View Article Online / Journal Homepage / Table of Contents for this issue

TECHNICAL NOTE www.rsc.org/jem | Journal of Environmental Monitoring

Interpretation of standard leaching test BS EN 12457-2: is your sample

hazardous or inert?
Published on 05 October 2007. Downloaded by CASE WESTERN RESERVE UNIVERSITY on 30/10/2014 18:18:15.

Mohammad Zandi,a Nigel V. Russell,*a Robert G. J. Edyvean,a Russell J. Handb

and Philip Wardb
Received 22nd August 2007, Accepted 20th September 2007
First published as an Advance Article on the web 5th October 2007
DOI: 10.1039/b712957b

A slag sample from a lead refiner has been obtained and given to two analytical laboratories to
determine the release of trace elements from the sample according to BS EN 12457-2. Samples
analysed by one laboratory passed waste acceptance criteria, leading it to be classified as an inert
material; samples of the same material analysed by the other laboratory failed waste acceptance
criteria and were classified as hazardous. It was found that the sample preparation procedure is
the critical step in the leaching analysis and that the effects of particle size on leachability should
be taken into account when using this standard. The purpose of this paper is to open a debate on
designing a better defined standard leaching test and making current waste acceptance criteria
more flexible.

Introduction sample is not well defined in the BS EN 12457-2 leach test and
it is well known that particle size has a great impact on the
The UK produces about 335 million tonnes of waste annually. leachability of trace elements from solid matter.9 BS EN
The majority of this waste goes to landfill, while only 8% is 12457-2 only indicates that ‘‘95% of the sample particles
incinerated and 18% is recycled. It is estimated that 600 should be less than 4 mm in size’’.10 As demonstrated in this
million consumer batteries, representing 20 000 to 40 000 paper, this can lead to different interpretation by different
tonnes of waste, are disposed of every year, with each battery users and the reporting of different leaching results.
requiring 50 times more energy to produce than it generates This paper reports the results of trace element leaching from
during its working life.1 There is, however, limited recycling of a slag sample from recycling lead-acid batteries determined in
consumer batteries. Similarly, it is estimated that around 10 two different laboratories. Two analytical laboratories exam-
million lead-acid automotive batteries are scrapped in the UK ined the sample independently using BS EN 12457-2 leaching
each year;2 in this case there is a significant recycling effort, but standard. Each laboratory prepared its samples based on its
naturally some further wastes arise from the recycling that is own interpretation of the standard. Leaching results from
conducted. There is a current drive by government and society both laboratories have been compared and a method for
to minimise waste production by reducing, reusing and recy- reporting results proposed.
cling. The EU Landfill Directive promotes a decrease in land-
filling of waste.3 The aim of the directive is to decrease the
adverse affects of landfill on the environment. The UK govern- Experimental
ment has set a target of waste recycling of 75% by 2020,
Sample
however some wastes will still need to be landfilled. Standard
leaching tests, such as BS EN 12457-2, are widely used as A slag sample from a lead smelter at a lead-acid battery
indicators to estimate the release potential of hazardous and recycling facility was provided. Large lumps of the sample
toxic elements from solid waste under laboratory conditions, were stored in two sealed containers and were given to
in order to classify the examined waste for landfilling or Laboratories A and B. Laboratory A conducted the chemical
reuse.4–7 These tests are often criticised on the grounds that analysis of the sample according to BS EN 13656; analysis was
the results obtained are neither reliable nor able to be extra- performed using ICP-MS (ELAN DRC II, Perkin Elmer).
polated to the application. The lack of agreement between the Laboratory B used sodium peroxide to digest the sample and
estimates by standard leaching tests and on-site measurements analysed the digested solution by ICP-OES (ARL 3580).
are usually the result of inadequate specification of the phy- Table 1 shows the chemical composition of the slag as
sical and chemical conditions used in the test,8 or poorly determined by both laboratories.
defined leaching tests. The particle size distribution of the
Sample preparation
a
Department of Chemical and Process Engineering, The University of Laboratory A took three kilograms of the slag and crushed it
Sheffield, Mappin Street, Sheffield, UK S1 3JD. E-mail: to less than 4 mm by percussion mortar and pestle. 98% of the
n.russell@sheffield.ac.uk sample passed through a 4 mm sieve.
b
Department of Engineering Materials, The University of Sheffield,
Mappin Street, Sheffield, UK S1 3JD. E-mail: Laboratory B used a motorised pestle mill to reduce the size
n.russell@sheffield.ac.uk of the sample to less than 4 mm. Prior to performing leaching

1426 | J. Environ. Monit., 2007, 9, 1426–1429 This journal is

c The Royal Society of Chemistry 2007
 View Article Online

Table 1 Average metals content of the slag determined by two Table 2 Leaching results (mg kg 1) of slag samples determined by
independent laboratories two independent laboratories using BS EN 12457-2
1 1 1 1
Element Laboratory A/g kg Laboratory B/g kg Element Laboratory A/mg kg Laboratory B/mg kg
Al 18.00 17.07 As 4.88  0.02 o0.1
Published on 05 October 2007. Downloaded by CASE WESTERN RESERVE UNIVERSITY on 30/10/2014 18:18:15.

As 0.40 0.78 Ba 2.41  0.01 1.2  0.1

Ba 15.10 13.62 Cr o0.01 o0.1
Ca 97.10 92.52 Mo 3.85  0.09 o0.1
Cr 3.70 Not analysed Ni o0.01 o0.1
Fe 295.8 287.5 Pb 24.22  0.02 o0.5
Mg 7.92 8.97 Sb 74.36  0.43 o0.5
Na 39.8 41.1 Zn 0.16  0.01 o0.1
Pb 22.60 26.47 pH 11.90 12.35
Sb 4.40 4.11
Zn 1.70 2.15
Also, the difference between leaching rates could not be due
to their analytical methods, as the chemical composition
tests the samples were passed through a 500 mm sieve to
analyses are in good agreement. The key to explaining the
remove the dust, which was then discarded.
different leaching results lies in sample preparation. About
Leaching tests 20% of the sample prepared by Laboratory A was less than
500 mm in size. The exclusion of fine particles from the sample
Both Laboratories A and B examined their samples according by Laboratory B has resulted in a dramatic decrease in
to BS EN 12457-2, using polypropylene bottles (supplied by leachability of the trace elements from the sample. It is well
VWR International, UK) and Stuart roller mixers (SRT2, known that particle size has a great impact on the leachability
supplied by VWR International, UK). Both laboratories also of trace elements from solid matter,9 due to the effective
used 0.45 mm filters. Laboratory A used ICP-MS (ELAN increase in sample surface area to solution volume that occurs
DRC II, Perkin Elmer) and Laboratory B used ICP-OES as particle size is reduced. Also, it has been reported that more
(ARL 3580) for trace element analysis. Both laboratories trace elements leach from fine particles.11 Laboratory A
duplicated their leaching tests. reported leaching results, in particular for arsenic, antimony
and lead, that would mean the sample would fail to meet waste
acceptance criteria (Table 3).12 Contrary to this, Laboratory B
Results and discussion
reported that the sample would pass waste acceptance criteria,
Both laboratories analysed the leachates for trace elements of leading it to be classified as inert, based on the results exclud-
environmental concern according to BS EN 12457-2 guide- ing the o500 mm dust.
lines. The leachant (deionised water) and product of the blank In order to investigate if the inclusion of the dust would
leaching test were analysed for contamination; none was change the final results reported by Laboratory B, the sample
detected during the test period by either laboratory. containing the dust produced during sample preparation was
Comparison between chemical analyses carried out by both analysed by Laboratory B (Table 3). The results changed
laboratories (Table 1) indicated that although each laboratory dramatically. This time, Laboratory B classified the sample
used its own analytical method, the results are in good as hazardous and the results were more comparable to the
agreement and comparable. The results for the leaching tests results of Laboratory A, although Laboratory A reported
however, are not (Table 2), despite both laboratories following higher leaching rates for lead. The element of major concern
the same standard procedure. Each step in the leaching was antimony, and this is the subject of further work.
analysis carried out by the laboratories was verified in order It can be seen that the sample preparation procedure is a
to find the source of deviation in the final results. First, the pH critical step in determining leachability of trace elements from
of the leachates was measured (Table 2) and found to be solid waste materials. Sample preparation method and particle
comparable. Therefore, the difference between leaching rates size distribution should be included in the analytical report
could not be due to the effects of pH.7 produced by the laboratory as the mobility of trace elements

Table 3 Leaching results reported by two laboratories compared to waste acceptance criteria

Waste acceptance criteria

Laboratory B Laboratory B
Inert Non- hazardous Hazardous Laboratory A Sample 4–0.5 mm Sample o4 mm
Element omg kg 1
omg kg 1 omg kg 1 mg kg 1 mg kg 1 mg kg 1
As 0.5 2 25 4.88 o0.1 4.3
Ba 20 100 300 2.41 1.2 3.8
Cr 0.5 10 70 o0.01 o0.1 o0.1
Mo 0.5 10 30 3.85 o0.1 o0.1
Ni 0.4 10 40 o0.01 o0.1 o0.1
Pb 0.5 10 50 24.22 o0.5 1.6
Sb 0.06 0.7 5 74.36 o0.5 96.4
Zn 4 50 200 0.16 o0.1 0.4
Classification Hazardous Inert Hazardous

This journal is
c The Royal Society of Chemistry 2007 J. Environ. Monit., 2007, 9, 1426–1429 | 1427
 View Article Online

Table 4 Example of a proposed analytical report for leaching results obtained. Final waste classification depends strongly on sample preparation
step and particle size distribution. In addition to leaching rates, this information also should be part of the final report
Published on 05 October 2007. Downloaded by CASE WESTERN RESERVE UNIVERSITY on 30/10/2014 18:18:15.

from the sample can be affected by particle size (Table 4). This Directive, whilst results from the other showed the material to
indicates that there is a need for better definition of sample be hazardous. The effects of particle size, particularly the dust
preparation in BS EN 12457-2 in order to reduce disagree- fraction, should be taken into account when reporting results
ments in leaching results reported by different users. Different using BS EN 12457-2, and on this basis, BS EN 12457-2, in its
interpretations can lead to reporting different leaching results, current form, is not fit for purpose. A template for reporting
and hence classification of the sample into different categories. leaching analysis has been proposed in this study and it is
It is notable that leaching tests, such as the product consis- hoped that the standard will be revised to take better account
tency test (PCT), developed for use in the US nuclear waste of particle size.
industry, specifies the particle size fraction to ensure that this
problem does not arise.13
References
1 DEFRA, Estimated total annual waste arising by sector 2004,
Conclusions Department for Environment, Food and Rural Affairs, http://
www.defra.gov.uk/environment/statistics/waste/kf/wrkf02.htm,
In this study, a slag sample from a lead refiner has been UK, 2007.
2 DEFRA, Progress with various waste streams, Department for
obtained and given to two independent analytical laboratories Environment, Food and Rural Affairs, p. 110, http://www.defra.-
to determine the trace element release according to standard gov.uk/environment/waste/strategy/, UK, 2007.
method BS EN 12457-2. Since this standard does not clearly 3 EUROPA, Council Directive 1999/31/EC of 26 April 1999 on the
define the sample size distribution to be used, interpretation landfill of waste, The European Commission, http://ec.europa.eu/
environment/waste/landfill_index.htm, Brussels, Belgium, 2007.
led to one laboratory classifying the material as inert, accord- 4 E. Egemen and C. Yurtri, Regulatory leaching tests for fly ash:
ing to waste acceptance criteria, as defined by the EU Landfill A case study, Waste Manage. Res., 1996, 14, 43–50.

1428 | J. Environ. Monit., 2007, 9, 1426–1429 This journal is

c The Royal Society of Chemistry 2007
 View Article Online

5 A. Baba and A. Kaya, Leaching characteristics of solid for environmental risk assessment, Sci. Total Environ., 1996, 178,
wastes from thermal power plants of western Turkey and compar- 133–139.
ison of toxicity methodologies, J. Environ. Manage., 2004, 73, 10 BS EN 12457-2, Characterisation of Waste–Leaching–Compliance
199–207. test for leaching of granular waste materials and sludges, British
6 A. Ghosh, M. Mukiibi and W. Ela, TCLP underestimates leaching Standard, UK, 2002.
Published on 05 October 2007. Downloaded by CASE WESTERN RESERVE UNIVERSITY on 30/10/2014 18:18:15.

of arsenic from solid residuals under landfill conditions, Environ. 11 M. Zandi, N. V. Russell, R. G. Edyvean, R. J. Hand and P. Ward,
Sci. Technol., 2004, 38, 4677–4682. Effects of particle size on the leachability of trace elements,
7 M. Zandi and N. V. Russell, Design of a leaching test framework Proceedings of the International Conference on Coal Science and
for coal fly ash accounting for environmental conditions, Environ. Technology, Nottingham, UK, August 2007.
Monit. Assess., 2007, 131, 509–526. 12 UK Landfill Directive, Department for Environment, Food and
8 R. D. Jones, The leaching of major and trace elements from coal ash. Rural Affairs, http://www.defra.gov.uk/environment/waste/topics/
Environmental aspects of trace elements in coal, ed. D. J. Swaine landfill-dir/, UK, 2007.
and F. Goodarzi, Kluwer Academic Publishers, the Netherlands, 13 C. M. Jantzen, N. E. Bibler, D. C. Beam and W. G. Ramsey,
1995, p. 221. Nuclear waste glass product consistency test (PCT)—version 7.0
9 Ph. Quevauviller, H. A. van der Sloot, A. Ure, H. Muntau, A. (U), available from http://www.osti.gov/bridge/servlets/purl/
Gomez and G. Rauret, Harmonization of leaching/extraction tests 10176796-8GjPtv/native/10176796.PDF, 1994.

This journal is
c The Royal Society of Chemistry 2007 J. Environ. Monit., 2007, 9, 1426–1429 | 1429