þ (cid:2) ðv3=a3Þ (cid:2) : (cid:2) ðvi=aiÞ (cid:2) ð100=aÞ

M e t h o d 10.9

Determination of manganese in fertiliser extracts by titration

Scope

This Method describes a procedure for determining manganese in fertiliser extracts.

Field of application

This procedure is applicable to extracts from samples of fertilisers obtained by Methods 10.1 and 10.2 for
which a declaration of manganese is required by Annex I E to this.

Principle

If chloride ions are present in the extract, they are driven off by boiling the extract with sulphuric acid. The
manganese is oxidised by sodium bismuthate in a nitric acid medium. The permanganate formed is reduced
by an excess of ferrous sulphate. This excess is titrated with a potassium permanganate solution.

Reagents

Concentrated sulphuric acid (H2SO4, d20 = 1,84 g/ml)

Sulphuric acid, about 9 mol/l

1.

2.

3.

4.

4.1.

4.2.

Carefully mix 1 volume of concentrated sulphuric acid (4.1) with 1 volume of water.

4.3.

Nitric acid, 6 mol/l

Mix 3 volumes of nitric acid (HNO3, d20 = 1,40 g/ml) with 4 volumes of water.

4.4.

Nitric acid, 0,3 mol/l

Mix 1 volume of 6 mol/l nitric acid with 19 volumes of water.

4.5.

4.6.

4.7.

4.8.

Sodium bismuthate (NaBiO3) (85 %).

Kieselguhr

Orthophosphoric acid, 15 mol/l (H3PO4, d20 = 1,71 g/ml)

Ferrous sulphate solution, 0,15 mol/l

Dissolve 41,6 g of ferrous sulphate heptahydrate (FeSO4.7H2O) in a 1 litre volumetric flask.

Add 25 ml of concentrated sulphuric acid (4.1) and 25 ml phosphoric acid (4.7). Make up to 1 000 ml.
Mix.

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4.9.

Potassium permanganate solution, 0,020 mol/l

Weigh out 3,160 g of potassium permanganate (KMnO4) to within 0,1 mg. Dissolve and make up to
1 000 ml with water.

4.10.

Silver nitrate solution, 0,1 mol/l

Dissolve 1,7 g of silver nitrate (AgNO3) in water and make up to 100 ml.

5.

5.1.

5.2.

6.

6.1.

6.2.

Apparatus

Filter crucible P16/ISO 4 793, porosity 4, capacity 50 ml, mounted on a 500 ml filtration flask.

Magnetic stirrer

Preparation of the solution to be analysed

Manganese extract solution

See Methods 10.1 and 10.2. If it is not known whether chloride ions are present, perform a test on the
solution with one drop of the silver nitrate solution (4.10).

In the absence of chloride ions, place an aliquot of the extract containing 10 to 20 mg of manganese in a
tall form 400 ml beaker. Bring to a volume of about 25 ml either by evaporation or by adding water. Add
2 ml of concentrated sulphuric acid (4.1)

6.3.

If chloride ions are present, it is necessary to remove them as follows

Place an aliquot of the extract containing 10 to 20 mg of manganese in a tall form 400 ml beaker. Add
5 ml of 9 mol/l sulphuric acid (4.2). Under a fume hood, bring to boiling on a hotplate and allow to boil
until copious white fumes are released. Continue until the volume is reduced to about 2 ml (thin film of
syrupy liquid at the bottom of the beaker). Allow to cool to ambient temperature.

Carefully add 25 ml of water and once again test for the presence of chlorides with one drop of the silver
nitrate solution (4.10). If chlorides still remain, repeat the operation after adding 5 ml of 9 mol/l sulphuric
acid (4.2).

7.

Procedure

Add 25 ml of 6 mol/l nitric acid (4.3) and 2,5 g of sodium bismuthate (4.5) to the 400 ml beaker
containing the test solution. Stir vigorously for three minutes on the magnetic stirrer (5.2).

Add 50 ml of 0,3 mol/l nitric acid (4.4) and stir again. Filter in vacuo through a crucible (5.1), the bottom
of which is covered with Kieselguhr (4.6). Wash the crucible several times with the 0,3 mol/l nitric acid (4.4)
until a colourless filtrate is obtained.

Transfer the filtrate and the washing solution into a 500 ml beaker. Mix and add 25 ml of 0,15 mol/l
ferrous sulphate solution (4.8). If the filtrate turns yellow after the addition of ferrous sulphate, add 3 ml of
15 mol/l orthophosphoric acid (4.7).

Using a burette, titrate the excess ferrous sulphate with 0,02 mol/l potassium permanganate solution (4.9)
until the mixture turns pink, the colour remaining stable for one minute. Perform a blank test under the
same conditions, omitting only the test sample.

N o t e

The oxidised solution must not come into contact with rubber.

8.

Expression of results

1 ml of 0,02 mol/l potassium permanganate solution corresponds to 1,099 mg of manganese (Mn).

The percentage of manganese in the fertiliser is given by:

Mn (%) where ¼ ðxb (cid:1) xsÞ (cid:2) 0,1099 (cid:2)

V
a (cid:2) M

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Where

xb is the volume in ml of the permanganate used for the blank;

xs is the volume in ml of the permanganate used for the test sample;

V is the volume in ml of the extract solution in accordance with Methods 10.1 and 10.2;

a is the volume in ml of the aliquot portion taken from the extract;

M is the mass in g of the test sample.

Determination of molybdenum in fertiliser extracts by the gravimetric method with 8-Hydroxyquinoline

M e t h o d 10.10

1.

2.

3.

4.

4.1.

Scope

This document describes a procedure for determining molybdenum in fertiliser extracts.

Field of application

This procedure is applicable to extracts from samples of fertilisers obtained by Methods 10.1 and 10.2 for
which a declaration of molybdenum is required by Annex I E to this Regulation.

Principle

The molybdenum level

is determined by precipitation as molybdenyl oxinate under specific conditions.

Reagents

Sulphuric acid solution, approximately 1 mol/l

Carefully pour 55 ml of sulphuric acid (H2SO4, d20 = 1,84 g/ml) into a 1 litre volumetric flask containing
800 ml of water. Mix. After cooling, make up to one litre. Mix.

4.2.

Diluted ammonia solution (1: 3)

Mix 1 volume of concentrated ammonia solution (NH4OH, d20 = 0,9 g/ml) with 3 volumes of water.

4.3.

Diluted acetic acid solution (1: 3)

Mix 1 volume of concentrated acetic acid (99,7 % CH3COOH, d20 = 1,049 g/ml) with 3 volumes of water.

4.4.

Solution of disodium salt of ethylene diamine tetraacetic acid (EDTA)

Dissolve 5 g of Na2EDTA in water in a 100 ml volumetric flask. Make up to the calibration mark and mix.

4.5.

Buffer solution

In a 100 ml volumetric flask, dissolve 15 ml of concentrated acetic acid and 30 g of ammonium acetate in
water. Make up to 100 ml.

4.6.

7-Hydroxyquinoline (oxine) solution

In a 100 ml volumetric flask, dissolve 3 g of 8-Hydroxyquinoline in 5 ml of concentrated acetic acid. Add
80 ml of water. Add the ammonia solution (4.2) drop by drop until the solution becomes cloudy and then
add the acetic acid (4.3) until the solution becomes clear again.

Make up to 100 ml with water.

Apparatus

Filter crucible P16/ISO 4 793, porosity 4, capacity 30 ml

5.

5.1.

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5.2.

5.3.

6.

6.1.

7.

7.1.

pH meter with glass electrode

Drying oven at 130 to 135 °C

Preparation of the solution to be analysed

Preparation of the molybdenum solution. See Method 10.1 and Method 10.2

Procedure

Preparation of the test solution

Place an aliquot portion containing 25 to 100 mg Mo in a 250 ml beaker. Make up the volume to 50 ml
with water.

Adjust this solution to pH of 5 by adding the sulfuric acid solution (4.1) drop by drop. Add 15 ml of EDTA
solution (4.4) and then 5 ml of buffer solution (4.5). Make up to about 80 ml with water.

7.2.

Obtaining and washing the precipitate

Obtaining the precipitate

Heat the solution slightly. Stirring constantly, add the oxine solution (4.6). Continue the precipitation until
formation of a deposit is no longer observed. Add further reagent until the supernatant solution turns
slightly yellow. A quantity of 20 ml should normally be sufficient. Continue to heat the precipitate slightly
for two or three minutes.

Filtration and washing

Filter through a filter crucible (5.1). Rinse several times with 20 ml of hot water. The rinse water should
gradually become colourless indicating that oxine is not longer present.

7.3.

Weighing the precipitate

Dry the precipitate at 130 to 135 °C to constant mass (at least one hour).

Allow to cool in a desiccator and then weigh.

8.

Expression of the results

1 mg of molybdenyl oxinate, MoO2(C9H6ON)2, corresponds to 0,2305 mg Mo.

The percentage of molybdenum in the fertiliser is given by:

Mo ð%Þ ¼ X (cid:2) 0,02305 (cid:2)

V (cid:2) D
a (cid:2) M

Where

X is the mass in mg of the molybdenyl oxinate precipitate;

V is the volume in ml of the extract solution in accordance with Methods 10.1 or 10.2;

a is the volume in ml of the aliquot taken from the last dilution;

D is the dilution factor of the aliquot;

M is the mass in g of the test sample.

Determination of zinc in fertiliser extracts by atomic absorption spectrometry

M e t h o d 10.11

1.

Scope

This Method describes a procedure for determining zinc in fertiliser extracts.

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2.

3.

4.

4.1.

Field of application

This procedure is applicable to extracts from samples of fertilisers obtained by Methods 10.1 and 10.2 for
which a declaration of zinc is required by Annex I E to this Regulation.

Principle

After suitable treatment and dilution of the extracts, the zinc level
spectrometry.

is determined by atomic absorption

Reagents

Hydrochloric acid solution, about 6 mol/l

See Method 10.4 (4.1).

4.2.

Hydrochloric acid solution, about 0,5 mol/l

See Method 10.4 (4.2).

4.3.

Lanthanum salt solutions (10 g of La per litre)

See Method 10.4 (4.3).

4.4.

Zinc calibration solutions

4.4.1.

Zinc stock solution (1 000 µg/ml)

In a 1 000 ml volumetric flask, dissolve 1 g of zinc powder or flakes weighed to within 0,1 mg in 25 ml
of 6 mol/l hydrochloric acid (4.1). When completely dissolved, make up to volume with water and mix
thoroughly.

4.4.2.

Zinc working solution (100 µg/ml)

In a 200 ml volumetric flask, dilute 20 ml of the stock solution (4.4.1) in 0,5 mol/l hydrochloric acid
solution (4.2). Make up to a volume with the 0,5 mol/l hydrochloric acid solution and mix thoroughly.

5.

Apparatus

Atomic absorption spectrometer.

See Method 10.4 (5). The apparatus must be fitted with a source of lines characteristic of zinc (213,8 nm).
The spectrometer must allow background correction to be made.

6.

6.1.

Preparation of the solution to be analysed

Zinc extract solution

See Method 10.1 and/or 10.2.

6.2.

Preparation of the test solution

See Method 10.4 (6.2). The test solution must contain 10 % by volume of lanthanum salt solution (4.3).

7.

7.1.

Procedure

Preparation of the blank solution

See Method 10.4 (7.1). The blank solution must contain 10 % by volume of the lanthanum salt solution used
in 6.2.

7.2.

Preparation of the calibration solutions

See Method 10.4 (7.2). For an optimum interval of 0 to 5 µg/ml of zinc, place 0, 0,5, 1, 2, 3, 4 and 5 ml,
respectively, of the working solution (4.4.2) in a series of 100 ml volumetric flasks. Where necessary, adjust
the concentration of hydrochloric acid to bring it as close as possible to that of the test solution. Add 10 ml
of the lanthanum salt solution used in (6.2) to each volumetric flask. Make up to 100 ml with the 0,5 mol/l
hydrochloric acid solution (4.2) and mix thoroughly.

These solutions contain, respectively, 0, 0,5, 1, 2, 3, 4 and 5 µg/ml of zinc.

7.3.

Determination

See Method 10.4 (7.3). Prepare the spectrometer (5) for measurements at a wavelength of 213,8 nm.

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8.

Expression of results

See Method 10.4 (8).

The percentage of zinc in the fertiliser is given by:

Zn ð%Þ ¼ ½ðxs (cid:1) xbÞ (cid:2) V (cid:2) D(cid:3) = ðM (cid:2) 104Þ

If Method 10.3 has been used:

Zn ð%Þ ¼ ½ðxs (cid:1) xbÞ (cid:2) V (cid:2) 2D(cid:3) = ðM (cid:2) 104Þ

Where

Zn is the quantity of zinc expressed as a percentage of the fertiliser;

xs is the concentration in µg/ml of the test solution;

xb is the concentration in µg/ml of the blank solution;

V is the volume in ml of the extract solution obtained in accordance with Method 10.1 or 10.2;

D is the factor corresponding to the dilution performed in (6.2);

M is the mass in g of the test sample taken in accordance with Method 10.1 or 10.2.

Calculation of the dilution factor D:

where (a1), (a2), (a3), . . ., (ai) and (a) are successive aliquot portions and (v1), (v2), (v3), . . ., (vi) and (100)
are the volumes in ml corresponding to their respective dilutions, the dilution factor D is given by:

D ¼ ðv1=a1Þ (cid:2) ðv2=a2Þ (cid:2) ðv3=a3Þ (cid:2) ::: (cid:2) ðvi=aiÞ (cid:2) ð100=aÞ

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ANNEX V

A. LIST OF DOCUMENTS TO BE CONSULTED BY MANUFACTURERS OR THEIR REPRESENTATIVES IN
ORDER TO COMPILE A TECHNICAL FILE FOR A NEW TYPE OF FERTILISERS TO BE ADDED TO
ANNEX I OF THIS REGULATION

1. Guide to the compilation of a technical file on application to designate fertilisers ‘EC fertiliser’.

Official Journal of the European Communities, C 138 of 20.5.1994, p. 4.

2. Commission Directive 91/155/EEC of 5 March 1991 on defining and laying down the detailed arrangements for the
system of specific information relating to dangerous preparations in implementation of Article 10 of Directive
88/379/EEC.

Official Journal of the European Communities, L 76/35 of 22.3.1991, p. 35.

3. Commission Directive 93/112/EC of 10 December 1993 on amending Commission Directive 91/155/EEC defining
and laying down detailed arrangements for the system of specific information relating to dangerous preparations in
implementation of Article 10 of Council Directive 88/379/EEC.

Official Journal of the European Communities, L 314 of 16.12.1993, p. 38.

B. STANDARDS OF ACCREDITATION CONCERNING THE LABORATORIES THAT ARE COMPETENT TO
PROVIDE THE NECESSARY SERVICE FOR CHECKING COMPLIANCE OF EC FERTILISERS WITH THE
REQUIREMENTS OF THIS REGULATION AND ITS ANNEXES

1. Standard applicable at the level of the laboratories:

EN ISO/IEC 17025, General requirements for the competence of testing and calibration laboratories.

2. Standard applicable at the level of the accreditation bodies:

EN 45003, Calibration and testing laboratory accreditation system, general requirements for operation and recog-
nition.