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Environmental Evaluation of Stabilized and Solidified Products in Brazil: A


Review

Article  in  Materials Science Forum · August 2016


DOI: 10.4028/www.scientific.net/MSF.869.756

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Materials Science Forum Submitted: 2016-03-07
ISSN: 1662-9752, Vol. 869, pp 756-760 Accepted: 2016-06-21
doi:10.4028/www.scientific.net/MSF.869.756 Online: 2016-08-31
© 2016 Trans Tech Publications, Switzerland

Environmental Evaluation of Stabilized and Solidified Products in Brazil:


A Review
Elenize Ferreira Maciel1,a, Feliciane Andrade Brehm1,b,
Marlova Piva Kulakowski1,c, Claudio de Souza Kazmierczak 1,d
1
Engineering Post-Graduation Program, Universidade do Vale do Rio dos Sinos (UNISINOS)
Av. Unisinos, 950, 93022-000 São Leopoldo, RS, Brazil.
a
elenizefm@yahoo.com.br, bfelicianeb@unisinos.br, cmarlovak@unisinos.br,dclaudiok@unisinos.br

Keywords: solidification/stabilization (S/S), leaching, waste, new materials.

Abstract. The diversity of industrial solid waste has grown exponentially in recent years, requiring
waste management strategies focused on the reduction of associated environmental impacts. The
solidification/stabilization (S/S) technique is increasingly used in the disposal or recycling of this
waste. The Brazilian standard about the leaching of hazardous compounds in waste is being used to
evaluate S/S products in their end disposal in landfills, with no description of any protocol to
investigate performance during their life cycle, as observed when they are used as admixture to
building materials. In this context, this study describes a qualitative review of leaching methods in
use to assess S/S products in Brazil, in comparison with the main techniques adopted in other
countries.

Introduction
Solidification and stabilization were first used in the 1950’s to treat nuclear waste and, from the
1970’s on, to treat other types of waste as well [1]. Since then, these methods have been
implemented in combination, to treat industrial waste produced at large scale and sediments
contaminated with hazardous waste, for instance.
Stabilization reduces the hazard potential of a given waste, converting a contaminant into less
soluble forms, while solidification encapsulates waste in a monolithic solid with high structural
integrity [1]. The methods prevent the migration of contaminants in waste and the exposure of the
environment to these substances [2].
The solidification/stabilization technique (S/S) is seen as a promising tool to treat hazardous
substances present in industrial waste [3]. In this sense, S/S stands as an interesting indirect solution
in the disposal of waste containing heavy metals [4]. S/S is commonly chosen when a hazardous
waste is to be disposed of in an industrial landfill, or when it is considered for use as raw material in
the manufacture of a given product.
The potential danger to the environment and human health may manifest at different stages in a
product’s life cycle (manufacture, distribution, construction, use, end of life). However, it is exactly
at the end-of-life stage that these hazards become more relevant, since it is then that products pose
greater risks associated with leaching as a consequence of the effect of rainwaters, for example,
with potential risks to the environment [5].
The S/S process based on the use of Portland cement, ceramics, polymers, or glass as matrix is
often suggested as one of the best approaches to manage contaminants that may not be recycled or
whose levels are too difficult to cut down. Solubility of materials is also affected in S/S, due to the
changes in pH, the formation of insoluble chemical structures, and the encapsulation process itself
[6]. The applications of the S/S technique are quite varied, and include the treatment of waste from
the metallurgic, chemical, and petrochemical industries. The technique is also advantageous in the
environmental management of wastewater sludge and ash from biomass combustion, besides
various waste-generating processes, ranging from metal purification through galvanization and
nuclear operations [7]. Yet another interesting application of S/S is clear the development of new
materials based on the use of a given waste in combination with raw or even reused materials.

All rights reserved. No part of contents of this paper may be reproduced or transmitted in any form or by any means without the written permission of Trans
Tech Publications, www.ttp.net. (#69404665-02/09/16,22:25:51)
Materials Science Forum Vol. 869 757

The advantages of the S/S technique also manifest as benefits to the environment. The method
helps companies in their efforts to reduce environmental liabilities, to mitigate the effects associated
with final disposal, and to minimize environmental impacts inherent to the primary extraction of
raw materials from natural sites.
In spite of these benefits, the waste encapsulated by S/S in construction matrixes such as plasters,
concrete or ceramics should undergo environmental assessment based on tests like the leaching of
materials and waste. This analysis is essential, in that it helps predict the long-term release of
substances that may be potentially harmful to the environment [8]. Specifically in Brazil, the
leaching assay is described in the standard NBR 10.005 [9], which rules on the extraction of
leachate from S/S products. These are classified according to another standard, NBR 10.004 [4].
A review of the literature published in portals such as ScienceDirect and in Brazilian research
databases like the CAPES Journals afforded to conclude that there is a wide array of studies on the
leaching of stabilized and solidified materials. Table 1 presents the numbers of studies on the topic
and relevant inputs used in the search.
Table 1 – Number of studies on leaching of S/S products, as of August 2014.
Research portal Keywords Field Number of studies
searched published
Domestic Leaching AND stabilization
Title 377
(CAPES) AND solidification
Abstract,
International Leaching AND stabilization
Title, 1487
(ScienceDirect) AND solidification
Keyword
However, the search revealed that studies solely address the incorporation of industrial waste.
The most relevant papers were those by Abreu (2006), Basegio (2004), Brehm et al. (2013), Brito
(2007), Chen et al. (2011), Eighmy et al (1997), Franco (2011), Malviya (2006), Oliveira (2008),
Pinto (2005), Rosa (2001), Silveira (2007), Singhal et al. (2008), Stegemann and Buenfeld (2002),
Schaefer (2007), Silva (2007), Trezza and Ferraiuelo (2013), van Gerven et al (2002), Vollpracht
and Brameshuber (2010), Yousuf et al. (1995), as well as the studies that introduce new leaching
methodologies for S/S products, like the articles published by Conner (1990), Conner and Hoffner
(1998), Jacob (2012), Jonh and Ângulo (2003), Lunkes (2013), Shiopu et al. (2009), Sloot (1998),
Townsend et al. (2003).
In this scenario, the present study examines the leaching methods used in the evaluation of S/S
products in Brazil, from the environmental perspective. The methods are compared with the main
techniques adopted for this purpose around the world.

The Brazilian method


In Brazil, the method used to obtain the leachate from solid waste is described in the standard
NBR 10.005 [9]. The results of the leachate analysis are compared with the thresholds established
in another standard, NBR 10.004 [10]. Based on this comparison, the extracts are classified as
hazardous (Class I) or non-hazardous (Class II) waste. However, the method simulates the exposure
of materials in a landfill, given that no standard has been published specifically to test leaching of
S/S products. The standard NBR 10.005 [9] defines leaching as the process that transfers organic or
inorganic substances from solid waste to the surroundings, based on the dissolution in an extractor
medium.
The methodology and the materials prescribed in the Brazilian leaching standard [9], such as pH
of the leaching solution, shaking times, sample:liquid phase ratio, apart from the size of sample
particles, simulates a rather harsh scenario of exposure to environmental factors. For example, the
use of acetic acid may increase the solubility of mineral phases that contain metallic oxides and
carbonates. In like manner, shaking and the minute size of sample fragments may intensify the
contact of the waste with the leaching solution, lowering surface tension and, as a result, increasing
mass transfer [11].
758 21st Brazilian Conference on Materials Science and Engineering

The standard also prescribes a rather high sample:liquid phase ratio (1:20). In other words,
materials are analyzed in a quite diluted form. The run time for contact of materials with the
leaching medium is 18 h. It is known that the shorter the contact, the lower the concentration of
released constituents [12].
These factors, as prescribed in the leaching methodology used in Brazil, are associated with the
conditions observed in a landfill, when it is considered the end disposal site. However, in light of
the array of materials currently developed, these factors may not be applicable in the evaluation of
materials developed with waste as admixture.

What leaching methods used worldwide have in common with the Brazilian standard
technique
In the U.S., the leaching assays most commonly employed in products containing admixed waste
include a variety of protocols, like toxicity and extraction procedures (EP, U.S. EPA Method 1310),
leaching procedure and toxicity characteristics (TCLP U.S. EPA Method 1311), extraction assay
and multiple extraction process (MEP, U.S. Method EPA 1320), ANS 16.1 (American Nuclear
Society). In turn, the assays most used in Europe are ANC (Acid-Neutralizing Capacity), DIN
38414 (German Standard Methods), AFNOR (NF X31-211, Association Française de
Normalization), the Dutch standard column test (NEN 7343:1995, Netherlands Standardization
Institute), the Dutch availability test (NEN 7371:2004, Netherlands Standardization Institute) and
the Dutch standard tank test (NEN 7345:1995 and NEN 7375:2004, Netherlands Standardization
Institute) [7, 11, 13, 14, 15, 16]. Table 2 lists a comparison of methodologies adopted in various
countries.
Table 2 – Leaching methods most commonly used in S/S products worldwide.
Sample: liquid Sample
Country Standard Liquid medium Duration
ratio presentation
acid solution triturated
1:20 24 h
EP pH 5 (< 9.5 mm)
distilled water triturated (9.5
TCLP 1:20 18 h
pH < 5 mm)

acid solution pH 5 1:16 (first 24 h)


U.S. initial extraction
MEP (first 24 h) and and
lasting 24 h + 8 --
pH 3 (8 1:20 (8
24-h extractions
extractions) extractions)
initial 30-s
ANS 16.1 solid block
distilled water 1:10 rinsing+
(monolith)
extraction series
triturated
Germany DIN 38414 distilled water 1:10 24 h
(< 10 mm)
solid block
(monolith) or
France AFNOR distilled water 1:10 48 h
triturated (10 to
20 mm)
triturated
NEN 7343 distilled water 0.1 to 10 L/kg --
(< 4 mm)
distilled water and triturated
NEN 7371 -- 6h
acid solution pH 4 (125 μm)
Netherlands
solid block
NEN 7345 acid solution pH 4 1:5 0.25 to 64 days
(monolith)
solid block
NEN 7375 distilled water 1:5 0.25 to 64 days
(monolith)
triturated
Brazil NBR 10.005 acid solution pH 5 1:20 18 h
(9.5 mm)
Materials Science Forum Vol. 869 759

Inspection of the leaching methods presented in Table 2 reveals the differences in liquid medium
characteristics, sample:liquid phase ratio, contact span of liquid medium and sample, and physical
conditions of the sample. The Brazilian standard NBR 10.005 [9] establishes similar leaching
criteria as those prescribed in U.S. standards TCLP and EP. Interestingly, the leachate extraction
devices specified in the two standards are virtually similar. It becomes clear that most leaching tests
applied to characterize S/S products are based on the premise of landfill as end disposal site, which
requires the use of fractionated samples.
Nevertheless, few are the tests that use whole samples, like the Dutch standard NEN 7345, which
rules that samples are placed soaked in acidic distilled waster (pH 4) with nitric acid (HNO3) and a
1:5 sample-to-liquid phase ratio. The method is divided in eight stages, when the leaching solution
is replaced at regular intervals (0.25, 1, 2.25, 4, 9, 46, and 64 days) and the leached extract obtained
is vacuum-filtered in 28-μm-mesh filter paper. In turn, the NEN 7375 standard differs from NEN
7345 solely in the use of distilled water in place of acidic water.
Yet another standard that uses a monolith sample is the U.S. ANS 16.1, which rules on the S/S in
radioactive waste. Samples are kept in a tank containing distilled water (1:10). Leachates are
collected at predetermined intervals (2, 7, 24, 48, 72, 96, 120, 168, 336, 456 and 672 h, totaling 28
days), when the leaching solutions are replaced 11 times.
The methods based on a monolithic sample would be best in the evaluation of new materials
containing stabilized and solidified waste, since it affords to discover whether time influences
leaching of toxic compounds into the environment, and whether these substances are being factually
encapsulated in the construction materials matrix.

Conclusions
The results obtained in the present study underline the lack of properly conceived
methodologies, in Brazil and worldwide, to assess S/S products in the context of the environmental
sciences. Most methods currently employed address only the analysis of the leachate obtained from
the waste in question in a scenario of end disposal in a landfill. This creates the need for a critical
evaluation of the ways the Brazilian standard NBR 10.005 is adopted in S/S products. Due to the
lack of a proper standard or specific regulations, lately it has been used as a reference publication in
studies about the environmental evaluation of hazardous waste, as admixture in building materials.
An appropriate official evaluation protocol for leaching of new materials becomes essential in a
panorama of growing use of waste in the production of building materials. Such analysis framework
should enable the investigation of the environmental performance of these admixtures during use, in
addition to their ecological impact as of end disposal.

Acknowledgements
The authors thank CNPq, FINEP and CAPES for the research grants given.

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21st Brazilian Conference on Materials Science and Engineering
10.4028/www.scientific.net/MSF.869

Environmental Evaluation of Stabilized and Solidified Products in Brazil: A Review


10.4028/www.scientific.net/MSF.869.756

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