SIST EN 13656:2020

SLOVENSKI STANDARD
oSIST prEN 13656:2019
01-oktober-2019
Tla, obdelani biološki odpadki, blato in odpadki - Razklop z zmesjo klorovodikove
kisline (HCl), dušikove(V) kisline (HNO3) in tetrafluoroborove kisline (HBF4) ali
fluorovodikove kisline (HF) za določevanje elementov
Soil, treated biowaste, sludge and waste - Digestion with a hydrochloric (HCl), nitric
(HNO3) and tetrafluoroboric (HBF4) or hydrofluoric (HF) acid mixture for subsequent
determination of elements
Ta slovenski standard je istoveten z: prEN 13656
ICS:
13.030.40 Naprave in oprema za Installations and equipment
odstranjevanje in obdelavo for waste disposal and
odpadkov treatment
oSIST prEN 13656:2019 en,fr,de
2003-01.Slovenski inštitut za standardizacijo. Razmnoževanje celote ali delov tega standarda ni dovoljeno.

---------------------- Page: 1 ----------------------
oSIST prEN 13656:2019

---------------------- Page: 2 ----------------------
oSIST prEN 13656:2019


DRAFT
EUROPEAN STANDARD
prEN 13656
NORME EUROPÉENNE

EUROPÄISCHE NORM

September 2019
ICS 13.030.40 Will supersede EN 13656:2002
English Version

Soil, treated biowaste, sludge and waste - Digestion with a
hydrochloric (HCl), nitric (HNO3) and tetrafluoroboric
(HBF4) or hydrofluoric (HF) acid mixture for subsequent
determination of elements

This draft European Standard is submitted to CEN members for enquiry. It has been drawn up by the Technical Committee
CEN/TC 444.

If this draft becomes a European Standard, CEN members are bound to comply with the CEN/CENELEC Internal Regulations
which stipulate the conditions for giving this European Standard the status of a national standard without any alteration.

This draft European Standard was established by CEN in three official versions (English, French, German). A version in any other
language made by translation under the responsibility of a CEN member into its own language and notified to the CEN-CENELEC
Management Centre has the same status as the official versions.

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

Recipients of this draft are invited to submit, with their comments, notification of any relevant patent rights of which they are
aware and to provide supporting documentation.

Warning : This document is not a European Standard. It is distributed for review and comments. It is subject to change without
notice and shall not be referred to as a European Standard.


EUROPEAN COMMITTEE FOR STANDARDIZATION
COMITÉ EUROPÉEN DE NORMALISATION

EUROPÄISCHES KOMITEE FÜR NORMUNG

CEN-CENELEC Management Centre: Rue de la Science 23, B-1040 Brussels
© 2019 CEN All rights of exploitation in any form and by any means reserved Ref. No. prEN 13656:2019 E
worldwide for CEN national Members.

---------------------- Page: 3 ----------------------
oSIST prEN 13656:2019
prEN 13656:2019 (E)
Contents Page
European foreword . 3
Introduction . 4
1 Scope . 5
2 Normative references . 5
3 Terms and definitions . 5
4 Principle . 6
5 Interferences and sources of errors . 7
5.1 General information . 7
5.2 Closed vessel system for microwave digestion . 7
6 Reagents . 7
7 Apparatus . 8
8 Procedure . 9
8.1 General . 9
8.2 Blank test . 9
8.3 Method A: Heating block digestion using HCl, HNO and HBF . 9
3 4
8.4 Method B: Microwave digestion . 10
9 Test report . 12
Annex A (normative) Calibration of the power adjustment . 13
Annex B (informative) Repeatability and reproducibility data – Method A and B1 . 14
Annex C (informative) Repeatability and reproducibility data – Method B2. 23
Bibliography. 35

2

---------------------- Page: 4 ----------------------
oSIST prEN 13656:2019
prEN 13656:2019 (E)
European foreword
This document (prEN 13656:2019) has been prepared by Technical Committee CEN/TC 444 “Test
methods for environmental testing of solid matrices”, the secretariat of which is held by NEN.
This document is currently submitted to the CEN Enquiry.
This document will supersede EN 13656:2002.
In comparison with EN 13656:2002, the following modifications have been made:
— addition of HBF as acid. For safety reasons the use of HBF is preferred over HF;
4 4
— addition of a heating block digestion procedure;
— addition of a microwave digestion procedure temperature-controlled;
— removal of the microwave digestion with semi-open vessel system.
3

---------------------- Page: 5 ----------------------
oSIST prEN 13656:2019
prEN 13656:2019 (E)
Introduction
The methods specified in this document are providing a multi-element digestion of soil, treated biowaste,
sludge and waste prior to analysis. Elements extractable by this procedure can in many instances be
described as "total", although this will be sample dependent. On the other hand, they cannot be regarded
as available for leaching, as the extraction procedure is too vigorous to represent natural processes.
This document is validated for several types of matrices as indicated in Table 1.
Table 1 — Matrices for which EN 13656 is validated
Materials used in the validation test Validated for digestion Validated for digestion
with HCl:HNO :HBF with HCl:HNO :HF
3 4 3
(see Annex B) (see Annex C)
City waste incineration ash X X
(BCR176/BCR176R)
Ink waste sludge (organic matrix) X X
Electronic industry sludge (“metallic” X X
matrix)
Sediment X
Coal fly ash X
Steel slag X
Copper slag X
City waste incineration fly ash  X
("oxidised" matrix)
City waste incineration bottom ash  X
("silicate" matrix)
Sewage sludge (BCR 146R)  X
WARNING — Persons using this document should be familiar with usual laboratory practice. Most
of the reagents used in this document are extremely corrosive and very toxic. Safety precautions
are absolutely necessary, not only due to the strong corrosive reagents employed, but also to the
high temperature and pressures employed.
The use of laboratory-grade microwave equipment with isolated and corrosion resistant safety
devices is essential. Domestic (kitchen) type microwave ovens should not be used, as corrosion by
acid vapours may compromise the function of the safety devices and prevent the microwave
magnetron from shutting off when the door is open, which could result in operator significant
hazardous exposure to microwave energy.
All procedures should be performed in a fume hood or in closed force-ventilated equipment. By
the use of strong oxidising reagents, the formation of explosive organic intermediates is possible,
especially when dealing with samples with a high organic content. Do not open pressurized
vessels before they have cooled down. Avoid contact with the chemicals and the gaseous reaction
products.
IMPORTANT — It is absolutely essential that tests conducted according to this document be
carried out by suitably trained staff. People performing the test should be informed on the specific
risks associated with the use of HBF and HF.
4
4

---------------------- Page: 6 ----------------------
oSIST prEN 13656:2019
prEN 13656:2019 (E)
1 Scope
This document specifies three methods for the digestion of soil, treated biowaste, sludge and waste by the
use of an acid mixture composed of hydrochloric (HCl), nitric (HNO ) and tetrafluoroboric (HBF ) or
3 4
hydrochloric (HCl), nitric (HNO ) and hydrofluoric (HF) acid as the digestion solution.
3
Digestion with these acids is effectively considered as a total decomposition of the sample. For a broad
range of samples the extracted analyte concentrations will reflect the total content in the sample.
This document is applicable for the following elements:
Aluminium (Al), antimony (Sb), arsenic (As), barium (Ba), beryllium (Be), cadmium (Cd), calcium (Ca),
chromium (Cr), cobalt (Co), copper (Cu), iron (Fe), lead (Pb), magnesium (Mg), manganese (Mn), mercury
(Hg), molybdenum (Mo), nickel (Ni), phosphorus (P), potassium (K), selenium (Se), silver (Ag), sodium
(Na), strontium (Sr), sulfur (S), tellurium (Te), thallium (Tl), tin (Sn), titanium (Ti), vanadium (V), and
zinc (Zn).
This document can also be applied for the digestion of other elements, provided the user has verified the
applicability.
2 Normative references
The following documents are referred to in the text in such a way that some or all of their content
constitutes requirements of this document. For dated references, only the edition cited applies. For
undated references, the latest edition of the referenced document (including any amendments) applies.
EN 15002, Characterization of waste - Preparation of test portions from the laboratory sample
EN 15934, Sludge, treated biowaste, soil and waste - Calculation of dry matter fraction after determination
of dry residue or water content
EN 16179, Sludge, treated biowaste and soil - Guidance for sample pretreatment
3 Terms and definitions
For the purposes of this document, the following terms and definitions apply.
ISO and IEC maintain terminological databases for use in standardization at the following addresses:
— IEC Electropedia: available at http://www.electropedia.org/
— ISO Online browsing platform: available at https://www.iso.org/obp
3.1
digestion
mineralization of the organic matter of a sample and dissolution of its mineral part, more or less
completely, when reacting with a reagent mixture
3.2
dry residue
dry matter expressed as a percentage by mass after drying at 105 °C ± 5 °C to the constancy of weight
3.3
laboratory sample
sample intended for laboratory inspection of testing
[SOURCE: EN ISO 11074:2015, 4.3.7]
5

---------------------- Page: 7 ----------------------
oSIST prEN 13656:2019
prEN 13656:2019 (E)
3.4
sample
portion of material selected from a larger quantity of material
3.5
test portion
quantity of material, of proper size for measurement of the concentration or other property of interest,
removed from the test sample
Note 1 to entry: The test portion may be taken from the laboratory sample directly if no preparation of sample is
required (e.g. with liquids), but usually it is taken from the prepared test sample.
Note 2 to entry: A unit or increment of proper homogeneity, size and fineness, needing no further preparation,
may be a test portion.
[SOURCE: EN ISO 11074:2015, 4.3.15]
3.6
test sample
portion of material resulting from the laboratory sample by means of an appropriate method of sample
pretreatment and having the size (volume/mass) necessary for the desired testing or analysis
[SOURCE: EN ISO 11074:2015, 4.3.16]
4 Principle
A test portion is digested according to one of the following heating procedures:
— Method A: Heating block digestion
— A: Digestion with HCl, HNO and HBF using a heating block at (105 ± 5) °C for 2 h, followed by
3 4
filtration/centrifugation.
— Method B: Microwave digestion
— B1: Digestion with HCl, HNO and HBF using a microwave with temperature-controlled
3 4
procedure in a closed vessel followed by filtration/centrifugation.
— B2: Digestion with HCl, HNO and HF using a microwave with power-controlled procedure in a
3
closed vessel followed by filtration/centrifugation.
NOTE Alternatively, microwave digestion with temperature-controlled procedure in a closed vessel can be
used, provided the user has verified the applicability.
Due to safety considerations, the digestion with HCl, HNO and HBF is strongly recommended over the
3 4
much more hazardous digestion using HCl, HNO and HF.
3
6

---------------------- Page: 8 ----------------------
oSIST prEN 13656:2019
prEN 13656:2019 (E)
5 Interferences and sources of errors
5.1 General information
The container in which the sample is delivered and stored can be a source of errors. Its material shall be
chosen according to the elements to be determined (e.g. elemental Hg can penetrate polyethylene walls
very rapidly in both directions. Glass can contaminate samples with elements that it contains: - e. g. Na, K,
Al).
Grinding or milling samples includes a risk of contamination of the sample by the environment (air, dust,
wear of milling equipment). Due to elevated temperature, losses of volatile elements/compounds are
possible.
For the determination of elements forming volatile elements/compounds (e. g. Hg, As, Pb), special care
has to be taken at sample pre-treatment.
In the case of filtration of the digested solution, it is necessary to take care that the filtration procedure
does not introduce contaminants.
Ensure that all of the test portion is brought into contact with the acid mixture in the digestion vessel.
Some elements of interest can be lost due to precipitation with ions present in the digest solution, e.g. low
soluble chlorides, fluorides and sulfates.
5.2 Closed vessel system for microwave digestion
The upper limits of mass of the test portion according to the manufacturer's specifications have to be
taken into account.
Very reactive or volatile materials that may create high pressures when heated may cause a venting of the
vessels with potential loss of sample and analytes. The complete decomposition of either carbonates, or
carbon based samples, may cause sufficient pressure to vent the vessel.
After digestion, the vessel shall be cooled to room temperature before opening.
6 Reagents
Use only acids and reagents of recognized analytical grade to avoid high blank values for subsequent
analytical measurements. Use a test blank solution throughout the procedure applying all steps with the
same amount of acids, but without a sample.
6.1 Water, e.g. deionized.
6.2 Tetrafluoroboric acid (HBF ), c(HBF ) ≈ 6 mol/l, w(HBF ) =38 % to 48 %.
4 4 4
6.3 Hydrofluoric acid (HF), c(HF) ≈ 23 mol/l; w(HF) =40 % to 45 %.
6.4 Boric acid (B(OH) ), solid.
3
6.5 Boric acid (B(OH) ) solution, e.g. 4% (m/m) solution.
3
Dissolve 40 g of boric acid (6.4) in water and dilute to 1 l of water (6.1).
6.6 Hydrochloric acid, c(HCl) ≈ 12 mol/l; w(HCl) = 35 % to 37 %.
6.7 Nitric acid, c(HNO ) ≈ 15 mol/l, w(HNO ) = 65 % to 70%.
3 3
7

---------------------- Page: 9 ----------------------
oSIST prEN 13656:2019
prEN 13656:2019 (E)
7 Apparatus
Usual laboratory apparatus. All glassware and plastics ware shall be adequately cleaned and stored in
order to avoid any contamination.
Depending on the concentration of the element of interest, particular caution shall be taken with respect
to the cleaning of the vessels.
7.1 Method A: heating block digestion
7.1.1 Digestion tube, 50 ml polypropylene tube with a screw cap from polyethylene.
The material of the tube and screw cap shall be tested in order to be sure that release of elements of
interest does not take place. Other materials and vessels with other volumes than mentioned above are
allowed to be used if suitability has been proven.
7.1.2 Temperature-controlled heating block, heating block able to heat the tube(s) to a temperature
of (105 ± 5) °C.
7.2 Method B: microwave digestion, temperature and/or power-controlled, closed vessels
7.2.1 Digestion vessel, for pressurized microwave digestion, typically of 100 ml volume, reagent-,
temperature- and pressure-resistant and capable of containing the mixture of sample and digest solution.
The vessel shall be suitable for the safe application in the temperature and pressure range applied,
capable of withstanding pressures of at least 3 000 kPa.
Digestion vessels made of modified polytetrafluoroethene (PTFE) and equipped with a safety pressure
releasing system to avoid explosion of the vessel, shall be used. The inner wall of the vessel shall be inert
and shall not release contaminations to the digest solution.
NOTE It can be necessary to periodically clean the digestion vessels with a suitable surfactant to remove
persistent deposits.
7.2.2 Microwave digestion system, temperature-controlled, corrosion resistant and well ventilated.
All electronics shall be protected against corrosion for safe operation.
Use a laboratory-grade microwave oven with temperature feedback control mechanisms.
The microwave digestion system should be able to control the temperature with an accuracy of ± 5 °C and
automatically adjust the microwave field output power within 2 s of sensing. Temperature sensors shall
be accurate to ± 2 °C, including the final reaction temperature of (175 ± 5) °C. Temperature feedback
control provides the primary performance mechanism for the method. Due to the variability in sample
matrix types and microwave digestion equipment (i.e. different vessel types and microwave designs),
control of the temperature during digestion is important for reproducible microwave heating and
comparable data.
The accuracy of the temperature measurement system should be periodically tested at an elevated
temperature according to the manufactures instructions. If the temperature deviates by more than 2 °C
from the temperature measured by an external, calibrated temperature measurement system, the
microwave temperature measurement system should be re-calibrated.
7.2.3 Microwave digestion system, power-controlled, corrosion resistant and well ventilated. All
electronics shall be protected against corrosion for safe operation.
The microwave unit should be able to provide programmable power which can be programmed to within
± 10 W of the required power. Typical units provide a nominal 600 W to 1 200 W of power. If necessary
(referring to manufactures specifications) calibration of the microwave unit has to be performed (see
Annex A).
8

---------------------- Page: 10 ----------------------
oSIST prEN 13656:2019
prEN 13656:2019 (E)
The microwave unit shall be designed in a way that guarantees homogeneous heating of the samples.
The microwave unit cavity has to be built in a way that even in case of leakage or explosion of the vessels
the safety of the operators can be guaranteed. Household instruments are not suitable for laboratory use.
The microwave unit should include a temperature and/or pressure control system.
7.3 Sample containers, plastic and glass containers are both suitable.
7.4 Filter, usually with a pore size of 0,45 µm and resistant to the employed acid mixture.
7.5 Volumetric flasks, usually of nominal capacity of 50 ml or 100 ml.
7.6 Analytical balance, with an accuracy of 1 mg or better.
8 Procedure
8.1 General
Pre-treat, if not otherwise specified, soil, sludge and biowaste samples according to EN 16179 and waste
samples according to EN 15002.
Determine the dry matter content, depending on the matrix of the sample, according to EN 15934.
Pre-treatment should include drying or grain size reduction below a particle size of 250 µm or
homogenizing by use of a high speed mixer or sonification for liquid samples.
The mass of test portion for a single digestion has to be selected in a way that:
— it is representative for the laboratory sample;
— it complies with the specifications of manufacturer of the digestion unit.
If the required representative test portion exceeds the manufacturers' specifications, the test portion
should be divided into smaller quantities and digested separately. The individual digests should be
combined prior to analysis.
8.2 Blank test
Carry out a reagent blank test digestion in parallel with the determination, using the same procedure and
the same quantities of all the reagents as in the determination, but omitting the test portion. The
laboratory should define acceptable limits.
NOTE The measurement of a blank is introduced to determine the contribution of the extracting solution,
digestion tube and filter used to the measured value.
8.3 Method A: Heating block digestion using HCl, HNO and HBF
3 4
Weigh approximately 0,2 g to 0,5 g of the dried and pre-treated test portion with an accuracy of 0,001 g
and transfer to the digestion tube (7.1.1).
The amount of the test sample depends on the amount of organic matter. The maximum amount of
organic carbon shall not exceed 0,15 g when 8 ml of HCl and HNO is used. Per additional 0,1 g organic
3
carbon (more than this 0,15 g), 1 ml of additional concentrated HNO (6.7) shall be added before the
3
digestion process is started.
If necessary, moisten the test portion with a few drops of water (6.1). Add (6,0 + 0,1) ml hydrochloric acid
(6.6) followed by (2,0 + 0,1) ml nitric acid (6.7) and (4,0 + 0,1) ml tetrafluoroboric acid (6.2). Let stand at
room temperature until any effervescence almost ceases to allow for slow oxidation of the organic matter
in the sample.
9

---------------------- Page: 11 ----------------------
oSIST prEN 13656:2019
prEN 13656:2019 (E)
Turn the screw cap gently (not very tight!) and place the digestion tube on the heating block (7.1.2) and
slowly increase the temperature to (105 ± 5) °C. Keep this temperature during 120 min.
Let the tube cool down to room temperature and add water (6.1) to the volume mark.
If a non-graduated digestion tube is used, transfer quantitatively the solution content into a suitable sized
volumetric flask and add water (6.1) to the volume mark. Alternatively, another procedure can be
applied, such that the adjustment to volume shall be carried out immediately after digestion.
If the measurement solution contains suspended particles which may clog nebulizers or interfere with an
injection of the sample into the instrument, the sample may be centrifuged or filtered (7.4).
The measurement solution is now ready for the determination of the elements of interest using
appropriate elemental analysis techniques.
8.4 Method B: Microwave digestion
8.4.1 Method B1: Digestion with HBF , HNO and HCl using microwave heating, temperature-
4 3
controlled, closed vessels
Weigh an amount between 0,2 g to 0,5 g of the dried and pre-treated test portion with an accuracy of
0,001 g and transfer it into the digestion vessel (7.2.1).
The amount of the test sample depends on the amount of organic matter. The maximum amount of
organic carbon shall not exceed 0,15 g when 8 ml of HCl and HNO is used. Per additional 0,1 g organic
3
carbon (more than this 0,15 g), 1 ml of additional concentrated HNO (6.7) shall be added before the
3
digestion process is started.
Referring to the manufacturer’s instructions, the upper limits of mass of the test portion shall be taken
into account.
If necessary, moisten the test portion with a few drops of water (6.1). Add (6,0 + 0,1) ml hydrochloric acid
(6.6) followed by (2,0 + 0,1) ml nitric acid (6.7) and (4,0+ 0,1) ml tetrafluoroboric acid (6.2).
If a vigorous reaction occurs, allow the reaction cease before capping the vessel.
Cap the digestion vessel according to the manufacturer’s instructions. Place in all positions of the
microwave carrousel (usually 6, 12, 16 or 40 positions) sample vessels. If a lower number of samples are
available compared to the vessel positions, place vessels filled with same amount of the acid mixture
without sample. This is to ensure the same microwave energy absorption occurs during each digestion
procedure. This method is an operationally defined method, designed to achieve consistent digestion of
samples by specific reaction conditions. The temperature of the digestion mixture in each vessel shall be
raised with a heating rate of approximately 10 °C/min to 15 °C/min to (175 ± 5) °C and remain at
(175 ± 5) °C for (10 ± 1) min. Cool down to room temperature.
WARNING — A too high temperature increase may cause a vigorous, exothermic reaction in the digestion
solution with high pressure increase and blow-off of the security valve. Losses of analytes are then
possible.
At the end of the microwave programme, allow the vessels to cool according to the manufacturer's
instructions before removing them from the microwave system. Cooling of the vessels may be accelerated
by internal or external cooling devices.
After reaching room temperature, check if the microwave vessels maintained their seal throughout the
digestion. Due to the wide variety of vessel designs, a single procedure is not appropriate.
Carefully uncap and vent each vessel in a well-ventilated fume hood according to the manufacturer's
instructions. Transfer quantitatively the solution content of each vessel into a suitable sized volumetric
flask and add water (6.1) to the volume mark.
Alternatively, another procedure can be applied, such that the adjustment to volume with the solid
residue still present shall be carried out immediately after digestion.
10

---------------------- Page: 12 ----------------------
oSIST prEN 13656:2019
prEN 13656:2019 (E)
If the measurement solution contains suspended particles which may clog nebulizers or interfere with an
injection of the sample into the instrument, the sample may be centrifuged or filtered (7.4).
The measurement solution is now ready for the determination of the elements of interest using
appropriate elemental analysis techniques.
8.4.2 Method B2: Digestion with HF, HNO and HCl using microwave heating, power-controlled,
3
closed vessels
Weigh an amount between 0,2 g to 0,5 g of the dried and pre-treated test portion with an accuracy of
0,001 g and transfer it into the digestion vessel (7.2.1).
The amount of the test sample depends on the amount of organic matter. The maximum amount of
organic carbon shall not exceed 0,15 g when 8 ml of HCl and HNO is used. Per additional 0,1 g organic
3
carbon (more than this 0,15 g), 1 ml of additional concentrated HNO3 (6.7) shall be added before the
digestion process is started.
Referring to the manufacturer’s instructions, the upper limits of mass of the test portion shall be taken
into account.
If necessary, moisten the test portion with a few drops of water (6.1). Add (6,0 + 0,1) ml hydrochloric acid
(6.6) followed by (2,0 + 0,1) ml nitric acid (6.7) and (2,0+ 0,1) ml hydrofluoric acid (6.3).
If a vigorous reaction occurs, allow the reaction cease before capping the vessel.
Cap the digestion vessel according to the manufacturer’s instructions. Place in all positions of the
microwave carrousel (usually 6, 12, 16 or 40 positions) sample vessels and start the digestion procedure.
The power programme (see Table 2) is intended to be used for batches of 6 samples. Commercial
available microwave units may contain more or less sample positions. In order to ensure consistant
reaction conditions in these cases the power programme has to be adjusted according to the
manufactures instructions. If a lower number of samples are available compared to the vessel positions,
place vessels filled with same amount of the acid mixture without sample. This is to ensure the same
microwave energy absorption occurs during each digestion procedure.
Table 2 — Power programme
Time Power
min W
2 250
2 0
5 250
5 400
5 500
WARNING — A too high temperature increase may cause a vigorous, exothermic reaction in the digestion
solution with high pressure increase and blow-off of the security valve. Losses of analytes are then
possible.
At the end of the microwave programme, allow the vessels to
...