Tesis-Extraccion Metales Pesados de Lodos

Heavy metals removal from
anaerobically digested sludge
Marina Maya Marchioretto

Promotor
Prof. Dr. Ir. W. H. Rulkens
Hoogleraar in de Milieutechnologie, Wageningen Universiteit
Co-promotor
Dr. Ir. H. Bruning
Universitair docent, Sectie Milieutechnologie, Wageningen Universiteit
Samenstelling promotiecommissie
Prof. Dr. M. A. P. Reali (São Paulo Universiteit, EESC-USP, Brazilië)
Prof. Dr. W. H. van Riemsdijk (Wageningen Universiteit, Nederland)
Prof. Dr. Ir. C. J. N. Buisman (Wageningen Universiteit, Nederland)
Dr. Ir. A. H. M. Veeken (Wageningen Universiteit, Nederland)
Marina Maya Marchioretto

anaerobically digested sludge
Proefschrift
ter verkrijging van de graad van doctor
op gezag van de Rector Magnificus
van Wageningen Universiteit,
Prof. Dr. Ir. L. Speelman,
in het openbaar te verdedigen
op maandag 3 november 2003
des namiddags te 13:30 in de Aula.
Author: Marchioretto, M. M.
Title: Heavy metals removal from anaerobically digested sludge
Publication year: 2003
Thesis Wageningen University, Wageningen, the Netherlands - with summary in
Dutch and Portuguese
Keywords: anaerobically digested sludge, bioleaching, chemical leaching, heavy
metals, hydroxide precipitation, sulfide precipitation
ISBN: 90-5808-908-8
To my parents - my first instructors
To my brother - my first friend

ABSTRACT
Marchioretto, M. M. (2003). “Heavy metals removal from anaerobically

digested sludge”. Doctoral thesis, Wageningen University, the Netherlands,
142 pages.
Although studies in the field of heavy metals removal from sewage sludges
are numerous, knowledge gaps still exist, which are the reason for the low
attention paid to the implementation of techniques for this purpose. Such
techniques still remain in laboratory and pilot plant scale. This work aims to
contribute to the further applicability of technologies that might be used to
remove heavy metals from anaerobically digested sludge.
A physical classification scheme based on wet-sieving was applied and

showed that heavy metals prevailed in the fractions < 0.063 mm,
constituting 70 % of the total sludge mass and 78-85 % of the heavy metals
present in the sludge. In all the separated fractions, however, most of the
metals concentrations exceeded the Dutch standard for sludge application
on land. To determine the chemical forms of heavy metals in the sludge,
three sequential chemical extraction (SCE) schemes were tested: Tessier
(1979), Veeken (1998), and Sims & Kline (1991). Modified versions of the
original schemes were also applied as a tentative to investigate the
differences among them. Despite uncertainties, the SCE method gives useful
information concerning metals availability. The results demonstrated that Cr
(65-67 %) and Cu (65-87 %) were released in an oxidizing environment. Zinc
(78-86 %) was extracted by a reducing agent, whereas Pb was solubilized at
strong acidic conditions and high temperature. A chelating agent released
considerable amounts of Cr (56-57 %), Pb (57-78 %) and Zn (50-62 %).
About 70 % of Cu was also extracted at a pH of 12.6. The modified schemes
were valuable to interpret the differences in the results of the original
schemes.
To assess the heavy metals solubilization, several organic and inorganic

acids were tested at different conditions of pH, reaction time, and redox
potential. Oxidation with aeration or H2O2 was also investigated. The best
results achieved with the most effective acid (HCl) were: Cr: 85 % with H2O2,
Cu: 100 % with H2O2, Pb and Zn: 100 % with aeration and H2O2. Moreover,
Cu solubilization was highly influenced by oxidation. The effect of
bioleaching on heavy metals extraction, with application of elemental sulfur
and ferrous iron, was studied. The results were compared to those obtained
by chemical leaching with H2SO4 and HCl. With addition of ferrous iron, the
maximum extraction achieved for Zn was 80.8 % with a pH of 2.7. For Cu, it
was 65.5 % with a pH of 2.5. Chromium was solubilized only when the pH
was 2.5 and less than 1 % of Pb was extracted by bioleaching. HCl is more
effective than H2SO4 to solubilize all the metals studied.
After metals solubilization, the next step was the separation of the sludge
solids from the metal-rich acidic liquid (leachate) by centrifugation and
filtration. The filtered leachate was submitted to hydroxide precipitation with
NaOH and sulfide precipitation with Na2S, both separately and in
combination. Each precipitation step was followed by filtration. The results
showed that, when Fe and Al are present in the sludge (as it was the case),
adsorption and/or coprecipitation of the heavy metals to ferric or aluminium
hydroxide precipitate might occur. This was especially observed when
hydroxide precipitation was solely applied. The use of NaOH at a pH of 4-5
followed by filtration and further addition of Na2S to the filtered liquid at a
pH of 7-8 considerably decreased the dosage of the second precipitant, when
this was exclusively applied. The best removal efficiencies achieved were: Pb:
100 %, Cr: 99.9 %, Cu: 99.7 %, and Zn: 99.9 %.
Two conceptual designs of a treatment process to be applied in practice for

heavy metals removal from sewage sludge were discussed. One referred to a
physical-chemical treatment and the other to a biological-physical-chemical
treatment. In the first concept, heavy metals solubilization is achieved with
HCl and an oxidative pre-treatment with aeration or H2O2. In the second
concept, the approach is the use of the bioleaching to solubilize heavy
metals. This system consists of an aerobic bioreactor fed with So. A
biological sulfate-reducing reactor, where sulfate is converted into sulfur, is
included and a closed sulfur cycle is achieved. Based on a brief technical,
environmental and economical evaluation, the biological-physical-chemical
process seems to be more attractive than the physical-chemical process. In
further development of the process to a practical scale, attention has to be
paid to the reuse possibilities of heavy metals recovered from the sludge and
how to deal with the remaining liquid residues.
CONTENTS
Chapter 1 - General introduction 1
Chapter 2 - Sludge characterization 17
Chapter 3 - Chemical leaching of heavy metals 37
Chapter 4 - Bioleaching of heavy metals 63
Chapter 5 - Heavy metals removal from the leachate 81
Chapter 6 - General discussion 97
Chapter 7 - Summary 112

- Samenvatting 117
- Sumário 122
References 129
Acknowledgements 136
Curriculum vitae 139

Chapter 1
General introduction
Chapter 1
ORIGIN OF SEWAGE SLUDGE
Increasing urbanization and industrialization has culminated in a dramatic

growth in the volume of municipal wastewater produced worldwide. This
wastewater contains all the substances that enter in human metabolism,
such as food, beverages, pharmaceuticals, a great variety of household
chemicals and the substances discharged from trade and industry to the
sewer system (Kroiss, 2003). Moreover, rain water and its contact materials
also contribute to this composition. As a result, the constituents of the
municipal wastewater discharged into the sewer system are a mirror of our
civilization and of human and urban metabolism.
Besides the gas production (e.g., carbon dioxide and methane), municipal
wastewater treatment results in two products, which are closely related in
their chemical composition (Kroiss, 2003):
Treated wastewater to be discharged to the receiving surface water;
Wastewater sludge to be treated and disposed or reused without
creating new (environmental) problems.
The several levels of the municipal wastewater treatment are known as

preliminary, primary, advanced primary, secondary (without/with nutrient
removal), and tertiary (or advanced) treatment. The description of each
treatment level, as given by Metcalf and Eddy (2003) is shown in Table 1.1.
Table 1.1 - Levels of wastewater treatment (Metcalf and Eddy, 2003)

Treatment level Description
Preliminary Removal of rags, sticks, floatables, grit, and grease that may cause
maintenance or operational problems with the treatment system
Primary Removal of a portion of the suspended solids and organic matter by a
physical operation
Advanced primary Enhanced removal of suspended solids and organic matter. Usually
performed by chemical addition or filtration
Secondary Removal of biodegradable organic matter and suspended solids by
biological or chemical processes. Disinfection is also typically included
in the definition of conventional secondary treatment
Secondary with Removal of biodegradable organics, suspended solids, and nutrients
nutrient removal (nitrogen and/or phosphorus)
Tertiary Removal of residual suspended solids (after secondary treatment),
usually by granular medium filtration or microscreens. Disinfection
and nutrient removal are also often included
Advanced Removal of dissolved and suspended materials remaining after normal
biological treatment when required for various water reuse
applications. Usually accomplished by combined processes
2
To treat municipal wastewater streams, biological methods are usually

applied. The overall objectives of the biological treatment of domestic
wastewater are:
To transform dissolved and particulate biodegradable components into
acceptable end products;
To capture and incorporate suspended and non-settleable colloidal
solids into a biological floc or biofilm;
To remove or reduce the concentration of organic and inorganic
compounds (e.g., heavy metals);
To remove pathogens and other microorganisms;
To transform or remove nutrients, such as nitrogen and phosphorus;
In some cases, to remove specific trace organic constituents and
compounds;
To produce effluent that can be discharged to surface water.
A conventional biological treatment process, which is worldwide used in

practice to treat municipal wastewaters, is the activated sludge system (see
scheme in Figure 1.1). Such system is basically constituted of a bioreactor
in which the microorganisms responsible for the treatment are kept in
suspension and aerated.
Grid Sand First Aeration Secondary

tank settler tank settler
Influent Effluent
Secondary
Returned
Sand sludge
Coarse sludge
material Primary
sludge
Secondary
surplus sludge
Figure 1.1 - Scheme of an activated sludge system
After the preliminary and primary treatment phases, the liquid is kept in the
reactor for about 6 hours and flows into a settling tank. The biomass and
fine solids settle as sludge and the treated liquid can be discharged. The
settled sludge is partly returned to the aeration tank and the surplus
amount is mixed with the primary sludge and normally stabilized
3
Chapter 1
biologically at anaerobic conditions. This process is carried out in closed

biologic reactors, known as anaerobic digesters. Despite the relatively high
quality effluent produced by this type of system, it has the serious drawback
of excessive sludge production.
The main focus on municipal treatment over the last 30 years has been on
improving the quality of the effluent by including the construction of
secondary and advanced wastewater treatment units in the treatment plant.
As such, higher levels of treatment have been achieved not only for the
common wastewater constituents but also for the removal of specific
compounds such as nutrients and heavy metals. A by-product of these
approaches is the increased amount of sludge generated. Sludge processing,
reuse, and disposal represent the most complex problem facing the engineer
in the field of municipal wastewater treatment. Sludge treatment often
represents more than 50 % of the total costs of municipal wastewater
treatment (Rulkens 2003a).
COMPOSITION OF SEWAGE SLUDGE
The problems dealing with sewage sludge are complex because it is largely
constituted of those substances responsible for the offensive character of
untreated wastewater (Metcalf and Eddy, 2003). Besides the potentially
hazardous materials, however, sludge also contains valuable materials. To
identify potential alternatives for a sustainable treatment, it is useful to
evaluate the composition of the sludge. This composition can be roughly
characterized by five groups of components, which are present in the sludge
(Rulkens, 2003b):
Non-toxic organic carbon compounds, Kjeldahl-N, phosphorus
containing components;
Toxic pollutants:
Heavy metals, such as Zn, Pb, Cu, Cr, Ni, Cd, Hg, As (varying
from more than 1000 ppm to less than 1 ppm);
PCBs, PAHs, dioxins, pesticides, endocrine disrupters, linear-
alkyl-sulfonates, nonyl-phenols, etc.
Pathogens and other microbiological pollutants;
Inorganic compounds such as silicates, aluminates, calcium and
magnesium containing compounds;
4
Water, varying from a few percent to more than ninety five percent.
Nitrogen, phosphorus, and organic carbon containing compounds can be

considered as valuable compounds, as well as some inorganic compounds. A
sustainable treatment includes the recovery and useful reuse of the valuable
products and the minimization of the possible adverse environmental and
human impact of sewage sludge. The management of the solids and
concentrated contaminants present in the sludge is still one of the most
difficult and expensive problems in the field of wastewater engineering.
SEWAGE SLUDGE PROCESSING
The principal methods used for sludge solids processing are listed in Table
1.2 (partly adapted from Metcalf and Eddy, 2003):
Table 1.2 - Sewage sludge processing

Method Function
Thickening Volume reduction
Stabilization Removal of easy biodegradable compounds
Conditioning Improve dewaterability
Dewatering Volume reduction
Drying Volume reduction
Incineration Volume reduction, energy production
Wet oxidation Conditioning, volume reduction
Gasification Volume reduction, energy production
Pyrolysis Volume reduction, energy production
Landfill Disposal
Land application Beneficial use
Cement and bricks production Beneficial use
Conveyance and storage Solids transport and storage
Thickening, conditioning, dewatering, and drying are used primarily to

remove moisture from the sludge. These processes are important, for
example, when the sludge is to be incinerated. For avoiding any external
energy input in the incineration process, the sludge must be dewatered to a
cake solids content of at least 30-35 % (Priestley, 2001). Another example is
when the sludge is to be disposed to controlled landfills. In this case, the
5
Chapter 1
sludge volume should be minimized to reduce transport costs and dumping

areas.
Controlled landfill still continues to be used widely for the disposal of

sludges, either in sludge-only monofills or along with municipal solid waste.
The number and capacity of landfills, however, have been reduced, and new
landfill locations that attend to public and regulatory acceptance as well as
economic requirements are increasingly difficult to find. In many cases, the
easiest and least costly way of reuse of the valuable compounds of the
sludge is the application of the sludge on land for agricultural purposes.
This improves soil structure, cation-exchange capacity, water holding
capacity, water infiltration, tilth, and soil aeration. It also helps in plant
growth due to the supply of nutrients, such as nitrogen, phosphorus,
potassium, iron, zinc, manganese, etc. Moreover, the nutrients in the sludge
also substitute partially expensive chemical fertilizers. Depending on the
sludge composition, however, it might be necessary to remove undesirable
substances (e.g., heavy metals) present in the sludge before its application
as agricultural fertilizers. Nevertheless, if the beneficial use of sludge in
agriculture is not possible or feasible, other technical solutions for final
sludge disposal, such as use for landscaping, re-cultivation and landfill
disposal can be applied (Kroiss, 2003).
Anaerobic digestion is one of the oldest processes used for the stabilization
of sludges. It comprises the decomposition of organic matter and inorganic
matter (especially sulfate) in the absence of molecular oxygen. Anaerobic
digestion is mainly applied in the stabilization of concentrated sludges
resulted from the treatment of municipal and industrial wastewater. In
anaerobic digestion, part of the volatile compounds is converted into biogas
(methane), which can be applied as an energy resource either at the
wastewater treatment plant itself or elsewhere.
The biological conversion of organic matter in aerobic digestion occurs in the

presence of oxygen, usually in an open-top tank. This process is much
simpler to operate than an anaerobic digester, but no usable gas is
produced. The process is energy-intensive because of the power
requirements necessary for mixing and oxygen transfer (Metcalf and Eddy,
2003).
With respect to composting, this process involves aerobic degradation of

organic matter, as well as a potential decrease of the sludge water content.
6
In essence, the activity of microorganisms causes both an increase in

temperature, hence pathogen destruction, and a release of energy, carbon
dioxide, water, and other components. The costs are elevated when sludge is
composted, in contrast to, for example, direct application of sludges in
agriculture. However, the market and health aspects such as pathogen risk,
odor, and nutrient control often emphasize and require the demand for
alternative solutions, justifying composting as a promising stabilization
option (Coulomb and Myrope, 1997).
A common possibility for sludge volume reduction is incineration. This

process involves the total conversion of organic solids to oxidized end
products, primarily carbon dioxide, water, and ash. The major advantages
(A) and disadvantages (D) of incineration, according to Metcalf and Eddy
(2003) are:
Maximum volume reduction, decreasing disposal requirements (A);
Destruction of pathogens and toxic compounds (A);
Energy recovery potential (A);
High capital and operating cost (D);
Highly skilled operating and maintenance staffs required (D);
The residuals produced (air emissions and ash) may have adverse
environmental effects, such as green house effect (McBean et al.,
1995) (D);
Disposal of residuals, which may be classified as hazardous wastes, if
they exceed prescribed maximum pollutant concentrations (D).
In the last fifteen years, several technologies have been developed with the
objective to reuse sludge within a city. Among them, brick making sounds
attractive, due to its simple operation and marketability (Okuno and
Takahashi, 1997). The process, developed in Japan, can produce bricks
from 100 % of incinerated sludge ash without any additives, yielding the
least amount of end products. Moreover, according to Okuno and Takahashi
(1997), no heavy metals leach out from the brick, even at a rough
environment of pH levels below 3. In general, however, the supply of the
sewage bricks exceeds the demand and the production costs of the
traditional ones. As such, an alternative destination of sewage sludge is its
utilization as raw material for Portland cement production, which is being
developed in Japan also (Taruya et al., 2001). The authors defend that the
direct injection of dewatered sludge into Portland cement kilns was more
attractive than sludge incinerator ash and dried powder sludge.
7
Chapter 1
Wet oxidation, pyrolysis and gasification processes have attracted a lot of

attention as potentially attractive ways of recovering value from waste, but
these technologies are relatively new and are still for a large part under
development. In wet oxidation the organic content of sludge is oxidized in
specific reactors at high temperatures (200-300 °C) and low/high pressure
systems (30-150 bar) (Utvik and Matter, 1997). Both pyrolysis and
gasification turn wastes into energy rich fuels by heating the waste under
controlled conditions. In contrast to incineration, which fully converts the
input waste into energy and ash, these processes limit the conversion so
that combustion does not take place directly. Instead, they convert the
waste into valuable intermediates that can be further processed for
materials recycling or energy recovery (Schwager, 2001).
SEWAGE SLUDGE MANAGEMENT POLICY WORLDWIDE
Current aspects
The correct management of sewage sludge and other biodegradable wastes

requires the development of proper normative and regulations to maximize
the use of waste material and energy and minimize the impact of waste on
the environment (Spinosa and Lattarulo, 2003). Especially in the developed
countries, several attempts have been made to improve regulations that
protect public health and the environment. In addition, some of those
regulations are under review or improvement to further reduce the risks
derived from reuse practices. In the EU, the revision of the Directive
86/278/EEC on sludge land application, and the development of a Biowaste
Directive have been planned as necessary actions (Spinosa and Lattarulo,
2003). In certain cases, however, developing countries face the problem of
adapting regulations with little or no modifications. This situation is not
always feasible and acceptable, since the sludge characteristics are strongly
site-dependant (Jiménez and Spinosa, 2001).
In developing countries, wastewater treatment hardly reaches 10 % of the

volume generated, and only in a few of the existing plants, sludge treatment
is carried out. As a consequence, these countries are in a position that
allows the application of new or different strategies to reuse or dispose the
sludge, compared to those applied in developed countries. The beneficial use
8
of sludge for land application, instead the use of commercial fertilizers, is an

example of such strategy, but its development requires that the countries
execute industrial pre-treatment programs, as well as the integral
management of sludge to avoid diseases spreading (Jiménez and Spinosa,
2001).
Many countries are at many different levels of development in sludge

regulation and management. Even within countries there can be a vast
diversity of approaches, as in Brazil only 66.2 % of the country’s 170 million
population (IBGE, 2000) is connected to sewers and only 25.6 % of this
population is connected to treatment plants (SNIS, 2001). In fact, only
recently the number of wastewater treatment plants is increasing in Brazil,
and consequently the sludge production is growing. According to Santos and
Tsutiya (1997) the estimated total sludge production will be a volume of 750
dry tons per day in São Paulo state in the year 2015. The city of Jundiaí, in
São Paulo state, is an example of the environmental contrast existent in the
country. This city has installed over 95 % piped sewerage cover, and all the
sewage from 320 000 people and many industries is fully treated. A well-
developed sludge management policy intends to use all of the dewatered and
dried sludge applied in sugar cane plantations and reforested land (McCann,
2002). Moreover, the cities of Curitiba and Brasília are nowadays applying
the sludge in large scale in agriculture, whereas the sludge generated in the
metropolitan region of São Paulo is fully landfilled (Fernandes et al., 2001).
In Vietnam, large volumes of sludge generated in municipal wastewater

treatment plants from big cities such as Ho Chi Minh City and main
economic areas of the south are, so far, disposed to open field. This results
in serious problems due to the shortage of disposal capacity and leaching of
heavy metals to underground water, surface water and soil (Marchioretto et
al., 2002).
In the USA, regulatory influences on both federal and state levels have
encouraged the beneficial use of sewage sludge (biosolids). Research and
technology in the field have helped alleviate public concern regarding the
human health and environmental impacts of sludge. In addition, education
and marketing efforts have been improving public perceptions in some areas
of the USA about the beneficial use of sludge, although public acceptance
problems persist in other areas (U.S.EPA, 1999). The Part 503 Biosolids
Rule clearly defines sludge quality requirements for use or disposal and has
become a useful tool for sludge managers in marketing efforts.
9
Chapter 1
The solutions for sludge management will vary over time and regions and
economic criteria will play an important role (Kroiss, 2003). Nevertheless
experiences from all over the world should be shared to increase the
knowledge and establish certain criteria to reach a successful sludge
management program. Moreover, education and communication play an
important function in increasing public acceptance towards sludge reuse. In
addition, standardized techniques for sludge sampling and analysis need to
be established to ease the enforcement of local and international
regulations. Different aspects, like soil characteristics, economics, technical
capabilities, and health levels are issues that cannot be neglected when
developing regulations. Also, adequate monitoring and enforcement policies
are important for future management programs (Jiménez et al., 2003).
Sustainable sewage sludge treatment
Future sludge treatment should be progressively focused on an improved

efficiency and environmental sustainability of the process. In this context,
special attention must be paid to those processes that are simultaneously
concentrated upon the elimination of the risks for environment and human
health and on the recovery or beneficial use of the valuable compounds in
the sludge.
There are five basic approaches to tackle the sludge problem (Rulkens,
2003b). Such approaches are often applied in combination with each other,
particularly if the treatment process is applied in practice:
Beneficial use of organic carbon and inorganic compounds;
Recovery of phosphates from sludge for reuse;
Reduction of the total amount or volume of sludge;
Change in treatment scenario of municipal wastewater:
Centralized treatment primarily based on physical-chemical
treatment with attention to complete removal of colloidal and
suspended particles;
Decentralized sanitation applied to avoid discharge of heavy
metals and other pollutants from point sources or diffuse
sources.
Sludge quality improvement:
Prevention of discharge of pollutants to the sewer and
disconnection of the rainwater;
10
Removal of colloidal and suspended particles from the influent

as a first treatment step;
Removal of toxic organics and pathogens;
Removal of heavy metals – this thesis is primarily focused on
this issue.
REMOVAL OF HEAVY METALS FROM SEWAGE SLUDGE
Today much is known about the health effects of heavy metals. Exposure to
heavy metals has been linked with developmental retardation, various
cancers, kidney damage, and even death in some instances of exposure to
very high concentrations. Despite abundant evidence of these deleterious
health effects, exposure to heavy metals continues and may increase in
certain areas with the absence of planned policy actions. For instance,
mercury is still extensively used in gold mining in many parts of Latin
America. Arsenic, along with copper and chromium compounds, is a
common ingredient in wood preservatives. Lead is still widely used as an
additive in gasoline. Increased use of coal in the future will increase metal
exposures because coal ash contains many toxic metals and can be
breathed deeply into the lungs (Nriagu, 1996).
Heavy metals can be removed from sewage sludge by chemical leaching with
inorganic and organic acids or by bioleaching. With these methods, a
substantial reduction in heavy metal concentration can be achieved
especially in case of very strongly polluted sludges. The benefits of heavy
metals removal from this type of sludge include:
Sludge can be disposed to landfills with lower risk of heavy metals
leaching to surface and groundwater or uptake by plants;
Sludge can be used as soil improver;
Sludge can be applied with lower risk as energy source in co-
incineration. In addition, the off-gas treatment system would be less
complex than when the sludge is metal polluted;
Dewatered sludge or sludge fly ashes can be applied with lower risk as
raw material for Portland cement and bricks production.
11
Chapter 1
State of the art of the most common techniques for heavy metals
removal from sewage sludges
Basically there are three approaches (Rulkens et al., 1989) available to

reduce the concentration of heavy metals in sewage sludges. The first
approach is control of industrial sources and other point sources of
wastewater discharges to the sewer system. However, the source control
might be a difficult task, as it is very difficult to identify all these sources. In
some places, there is even the presence of illegal factories discharging their
effluents direct to the sewer. A second approach is control of diffuse sources,
for instance by using lead-free gasoline, copper-free tap water transport
systems and uncoupling rain water discharge on the sewerage system. The
third approach is the extractive removal of heavy metals from sewage sludge.
The widespread use of anaerobic digestion in the treatment of sewage

sludges in recent years underlines the importance of investigations in the
field of heavy metals removal from anaerobically digested sludges. Heavy
metals can be present in (anaerobically digested) sewage sludge in a number
of forms. They can be dissolved in the water phase either as ions, as organic
and inorganic complexes (this amount is in general negligible), precipitated
as salts or hydroxides, co-precipitated with metal oxides, adsorbed to
suspended solids, or associated with biological residues. The distribution of
the metals over these forms depends on the chemical properties of the
specific metal and on the sludge characteristics, which are determined by
pH, temperature, redox potential, and presence of complexing agents.
The choice of the most worthwhile speciation technique to determine metals

distribution is difficult. Currently, despite its limitations, sequential
chemical extraction (SCE) procedures may provide useful information
concerning the availability of the metals in the sludge. Furthermore, an
additional tool to the evaluation of metals mobility in the sludge is the
application of acidification tests, with progressive pH variations. With a
rational combination of the existing methods, it will be possible to draw
consistent conclusions about the heavy metals speciation in the sludge, so
that proper extraction technologies can be designed. But still, basic research
is necessary for the validation of extraction tests in relation to the actual
field conditions.
A treatment process to remove heavy metals from (anaerobically digested)

sludges is generally accomplished by four steps. The first treatment step
12
consists of solubilization of the heavy metals. The second step comprises the
separation of the water phase containing the mobilized heavy metals and the
sludge particles. The sludge particles are removed as a concentrated sludge
and the liquid containing the solubilized metals (leachate) is subjected to the
third treatment step, in which the heavy metals will be precipitated and
removed from the leachate in a fourth treatment step.
To promote the solubilization of heavy metals it is mainly necessary to

decrease the pH of the sludge to values around 1-2 with a previous increase
in the redox potential of the sludge, especially in the case of anaerobically
digested sludge. The combination of these two conditions will favor, for
example, the formation of soluble metal complexes, oxidizing insoluble
reduced metal forms (e.g., Cu2S) to soluble forms (e.g., CuSO4). The
solubilization step can be accomplished by means of chemical leaching and
bioleaching.
In the case of chemical leaching, a previous oxidation step might be

executed in order to raise the redox potential of the (anaerobically digested)
sludge. This can be performed by aeration or by the addition of an oxidating
agent, like H2O2 (Yoshizaki and Tomida, 2000). Then the acidification step
takes place. According to literature, several acids have been tested and the
most common are inorganic acids such as hydrochloric acid (Fytianos et al.,
1998), nitric acid (Naoum et al., 2001), sulfuric acid (Cheung, 1988), and
phosphoric acid (Yoshizaki and Tomida, 2000). Organic acids like citric and
oxalic acid (Veeken and Hamelers, 1999) are also used. Chelating agents
such as EDTA (Pérez-Cid et al., 2002) and NTA (Samanidou and Fytianos,
1990) are employed as well. Depending on the conditions that these
chemicals are applied, such as pH, redox potential, and reaction time, high
heavy metals solubilization efficiencies can be achieved.
A promising alternative to the chemical leaching is the microbiological

leaching (bioleaching) of heavy metals, which is mediated by acidophilic
bacteria (genus Thiobacillus) able to produce acid. The acid added in the
chemical leaching process is now replaced by an electron donor addition
such as elemental sulfur or ferrous iron. Under aerobic conditions, these
components are oxidized by Thiobacillus and converted to sulfuric acid. Over
the last two decades bioleaching of heavy metals from sewage sludge has
been widely studied (e.g., Lombardi and Garcia Jr., 2002; Filali-Meknassi et
al., 2000; Sreekrishnan and Tyagi, 1996; Couillard and Mercier, 1994;
Hayes et al., 1980). Nevertheless, the application of this technique in the
13
Chapter 1
solubilization of heavy metals from sewage sludge still prevails under

laboratory and pilot plant scale. On this regard, investigations must be
carried out to elucidate the bioleaching process scale-up.
The second step in the sludge treatment aiming at heavy metals removals is
the separation of the water phase containing the mobilized heavy metals and
the sludge particles. This separation step can be accomplished in a
centrifuge, a hydrocyclone, a settler, a flotation tank or a filtration device.
The “clean” sludge particles are removed as a concentrated sludge, which,
after dewatering and pH corrections, can be landfilled, applied as soil
improver, used as raw material for Portland cement production, or even
incinerated. Moreover, it is likely that the extreme pH conditions applied
during the (bio)leaching step causes a reduction of the pathogens
organisms.
To remove the solubilized heavy metals from the acidic liquid (leachate), the
precipitation process followed by a separation step is a feasible option.
Common precipitating reagents used include alkalis such as CaO, NaOH,
NaHCO3, etc. Sulfides such as Na2S, H2S, NaHS, or FeS can be also used, as
it has been found for industrial wastewaters containing heavy metals
(Brooks, 1991). The lower solubility of the metal sulfides in the acid region
below pH value of 7 permits reduction of metal solubility to values that are
orders of magnitude lower than are attainable by hydroxide precipitation.
Nowadays, a combination of hydroxide and sulfide precipitation for optimal
metals removal is also being considered (U.S.EPA, 1998).
SCOPE AND OUTLINE OF THIS THESIS
Although numerous studies have appeared in the field of heavy metals

removal from sewage sludges, less attention has been paid to the
implementation of techniques for this purpose. Such techniques still remain
in the laboratory and pilot plant scale. The main objective of this thesis is to
gain more scientific and practical insights into the heavy metals removal
from anaerobically digested sludge, and to develop some conceptual designs
that may be applied in practice.
Chapter 2 describes the materials and main analysis procedures used in the
experimental part of the research, and shows the physical and chemical
14
characteristics of the applied sludge. The concentration of the heavy metals

present in the sludge is emphasized and legal standards for metals disposal
on land are shown and discussed. A physical classification scheme, based
on differences in the particle size of sludge is applied in order to determine
the heavy metal content of the various fractions of the sludge. An analytical
approach for determining the chemical forms of heavy metals in the sludge
based on sequential chemical extraction procedures is executed.
Chapter 3 deals with the chemical leaching process applied in the crucial
step of the sludge treatment aiming heavy metals removal: the metals
solubilization step. Moreover, the study stresses the possibility of using
chemical leaching as an applicable part of the treatment. For this aim,
several acids are tested at different conditions of pH, reaction time and
redox potential. The effect of acidification is intensively tested for liquid
samples of the sludge and briefly tested for dried and crushed sludge
samples. In addition, the influence of the chemical oxidation on the heavy
metals solubilization is also investigated by applying aeration or adding
hydrogen peroxide.
Chapter 4 evaluates the application of bioleaching in the solubilization of Cr,

Cu, Pb and Zn from anaerobically digested sludge. The aim of this chapter is
to get more comprehension concerning the practical application of
bioleaching, its advantages and shortcomings. Bioleaching using elemental
sulfur and ferrous iron as substrates is investigated and compared with
chemical leaching with sulfuric acid. Finally, there is a comparison of these
results with those of the literature and of the previous experiments with
hydrochloric acid described in Chapter 3.
Chapter 5 refers to the precipitation of heavy metals from the leachate that
is obtained after metals solubilization and separation from the sludge
particles. On the basis of literature, hydroxide precipitation with NaOH and
sulfide precipitation with Na2S are investigated here. Both precipitating
agents are applied solely and in combination.
An overall evaluation of the investigated topics is presented in Chapter 6. In

addition, the practical implementation of the sewage sludge treatment
process aiming at heavy metals removal is also discussed.
Finally, a summary of all the chapters is presented in Chapter 7.
15
Chapter 2
Sludge characterization
Abstract
The materials and main analysis procedures used in this research are described,
and the physical and chemical characteristics of the sludge are evaluated. A
physical classification scheme, based on differences in particle sizes was first
applied to determine the heavy metal content of the various size fractions of the
sludge. Metals were mostly concentrated in the fractions < 0.063 mm, but in all
the separated fractions, most of the metals concentrations exceeded the Dutch
standard (BOOM). Sequential chemical extraction (SCE) was used, starting with
Tessier (1979), followed by Veeken (1998) and Sims & Kline (1991) schemes.
Afterwards, modified versions of Tessier and Veeken schemes were applied.
Despite some bottlenecks, SCE procedures provide useful information about the
availability of the metals. The modified schemes were useful for interpretation of
the differences between the results of the original schemes. The SCE results
showed that Cr (65-67 %) and Cu (65-87 %) were effectively released in an
oxidizing environment. Zinc (78-86 %) was extracted by a reducing agent at
96 °C and pH of 2, whereas Pb (62-81 %) was solubilized in strong acidic
conditions at 150 °C in the microwave oven. A chelating agent was able to
release considerable amounts of Cr (56-57 %), Pb (57-78 %) and Zn (50-62 %).
About 70 % of Cu could be extracted with application of high pH (12.6) at 20 °C.
Part of this chapter has been published as: M.M. Marchioretto, H. Bruning, N.T.P. Loan and
W.H. Rulkens. (2002). Removal of heavy metals from anaerobically digested sludge. Water
Science and Technology 46(10): 1-8.
Chapter 2
INTRODUCTION
Digested sludge is a complex mixture of primary mineral grains and

fragments of biological and industrial materials. This mixture is held in a
matrix of bacterial fragments and organic colloids, together with secondary
precipitates of the ions released during anaerobic digestion (MacNicol and
Beckett, 1989).
The physical-chemical forms of heavy metals in solid matrices are usually

determined by a two-step approach (Veeken, 1998). In the case of sewage
sludge, it can be first physically separated into different particle-sized
fractions by a wet-sieving operation, after which, the organic and mineral
particles in one size class can be separated by a water-elutriation process.
Second, the total heavy metal concentration is determined in each size class
and the sludge and its particle-sized fractions are subjected to a sequential
chemical extraction (SCE) procedure.
Physical characterization
The main components of digested sewage sludge are (MacNicol and Beckett,
1989):
Primary or detrital components:
Mineral grains of all sizes (0.002-2 mm);
Plastics, hairs, pigments, and organic residues including plant
detritus.
Secondary components:
Inorganic precipitates;
Amorphous degraded organic matter;
Together forming
Digester biomass;
the organic matrix.
Microbial detritus.
According to the mentioned authors, however, to achieve a complete

fractionation of digested sludge is a difficult task, since many of the sludge
components are coated on, or embedded in each other. In practice, to
evaluate the distribution of heavy metals between the principal constituents
of digested sewage sludge, not only the particle sizes, but also the particle
densities should be considered. Nevertheless, to find an accurate technique
to determine the distribution of heavy metals in each sludge component is
still difficult. In the case of the present work, a wet-sieving operation was
employed to separate the sludge sample into different particle-sized
18
fractions. This procedure might provide a sufficient basis for the physical
characterization of the heavy metals in the sludge.
Chemical characterization
Total concentration of heavy metals in sewage sludges indicate the extend of

contamination, but give little insight into the forms in which the metals are
present, or their potential for mobility and bioavailability after dispersal in
the environment (Lombardi and Garcia Jr., 1999; Pérez-Cid et al., 1999;
Zufiaurre et al., 1998; McBride, 1995).
An experimental approach commonly used for studying the mobility,

transport and bioavailability of metals in sludges is the use of sequential
chemical extraction (SCE) procedures (Forstner et al., 1989). Such
techniques comprise the utilization of a series of chemical extractants in a
sequence of reagents of increasing harshness. For each extraction step, a
particular chemical form of the metal is expected to dissolve. Although
varying in manipulative complexity, SCE techniques usually fractionate
metals in sludges (or soils) into more or less five extraction steps (Lake,
1987):
1. Exchangeable phase: extraction by an electrolyte solution (MgCl2, KNO3,
BaCl2 or NH4Ac) at a pH value of 7;
2. Carbonate phase: extraction at a pH value around 5, with NaAc, and HAc;
3. Reducible phase: incorporating metals absorbed by iron and manganese
oxides. Extraction is usually by an acidified reducing agent (NH2OH),
eventually coupled with HAc or HCl, at a pH value between 2-4;
4. Oxidizible phase: incorporating metals bound to organic matter and
sulfides. Hot H2O2 in an HNO3 medium (pH value of 2) is generally used;
5. Residual phase: consisting of metals held within the crystal lattices of
primary and secondary minerals. Extraction involves digestion with
mixtures of strong acids, such as HF or HNO3 and HCl.
Among SCE schemes, that developed by Tessier et al. (1979), has been
widely employed, especially in soils and sediments (Pérez-Cid et al., 1999;
Zufiaurre et al., 1998; Veeken, 1998; McGrath, 1996). Pérez-Cid et al. (1999)
compared the five-stage Tessier and the four-stage BCR (proposed by the
European Community Bureau of Reference) SCE schemes for metals
partitioning in sewage sludge and found similar extractable metal contents.
After critical evaluation of SCE with respect to the selectivity of reagents,
Veeken (1998) chose the Tessier scheme as the basis for determining the
19
Chapter 2
chemical distribution of heavy metals in biowaste. As biowaste is

largely composed of organic matter, an additional step was included to
distinguish between metals adsorbed to organic matter and metals
incorporated in organic matter.
In this way, both Tessier and Veeken SCE schemes were chosen to be
applied and compared in this research. In addition, to make the
comparisons more complete, a third SCE scheme was tested. This scheme
was proposed by Sims and Kline (1991) for soils and was used by Walter
and Cuevas (1999) in soil samples repeatedly amended with sewage sludge.
This SCE scheme was chosen due to its relatively experimental simplicity
comparing to Tessier and Veeken SCE schemes, since it is made-up of four
fractions carried out at 20 °C (except in the residual step).
Important aspects of SCE schemes

Problems associated with the application of SCE techniques in wastewater
matrices and soils include the diversity of reagents used to extract specific
metal forms, as well as the variety of extraction procedures employed
(Lombardi and Garcia Jr., 1999). As reviewed by Veeken (1998), the
disadvantages of SCE techniques include:
1. Lack of specificity: extraction reagents cannot destroy one phase without
solubilizing the other phases;
2. Absence of selectivity: extraction reagents cannot release metals bound to
one specific phase and not to other phases;
3. Readsorption: heavy metals that are solubilized by an extracting agent
can be readsorbed to the remaining solid phases;
4. Dependence on many factors, such as type of sample, size of particulates,
pH, temperature, contact time, concentration of extractant, and solid-to-
liquid ratio.
Despite uncertainties, the use of SCE procedures provides qualitative

information that may allow for the prediction of the biological and physical
chemical availability, mobilization and transport of heavy metals (Clevenger,
1990; Lake, 1987).
Scope of the study
The present chapter describes characteristics of the anaerobically digested

sludge applied in this research. In order to understand better the
contributions of the various grain size classes to the total heavy metal
20
content, the sludge was divided into different physical fractions by means of
wet sieving. The chemical distribution of some heavy metals in the sludge
was also investigated, following sequential extraction procedures used for
the evaluation of these elements in the sludge.
EXPERIMENTAL
Origin of the sludge
The sludge applied in this research originated from an anaerobic digester of

a wastewater treatment plant (WWTP) located in Schijndel, the Netherlands.
This plant has a capacity of 10 000 m3/day and receives both industrial
(about 35 %) and domestic (about 65 %) influents. The treatment is based
on a two-stage activated sludge system followed by anaerobic digestion of
the primary and secondary sludges. After digestion, the sludge is
transported to another WWTP, dewatered, mixed with other sludges,
incinerated, and disposed to a landfill. After being collected from the
anaerobic digester, the sludge used in the present work was stored at 4 °C
when not directly used.
Physical and chemical characteristics of the sludge
Table 2.1 shows some physical and chemical characteristics of the sludge
applied herein. To have insights about the applicability of this research to
other anaerobically digested sludges coming from different locations, some
characteristics of the sludge applied in this research are compared to those
of a Brazilian sludge. This sludge is produced in a WWTP located in the
Metropolitan Region of São Paulo, Barueri. This plant has a capacity of 820
800 m3/day and is similar to the Dutch WWTP in terms of mixed influent,
conventional treatment and digestion of the primary and secondary sludge.
The difference between the two WWTP’s is the final destination of the sludge.
After digestion, the Brazilian sludge is dewatered and sent directly to a
landfill. Despite this fact, both sludges are comparable in terms of dry
matter, organic matter, and COD (see Table 2.1).
21
Chapter 2
Table 2.1 - Some characteristics of the Dutch anaerobically digested sludge

and comparisons with a Brazilian sludge
Parameter Dutch sludge Brazilian sludge
- Schijndel - - Barueri -
Dry matter (g/L) 26.5 22.7
Organic matter (g/L) 14.8 12.4
Humidity (%) 97.3 c
COD (g/kg DMa) 950 1000

BOD (g/kg OMb) 0.03 c
Nkjeldahl (g/kg DMa) 71.6 c
S (g/kg DMa) 11.6 c
Sulfide (g/kg DMa) 0.9 c
P (g/kg DMa) 25.5 c
a Dry matter; b Organic matter; c Not available.
To continue with comparisons, some metals concentrations are shown in

Table 2.2. In addition, the Dutch standard for sludge disposal to agricultural
soils - BOOM (SDU, 1991) is presented. The Brazilian standard for heavy
metals disposal to agricultural land, which follows, with some exceptions,
the limits established by U.S.EPA-40 (U.S.EPA, 1993), CFR Part 503.13, is
also given. For further comparison, the proposed standard by EU
Commission is included in Table 2.2.
Table 2.2 - Some metals content of the Dutch sludge and comparisons with
the Brazilian sludge and legal standards
Element Dutch sludgea Brazilian sludge BOOM U.S.EPA-40 EU
- Schijndel - - Barueri - CFR 503.13 Commission
(mg/Kg DMb) (mg/Kg DMb) (mg/Kg DMb) (mg/Kg DMb) (mg/Kg DMb)
Al 25 660-30 500 c c c c
Ca 37 100-41 500 c c c c
Cd 2-3 40 1.25 39 2
Cr 345-495 542 75 3 000 c
Cu 745-1050 1 180 75 1 500 600

Fe 18 800-24 500 c c c c
K 5 800-7 000 c c c c
Mg 4 600-5 400 c c c c
Mn 280-420 c c c c
Na 3 700-4 700 c c c c
Ni 20-40 288 30 420 100

Pb 185-205 313 100 300 200
Zn 1 320-2 330 1 772 300 2 800 1 500
a Data from the present research; b Dry matter; c Not available.
22
Table 2.2 demonstrates that the concentrations of Cr, Cu, Pb and Zn in the
Dutch sludge are comparable to those of the Brazilian sludge. These
similarities (see Table 2.2 and Table 2.1) are of interest for the general
applicability of the results of the present research. They indicate, roughly,
that similar sewage sludge treatment methods might be applicable to
different countries.
According to Table 2.2, both sludges are exceeding the allowed limits of the
Dutch standard, which is very strict. Both sludges are also surpassing the
limits of the EU Commission standard (with exception of Ni in the Dutch
sludge). In contrast, according to U.S.EPA-40, the Dutch sludge could be
disposed to agricultural land. Comparisons among total amount of heavy
metals, however, is very general and implies that all forms of a given metal
are equally soluble (Van Herck and Vandecasteele, 2001) and exert the same
impact on the environment (Solís et al., 2002). The total heavy metals
concentration values are excellent criteria to define the extend of metals
contamination in the sludge and in the soil, when this is the final
destination of the sludge. But to forecast the ecological impact, the total
content is of little value, since it has been observed that plant metal
concentrations are not only correlated with soil total metal content (Gupta et
al., 1996). Besides the determination of the total metals concentration, a
deep investigation of the metals speciation in the sludge, emphasizing the
mobility capacity of these metals should be done.
Physical distribution of heavy metals in the sludge
To evaluate the metals distribution in the solid and liquid parts of the
sludge, centrifugation was applied to the sludge during 20 minutes at 4000
rpm and the supernatant was analysed for its heavy metal content. In
addition, experiments concerning the physical fractionation of the sludge
were performed based on wet sieving operation. The vibrating sieving system
(Retsch Labor-Siebmachine Type VIBRO) was equipped with stainless steel
sieves of mesh sizes 5.0, 1.0, 0.5, 0.2, 0.09, 0.063, 0.032, and 0.02 mm (see
scheme in Figure 2.1). The fraction collected in each sieve and the remaining
liquid (fraction smaller than 0.02 mm) was analysed for its heavy metals
content. The experiments were performed in triplicate.
23
Chapter 2
1L
sludge
5 mm
1 mm
0.5 mm
Heavy
0.2 mm
metals
0.09 mm
analysis
0.063 mm
0.032 mm
0.02 mm
< 0.02
mm
Figure 2.1 - Scheme of the sieving experiments
Sequential chemical extraction (SCE)
Three sequential chemical extraction schemes were tested in this research:

Tessier (1979), Veeken (1998), and Sims & Kline (1991). Table 2.3 shows a
resume of these three schemes. Each experiment was carried out in
duplicate. Samples of 2-g dried (103 °C) sludge (Tessier), 10-g dried (40 °C)
sludge (Veeken), 2-g dried (40 °C) sludge (Sims & Kline) were put into 250
ml polypropylene centrifuge tubes. After each extraction step, samples were
centrifuged at 4000 rpm for 30 minutes. The supernatant was analyzed for
its heavy metal content and the subnatant was washed (centrifuged) with
distilled water prior to extraction, in the proportion: 8 ml/g (Tessier), 10
ml/g (Veeken), and 25 ml (Sims & Kline). The details about the SCE
schemes, chemicals used, pH, temperature, and reaction time conditions
are presented in Table 2.3.
24
Table 2.3 - SCE schemes

Step Reagent Time and
Temperature
Exchangeable MgCl2 1M, pH= 7, 8 (v/w)a 1h - 20 °C
T
Bound to carbonates NaAcb 1M, pH= 5, 8 (v/w)a 5h - 20 °C
e
s Bound to Fe-Mn oxides NH2OH.HCl 0.04M, 20 (v/w)a, pH= 2 6h - 96 °C
s Bound to organic matter HNO3 0.02M, 3 (v/w)a, 30 % H2O2, 2h - 85 °C
i 5 (v/w)a, pH= 2, 30 % H2O2, 5 (v/w)a 3h - 85 °C
e NH4Acb 3.2M, 5 (v/w)a 30min - 20 °C
r Residual 5ml H2O, 4ml HNO3 70 %, 1ml HCl 35 %, 26min - MOe
2ml HF 48 %
Exchangeable NH4Acb 0.5M, pH= 7, 10 (v/w)a 3h - 20 °C
Bound to carbonates NaAc/HAcb 0.1M, pH= 5.5, 10 (v/w)a 5h - 20 °C
V
e Bound to Fe-Mn oxides NH2OH.HCl 0.1M, 20 (v/w)a, pH= 4 6h - 20 °C
e Bound to org-inorganic EDTA 0.1M, pH= 4.5, 20 (v/w)a 16h - 20 °C
matter
k
e Incorporated in organic HNO3 0.02M, 3(v/w)a, 30 % H2O2, 5(v/w)a, 20h - 85 °C
matter and organic-
n pH= 2, 30 % H2O2, 5 (v/w)a 30min - 20 °C
mineral aggregates
NH4 Acb 3.2M, 5 (v/w)a 4h - MOe
Residual Aqua regia - HCl : HNO3 - 3 : 1 30min - MOe
S Exchangeable KNO3 0.5 M, 12.5 (w/w)c, pH= 6.2 16h - 20 °C

Bound to organic matter NaOH 0.5 M, 12.5 (w/w)c, pH= 12.6 16h - 20 °C
&
Inorganic precipitate Na2EDTA 0.05 M, 12.5 (w/w)c, pH= 4.5 6h - 20 °C
Kd Residual HNO3 4 M, 12.5 (w/w)c, pH= 0.6 16h - 80 °C
a Liquid-to-solid ratio (v/w): v is the volume of the extractant (ml); w is the mass of the sample (g);
b Acetate; c Weight-to-weight (w/w): w is the mass of the extractant (g); w is the mass of sample (g);
d Sims & Kline; e Microwave oven.
As a second study concerning SCE, modified versions of Veeken and Tessier

schemes were applied as a tentative to investigate the causes of the
differences between both schemes. In this regard, some conditions were
slightly altered from original ones. These modifications are presented in
Table 2.4.
Table 2.4 - Modified steps of Tessier and Veeken SCE schemes

Tessier Scheme Veeken Scheme
Step Conditions Step Conditions
Bound to organic Na2EDTA 0.05M, Bound to Fe-Mn NH2OH.HCl 0.04M,
and inorganic pH= 4.5, 20 (v/w), oxides pH= 2, 20 (v/w),
matter 6h - 20°C 6h - 96 °C
(from Sims & Kline (from Tessier scheme)
scheme)
25
Chapter 2
The new extraction step included in the modified Tessier scheme was set
before the step bound to organic matter in the original version, which was
then named incorporated in organic matter and organic-mineral aggregates,
as proposed by Veeken (1998).
Analysis and apparatus
The heavy metals chosen to be studied in this research are chromium,

copper, lead, and zinc. The choice was based on the relatively high
concentration of these metals in the sludge compared to other metals such
as nickel and cadmium (as shown in Table 2.2). Moreover, the concentration
of these metals exceeds the Dutch standard (BOOM).
The heavy metals were analysed by the Inductively Coupled Plasma - Mass
Spectrometry Method (ICP-MS, Elan 6000, Perkin Elmer). Liquid samples
(resulted from the extraction experiments) for heavy metals analysis were
filtered with paper filters (Schleicher & Schuell no 595½, black ribbon, 12-25
µm), diluted 10 times with HNO3 (0.14 M), and stored at 4 °C before
analysis. Solid samples and liquid samples of the original sludge were
previously digested in the microwave (MDS-2100 CEM) with addition of aqua
regia (HCl:HNO3 - 3:1) before final dilution for ICP-MS measurement,
following the Dutch norm NEN 6465, as described by Veeken (1998).
Heavy metal extraction efficiency was calculated as the ratio between the
solubilized metal in the sludge after the extraction and the non-solubilized
metal in the sludge before the extraction.
ICP-AES (Spectro-Flame FVM04) was used to measure Al, Ca, K, Mg, Mn,
Na, and S.
BOD was determined with the Oxitop method. COD and Kjeldahl-N were
determined according to the Standard Methods. Sulfide was measured with
a Spectronic 20 Genesys.
pH was determined with Knick type 510 pH-meter. Oxidation-reduction

potential was measured with a WTW-OXI 197.
For samples agitation, a mixer Snijders Scientific was used and the samples
were centrifuged in an IEC Centra MP4.
The chemicals used in the experiments were pure for analysis (Merck).
26
RESULTS AND DISCUSSIONS
Figure 2.2 shows the proportion of heavy metals present in the supernatant
of the centrifuged sludge in relation to the total heavy metals content of the
original sludge (HM-OS). Metals are mostly present in the solid fraction of
the sludge and must be therefore dissolved in the liquid, before being
removed from the sludge.
Cr: 0.5 - 1 % HM-OS

Cu: 0.7 - 1.4 % HM-OS
Centrifugation Pb: 0.4 - 0.7 % HM-OS
Zn: 0.4 - 0.6 % HM-OS
Original
Sludge (OS)
Figure 2.2 - Heavy metals proportion present in the liquid

fraction of the sludge
The heavy metals distribution in the different size fractions of the sludge is
presented in Table 2.5. The Dutch standard for sludge disposal on
agricultural soils (BOOM, 1991) is also included, for comparison. Relative
standard deviations for triplicates were < 8 %.
Table 2.5 - Some characteristics of the anaerobically digested sludge

Fraction Contribution Organic Heavy metal content
% matter mg/kg DMa
(on DMa basis) % DMa Cr Cu Pb Zn
Original Sludge - 60 452 893 160 2 032
5.0-1.0 mm 7.0 89 122 232 52 708
1.0-0.5 mm 3.8 82 199 318 88 902
0.5-0.2 mm 5.2 64 256 389 139 1 360
0.2-0.09 mm 13.3 58 358 589 152 1 484
0.09-0.063 mm 15.7 59 447 935 166 1 903
0.063-0.032 mm 26.0 54 499 1 014 186 2 142
0.032-0.02 mm 7.0 56 568 1 172 197 2 440
< 0.02 mm 22.0 54 468 1 013 166 2 230
BOOM (1991) - - 75 75 100 300
a Dry matter.
27
Chapter 2
From Table 2.5 it is clear that heavy metals are largely concentrated in the
fractions < 0.063 mm, constituting about 70 % of the total sludge mass and
contributing 78-85 % of the heavy metals present in the sludge. MacNicol
and Beckett (1989), observed that most of the Cu and Zn present in an
anaerobic sludge were held in the particle-sized fraction > 0.04 mm. Besides
the predominance of heavy metals in the fractions < 0.063 mm of the
studied sludge, in almost all the fractions the amount of metals exceeded
the Dutch standard. This suggests that if land application is considered,
then the whole sludge has to be treated, without previous separation.
Figure 2.3 shows the extraction percentages of Cr, Cu, Pb and Zn obtained
with the three SCE schemes. To make the comparisons of the SCE schemes
more consistent, the extraction results of all experiments were recalculated
to 100 %. Differences between duplicates were within 3 %.
Tessier Scheme Veeken Scheme

100 100
Extraction (%)
80 80
60 60
40 40
20 20
0 0
Cr Cu Pb Zn Cr Cu Pb Zn
Sims & Kline Scheme Residual

100 Bound to organic matter
Extraction (%)
80 Bound to Fe-Mn oxides

60 Bound to carbonates
40 Exchangeable
20 Incorporated in organic matter
and organic-mineral aggregates
0
Bound to org-inorganic matter
Cr Cu Pb Zn
Inorganic precipitate
Figure 2.3 - Results of the three SCE schemes
According to Figure 2.3, 67 % of Cr was bound to organic matter in Tessier

scheme, 56 % bound to organic and inorganic matter in Veeken scheme and
28
57 % present as inorganic precipitate in Sims & Kline scheme. The

predominance of Cr in the organic matter fraction of the sewage sludge is in
accordance with Qiao and Ho (1996), who found about 62 % of Cr in this
fraction, based on a Tessier scheme. Also using a Tessier scheme, Zufiaurre
et al. (1998) concluded that about 40 % of Cr was present in the organic and
sulfidic fractions of a sewage sludge sample. In contrast, Pérez-Cid et al.
(1999; 1996) and Solís et al. (2002) observed that Cr was prevalent in the
residual fraction of sewage sludge samples, obtained according to the
application of Tessier and BCR schemes.
Copper was mainly found in the organic matter fraction according to the
three schemes applied. These results agree with the literature referring to
Cu speciation in sewage sludges (Solís et al., 2002; Zufiaurre et al., 1998;
Qiao and Ho, 1996). On the other hand, Pb was 81 % present in the residual
fraction of Tessier scheme, 78 % bound to organic and inorganic matter in
Veeken scheme and 58 % found as inorganic precipitate in Sims & Kline
scheme. Zufiaurre et al. (1998) observed that about 60 % of Pb was
extracted in the residual fraction of a sewage sludge sample with Tessier
scheme application.
About 79 % of Zn predominated in the fraction bound to Fe-Mn oxides in

Tessier scheme, bound to organic and inorganic matter in Veeken scheme
(51 %) and inorganic precipitate in Sims & Kline scheme (62 %). Zufiaurre et
al. (1998) and Qiao and Ho (1996) detected about 32 % of Zn also in the
fraction bound to Fe-Mn oxides of a sewage sludge sample with Tessier
scheme application. In contrast, Gupta et al. (1990), Oake et al. (1984), and
Stover et al. (1976), found that most of Zn was present in the organic
fraction of sewage sludge samples with Stover scheme application. In the
present research, it is difficult to know whether Zn was indeed extracted by
the reducing agent or by the conditions of pH and temperature applied in
Tessier scheme. This uncertainty remained when Veeken scheme was
applied. In this case, most of Zn was not extracted by the reducing agent,
since the pH and temperature conditions in this scheme were milder than
those applied in Tessier scheme.
Comparing the heavy metals behavior in all the fractions among the three
SCE schemes, the results of Veeken and Sims & Kline schemes are
consistent, although it is difficult to distinguish between what is bound to
organic and to inorganic matter in Veeken scheme. On the other hand, the
Tessier and Veeken schemes are different in several aspects. One possible
29
Chapter 2
reason for that is due to the experimental conditions (see Table 2.3)
employed in the fraction bound to Fe-Mn , such as temperature, molarity of
the chemical and pH value. Another cause might be the absence of EDTA in
the Tessier scheme.
Because Tessier and Veeken schemes gave very different results, it was
decided to slightly modify both procedures as a tentative to investigate the
causes of the differences between them. Modified steps of Tessier and
Veeken SCE schemes are present in Table 2.4. Figure 2.4 indicates the
extraction efficiency of metals for both modified versions.
Modified Tessier Scheme

100
Extraction (%)
80
60
40
Residual
20
0 Bound to Fe-Mn oxides
Cr Cu Pb Zn Bound to carbonates
Modified Veeken Scheme Exchangeable

100 Incorporated in organic matter
Extraction (%)
80 and organic-mineral aggregates

60 Bound to org-inorganic matter
40
20
0
Cr Cu Pb Zn
Figure 2.4 - Results of the modified SCE schemes
The fraction profile given in Figure 2.4 shows that the heavy metals behavior
in the two modified schemes is very similar. In both modified and original
SCE schemes the extraction percentages for heavy metals in the fractions
exchangeable and bound to carbonate of both modified schemes were
negligible. With respect to the fraction bound to Fe-Mn oxides, the extraction
percentage for Zn was relatively high in the two schemes (82.5 to 85.5 %),
while less than 12.5 % of Cr and 9 % of Pb were detected in this fraction and
the percentage for Cu was very low. These results differ highly from the
original Veeken scheme, because at a low pH value (around 2) and at a high
30
temperature (96 °C), hydroxylamine can easily reduce ferric iron to ferrous
iron and, in this way, ferric hydroxides precipitates are dissolved.
A small proportion of the metals was bound to the organic and inorganic
matter fraction, with exception of Pb. Results obtained for modified and
original Veeken schemes are very dissimilar. In the modified Veeken scheme
all the metal extraction efficiencies were lower than in the original version.
The reason might be that before the fraction bound to organic and inorganic,
almost all metals were already extracted with hydroxylamine in acidic
medium at high temperature. About 78 % of Pb was bound to organic and
inorganic matter in the original Veeken scheme and only 23 % in the
modified version. Comparing to Pb, the extraction level of Cr was even lower
(2 %) using EDTA in the modified version. Chromium and Cu were mainly
incorporated in organic matter and organic-mineral aggregates, according to
the modified schemes. The extraction percentages in the residual fraction for
both modified schemes were similar. In contrast, concerning Veeken
scheme, the extraction percentage for Pb was higher in the residual fraction
of the modified version.
The results demonstrated that the two modified schemes provided valuable
information for interpretation of the differences in the results obtained with
the application of the original schemes.
The heavy metals speciation given by the five SCE schemes applied clearly
demonstrated the uncertainty of the SCE method with respect to selectivity
and specificity, leading to difficulties in the interpretation of these results. It
is important to realize that the results of the SCE procedure are influenced
by the type of leaching solutions, as well as the conditions (pH, temperature,
contact time) and sequence in which they are applied. These observations
serve to highlight the problems inherent in attempting rigorous division of
metal species within sludge, when such species are likely to be involved in a
diversity of interactions. It seems more rational that, instead of calling a
fraction “bound to organic matter” or “bound to inorganic matter”, the type
of chemicals used would better determine a fraction designation. For
instance, when a combination of H2O2 and HNO3 are applied, this phase
could be simply named “oxidizible phase”.
In order to reinforce this idea, Table 2.6 summarizes the most relevant
percentages of the heavy metals extracted in the several fractions of the five
SCE schemes tested. This table shows that, despite the differences among
31
Chapter 2
the fractions names given by the authors of the SCE schemes, the type of
extracting agents applied to release one specific metal are very similar.
Table 2.6 - Most relevant extractions of the heavy metals obtained with the
application of the SCE schemes
Metal Extraction Temp.(°C); pH Extraction Fraction name
(%) situation
Cr 67(T) 85; 2 Oxidizing agent Bound to organic matter
64(T’); 65(V’) 85; 2 Oxidizing agent Incorporated in org. matter
and org.-mineral aggregates
56(V) 20; 4.5 Chelating agent Bound to org.-inorg. matter
57(S & K) 20; 4.5 Chelating agent Inorganic precipitate
Cu 84(T) 85; 2 Oxidizing agent Bound to organic matter
65(V); 87(T’); 77(V’) 85; 2 Oxidizing agent Incorporated in org. matter
and org.-mineral aggregates
71(S & K) 20; 12.6 High pH Bound to organic matter
Pb 81(T); 66(T’); 63(V’) 150; <1 Strong acids Residual
Zn 79(T); 83(T’) 96; 2(T, T’) Reducing agent Bound to Fe-Mn oxides
85(V’) 20; 4(V’) Reducing agent Bound to Fe-Mn oxides
T: Tessier scheme; V: Veeken scheme; S & K: Sims and Kline scheme; T’: Modified Tessier scheme;
V’: Modified Veeken scheme.
Table 2.6 shows that it is indeed easier to evaluate the SCE schemes
according to the type of chemicals used (Van Herck and Vandecasteele,
2001), associated, of course, to the experimental situations applied. The
table demonstrates that at least 50 % of Cr, Pb and Zn were extracted by
EDTA at a pH value of 4.5 and 20 °C. However, this was not the best
extracting condition for Zn, which was better released by a reducing agent at
a pH value of 2 and 96 °C. In contrast, at a pH value around 12.6 and 20 °C,
Cu was efficiently extracted. Copper was also released in an oxidizing
environment. In this case, as oxidation occurred and Cu bound (or
incorporated) to the organic fraction of the sludge was solubilized, other
reduced forms that might be present in the sludge were also oxidized, such
as Cu2S to CuSO4.
For further experiments, the selection of metal leaching agents will mainly
focus on oxidizing agents and strong acids. EDTA will not be applied,
because according to the results of the SCE schemes, the chelating agent
32
did not satisfactorily remove Cu. Moreover, it must be investigated whether

the metals extracted by EDTA (e.g., Cr, Pb, and Zn) will be also extracted by
an oxidizing agent or not. When it was included in a SCE scheme, the
chelating step always came before the oxidizing step.
In this way, the results given by the SCE procedures must be evaluated
carefully. Their interpretation is only qualitative and the selectivity of the
method is not good enough to investigate the real speciation of the metals in
the sludge (van Herck and Vandecasteele, 2001). Yet the SCE procedure
provides a way of obtaining useful information concerning the availability of
the metals. It also allows for the determination of the chemical differences
between samples and thus may indicate the differences in availability
(Clevenger, 1990). From a SCE scheme, it can be deduced whether a large
fraction of the sludge material dissolves in water or acid or whether oxidizing
or reducing conditions are necessary. This renders the SCE schemes an
important tool for predicting metals mobilization in the sludge matrix and a
complementary support in results discussions when the sludge is submitted
to further treatment aiming at heavy metal removal.
Quevauviller et al. (1996) pointed out that basic research is still necessary
for the validation of extraction tests in relation to the actual field conditions.
This research would, however, probably take a long time and a faster
validation of existing tests is required in legislation. A strategy could be, in
the short-term, to validate the existing tests required by the regulations
through interlaboratory studies and initiate a project with a broad scope,
which would, in the long-term, allow more accurate, harmonized procedures
adapted to the different purposes and matrices to be developed. Additionally,
models should be developed as a systematic approach for selecting the tests
adapted to specific case studies (Quevauviller et al., 1996). Frontline
research on NMR (nuclear magnetic resonance) might also provide further
information. It is still doubtful, however, that further research will
substantially increase the insight of the heavy metals binding to sludge.
33
Chapter 2
CONCLUSIONS
Heavy metals solubilization
The proportion of heavy metals present in the water phase of the studied
sludge is not higher than 1.5 % in relation to the total heavy metals present
in the original sludge. This leads to the conclusion that as mostly the metals
are present in the solid fraction of the sludge, they must be dissolved in the
liquid, before being removed from the sludge.
Besides the predominance of heavy metals in the fraction < 0.063 mm of the
sludge, in almost all the sized-fractions the amount of metals exceeded the
Dutch standard for heavy metals disposal on agricultural soils. This
indicates that if land application of the sludge is considered, then the full
sludge must be treated, without prior fractionation.
The results of the heavy metals speciation given by the five SCE schemes
clearly demonstrated the uncertainty of the method with respect to the
selectivity and specificity, leading to difficulties in the interpretation of these
results. The results of SCE procedures are influenced by the type of leaching
solutions, as well as the conditions (pH, temperature, contact time) and
sequence in which they are applied.
Despite some bottlenecks, the SCE procedure provides a way of obtaining

useful information concerning the availability of the metals. This renders the
SCE schemes a complementary tool for evaluating metals mobilization in the
sludge matrix and a complementary support for discussing further results
achieved with a sludge treatment technique.
The SCE results of the investigated sludge showed that Cr (65 - 67 %) and
Cu (65 - 87 %) could be effectively released in an oxidizing environment
(85 °C, pH= 2). Zinc (78 - 86 %) could be extracted by a reducing agent
(96 °C, pH= 2), whereas Pb (62 - 81 %) could be solubilized at strong acidic
conditions at high temperature (150 °C in the microwave oven).
Furthermore, a chelating agent (20 °C, pH= 4.5) was able to release
considerable amounts of Cr (56 - 57 %), Pb (57 - 78 %), and Zn (50 - 62 %).
34
About 70 % of Cu could also be extracted with application of high pH (12.6)

at 20 °C.
35
Chapter 3
Chemical leaching of
heavy metals
Abstract
This work evaluates, firstly, the chemical leaching using progressive acidification
as the most common technique applied in the study of heavy metals mobilization
in sewage sludge. Secondly, the study emphasizes the possibility of using
chemical leaching as an applicable part of the sludge treatment aiming at heavy
metals removal. Organic acids (citric and oxalic) and inorganic acids (nitric,
hydrochloric and phosphoric) were tested at different conditions of pH, reaction
time, and oxidation-reduction potential. The effect of acidification was intensively
tested for liquid samples of the sludge and briefly tested for dried and crushed
sludge samples. In addition, the influence of the chemical oxidation on the heavy
metals solubilization was also investigated by applying aeration or adding
hydrogen peroxide. The results showed that the option including chemical
oxidation with either aeration or hydrogen peroxide followed by acidification with
HCl resulted in the highest extraction yields of most heavy metals. Especially Cu
extraction was highly influenced by oxidation. The best results achieved were:
Cr: 85 % with H2O2, Cu: 100 % with H2O2, Pb: 100 % with aeration or H2O2, and
Zn: 100 % with aeration or H2O2.
Part of this chapter has been published as: M.M. Marchioretto, H. Bruning, N.T.P. Loan
and W.H. Rulkens. (2002). Removal of heavy metals from anaerobically digested sludge.
Water Science and Technology 46(10): 1-8.
Chapter 3
INTRODUCTION
Usually, in sewage sludges, heavy metals are so tightly incorporated or

absorbed in minerals and organic solids that only under extreme acidic
conditions achieved by chemical leaching or bioleaching, these metals can
be satisfactorily solubilized. It is known, however, that chemical leaching
has the drawback of high cost due to the acids addition. Despite this fact, it
is still very useful to consider chemical leaching as a practical method for
heavy metals extraction. Especially from such a complex matrix as sewage
sludge, which may contain a mixture of several heavy metals. Each metal
might behave differently from one another and, in most cases, their
solubilization occur only at high redox-potential conditions and with the
application of acidification techniques, such as chemical leaching and
bioleaching.
This work starts with an evaluation of the chemical leaching using

progressive acidification as the most common technique applied in the study
of heavy metals mobilization in sewage sludge. Second, the study
emphasizes the possibility of using chemical leaching as an applicable
technique for the sewage sludge treatment, aiming at heavy metals removal.
To be removed from the sewage sludge particles, heavy metals must be
previously released into the liquid. Then this liquid containing the
solubilized heavy metals (leachate) is separated from the sludge particles
(e.g., by centrifugation) and sent to a precipitation step. The heavy metals
are then precipitated and removed from the liquid by a physical separation
technique.
Heavy metals speciation and extraction
Because of the wide spectrum of results that can be obtained from different
extraction procedures, as observed in Chapter 2, the choice of the most
worthwhile speciation technique remains a difficult task. As such, it seems
wise to subject the sludge to both SCE (sequential chemical extraction)
procedures and single extractions with progressive acidification. With a
rational combination of these methods, it might be possible to draw more
consistent conclusions about the heavy metals profile in the sludge. This
was an important aspect for the set-up of the present research. Continuing
the study of heavy metals speciation started in Chapter 2 with SCE
38
Chemical leaching of heavy metals
schemes, chemical leaching of heavy metals based on single acidification

techniques are discussed here.
The starting point of the present research is the investigation of a

progressive acidification technique (PAT) applied for the dried and crushed
sewage sludge. The PAT comprises the progressive decrease of the initial pH
of the sludge by adding acid, followed by heavy metals analysis in the liquid
fraction. This technique can be more advantageous comparing to SCE
schemes for routine analysis of potential heavy metal availability. It can be
executed more easily and rapidly than SCE and it is not limited by fraction
definition (Rudd et al., 1988). In addition, making the sludge sample more
homogeneous by drying and crushing it before the PAT application is a
useful reference for further comparison with PAT applied to the original
sludge slurry.
Dried versus liquid sludge
Differences observed in the behavior of the liquid and dried forms of the
sludges using PAT are that metals are more readily solubilized from dried
samples (Rudd et al., 1988). In contrast, the same authors quote that the
SCE indicates that drying of the sludges effectively reduced the extractability
of fractions that are readily available in the slurry form.
Although sludges may be dewatered to have their final volume reduced

before, for instance, land disposal, it is more realistic and useful to use the
original sludge slurry for experimentation (Rudd et al., 1988). Furthermore,
the process of drying and crushing the sludge does not seem to be feasible
in real and large scale, from a practical and economical point of view. This
last point must be considered when the acidification process is applied not
only with the purpose of heavy metals speciation, but also to solubilize
heavy metals for their further removal.
Solubilization control parameters
Heavy metals can be mobilized from sludge particles by changes in pH and

ORP (oxidation-reduction potential) conditions and by complexing with
synthetic complexing agents (NTA, EDTA), inorganic complexing agents (Cl-,
NO3-, S2-, PO43-, CO32-), or with natural chelating agents such as soluble
humic substances (Samanidou and Fytianos, 1990).
39
Chapter 3
The pH is one of the most powerful parameters to control the metals transfer
from immobile solid-phase forms to more mobile, and therefore more
bioavailable, solution-phase forms. This parameter influences adsorption
equilibria, the stability of organomineral complexes and ORP (Lake, 1987).
Sometimes instant heavy metals solubilization (Zn for example) can be
achieved by merely lowering the pH (Tyagi et al., 1988). Hayes et al. (1980),
however, observed that a low pH value is not always enough to promote a
satisfactory metals release from anaerobic sludge particles to the liquid,
unless acidification is preceded by a rise in the sludge ORP. The ORP of the
anaerobic sludge can be raised either by means of biological (see Chapter 4)
or chemical oxidation, which can be achieved through aerobic conditions.
Chemical oxidation can also occur by addition of an oxidizing agent like
hydrogen peroxide. Under reducing conditions, which prevail in anaerobic
digestion, extremely insoluble metal sulfides are formed (Couillard and Zhu,
1992). Chemical oxidation applied before acidification increases the ORP of
the sludge, promoting the oxidation of the non-soluble metal forms to crystal
forms that would be dissolved at low pH. Particularly when hydrogen
peroxide is applied, the highly oxidizing hydroxyl radicals (OH•) can be
formed, if there is enough iron present in the sludge. These reactions,
known as Fenton reactions, occur as follows (Walling, 1975):
Fe2+ + H2O2 ⇔ Fe3+ + OH- + OH• (4.1)
Fe3+ + H2O2 ⇔ Fe2+ + OOH• + H+ (4.2)
The standard oxidation potential of OH• is EOH• = -3.06 V, so application of

H2O2 can lead to locally extreme high oxidation-reduction potentials.
Scope of the study
In this chapter, the chemical leaching process was applied to assess the
mobilization of heavy metals present in the sludge and the possibility of
using chemical leaching as an applicable part of the treatment aiming at
heavy metals removal from sewage sludge. In this way, organic acids (citric
and oxalic) and inorganic acids (nitric, hydrochloric and phosphoric) were
tested at different conditions of pH, reaction time, and oxidation-reduction
potential. The effect of acidification was intensively tested for liquid samples
of the sludge and briefly tested for dried and crushed sludge samples. In
addition, the influence of the chemical oxidation on the heavy metals
solubilization was also investigated by applying aeration or adding hydrogen
40
peroxide. Although chemical leaching is an expensive process owed to the

high costs of acid addition, this technique can still be considered as a
practical step in the heavy metals removal from anaerobically digested
sludges.
EXPERIMENTAL
Anaerobically digested sludge
The origin and main characteristics of the sludge as well as the chemical
and physical distribution of heavy metals in the sludge applied in this
research are described in Chapter 2.
Analysis
The procedures and equipments for heavy metals and pH analysis are
mentioned in details in Chapter 2.
Experiments with the dried and crushed sludge: chemical leaching

using progressive acidification
Effect of leaching agents

In order to evaluate the mobilization of heavy metals in the sludge,
extraction by acids was performed. Therefore, three acids were tested
separately: nitric, oxalic and citric. As recommended by Veeken and
Hamelers (1999), oxalic and citric acids were chosen because extraction can
be performed at mildly acidic conditions and because they are
biodegradable. Nitric acid was used for comparison as it is a strong acid and
because of its oxidative character. A scheme of the experiments is shown in
Figure 3.1.
For each acid, seven bottles in duplicate containing 2-g air-dried sludge
(40 °C) were filled with 40 ml of distilled water followed by the acid addition
in such doses (see Table 3.1) to vary the pH values from 1 to 7. The bottles
were stirred continuously (125 rpm) during 30 minutes at room temperature
(20 °C) and the pH was monitored. From each bottle, two samples of 10 ml
were collected and centrifuged at 4000 rpm during 20 minutes. The
41
Chapter 3
supernatant was filtered through a paper filter and further analyzed in

duplicates for its heavy metals content.
2g air-dried sludge + 40 ml distilled water

+ Acid (nitric/citric/oxalic)
pH= 7 pH= 5 pH= 3 pH= 1

pH= 6 pH= 4 pH= 2
Figure 3.1 - Scheme of the progressive acidification experiments:

effect of leaching agents
Table 3.1 - Acid dosages applied in the progressive acidification experiments

(effect of leaching reagents)
pH Nitric acid Citric acid Oxalic acid
g/L mM/L g/L mM/L g/L mM/L
7 0.2 3.6 7.7 40 1.1 12.5
6 0.4 6 15.4 80 1.8 20
5 1.1 18 28.8 150 4.5 50
4 2.3 37 54.3 283 7.2 80
3 4.4 70 115.2 600 12.6 140
2 6.4 102 a 28.8 320
1 17.6 280 a a
aThe required dosage of citric acid (pK1= 3.14) to achieve pH= 2 was too high and was not considered.
The same explanation is given by oxalic acid (pK1= 1.23) to achieve pH= 1.
Leaching experiments as a function of time

The influence of the extraction time in the mobilization of the heavy metals
present in the sludge was checked. For that, three acids were tested: nitric,
citric and hydrochloric. Oxalic acid was no longer applied because according
to the experiments concerning the effect of leaching agents, oxalic acid
appeared to be not an effective extracting agent. Thus, for each acid, three
bottles in duplicate containing 7-g air-dried sludge (40 °C) were filled with
140 ml of distilled water and the pH was settled to 3 (for the three acids), 2
and 1 (for nitric and hydrochloric acids) (see applied dosages in Table 3.2).
Samples in duplicate were collected from each bottle after 30 minutes, 2
42
hours, 6 hours, 1 day, 5 days, and 7 days. The experiments and sampling
were accomplished following the same procedure applied in the previous
section. A scheme of these experiments is shown in Figure 3.2.
7g air-dried sludge + 140 ml distilled water

+ Acid
Acids
Nitric
Hydrochloric Citric
pH= 1 pH= 3 pH= 3
pH= 2
Figure 3.2 - Scheme of the progressive acidification experiments:

effect of leaching time
Table 3.2 - Acid dosages applied in the progressive acidification experiments

(effect of leaching time)
pH Nitric acid Hydrochloric acid Citric acid
g/L mM/L g/L mM/L g/L mM/L
3 4.4 70 3.3 90 115.2 600
2 6.4 102 6.8 187 a
1 17.7 280 11.7 320

a The required dosage of citric acid (pK1= 3.14) to achieve pH= 2 was too high and was not considered.
After carrying out experiments with dried and crushed sludge samples, and
choosing the most effective situation in terms of leaching results, the next
step was to apply this situation to the original liquid sludge sample and
compare the results. On this basis, the next experiments were set up.
Experiments with the liquid sludge: effect of oxidation with aeration
Aeration influence on heavy metals extraction

Five bottles in duplicate filled with 150 ml of the original sludge were
submitted to five different experimental situations, at 20 °C (see scheme in
Figure 3.3). Aeration before and after acidification, simultaneous aeration
and acidification, only aeration and only acidification were the conditions
studied. Aeration and acidification with 13.9 g/L (380 mM/L) of HCl (to
43
Chapter 3
achieve a pH value of 1) were both applied during 24 hours with continuous

agitation (125 rpm). In the situation with simultaneous application, the total
experimental time was 24 hours. The sampling procedure was identical to
that followed in the former section.
HCl (pH= 1)
Air
a: only aeration
b: aeration before
acidification
c: aeration after
acidification
d: simultaneous aeration
°° ° °° ° °° ° °° °
°° °° °° °° °° °° °° °° and acidification
a b c d e e: only acidification
Figure 3.3 - Scheme of the experiments with different situations of

aeration and acidification
Effect of acidification time and aeration on heavy metals solubilization

To assess the most effective acidification time on metals solubilization and
the influence of aeration on that, these experiments were carried out. Two
bottles in duplicate filled with 150 ml of the original sludge were submitted
to acidification during 24 hours with HCl at a pH value of 1 with continuous
shaking (125 rpm) at room temperature (20 °C). One of the bottles was
aerated during 24 hours before aeration, as this was the best condition
found in the previous experiments. The acidification time was varied at 30
minutes, 5 hours, 1 day, 4 days, and 8 days. The sampling procedure was
the same applied in the former section.
Effect of aeration time and acidification time on heavy metals solubilization

These experiments were accomplished to investigate the best combination of
aeration and acidification regarding the application time. A scheme is shown
in Figure 3.4.
Five bottles in duplicate filled with 150 ml of the original sludge were
aerated during 0, 3, 5, 9, and 24 hours. Then the bottles were acidified
during 0.5, 2, 5, and 24 hours with HCl (pH= 1). Aeration and acidification
were carried out with continuous shaking (125 rpm) at 20 °C. The sampling
procedure was identical to that of the former section.
44
0.5 h
Air 2h
HCl
5h
(pH= 1)
24 h
°° ° °° ° °° ° °° °
°° °° °° °° °° °° °° °°
Aeration Aeration Aeration Aeration No

(24 h) (9 h) (5 h) (3 h) aeration
Figure 3.4 - Scheme of the experiments with aeration and

acidification time variations
Experiments with the liquid sludge: effect of oxidation with H2O2
Effect of H2O2 dosage on heavy metals extraction

The influence of H2O2 was studied to verify whether its effect on heavy
metals extraction would be higher than the aeration effect or not (see
scheme in Figure 3.5).
HCl 1 H3PO4
pH= 3/pH= 4 pH= 3/pH= 4
2 hours 2 hours
H2O2 2 H2O2
24 hours 24 hours
1.6 8.0 1.6 8.0

g/L 4.8 H 2O 2 g/L 4.8
g/L g/L
g/L dosages g/L
HCl 3 H3PO4
pH= 1.6 pH= 1.6
24 hours 24 hours
Figure 3.5 - Scheme of the several steps of the experiments with

H2O2 dosage variation
45
Chapter 3
In this way, H2O2 dosage was varied according to the concentration of iron
present in the sludge to have the ideal proportion of Fe:H2O2 necessary for
the occurrence of the Fenton reaction. According to Walling (1975), the
typical ranges are 1:5-25 - Fe:H2O2. Thus, the H2O2 dosages applied were:
1.6 g (47 mM) H2O2/L sludge (1:5 - Fe:H2O2), 4.8 g (141 mM) H2O2/L sludge
(1:15 - Fe:H2O2), and 8 g (235 mM) H2O2/L sludge (1:25 - Fe:H2O2).
After H2O2 application, the samples were kept shaking during 24 hours
(Figure 3.5).
Before the H2O2 addition, the pH value of 300 ml sludge was decreased with
HCl and H3PO4, till the values of 3 and 4, as the pH range for the Fenton
reaction is between 3-5 (Walling, 1975). The samples were kept shaking
during 2 hours. The combination of H3PO4 and H2O2 was introduced here,
following recommendation of Yoshizaki and Tomida (2000). After the
addition of H2O2 and the shaking time of 24 hours, the pH was decreased till
1.6 with both acids (lowest pH value achieved with H3PO4 in the
experiments) and the samples were kept shaking during 24 hours.
The experiments were carried out in duplicate, at 20 °C and the sampling

procedure was identical to that of the former sections (Figure 3.5). The
dosages of HCl used were: 48 mM/L (1.75 g/L) for pH= 4, 93 mM/L (3.4 g/L)
for pH= 3, and 190 mM/L (6.9 g/L) for pH= 1.6. The dosages of H3PO4 used
were: 156 mM/L (15.3 g/L) for pH= 4, 208 mM/L (20.4 g/L) for pH= 3, and
580 mM/L (56.8 g/L) for pH= 1.6.
Effect of oxidation time on heavy metals extraction

The influence of the H2O2 and the aeration application times were studied
and compared. A scheme of the experimental steps is shown in Figure 3.6.
The H2O2 application followed the same procedure of the previous

experiments. But now only the pH value of 3 was tested with HCl and H3PO4
and the H2O2 dosage was 4.8 g/L, as these were the best conditions found in
the last experiments. The oxidation times of 6 hours and 24 hours were
tested for both aeration and H2O2 application. The experiments were carried
out in duplicates, at 20 °C and the sampling procedure was identical to that
mentioned in the last section.
46
HCl/ H3PO4 Air

1 6h 24 h
pH= 3
2 hours
°°° °° °°° °°°

° °
H2O2 2 HCl/H3PO4
4.8 g/L pH= 1.6
24 hours
6h
24 h
HCl/ H3PO4 3
pH= 1.6
24 hours
Figure 3.6 - Scheme of the several steps of the experiments with

oxidation time variation
Experiments with the dried and crushed sludge: chemical leaching

using pH progressive changes
Effect of leaching agents

The effect of the pH on the heavy metals extraction with nitric acid (HNO3),
citric acid (C6H8O7), and oxalic acid (C2H2O4) are shown in Figure 3.7.
Differences between duplicates were within 3.8 %.
Figure 3.7 demonstrates that, in the presence of complexing agents such as

oxalic acid and citric acid, Cr extraction was not primarily governed by the
pH decrease. The complexing capacity of the oxalate and citrate are clearly
shown for Cr by comparing the extraction efficiency between nitric acid and
the organic acids at the same pH values. The potential of complexing agents
to form complexes with Cr (III) is consistent with the results obtained in the
SCE schemes, shown in Chapter 2.
47
Chapter 3
Cr Cu
100 100
Extraction (%) 80 80
60 60
40 40
20 20 HNO3
0 0
0 2 4 6 0 2 4 6 C6H8O7
Pb Zn 0246
100 100
Extraction (%)
80 80 C2H2O4
60 60
40 40
20 20
0 0
0 2 4 6 0 2 4 6
pH pH
Figure 3.7 - Heavy metals extraction by nitric, citric and oxalic acid
as function of pH
(Initial concentrations in mg/Kg: Cr= 473, Cu= 911, Pb= 167, Zn= 2330)
According to Veeken (1998) and Sims and Kline (1991) schemes, about 57 %
of Cr was extracted by EDTA at a pH value of 4.5. As such, when a
complexing agent like citric acid, oxalic acid or EDTA are applied, Cr can be
solubilized at a higher pH value (3-5) than when a strong acid such as HNO3
is applied (pH value < 3). In the Tessier (1979) scheme, about 65 % of Cr was
extracted by HNO3 and H2O2 at a pH value of 2. From Figure 3.7, citric acid
was able to solubilize about 60 % of Cr, at a pH value of 3. Approximately
the same amount was solubilized by oxalic acid at a pH value of 2 and by
nitric acid at a pH value of 1.5. Despite the fact that Cr extraction started at
the pH value of 5 with citric acid, the best extraction yield for Cr (72.3 %)
was achieved with nitric acid at a pH value of 1.
The difference between citric and oxalic acid in the solubilization of Cr could
be due to the chemical structure of both acids. Citric acid is formed by three
carboxylic groups whereas oxalic acid contains two carboxylic groups. A
high number of carboxylic groups might favor the complexing (or chelating)
capacity of the compound. Extraction based on chelation involves the
coordination of two or more donor atoms present in the chelating ligand to
the same metal ion in such a way so as to form a heterocyclic ring termed a
chelate (Lake, 1987). Citric acid, for example, is a tridentate ligand (i.e.,
48
contains three donor atoms capable of coordination to a single metal ion),

which forms three chelate rings when all donor atoms are coordinated to a
metal. Oxalic acid is a bidentate ligand.
Another reason for the better Cr extraction yielded with citric acid than with
oxalic acid is defended by Veeken and Hamelers (1999). When calcium is
present in the medium, as is the case of the present sludge, the calcium
oxalate precipitate causes that oxalate become less available for heavy
metals leading to a lower extraction comparing to citric acid extraction
(Veeken and Hamelers, 1999).
About 40.5 % of Cu was extracted by nitric acid at a pH value of 1, starting

at a pH value around 2, as observed by Lake (1987), and Wozniak and
Huang (1982). The organic acids were not efficient in Cu solubilization. This
might be due to the low pH value required for Cu to solubilize and to the
short acidification time of 30 minutes applied in these experiments (see next
section). Speciation schemes (see Chapter 2 and further discussion)
suggested that Cu was predominantly incorporated in the organic fraction of
the sludge and this makes its solubilization difficult. Therefore, an oxidating
agent like HNO3 might be more efficient to solubilize Cu, as confirmed by the
speciation schemes. In addition, as Cu presents high affinity for organic
complexes, it might be that the formation of Cu-citrate or Cu-oxalate
complexes was limited by the reactions kinetics. Perhaps a prolonged
reaction time would promote the formation of Cu soluble complexes.
Lead achieved its maximum extraction yield (94 %) with nitric acid at the pH
value of 1, starting at a pH value around 3. At a pH value of 5 Pb extraction
with citric acid started, achieving its maximum value (24.4 %) at the pH
value of 3. Although there is an influence of the complexing agent citrate in
Pb solubilization, this metal extraction is highly affected by low pH value.
This is in agreement with Lake (1987), Kiekens and Cottenie (1984), and
Wozniak and Huang (1982), who reported that the threshold of pH value for
Pb mobilization is near to 2.
The curves of Zn demonstrated that this metal solubilization is affected by

the decrease in the pH value, independent on the type of acid applied. Zinc
started to solubilize at the pH value around 5 with the three acids. The best
extraction yield for Zn (62.5 %) was achieved with HNO3 at the pH value of 2.
At the same pH value, around 51 % of Zn was extracted by oxalic acid.
The relatively low concentrations of soluble heavy metals measured at a pH
49
Chapter 3
value of 7 in the progressive acidification experiments could be comparable

to those extracted by the exchangeable fraction in the SCE (see Chapter 2).
Leaching experiments as a function of time

Data related to the time influence on the extraction of Cr, Cu, Pb and Zn are
shown in Figure 3.8. Differences between duplicates were within 3.5 %.
Copper extraction was the most affected by the time from all the metals
studied, followed by Zn. When citric acid was applied, Cr and Pb
solubilizations improved as long as the time increased (Figure 3.8).
Cr Cu
100 100
Extraction (%)
80 80 HNO3 - pH3
60 60
40 40 HCl - pH3
20 20
C6H8O7 - pH3
0 0
0.01
Pb 0.1 1 10 0.01
Zn 0.1 1 10 HNO3 - pH2
100 100
Extraction (%)
80 80 HCl - pH2
60 60
HNO3 - pH1
40 40
20 20 HCl - pH1
0 0
0.01 0.1 1 10 0.01 0.1 1 10
Time (d) Time (d)
Figure 3.8 - Heavy metals extraction with nitric, hydrochloric and citric
acid at different pH values as functions of time
(Initial concentrations in mg/Kg: Cr= 473, Cu= 911, Pb= 167, Zn= 2330)
The best extraction yield for Cr (89.6 %) was achieved with citric acid at a
pH value of 3 after 7 days. This might be explained by the Cr speciation in
the sludge and the tendency of Cr (III) to form complexes with organic acids.
In general, there was no difference between nitric and hydrochloric acid to
solubilize Cr. The best extraction yields for Cr with these two acids were
obtained at a pH value of 1, with no considerable differences due to a
change in the acidification time. These results are in accordance with those
presented in Figure 3.7. Chromium solubilization is first governed by the
presence of a chelating agent and this influence becomes stronger with an
50
increase in the acidification time. When other acids are applied, however,
their interference in Cr solubilization becomes almost competitive with the
chelating agent at the point in which the pH value decreases till 1.
As mentioned before, copper was found predominantly incorporated in the

organic fraction of the sludge (see Chapter 2 and further discussion). Thus,
as a strong bounded heavy metal, it takes a longer time to reach equilibrium
(Veeken and Hamelers, 1998; Hayes et al., 1980). The effect of citric acid in
Cu solubilization appeared after 6 hours, reaching the maximum extraction
(30.9 %) after 5 days. The maximum extraction yield (79 %) of Cu was
achieved with HCl at a pH value of 1 after one day.
Almost 100 % of Pb was extracted after 30 minutes with HNO3 and HCl.
Here the influence of the complexing agent citrate in Pb solubilization was
clear, but the minimum pH value of 3 achieved with this acid was not
enough to promote the almost 100 % extraction yielded with the other acids
at a pH value around 1.
Zinc solubilization was affected by the leaching time, especially at the

highest pH values. From Figure 3.8 it seems that there is no big difference
between the results obtained with HCl application at both pH values of 2
and 1. There is no consistent explanation for the immediate fall in the nitric
acid curve at pH value of 1 between 2 and 6 hours. The best extraction yield
(96 %) for Zn was obtained with HCl at the pH value of 2, after 7 days
followed by 93 % after 1 day.
Comparing the leaching effectiveness of all the acids as well as respective pH

values and leaching times applied in this research, the use of HCl at a pH
value of 1 during 24 hours was selected as the reference leaching situation
for further investigations. Citric acid was only effective in Cr solubilization
and HNO3 was as effective as HCl to promote Cu solubilization only after a
leaching time of about 5 days.
The progressive acidification process and the SCE schemes gave some
indication of the potential behaviour of heavy metals under conditions of
reduced pH value. In terms of sludge disposal to land, it should be wise to
apply again the SCE schemes in the sludge after the acidification process, in
order to evaluate whether the remaining heavy metals distribution has
changed or not. Rudd et al. (1988) applied a SCE scheme to the residues
obtained following sewage sludge acidification. According to these authors,
Cu and Pb forms were relatively stable, but Zn speciation was likely to
51
Chapter 3
change with decreasing pH. The solubility of Zn, in particular at pH around

4-5 (see Figure 3.7), emphasizes its importance as a limiting metal, as its
threshold pH can approach the pH values of some soils. In the presence of
organic acids Cr and Pb can also be available at a pH value around 5.
Experiments with the liquid sludge: effect of oxidation with aeration
Aeration influence on heavy metals extraction

Figure 3.9 shows the effect of aeration applied in different situations on
heavy metals extraction. Differences between duplicates were within 2.5 %.
The aeration process considerably influenced copper extraction.
When aeration was solely applied, about 11 % of Cu was extracted, whereas

less than 5 % of Cr, Pb and Zn was extracted. Speciation schemes (see
Chapter 2) suggested that Cu exists as an organic complex in the sludge, as
also observed by Tyagi et al. (1988), and Oliver and Carey (1976). For metals
that are organically bound, a prolonged exposure under more extreme acid
conditions would be required to bring about removal and recovery of heavy
metals, as confirmed by Figure 3.8 and investigations of Tyagi et al. (1988).
100 Only aeration

80
Extraction (%)
Only acidification
60
Simultaneous aeration
and acidification
40
Aeration before
acidification
20
Aeration after
0 acidification
Cr Cu Pb Zn
1 2 3 4
Figure 4.3 - Aeration influence on heavy metals extraction
with HCl at pH= 1
(Initial concentrations in mg/L: Cr= 10.1, Cu= 23.8, Pb= 5, Zn= 43)
According to Hayes et al. (1980), in anaerobic sludges the heavy metals are
present usually in their most reducible form, e.g., metal sulfides.
Accordingly, besides the predominance of Cu as bound to the organic
fraction of the sludge, Cu is also present as the insoluble Cu2S (solubility
product: Ksp= 2.5 x 10-48) in the sludge (Hayes et al., 1980). To solubilize Cu
52
is necessary to oxidize Cu2S to the more soluble form CuSO4 (stability

constant: Ko= 250).
Byukx et al. (2000) observed that Cu speciation in sulfide-rich freshwater

sediment was not affected by aeration. In the present case, Cu speciation
might have changed, because the effect of aeration on Cu extraction is
clearly demonstrated by Figure 3.9.
The situation where aeration is applied before acidification is the best one
for Cu and, to a lower extend, for Cr and Zn solubilizations. This is in
agreement with Hayes et al. (1978) who observed that only decreasing the
pH for anaerobic sludge does not end in a shift of metal sulfides to the
soluble ionic form until acidification is preceded by a raise in the sludge
ORP. The original ORP of the sludge was around – 90 mV. After aeration the
ORP value increased to + 674 mV.
For Cr, Zn and especially Cu, the results obtained when aeration was
applied after acidification were better than the results obtained when
simultaneous aeration and acidification were applied. This can be due to the
application times of aeration and acidification. During the simultaneous
aeration and acidification, the total extraction time was 24 hours whereas in
the other situations, acidification was applied during 24 hours followed by
another 24 hours of aeration.
The extraction yields of Cr, Pb and Zn resulted from all the situations
studied, are not considerably different from each other. The extraction
percentages are relatively high and do not differ much from the maximum.
The differences among the situations without aeration and aeration applied
before acidification are smaller (Cr: 8.6 %, Pb: 3.9 %, Zn: 8.9 %) comparing
to Cu (64.3 %).
Comparison of the best extraction results achieved with the dried and crushed
sludge and the liquid sludge
Table 3.3 shows that the results achieved for the liquid sludge sample with
application of aeration (24 hours) before acidification (with HCl, at pH= 1,
during 24 hours) are better than the results attained for the dried and
crushed sludge sample with application of HCl (at pH= 1, during 24 hours).
53
Chapter 3
Table 3.3 - Comparison of some extraction results (%) obtained with the
liquid sludge and the dried and crushed sludge
Situation Cu (%) Cr (%) Pb (%) Zn (%)
Liquid sludge: only acidificationa 30 72 96 89
Liquid sludge: aeration before acidificationa 94 81 100 98
Dried and crushed sludgeb 79 68 94 84
a Liquid sludge: 25gDM/L; b Dried sludge: 50gDM/L; Organic matter: 550g/KgDM.
Table 3.3 shows that, without aeration, the extraction yields for Cr, Pb and
Zn were approximately the same for the liquid and the dried sludge samples,
despite the differences in the solids content between the both sludges.
Copper extraction from the liquid sludge sample, however, required aeration
to be competitive to the extraction obtained with the dried sludge sample.
Rudd et al. (1988) observed that the differences in the behavior of the liquid
and dried forms of the sludges using the progressive acidification were that
the metals were more readily solubilized from the dried samples. On the
other hand, the SCE schemes indicated that drying of the sludges effectively
reduced the extractability of fractions that were readily available in the
liquid form (Rudd et al., 1988). The authors suggested that during the
drying process the organic matter is oxidized and a mineralization might
occur. Based on this, the size of the minerals particles are reduced and
homogenized during the crushing process. This might favors Cu extraction,
since this metal predominates in the organic fraction of the sludge.
In relation to the total solids concentration, Sreekrishnan et al. (1993),

reported that an increased concentration of solids in the sewage sludge
intensifies the buffering capacity, nutrient concentration and organic matter
content in the sludge. Thus, an increase in the buffering capacity of the
sludge will lead to a smoother and more gradual decrease in the pH value.
Therefore, the sludge solids concentration does not interfere directly with
the metal solubilization process, but affects by controlling the rate at which
the sludge is acidified, in terms of required acid dosage and leaching time.
Thus, the total solids concentration might interfere with the initial
acidification process, but not in the final result of heavy metals
solubilization.
Effect of acidification time and aeration on heavy metals solubilization

Figure 3.10 shows the influence of the acidification time on the
solubilization of Cu, Cr, Pb and Zn, in the situations without aeration and
54
with aeration applied before acidification. Differences between duplicates

were within 3.2 %. In the absence of aeration, the heavy metals (especially
Cu) needed a prolonged acidification time to solubilize effectively.
100 100
Cr
Extraction (%)
80 80
60 60 Cu
With Without
40 40 Pb
aeration aeration
20 20
Zn
0 0
0.01 0.1 1 10 0.01 0.1 1 10
Acidification time (d) Acidification time (d)
Figure 3.10 - Effect of acidification time on heavy metals extraction

with HCl at pH= 1
(Initial concentrations in mg/L: Cr= 9.8, Cu= 24.3, Pb= 4.9, Zn= 43)
Comparing both graphs, when aeration was applied, satisfactory extraction

yields were achieved with an acidification time of 5 hours for all the heavy
metals. Without aeration, however, only after 3-4 days Cu achieved
sufficient solubilization level.
Effect of aeration and acidification time on heavy metals solubilization

The effect of aeration and acidification time on heavy metals solubilization is
shown in Figure 3.11 in form of surface contours. Differences between
duplicates were within 3.0 %. The results show that each metal had a
different extraction profile concerning aeration and acidification times.
The solubilizations of Cu and, to a less extend, of Zn were related to the

aeration time rather than to the acidification time. To achieve an extraction
yield of around 100 % Cu and Zn always needed 24 hours of previous
aeration, but the acidification time could be reduced to 5 hours, or even less
in the case of Zn. The surface contours of Cr demonstrate that its
solubilization depended equally on the acidification and aeration times.
However, to follow the tendency of Cu and Zn to minimize the acidification
time and maximize the aeration time, with an acidification time of 20 hours
about 80 % of Cr could be solubilized.
55
Chapter 3
Cu Cr
100 % 80 %
Acidification time (h)
10 10
90 %
70 %
1 1
10 10
Zn Pb
Acidification time (h)
100 %
10 10
95 % 100 %
85 %
100 %
1 1
95 %
10 10
Aeration time (h) Aeration time (h)
Figure 3.11 - Heavy metals extraction as function of acidification

and aeration time
(Initial concentrations in mg/L: Cu= 22.2, Cr= 9.6, Pb= 5.1, Zn= 45.3)
About 100 % of Pb was already solubilized after 5 hours of aeration and

acidification. For the present work it is important to find the situation that
provides the most effective solubilization of all the metals studied. Thus, the
situation in which both aeration and acidification are applied during 24
hours will be considered as reference in further study.
56
Experiments with the liquid sludge: effect of oxidation with H2O2
Effect of H2O2 dosage on heavy metals extraction

Figure 3.12 shows the extraction yields of Cr, Cu, Pb and Zn achieved with
HCl and H3PO4 at initial pH values of 3 and 4, followed by H2O2 application
at different dosages and a second acid dosage to pH value of 1.6. Differences
between duplicates were within 4.5 %.
Cr Cu
100
Extraction (%)
100
90 90
80 80 HCl, H2O2 pH= 3
70 70
60 60 HCl, H2O2 pH= 4
1 3 5 7 1 3 5 7
Pb Zn
H3PO4, H2O2 pH= 3
Extraction (%)
100 100
90 90 H3PO4, H2O2 pH= 4
80 80
70 70
1 3 5 7 1 3 5 7
H2O2 dosage (g/L) H2O2 dosage (g/L)
Figure 3.12 - Heavy metals extraction by HCl and H3PO4 as function of

H2O2 dosage
(Initial concentrations in mg/L: Cr= 13.1, Cu= 27.8, Pb= 5.4, Zn= 53)
Despite the clear differences in the heavy metals behaviour, there were two
situations that promoted high heavy metals extraction. One of them was
with H3PO4 application at the initial pH value of 3 and 4.8 g H2O2/L. Similar
results were found in the situation with HCl at initial pH value of 3 and the
highest H2O2 dosage (8 g/L).
The fact that H3PO4 required a smaller H2O2 dosage than HCl to promote
similar Cr, Cu, Pb and Zn extraction might be due to the function of the
H3PO4 in the process. Phosphoric acid molecule might exert a positive effect
on the Fenton reactions. Phosphate is commercially used to block catalytic
surfaces, which promote the decomposition of H2O2 by the reaction:
57
Chapter 3
2H2O2 ⇒ O2 + 2H2O (4.3)
Zinc was the easiest metal to be extracted in all the situations. Even with
HCl at initial pH value of 4 and H2O2 dosage of 8 g/L, about 95.8 % of Zn
was extracted. In general, when H3PO4 was applied, the pH value of 3 was
more adequate to promote the Fenton reaction than the pH value of 4, as
also observed for Cr, Cu and Pb. Mostly high differences between the two
initial pH values did not affect heavy metals extraction with HCl. For further
study, the best situation with H3PO4 and HCl will be considered those with
initial pH value of 3 and H2O2 dosage of 4.8 g/L. Both conditions provided
satisfactory extraction yields for all the metals studied.
Effect of H2O2 addition, aeration, and acidification with HCl and H3PO4 on the
heavy metals extraction
Figure 3.13 shows the extraction percentages of Cr, Cu and Zn obtained at
different process conditions regarding way of oxidation (H2O2 or aeration),
acidification (HCl or H3PO4) and oxidation time (24 or 6 hours). Differences
between duplicates were within 6 %. The oxidation-reduction potential of the
sludge after H2O2 application was +723 ± 50 mV. The figure corresponding
to Pb is not shown here, since about 100 % of this metal was extracted in all
the situations studied.
Figure 3.13 highlights that when comparing both oxidation times, in

general, there are no considerable differences in applying 24 or 6 hours of
oxidation. In addition, Cu was not satisfactorily solubilized by the
combination of H3PO4 and aeration.
Generally the differences between the extraction yields for Cr with the
oxidation times of 24 and 6 hours were around 3 %, except in the situation
that H3PO4 and aeration were applied, with a difference between the
extraction efficiencies of 15.8 %. Comparing HCl and H3PO4, there were no
considerable differences between both acids in the Cr extraction. Aeration
was less effective (from 5 to 17 %) than H2O2 addition to solubilize Cr. This
is consistent with the speciation schemes of Tessier (1979) and Veeken
(1998), in which 58-65 % of Cr was detected in the fraction including H2O2
as reagent (see Chapter 2).
58
Cr - 24 h oxidation Cr - 6 h oxidation
100 100
60 60
40 40
20 20
0 0
Cu - 24 h oxidation Cu - 6 h oxidation
100 100
Extraction (%)
80 80 HCl
60 60 H3PO4
40 40 A= Aeration
20 20 H= H2O2
0 0
Zn - 24 h oxidation Zn - 6 h oxidation
100 100
Extraction (%)
80 80
60 60
40 40
20 20
0 0
A H A H A H A H
Figure 3.13 - Heavy metals extraction as function of aeration, H2O2 and

acidification with HCl and H3PO4
(Initial concentrations in mg/L: Cu= 26.5, Cr= 13.3, Zn= 52.5)
The maximum differences in the extraction efficiencies due to the different

oxidation times were around 5 % for Cu. Comparing HCl and H3PO4, the
first acid provided better extraction yields for Cu than the second acid, in all
situations. As observed for Cr, the effect of the H2O2 was superior to the
effect of aeration in Cu extraction. Again, there is coherence with the SCE
schemes (see Chapter 2). Copper was extracted mainly in the step that
included H2O2 as reagent in the Tessier (1979) and Veeken (1998) schemes.
Differently from Cr, however, the combination of H3PO4 and aeration was
ineffective to solubilize more than 20 % of Cu, suggesting that H3PO4 was
only effective in Cu extraction when this acid was combined with H2O2.
According to the SCE schemes (Chapter 2), Cu is mainly bound or
incorporated in the organic matter fraction and precipitated as Cu2S, as
emphasized by Hayes and Theis (1978). This suggests that the H2O2 added
reacted with the Fe-compounds of the sludge, forming the highly oxidizing
59
Chapter 3
hydroxyl radicals, which were perhaps able to oxidize the organic matter and
the Cu2S faster than aeration.
An explanation for the difference in the extraction efficiencies of Cu achieved

by the combination of aeration with H3PO4 or HCl, however, is still difficult.
It cannot be suggested by the SCE schemes or by comparing the critical
stability constants of the most likely stable Cu-chloro complex, e.g., CuCl+
(log Ko= 0.4) or Cu-phosphate complex, e.g., CuH2PO4+ (log Ko= 1.5). These
constants indicate that the Cu-phosphate complex is more stable than the
Cu-chloro complex. Although the phosphate solution has a higher extraction
capacity for Cu than the chloride solution, even at the pH value around 1.6,
HCl showed to be superior to H3PO4 in Cu extraction.
When H3PO4 is added at a pH value of around 1.6, the form H3PO4 (pK1=
2.12) prevails, whereas about 30 % of phosphoric acid is present as H2PO4-.
This is an indication that at this pH value, about the same amount of
phosphate species are available to complexate with Cu, compared to
chloride, when HCl is applied. This is because the H3PO4 dosage is about 3
times higher than the HCl dosage required to achieve a pH value of 1.6.
The presence of calcium in the sludge might exert a strong influence on Cu

extraction. Speciation calculations with Ecosat (Keizer and van Riemsdijk,
2002) showed that Ca could form stable complexes with phosphate species,
e.g., CaH2PO4+ (log Ko= 1.4), rather than with chloride. In addition to the
competition of Ca2+, Cu2+ also competes with H+ in the phosphate-complexes
formation. Speciation calculations with Ecosat (Keizer and van Riemsdijk,
2002) demonstrated, however, that the extraction capacity of the phosphate
solution is still high enough. These calculations also confirmed that the
formation of calcium phosphate minerals is unlikely to occur at such a low
pH value, eliminating the hypothesis of coprecipitation of Cu2+ with these
crystals.
Additionally to these hypothesis and according to the soil science (Kincheloe,

2003), phosphates and sulfates are adsorbed more strongly than nitrates
and chlorides to soil particles. Then it might occur that, parallel to soil
material, the phosphate species have a high affinity for binding to the
positively charged sites of the solid fraction of the sludge and therefore it
would not be available to form complexes with Cu2+ as chloride would. But
the amount of phosphate added to the sludge is at least three times more
than the dry matter content in the sludge. Thus, there would be enough
60
phosphate species available. In this way, the only remaining hypothesis is

whether the Cu-phosphate complexes have affinity to bind to organic
matter/other solid sites or not. But this is a hypothesis and its consistency
should be verified with additional experiments and/or modeling.
The only conditions where Zn extraction was affected by the oxidation time
were those when H3PO4 and aeration were applied. The other situations were
equally effective to solubilize about 100 % of this metal. As observed for Cu,
but in less proportion for Zn, the combination of H3PO4 and aeration was
not as efficient as the other situations to solubilize this metal.
Selection of method
To ease the comparison of the different leaching methods applied in this
research, the results are summarized in Table 3.4.
From Table 3.4 it is clear that an oxidative step with either aeration or
hydrogen peroxide favors the extraction of the heavy metals, especially Cu.
When hydrochloric acid was applied without the oxidation step, Cu
extraction efficiency for the dried sludge was better than that for the liquid
sludge.
Another point highlighted in Table 3.4 is that, particularly for Cu, the use of
nitric acid requires prolonged extraction times (about 5 days) to achieve
similar extraction efficiencies as obtained with hydrochloric acid at the same
pH value (around 1). Citric acid was advantageous only for Cr.
Table 3.4 - Heavy metals extraction efficiency (%) from anaerobically

digested sludge using different methods
Method pH Cr Cu Pb Zn
% Days % Days % Days % Days
HCla 1 72 1 49 1 96 1 89 1
Aeration + HCla 1.4 81 1+1c 94 1+1c 100 1+1c 100 1+1c
H2O2 + HCla 1.6 86 1+1c 100 1+1c 100 1+1c 100 1+1c
H2O2 + H3PO4a 1.6 92 1+1c 87.5 1+1c 100 1+1c 100 1+1c
HNO3b 1 72 1 56 1 87 1 66 1
HNO3b 1 81 5 74 5 90 5 77 5
HClb 1 68 1 79 1 94 1 84 1
Citric acidb 3 90 7 31 5 60 5 85 7
a Liquid sludge; b Dried and crushed sludge; c Oxidation time + acidification time; d Negligible.
61
Chapter 3
Both hydrochloric and phosphoric acids were able to solubilize high

percentages of heavy metals when applied in combination with hydrogen
peroxide (Table 3.4). However, the dosage of phosphoric acid (in mol/L)
needed to decrease the pH to a proper value is at least 2 times more than
the dosage of hydrochloric acid.
According to Table 3.4, the application of hydrochloric acid (pH around 1,

during 24 hours) with previous application of aeration or hydrogen peroxide
(with initial pH value of 3, during 24 hours) is able to promote the highest
extraction efficiencies of most heavy metals.
Considering that the highest difference between duplicates was 6 %, yet

there might be some metal content remaining in the sludge particles,
especially Cr. Depending on the final destination of this sludge it is
necessary to evaluate whether the remaining heavy metal amount will
respect the local management policy. Besides the total concentration of the
remaining heavy metals in the sludge it is also important to evaluate the
speciation and mobility of these metals. In the case of Cr, it is unlikely that
its hexavalent form occurs in anaerobically digested sludges. To avoid the
conversion of Cr6+ to Cr3+ requires an oxidation-reduction potential (ORP) of
+1100 mV under standard conditions (Weast, 1979). Under the oxidation
conditions applied in the present research, the ORP value of the sludge was
raised till the maximum value of +780 mV.
CONCLUSIONS
The results showed that the option including chemical oxidation with either
aeration or hydrogen peroxide followed by acidification resulted in the
highest extraction percentages of most heavy metals. The extraction yield is
very sensitive to the type of acid used. HCl was superior to other acids like
HNO3 and H3PO4. Copper extraction was highly influenced by oxidation. The
best results achieved were: Cr: 85 % with H2O2, Cu: 100 % with H2O2, Pb:
100 % with aeration and H2O2, and Zn: 100 % with aeration and H2O2.
62
Chapter 4
Bioleaching of heavy metals
Abstract
In the present work, the practical application of bioleaching in the solubilization
of Cr, Cu, Pb and Zn from anaerobically digested sludge is evaluated.
Bioleaching using elemental sulfur and ferrous iron and chemical leaching with
H2SO4 were applied. The results were compared with those found in the
literature and in previous leaching experiments with HCl. Bioleaching can be a
feasible alternative to promote Zn and Cu solubilizations, especially when
ferrous iron is added as substrate. Under this condition, the maximum
extraction yield achieved for Zn was 80.8 % with a pH value of 2.7. For Cu it was
65.5 % with the pH value of 2.5. Cr solubilization was possible when pH was
around 2.5 and Pb was not detected in solution. Chemical leaching with HCl at
pH value of 1 solubilized almost 100 % of Pb and also provided the best
extraction yield for Cr (around 72 %). At the same pH value, HCl is more effective
than H2SO4 to solubilize all the metals studied.
Marchioretto M.M., Bruning H., Hien N.T.P. and Rulkens W.H. Presented at Biosolids
2003, Wastewater Sludge as a Resource. Trondheim, Norway. June, 2003.
Chapter 4
INTRODUCTION
A safe use of sewage sludge as soil conditioner requires sewage sludge with
low heavy metal content. The sludge application rate is governed by the
cumulative metal loading of the soil (Sreekrishnan et al., 1993). Reduction of
heavy metals in sewage sludge can be achieved either by source control of
discharge to sewer systems or by removing the metals from the sludge. As
the major difficulty in source control is in identifying the sources, the only
possible practical solution is to remove the heavy metals from the sludge
(Sreekrishnan et al., 1993).
Heavy metals cannot be removed by a physical separation process without

being previously solubilized. Chemical leaching with acids or complexing
agents is an effective option to promote metals solubilization. A drawback of
this alternative is the large consumption of chemical agents (see Chapter 3).
Besides, its application becomes attractive only at high plant capacities
(Sreekrishnan and Tyagi, 1996). Biological leaching (bioleaching) can be a
feasible and sustainable alternative to reduce de costs of the chemical
leaching method.
The principle of bioleaching is the microbial production of sulfuric acid and

subsequent solubilization of heavy metals. Tichý (1998) defines bioleaching
as a process mediated by specific acidophilic bacteria capable of acid
production. Since many of these microbes belong to the genus Thiobacillus,
they are called thiobacilli-like organisms. Thiobacilli are able to oxidize
reduced sulfur or ferrous iron and thus produce the acidity (Tichý, 1998).
The main types of bacteria used in bioleaching are Thiobacillus ferrooxidans
and Thiobacillus thiooxidans. They occur widely in terrestrial and aquatic
habitats wherever inorganic sulfur and iron are present, such as in sewage
systems, estuaries and acid mine drainage (Lombardi and Garcia Jr., 1999).
The bioleaching process aims at especially the solubilization of heavy metals

but it also causes a reduction of pathogenic organisms. This is the result of
the extreme pH conditions introduced by Thiobacilli during the bioleaching
process operation. Thus, ideally the sludge coming out from a bioleaching
system would present reduced amounts of both toxic metals and pathogenic
organisms (Lombardi and Garcia, 1999).
Despite the positive aspects of bioleaching and its numerous studies over
the last two decades (e.g., Wong et al., 2002; Couillard and Zhu, 1992;
64
Hayes et al., 1980), these techniques, applied in the solubilization of heavy

metals from sewage sludge, still prevail under laboratory and pilot plant
scale. The aim of the present paper was to get more insights into the
practical application of bioleaching to solubilize heavy metals (Cr, Cu, Pb
and Zn) from anaerobically digested sludge, its advantages and
shortcomings. Bioleaching using elemental sulfur and ferrous iron as
substrates was investigated and compared with chemical leaching with
sulfuric acid. Finally, these results were compared with those found in the
literature and in the previous chemical leaching experiments with
hydrochloric acid described in Chapter 3.
EXPERIMENTAL
The origin and main characteristics of the sludge as well as the chemical
and physical distribution of heavy metals in the sludge applied in this
research are described in detail in Chapter 2.
Analysis
The procedures and equipments for heavy metals, pH and oxidation-

reduction potential (ORP) analysis are described in Chapter 2. Heavy metal
extraction efficiency was calculated as the ratio between the solubilized
metal in the sludge after the extraction and the non-solubilized metal in the
sludge before the extraction.
Chemical leaching experiments
Ten 1-L glass bottles were filled with 400-ml of sludge, continuously agitated
(125 rpm) at 30 °C and simultaneously exposed to intense aeration for 24
hours before and during the acidification. The effect of aeration in the heavy
metals solubilization of the present sludge was demonstrated in Chapter 3.
Aeration applied before acidification increases the ORP of the sludge,

promoting the oxidation of the non-soluble metal forms to precipitate forms
that would be dissolved at low pH. Here, aeration was not only applied
65
Chapter 4
before, but also during acidification. This was to ensure that the heavy
metals solubilization was carried out at optimal conditions.
Acidification with sulfuric acid was applied for each bottle to achieve initial
pH values of 5 (38 mM H2SO4/L sludge), 3 (64 mM H2SO4/L sludge), 2 (101
mM H2SO4/L sludge), and 1 (429 mM H2SO4/L sludge). The remaining
bottles were preserved with the natural pH (original pH of the sludge).
Samples in duplicates of 15 ml sludge were collected after acidification times
of 0, 5 hours, 7 hours, 9 hours, 1 day, 2 days, 4 days, and 5 days (see
scheme in Figure 4.1).
The ORP and the pH were measured at each time a sample was collected.
After collection, the samples were centrifuged at 4000 rpm during 20
minutes. The supernatant was filtered by paper filter S&S black ribbon (12-
25 µm) and subsequently analyzed for its terms of heavy metal (Cr, Cu, Pb
and Zn) content by ICP-MS (see description in Chapter 2).
H2SO4
Nat. pH pH pH pH
= = = =
pH 1
5 3 2
Air
Nat. pH pH pH pH
pH = = = =
5 3 2 1
Figure 4.1 - Chemical leaching scheme
Bioleaching experiments
All the sludge bottles were continuously agitated (125 rpm) at 30°C and
simultaneously exposed to aeration for 24 hours before and during the
bioleaching step, with a total running time of 15 days. Carbon dioxide was
applied as carbon source for the autotrophic bacterial growth. The pH was
measured every day and samples in duplicate of 15-ml sludge were collected
66
only when the pH value was stable (pH around 3-4, after 9 days). The
samples preparation for heavy metals analysis followed the same procedure
applied in the chemical leaching experiments.
With addition of elemental sulfur

Four 1-L glass bottles were filled with 400 ml of sludge and amended with
elemental sulfur microbiologically produced by a pilot plant treating sulfide-
rich paper mill wastewater in Eerbeek, The Netherlands (see Figure 4.2). In
order to check the necessity of acid addition, the pH of two bottles was
adjusted to 5 by sulfuric acid (38 mM H2SO4/L sludge) and the remaining
bottles were preserved with the natural pH (original pH of the sludge). The
amount of elemental sulfur added to the bottles was determined according
to reaction 1 (Couillard and Zhu, 1992) and to the amount of sulfuric acid
required to achieve pH value of 1 on the chemical leaching experiments.
S0 + 1.5O2 + H2O H2SO4 (1)
Nat. S0 pH S0
= Air
pH 5
CO2
Nat. S0 pH S0
=
pH 5
Figure 4.2 - Scheme of bioleaching with addition of elemental sulfur
With addition of ferrous iron

Eight 1-L glass bottles were filled with 400 ml of sludge and amended with
ferrous iron substrate in the form of FeSO4.7H2O (see reaction 2). The pH of
four bottles was adjusted to 5 by sulfuric acid and the remaining bottles
were preserved with the natural pH. A culture of growing bacteria
(T. ferrooxidans) was added to two pre-acidified bottles and to two non-
acidified bottles.
67
Chapter 4
The amount of ferrous iron added to the bottles was determined according to
stoichiometry of the reactions 2 (Couillard and Zhu, 1992) and 3 (Chartier
and Couillard, 1997) and the amount of sulfuric acid required to achieve pH
value of 5 in the chemical leaching experiments.
2FeSO4 + 0.5O2 + H2SO4 Fe2(SO4)3 + H2O (2)
Fe2(SO4)3 + 6H2O 2Fe(OH)3 + 3H2SO4 (3)
An exceeding amount of 5 g of FeSO4.7H2O was applied in order to be sure

that the substrate was not limiting.
With addition of a mixed substrate

These experiments were identical to those applied for bioleaching with
ferrous iron as substrate. But instead of ferrous iron solely, a mixture of
elemental sulfur and ferrous iron was applied.
Chemical leaching experiments
pH and oxidation-reduction potential (ORP)

Figure 4.4 shows the curves of the pH and ORP of the sludge during the
chemical leaching with sulfuric acid as functions of time. The pH and ORP
values of sludge under aeration and acidification did not vary considerably
with time.
10 700
Nat. pH
8
pH 5
ORP (mV)
500
6
pH
pH 3
4
300 pH 2
2
pH 1
0 100
0 48 96 144 0 48 96 144
Time (h) Time (h)
Figure 4.3 - pH and ORP variations during the simultaneous

aeration/acidification, after 24 hours of aeration
(Before previous aeration: natural pH= 7.9 and ORP= -90 mV)
68
The pH values gradually increased during the first 10 hours. This might be
due to sorption processes, including physical adsorption, chemical
adsorption and sorption based on ion exchange (Tichý et al., 1998). After 10
and 48 hours respectively, the natural pH (initially 7.9) and the initial pH
value of 5 decreased more than the other pH values, but they could not
reach the value of 4, which is the threshold value for satisfactory
mobilization of heavy metals (Lake, 1987). The decrease in the pH values
might be the result of chemical and microbial oxidation of reduced sulfur
compounds in sludge. The chemical oxidation was caused by aeration and
the microbial oxidation by the indigenous bacteria.
Similarly to the changes in the pH values, the ORP of the sludge varied
during the first 10 hours and became almost stable after that period. The
initial ORP value of -90 mV was high compared with the -300 mV to -520
mV values established by Hayes and Theis (1978) for anaerobically digested
sludges. The unavoidable aeration of the sludge during the collection at the
sewage plant and the manipulation of the sludge during the experiments
might be reasons for this difference. Previous aeration made the ORP value
increase considerably. Solubilization strategy requires optimum adjustment
of pH and ORP of the sludge so that the chemical equilibria will be shifted in
favor of dissolved metallic ion formation (Tyagi et al., 1988).

The extraction efficiencies of Cr, Cu, Pb and Zn as functions of time are
shown in Figure 4.4. Duplicate values differed from the mean by 3.5 % at
most. Zinc solubilization occurred at pH value of 3 or below, whereas the
other metals were only solubilized at pH value of 2 or below (see Figure 4.4).
There was a definite lag time of Cu extraction before measurable

solubilization. This was also observed by Hayes et al. (1980). The low
solubility of Cu in the beginning might be due to organic complexation
because Cu tends to form complexes with the organic matter in sludges
(Chen and Lin, 2000). The affinity of Cu to organic matter was suggested by
the speciation schemes presented in Chapter 2. Therefore, Cu extraction
needs prolonged time and low pH value (around 2) conditions. According to
Figure 4.4, the highest extraction efficiency observed for Cu (67.7 %) was
achieved after 96 hours at a pH value of 1. At a pH value of 2, the maximum
Cu extraction was 63.2 % after 120 hours.
69
Chapter 4
Cu Pb
100 100
60 60
40 40
20 20 pH= 1
0 0
0 48 96 144 0 48 96 144
pH= 2
Cr Zn
100 100
Extraction (%)
80 80 pH= 3
60 60
40 40
20 20
0 0
0 48 96 144 0 48 96 144
Time (h) Time (h)
Figure 4.4 - Heavy metals extractions as functions of time during

chemical leaching
(Initial concentrations in mg/L: Cu= 25.7, Pb= 5.3, Cr= 11.7, Zn= 51.9)
From Figure 4.4, the time necessary to approach the maximum Pb

extraction was 48 hours, at a pH value of 1. As reported by Wozniak and
Huang (1982), the initial removal of Pb (and Cu) usually represents less than
10 % of the maximum value under given pH conditions. In the present
research about 51.5 % of Pb was extracted. This value, however, was very
low when compared with Pb solubilization by HCl (see further discussion).
This indicates that some mechanism, such as the formation of a low soluble
precipitate (PbSO4) was preventing lead solubilization. This was also
observed by Chen and Lin (2001a;b), Chartier and Couillard (1997), and
Mercier et al. (1996). At a pH value of 2, the maximum Pb extraction was
42.8 %, after 48 hours. No Pb solubilization was observed at a pH value of 3.
This is in agreement with Kiekens and Cottenie (1984), who reported that
the threshold of pH value for Pb mobilization is near to 2.
Chromium solubilization was not highly affected by the treatment time as

shown in Figure 4.4. This is consistent with the results obtained in the
experiments with application of different acids described in Chapter 3. The
maximum value (64.8 %) was achieved after 48 hours at a pH value of 1.
70
Zinc presented the highest solubilization of all the heavy metals studied.
Even at a pH value of 3 a relatively high concentration of Zn was observed in
the liquid. These results agree with the previous leaching experiments
shown in Chapter 3. Wozniak and Huang (1982) also concluded that Zn was
extracted in large amounts immediately after acidification. The best
extraction yield for Zn was 93.5 %, at a pH value of 1 after 120 hours. A
further discussion about Zn, as well as Cu, Cr and Pb solubilizations is
presented later.
Bioleaching experiments
pH
Figure 4.5 shows the pH variation during the bioleaching experiments as
function of time at various conditions of substrate application. After about 8
days, the pH values became stable or decreased slowly.
The lowest pH value of 1.9 occurred in the sample with the addition of
S0/Fe2+/Acid/Culture after 15 days. T. ferrooxidans were cultured under
acidic conditions and the sulfur compounds might have been produced from
the elemental sulfur added. On the other hand, apparently T. ferrooxidans
oxidized elemental sulfur to generate sulfuric acid but this process occurred
more slowly than the oxidation of ferrous iron.
9 9 S0
S0/Acid
7 7
Fe2+
Fe2+/Acid
pH
5 5
Fe2+/Cult.
3 3 Fe2+/Cult./Acid
S0/Fe2+
1 1
S0/Fe2+/Acid
0 4 8 12 16 0 4 8 12 16 S0/Fe2+/Cult.
Time (d) Time (d) 191135
S0/Fe2+/Cult./Acid
Figure 4.5 - Variation in the pH value during the bioleaching tests

(before previous aeration: natural pH= 8.0)
During the first 4 days, the pH values of the samples without the addition of
acid decreased more than those of the samples with the addition of acid. All
samples reached a pH value around 4 after one day. This was a result of the
higher initial pH values of the samples without the addition of acid. A red-
71
Chapter 4
brown precipitate in these samples was observed after the ferrous iron
addition. It indicated the existence of ferric iron (Fe3+) in form of ferric
hydroxide, which was microbiologically or chemically oxidized from ferrous
iron. As the product of this reaction, hydrogen ions were generated and the
acidity increased. Ferric iron has a high oxidative power and is not able to
remain as an ion in the solution at the pH value above 4.5 (Evangelou and
Zhang, 1995), due to the reaction:
Fe3+ + 3H2O Fe(OH)3 + 3H+ (4)
Below the value of 4, the decrease in the pH was very slow. Probably ferric
hydroxide was reversely solubilized into the solution and no more hydrogen
ions were produced. During the experiment, a part of ferrous substrate was
lost because of this behaviour. Therefore, the addition of acid to reach the
initial pH value of 5 was needed.
The increase in the pH value of the sample with addition of S0/Acid in the
first day might have been caused by the absorption of hydrogen ions to the
solid particles and the microbial oxidation rate of elemental sulfur was not
fast enough to compensate the amount of hydrogen ions lost. After 9 days
the pH became approximately stable at the value of 4. This reduction could
be attributed to the action of T. ferrooxidans, which oxidizes elemental sulfur
to generate sulfuric acid.
The concentration of heavy metals was measured after 9 days, when the pH
values were relatively stable or slowly decreasing (see Figure 4.5). Figure 4.6
represents the variations of Zn, Cu and Cr extractions and pH (from Figure
4.5) over time for different bioleaching conditions. Duplicate values differed
from the mean by 5.8 % at most. Lead extraction was negligible and is not
shown. Figure 4.6 shows that bioleaching was well able to mobilize Zn and
Cu, but not Cr, even at the lowest pH (1.9) achieved after 15 days.
Zinc showed the highest solubilization of all the heavy metals studied. Its
maximum extraction yield was 86.3 %, in the situation with addition of
elemental sulfur and ferrous iron as substrates, at pH value of 3.4 after 9
days. The curves of Zn show that its extraction yield could be even higher
than the 86.3 % at a shorter period of time, for all the situations studied,
with exception of the one with ferrous iron and acid addition. The second
72
highest extraction percentage achieved for Zn was 80.8 % with addition of

ferrous iron and acid at a pH value of 2.7 after11 days.
90 90
75 75
Zn (%)
60 60
45 45
30 30
9 11 13 15 9 11 13 15
60 60 SS0
Cu (%)
SS0/Acid
40 40
Fe2+
20 20
Fe2+/Acid
0 0 Fe2+/Cult.
40 9 11 13 15 40 9 11 13 15 Fe2+/Cult./Acid
SS0/Fe2+
30 30
Cr (%)
SS0/Fe2+/Acid
20 20
SS0/Fe2+/Cult.
10 10 191135
SS0/Fe2+/Cult./Acid
0 0
9 11 13 15 9 11 13 15
3.5 3.5
pH
2.5 2.5
1.5 1.5
9 11 13 15 9 11 13 15
Time (d) Time (d)
Figure 4.6 - Heavy metals extraction as function of time during the

bioleaching experiments
(Initial concentrations in mg/L: Zn= 51.9, Cu= 25.7, Cr= 11.7)
Copper achieved its maximum extraction yield (65.5 %) in the sample with
addition of ferrous iron and acid, at pH value of 2.5 after 13 days. As
observed for Zn, it was not necessary to reach the lowest pH value of 1.9 for
Cu solubilization by bioleaching. At this minimum pH value, both metals
extractions were not strongly varied, since they were almost equivalent to
the maximum extraction yields achieved with pH 3.4 (Zn) and 2.5 (Cu).
Figure 4.6 shows that Cr extraction was considerably affected by the pH.
The maximum extraction percentage of this metal (33.5 %) was found from
73
Chapter 4
the sample with the addition of elemental sulfur, ferrous iron, acid, and
culture. It matched to the lowest pH value of 1.9 achieved in the 15th day.
Chromium speciation in the sludge might explain its low solubility achieved
by bioleaching, since this metal was found almost equally distributed in the
organic and inorganic fractions, as suggested by the speciation schemes
results shown in Chapter 2.
Lead speciation (see Chapter 2) might be also the reason for the absence of
this metal in solution when bioleaching was applied, because 80 % of this
metal could be distributed in the inorganic matter and/or inorganic
precipitates. In another scheme, about 45 % of Pb was found in the residual
fraction, in which minerals may hold metals in their crystal structure. This
makes lead extraction possible only at very low pH values. But as explained
before, the formation of PbSO4 during the bioleaching tests might be the
great cause of the negligible Pb solubilization.
Effect of substrates on heavy metals solubilization

Figure 4.6 shows that the addition of elemental sulfur resulted in less
effective heavy metals solubilization compared to the other substrate
conditions. As the samples with addition of elemental sulfur and acid were
comparable to those with sulfur only, the acid addition became
unnecessary. Although there was a response of bacteria, the decrease of the
pH values could not go further than 4. It was probably a result from the lack
of T. thiooxidans, which primarily use elemental sulfur as their substrate.
But there are other factors that probably affected the bioleaching process,
such as the difficulty to dissolve the elemental sulfur, the effectiveness of
the aeration system and the metals speciation in the sludge. The
distribution of metals between their specific forms depends especially on the
characteristics of the sludge (origin, pH, total solids content, particle size),
and the chemical properties of these metals.
Villar and Garcia Jr. (2002) could achieve lower pH value (around 1) for an
anaerobically digested sludge by using only elemental sulfur as the
substrate in the bioleaching. With this minimum pH, the extraction
efficiencies of Zn, Cu and Cr were considerably better than those at a pH
value of 4.
Comparing the ferrous iron and acid containing samples with and without
addition of T. ferrooxidans culture, there is no advantage from the culture
added. Probably the microorganisms did not adapt to the new medium or
74
there were not enough sulfides available in the sludge to produce hydrogen
ions.
The addition of both ferrous iron and elemental sulfur did not provide a real
improvement in the extraction of the heavy metals, except for Cr at pH 1.9.
At higher pH values (2.5-3.5) Zn and Cu already achieved their highest
extraction yields. In this way, there is no need to add the two substrates and
the situation with addition of ferrous iron and acid is considered as the most
effective here.
Solids content of the sludge

The solids concentration of the sludge was not varied in this research. As
mentioned in Chapter 2, the total solids content of the sludge is around 25
g/L and the organic matter represents 60 % of this amount. Sreekrishnan et
al. (1993), reported that an increased concentration of solids in the sewage
sludge intensifies the buffering capacity, nutrient concentration and organic
matter content in the sludge. Consequently, an increase in the buffering
capacity of the sludge will lead to a smoother and more gradual decrease in
the pH of the reactor. As a conclusion, the sludge solids concentrations do
not interfere directly in the metal solubilization process, but affect by
controlling the rate at which the sludge is acidified. In other words, the total
solids concentration might interfere in the initial acidification process, but
not in the final result of heavy metals solubilization.
According to Villar and Garcia Jr. (2002), the establishment of solubilization

patterns independent of the sludge solids concentration can be of great
usefulness when predicting the efficiency of bioleaching systems based on
pH measurements. From this point of view, the present research was carried
out. In practice, however, the total solids concentration might play an
important role in the amounts of substrate and acid required. In the cases of
chemical leaching and bioleaching with ferrous iron substrate the acid
amount must increase with an increase in the total solids concentration. On
the other hand, the possibility of metal extraction at higher sludge solids
concentration can reduce the process costs, by reducing the reactor volume
(Sreekrishnan and Tyagi, 1996). However, a dilution of the sludge, which is
produced in high amounts, will lead to serious operational problems for a
possible scale-up of the process (Lombardi and Garcia Jr., 2002).
75
Chapter 4
Comparison between chemical leaching and bioleaching
Although the pH values achieved with bioleaching were higher than the pH
value of 1 in the chemical leaching with sulfuric acid, Zn and Cu extraction
yields were not so different between the two methods. This is a positive
aspect of bioleaching, since it might reduce the costs of sludge treatment
after the metals solubilization. In contrast, there was almost no Pb and only
a small amount of Cr solubilized by bioleaching.
To easily compare the two leaching methods, the results of the experiments
are summarized in Table 4.1. From bioleaching, only the data referring to
the addition of ferrous iron and acid is shown. Extraction yields of Cr, Cu,
Pb and Zn found in the literature of bioleaching and in previous experiments
with HCl (see Chapter 3) are also included. The table shows the minimum
percentages of heavy metals that should be extracted (considering further
metals removal of 100 %) from the sludge to be under the Dutch standard
for sludge disposal on agricultural soils (SDU, 1991). The values were
calculated based on the initial heavy metals concentration in the sludge. To
allow a comparison of all the methods exposed in Table 4.1, one should
assume that all the sludges are similar, especially in terms of heavy metals
content, speciation, and total solids concentration
Table 4.1 - Heavy metals extraction (%) from sewage sludge

Method pH Cu Zn Cr Pb
% days % days % days % days
H2SO4 (this study)a 1 67.7 4 93.5 5 64.8 2 51.5 2

HCl with 24 h of previous 1 94 1 97.9 1 80.7 1 100 1
aeration (see Chapter 3)a
HCl (see Chapter 3)a 1 49.0 1 89.0 1 72.1 1 96.1 1
Bioleaching with Fe2+/Acid 2.5 65.5 13 80.8 11 25.5 15 c
(this study)a
Bioleaching with S0 - 1 85 d 97 d 56 d
Villar & Garcia Jr. (2002)
(approximated values)a
Bioleaching with Fe2+/Acid - 2 92 10 83 10 55 10 16 10
Xiang et al. (2000)a
Simultaneous sludge digestion 2 75 10 86 10 6 10 6 10
and metal leaching (with S0),
SSDML - Tyagi et al. (1997)b
BOOM (SDU, 1991) 92.3 87.6 83 55.8
a Anaerobically digested sludge; b Aerobically digested sludge; c Negligible; d Not mentioned.
76
Just lowering the pH value of the sludge to 1 is not enough to solubilize Cu

under the Dutch standard. The only situation where Cu extraction achieves
the required value is when HCl is added in combination with previous
aeration of the sludge. Copper might be predominantly incorporated in the
organic fraction of the sludge, which makes its solubilization difficult.
Besides this predominant form, in anaerobic digestion Cu can be present as
Cu2S (solubility product: Ksp= 2.5 x 10-48), which is an insoluble precipitate.
This form can be oxidized by three different reactions, solubilizing the Cu
(Madigan et al., 2003):
Cu2S + ½O2 + 2H+ CuS + Cu2+ + H2O (4)
CuS + 2O2 Cu2+ + SO42- (5)

T. ferrooxidans
CuS + 8Fe3+ + 4H2O Cu2+ + 8Fe2+ + SO42- + 8H+ (6)
From the reactions 4 and 5 it is clear the interference of aeration in the

solubilization of Cu. Reaction 6 shows the effect of the T. ferrooxidans in Cu
extraction. Speciation calculations with Ecosat (Keizer and Van Riemsdijk,
2002) show that when the pH value of the sludge is decreased to 1 with HCl,
soluble Cu-chloro compounds are formed, e.g., CuCl+ (stability constant
Ko= 2.5). On the other hand, when H2SO4 is added to the sludge to achieve
the pH value of 1, the very soluble form CuSO4 (Ko= 250) can be generated,
but in a lower proportion than the Cu-chloro compounds formed when HCl
is added. At a low pH value, however, HSO4- (Ko= 95) might be formed and,
therefore, SO42- is not available to the formation of CuSO4.
The extraction percentages of Zn achieved by chemical leaching with H2SO4,

HCl, and bioleaching with S0 (from Villar and Garcia Jr., 2002) are below the
value required by the Dutch standard. These situations correspond to those
with pH value of 1, leading to the conclusion that Zn solubilization is more
related to the pH than to the conditions of which the pH is achieved, no
matter whether it is by biological or chemical ways.
Although chemical leaching with HCl provides the best value for Cr
solubilization, this extraction value is still higher than the required one. It
was demonstrated that Cr requires a prolonged time at low pH value to be
solubilized by bioleaching. Due to the reducing conditions prevailing in
anaerobic sludges, it is likely that Cr predominates as the trivalent
hydroxide at neutral pH (Hayes et al., 1980; Olver et al., 1975). This is
consistent with speciation calculations with Ecosat (Keizer and Van
Riemsdijk, 2002). In this way, the low solubility product of Cr(OH)3 (Ksp= 1 x
77
Chapter 4
10-30) might explain the small Cr release. The low mobility observed for Cr
also suggests that the adsorption strength of this metal to distinct fractions
present in the sludge is not easily overcome by the acid and oxidative
environment of the bioleaching (Villar and Garcia Jr., 2002).
Lead extraction satisfies the Dutch standard only when HCl is applied to the
sludge, independently on the aeration process. The elevated concentration of
sulfate is a limitation factor to Pb solubilization. The solubility product of
PbSO4 is very low (Ksp= 1.6 x 10-8) and it explains that if the sulfate
concentration is increased, then the concentration of Pb2+ will decrease
accordingly (Mercier et al., 1996). If the concentration of sulfate is reduced,
however, it might increase the solubility of Pb, especially if sulfate ions are
replaced by chloride ions, which form soluble Pb-chloro complexes (Mercier
et al., 1996), e.g., PbCl2 (Ko= 126).
Differences in metals solubilization obtained by the several methods are due

to the different sources of sludge, metals content and speciation, total solids
concentration, and experimental conditions. Despite these factors, it is
possible to conclude which are the best solutions to mobilize Cr, Cu, Pb and
Zn, and their bottlenecks. Even when a more tolerable standard than the
Dutch one is used as reference, one should have in mind that only satisfying
the limits required is not a safe condition for metals disposal in the
environment. Heavy metals removal should be always recommended since
the accumulation of the metal load to a disposal site constitutes a serious
threat to the environment. In addition, the presence of toxic heavy metals in
the sludge is problematic, concerning its further use, leading to low quality
products (Naoum et al., 2001).
Bioleaching is not able to solubilize Pb and, in lower proportion Cr. But

there are advantages to apply this technique in heavy metals removal from
sewage sludge. A combined treatment consisting of bioleaching as a previous
acidification step, and chemical leaching with HCl as a second acidification
step should be investigated. In this way, the costs of the acid addition with
the solely chemical leaching would be reduced. Especially if elemental sulfur
is chosen as substrate, since Villar and Garcia Jr. (2002) showed attractive
results. In addition, the drawback due to the costs of the elemental sulfur
can be surpassed by the use of biological elemental sulfur produced in
micro-aerated reactors. In these reactors, sulfide, the most reduced sulfur
compound (produced in anaerobic reactors), is partially oxidized into
elemental sulfur (Janssen et al., 1998). In fact, elemental sulfur producing
78
reactors is a mature technology and already marketed in northern Europe

(Janssen et al., 2000).
CONCLUSIONS
The present research demonstrated that the bioleaching process can be a

feasible alternative to promote Zn and Cu solubilizations at moderate pH
values, especially when ferrous iron is added as substrate. Under this
condition, the maximum extraction yields obtained for Zn was 80.8 % with
pH value of 2.7, after 11 days and for Cu it was 65.5 % with pH value of 2.5,
after 13 days. Chromium solubilization improved when the pH was below
2.5 and the residence time increased over 11 days. Lead was not released by
bioleaching. From these results it is possible to conclude that bioleaching
optimization requires especial attention with the substrate addition for the
adequate growth of the bacteria, temperature, and aeration conditions. Yet
the results showed that the indigenous microflora of the sludge might be
enough to promote the heavy metals solubilization. Therefore, bioleaching
efficiency depends on how to find the best conditions for these bacteria to
act.
79
Chapter 5

the leachate
Abstract
After solubilization of heavy metals by chemical leaching with previous aeration,
the next step was the separation of the sludge solids from the metal-rich acidic
liquid (leachate) by centrifugation and filtration. Afterwards, the filtered leachate
was submitted to the application of hydroxide precipitation with NaOH and
sulfide precipitation with Na2S, separately and in combination, followed by
filtration. The results showed that when iron and aluminium are present in the
leachate, adsorption and/or coprecipitation of Cr, Pb and Zn with Fe(OH)3 and
Al(OH)3 might occur at increasing pH conditions. The combination of hydroxide
and sulfide precipitation was able to promote an effective removal of heavy metals
from leachate. Applying NaOH at a pH value of 4-5 as a first precipitation step,
followed by filtration and further addition of Na2S to the filtered liquid at pH
values of 7-8 as a second precipitation step, decreased considerably the dosage of
the second precipitant, compared to when it was solely applied. The best removal
efficiencies obtained were: Pb: ∼100%, Cr: 99.9%, Cu: 99.7%, and Zn: 99.9%.
Marchioretto M.M., Bruning H. and Rulkens W.H. Presented at the XXVIII Interamerican
Congress of Sanitary and Environmental Engineering. Cancún, Mexico. October, 2002.
Chapter 5
INTRODUCTION
General
Heavy metals concentrations in sewage sludges vary from one site to

another, depending on the contribution of domestic and industrial input
into the sewerage system. Heavy metals are usually so tightly bound or
incorporated in organic solids and minerals (see Chapter 2) that a mere
physical separation of the major fractions of these metals would be difficult.
Prior to the separation process, a treatment focused on the dissolving heavy
metals is necessary.
To solubilize heavy metals from the sludge solids into the sludge liquid, an
acidification process must be applied (see Chapters 3 and 4). The liquid
containing the solubilized metals is then separated from the suspended
solids fraction by a physical separation step, e.g., centrifugation. The soluble
metallic ions can be ideally converted to insoluble metallic forms by
chemical precipitation. The precipitate formed is subsequently removed from
the liquid by a physical separation process, e.g. sedimentation, flotation, or
membrane filtration. Some bottlenecks of the heavy metals precipitation
process may include (Freeman and Harris, 1995):
Reagent addition must be carefully controlled to prevent unacceptable
concentrations in treatment effluent;
Efficiency of the system relies on adequate solids separation
techniques;
Process generates heavy metals containing sludge, which requires
proper disposal;
Process can be costly depending on reagents used, required system
controls, and required operator involvement in system operation;
In some cases, chemical precipitation has to be performed in
conjunction with coagulation/flocculation processes to facilitate the
agglomeration of suspended and colloidal material (U.S.EPA, 1998).
Relevant aspects
Precipitation and solubility

The heavy metals precipitation step involves the addition of chemical
reagents to adjust the pH of the liquid. The desired pH is one in which the
metals exhibit low (or minimum) solubilities in water and therefore
82
Heavy metals removal from the leachate
precipitate. This ideal pH is dependent on the specific metal-reagent

combination (Freeman and Harris, 1995).
Common reagents used include alkalis, such as lime, magnesia, NaOH,

NaHCO3, Na2CO3, (NH4)2CO3, and NH4OH. Heavy metals like Cr, Cu, Pb and
Zn do not precipitate at a pH value below 7, permitting some possibility for
separation from ferric iron (Lee et al., 2002; Martínez and McBride, 1998;
Brooks, 1991) and aluminium (Lee et al., 2002; Martínez and McBride,
2000), which precipitate at a pH value below 6.5.
The association of heavy metal ions with a ferric or aluminium hydroxide

precipitate is controlled by adsorption or coprecipitation. Adsorption implies
the two-dimensional accumulation of a metal ion at the interface between a
preformed solid and the aqueous phase. Coprecipitation implies the
simultaneous removal of a metal ion during the formation of the primary
metal precipitates (Lee et al., 2002). Due to the potential for adsorption,
coprecipitation and the ion exchange characteristics of the colloidal
hydroxide precipitates, even clear differences in pH for hydroxide formation
are no guarantee of avoiding mixed precipitates when metal mixtures are in
solution (Brooks, 1991).
Sulfides such as Na2S, H2S, NaHS, or FeS can be used to precipitate metals
and have been applied frequently for metal removal from waste effluents to
achieve emission standard limitations (Brooks, 1991; Peters and Ku, 1988).
The lower solubility of metal sulfides in the acid region below pH value of 7
permits reduction of metal solubility to values that are orders of magnitude
lower than are attainable by hydroxide precipitation (Brooks, 1991). Other
advantages of sulfide over hydroxide precipitation are shown later.
To illustrate the solubilities of heavy metals (Al, Cr, Cu, Fe, Pb and Zn)
hydroxides and sulfides as functions of the pH, a diagram is shown in
Figure 5.1. The curves of metals hydroxides and sulfides were calculated on
the basis of the stability constants of the metals complexes and solubility
products of minerals involved, considering ionic strength value below 0.1 M
(Stumm and Morgan, 1996; Smith and Martell, 1981). In this way, according
to Moore (1976), the effect of the ionic strength on the solubility could be
considered negligible in the calculations of the equilibrium relationships of
all the species. As convenient here, the diagram was determined based on
the heavy metals of interest, present in the liquid under investigation.
83
Chapter 5
1.E+02 Pb(OH)2
Fe(OH)3
1.E+01 Cu(OH)2
FeS Zn(OH)2
1.E+00
[Metal] (mg/L)
PbS Cr(OH)3
1.E-01 Al(OH)3
Fe(OH)2
1.E-02 ZnS
1.E-03
1.E-04
CuS Fe(OH)3
1.E-05
0 2 4 6 8 10 12
pH
Figure 5.1 - Solubilities of metal hydroxides and metal sulfides as functions

of pH (calculated for the present research)
Advantages and limitations of sulfide and hydroxide precipitation

The most relevant advantages and limitations of hydroxide and sulfide
processes are included in Table 5.1 (Moore, 1998; Freeman and Harris,
1995; Peters and Ku, 1984):
Table 5.1 - Main advantages and limitations of precipitation methods

Hydroxide precipitation Sulfide precipitation
Advantages Advantages
Low capital and operating costs; Lower pH is required for efficient
Fewer safety-related problems in the removal compared to hydroxide;
treatment than when sulfide is used. Smaller sludge volume than hydroxide;
Sludge exhibits better thickening and
Limitations dewatering characteristics than
hydroxide sludges;
Tendency of resolubilization if the
Removes chromates and dichromates
solution pH is changed;
without previous reduction of chromium
The minimum solubilities for different
to its trivalent state;
metals occur at different pH values;
The influence of complexing agents
Greater sludge volume than sulfide;
(when present) in the precipitation of
Sludge may be difficult to dewater;
metals is less strong than in hydroxide
Hexavalent chromium is not
precipitation;
precipitated;
More complete heavy metals removal
Complexing agents (EDTA, NTA, soluble
than hydroxide.
organic matter, tartrate, etc.) may have
an adverse effect on metal precipitation;
Will not achieve removal efficiency as
Limitations
high as with sulfide. Higher capital and operating costs than
hydroxide;
Potential for toxic hydrogen sulfide gas
and residual sulfide in treated effluent.
84
Nowadays, a combination of hydroxide and sulfide precipitation for optimal

metals removal is being considered (U.S.EPA, 1998). A common
configuration is a two-stage process in which hydroxide precipitation is
pursued by sulfide precipitation with each stage followed by a separate
solids removal step. This will produce the high quality effluent of the sulfide
precipitation process. Moreover, it will reduce the consumption of sulfide
reagents, which are more expensive than hydroxide reagents (e.g., lime and
caustic), and will result in a smaller amount of sludge compared to the
hydroxide precipitation process alone (U.S.EPA, 1998).
Residues of the precipitation process

Chemical precipitation can remove heavy metals from the contaminated
liquid. But a factor that negatively affects the ranking of the technology is
that metal containing sludges are produced during the process. The disposal
of metal hydroxides and metal sulfides sludges will have to attend to
regulations. In some cases, the sludge may be dewatered to the maximum
extent possible, drummed and disposed of in a secure landfill (Freeman and
Harris, 1995). A process of metals recovery from the sludge in order to reuse
them as metal ore should be also evaluated. The water phase including high
concentration of sodium chloride, due to the use of HCl for metals
solubilization, and NaOH combined with Na2S for metals precipitation,
should be correctly discharged or reused in a proper way. In addition,
dissolved organics are also likely to be present in this liquid, as a result of
the acidification process.
Despite its bottleneck, chemical precipitation is still one of the most effective
alternatives to remove heavy metals from contaminated liquids. In case of
sewage sludges containing high amount of heavy metals, it is a promising
technique to separate mobilized heavy metals. Chemical precipitation is able
to remove the heavy metals from a huge fraction, e.g., sewage sludge,
producing a smaller amount of a metal rich sludge.
Normally, recovery and reuse of metals separated from metal rich sludges
will not be economical, unless the commercial value of the metals is high
enough to justify the costs of separating these metals from the sludge and
from the other metals in the sludge. In general, for sewage sludge or
wastewater contaminated with multiple metals, which have been previously
mobilized, a series of selective precipitation treatment steps using different
pH values and/or different treatment chemicals is being well considered
85
Chapter 5
(U.S.EPA, 1998). This alternative, however, might be only applicable if the

purpose is the recovery and sale of the high purity metal precipitates, as
demonstrated by Tabak and Govind (2002) for acid mine water. Each
precipitation step needs to be followed by a solids separation step in order to
prevent the resolubilization of metal precipitates during the subsequent
treatment step (U.S.EPA, 1998).
Nowadays, an interesting alternative to the use of chemically produced

sulfide compounds is the application of the biogenic hydrogen sulfide formed
from sulfate reduction by hydrogen consuming sulfate-reducing bacteria
(Gilbert et al., 2002; Tabak and Govind, 2002). Biogenic sulfide precipitation
has been investigated for treatment of acid mine drainage and industrial
wastewaters (Tabak and Govind, 2002; Foucher et al., 2001). This option is
also very promising in the treatment of sewage sludges aiming at heavy
metals removal. Especially when metals sulfate are present in the leachate,
which is a result, for instance, of the sludge acidification with sulfuric acid
produced by bioleaching process. This treatment possibility would prevent
the generation of the liquid containing high concentration of sodium chloride
(see detailed discussion in the next chapter).
Particle size of precipitates

The particle size of precipitates is an important factor in the present work,
as it will be demonstrated later. According to Veeken et al. (2003), the
particle size of precipitates depends on the competition between nucleation
and crystal growth. When the nucleation rate dominates the crystal growth
rate, colloidal particles (< 0.05 µm) will result. If the initial concentration of
the reactant is high, consequently increasing the concentration of the
precipitate, which has a low solubility, the resulting high supersaturation
leads to high rates of a primary nucleation (Mersmann, 1999). Primary
nucleation occurs with formation of clusters of molecules at the sub-
micrometer level. If a coarse product is desired, the supersaturation must be
kept low by using low concentration of the reactants (perhaps by dilution),
appropriate micromixing in the entire precipitator, and seeding by high
recycling rates of slurry to decrease local supersaturation peaks by crystal
growth (Mersmann, 1999).
When a mixture of heavy metals is present in the liquid to be treated, it is

likely that each metal precipitate particle size evolutes differently from the
86
others. Therefore, in practice, it might be difficult to find an optimal crystal

growth rate for all the metals studied. This point is discussed later.
Scope of the study
This chapter deals with the precipitation of heavy metals from the leachate,
which is separated from the sludge particles by centrifugation and filtration,
after the solubilization of the heavy metals. The objective is to gain insight in
the feasibility of the process, regarding the type of chemicals to be used, and
the required dosages. On the basis of literature, hydroxide precipitation with
NaOH and sulfide precipitation with Na2S are investigated here. Both
precipitating agents are applied solely and in combination, followed by a
filtration step. The chemicals are dosed according to pH values varying from
4 to 11 and the occurrence of adsorption and coprecipitation is considered.
EXPERIMENTAL
The origin and main characteristics of the sludge applied in this research as
well as the chemical and physical distribution of heavy metals in the sludge
are presented in detail in Chapter 2.
Analysis
The procedures and equipments for heavy metals and pH analysis are
described in Chapter 2.
To achieve the best conditions for heavy metals solubilization (see the
complete study in Chapter 3), samples of 1 L of the sludge were subjected to
previous aeration, followed by acidification, centrifugation and filtration.
Both aeration and acidification were applied during 24 hours, with
continuous shaking (150 rpm), at 20 °C. During aeration the air flow rate
was 1.5 L/h. Acidification with 13.9 g/L (380 mM/L) of hydrochloric acid
was applied to decrease the initial pH value of the original sludge (around 8)
to 1.
87
Chapter 5
The acidified samples were centrifuged at 4000 rpm during 30 minutes. The
acidic supernatant containing the dissolved heavy metals (leachate) was
filtered by paper filter S&S black ribbon (12-25 µm) to remove residual small
particles and the resulting liquid was used in the heavy metals precipitation
experiments. The heavy metals concentration in this filtered leachate and in
the original sludge is shown in Table 5.2. In this table, the concentrations of
aluminium and iron in the sludge and in the leachate are also shown in
order to facilitate further discussion.
Table 5.2 - Heavy metals content of the original sludge and the leachate
applied in the precipitation experiments
Fraction Heavy metals content in mg/L [% OS]a
Al Cr Cu Fe Pb Zn
Original Sludge (OS) 680 9.2 19.8 500 4.9 35
(pH= 8)
Leachate 578 [85] 7.2 [78.3] 18.4 [92.9] 450 [90] 4.8 [99.7] 34 [97]
(pH= 1)
a Percentage of heavy metals in the leachate related to the total heavy metals content in the sludge.
Precipitation experiments
The precipitation experiments were carried out in three phases. In the first
phase hydroxide precipitation was studied with NaOH application in such
doses to increase the original pH value of the liquid from 1 till 5, 7, 9 and
11. In the second phase, sulfide precipitation with Na2S was applied at the
same pH values used in the first phase. In the third phase of the
experiments a combination of hydroxide and sulfide precipitation was
investigated. Initially, NaOH was added to the liquid till the pH values of 4
and 5 were both achieved. These pH values were determined according to
the results of the previous phases. After NaOH addition the liquids were
filtered and submitted to Na2S addition in such dosage to reach the pH
values of 5, 5.5, 6, 7, and 8. The chemical dosages are shown in Table 5.3
and expressed in gram and millimol per litre of leachate.
After each experiment the liquid was filtered by paper filter S&S black
ribbon (12-25 µm) and two samples were collected and analyzed for their
heavy metals (Cr, Cu, Pb, and Zn) content. All the experiments were
performed in duplicates, with continuous shaking (100 rpm) during 60
minutes. Figures 5.2 to 5.4 show the schemes of the precipitation
experiments and the previous heavy metals solubilization procedure.
88
Table 5.3 - Chemical dosages applied in the experiments

Type of NaOH Na2S
experiment pH g/L mM/L pH g/L mM/L
Single 5 10.7 270 5 11.6 150
precipitation 7 11.4 290 7 18.6 240
9 13.2 330 9 26.3 340
11 16.4 410 11 35.5 460
Combined 4 10.3 260 5 0.042 0.54
precipitation I 5.5 0.046 0.59
6 0.049 0.63
7 0.063 0.81
8 0.095 1.2
Combined 5 10.7 270 5.5 0.003 0.038
precipitation II 6 0.004 0.051
7 0.014 0.18
8 0.056 0.72
Aeration Centrifugation
+
HCl
(pH= 1)
Filtration
Original Precipitation
sludge experiments
pH= 1 pH= 1 Heavy

metals analysis
Figure 5.2 - Scheme of the heavy metals solubilization experiments
89
Chapter 5
NaOH Na2S
Filtration
Heavy metals
analysis
Figure 5.3 - Scheme of the single precipitation experiments
Heavy metals
NaOH analysis Na2S
Filtration
Heavy metals
analysis
Figure 5.4 - Scheme of the combined precipitation experiments
Single precipitation
Figure 5.5 shows the percentage of the remaining heavy metals

concentration in the filtered liquids resulted from the precipitation
experiments, at different pH values. The duplicate values differed from the
mean by 4.5 % at most. When hydroxide precipitation was applied, Cu
removal was very low, independently on the range of the investigated pH. At
a pH value of 5, Zn removal was similar to Cu removal, but at higher pH
90
values it improved. In general, sulfide precipitation was more effective in

removing all the metals together even at pH value of 5.
Pb Cr Cu Zn
NaOH Na2S
1.E+02 100.00
1.E+01 10.00
[Metal] (mg/L)
1.E+00 1.00
1.E-01 0.10
1.E-02 0.01
1.E-03 0.00
0 2 4 6 8 10 12 0 2 4 6 8 10 12
pH pH
Figure 5.5 - Heavy metals content in the remaining liquid after

hydroxide and sulfide precipitation followed by filtration
(at pH= 1: initial metals concentration in the leachate)
Before explaining the results exposed in Figure 5.5, it is convenient to

observe Figure 5.6, which was plotted on basis of Figure 5.1. The diagrams
of metal sulfides and hydroxides are shown separately and the initial metals
concentration in the leachate is indicated in the curve of the correspondent
metal precipitate. The initial concentration of Pb is below the curve of
Pb(OH)2 and it appears only in the PbS curve. The initial Cu concentration is
above the CuS curve and it is not shown either.
1.E+03 1.E+03
Pb(OH)2
[Metal] (mg/L)
1.E+01
1.E+01 Zn(OH)
Al(OH)3
1.E-01
Fe(OH)3
1.E-01 Cr(OH)3 PbS
ZnS
1.E-03 FeS
Cu(OH)2 CuS
1.E-03 1.E-05
0 2 4 6 8 10 12 0 2 4 6 8 10 12
pH pH
Figure 5.6 - Solubilities of metal hydroxides and metal

sulfides as functions of pH
(• Initial metals concentration)
91
Chapter 5
Hydroxide precipitation
From Figure 5.6, it is clear that Cu, Cr, Zn, and Pb were not able to form
hydroxide precipitates at pH values below 6 (Cu), 7.2 (Cr), and 7.5 (Zn).
Figure 5.5 shows, however, that more than 99 % of Cr and Pb were already
removed at pH value of 5. When the pH value was higher than 5, Zn started
to be removed and when the pH achieved the value of 7.5, more than 99 %
of this metal was already removed. At the pH value of 9 Zn achieved its best
removal efficiency and this was close to the value obtained in Figure 5.6.
As exposed in Table 5.2 and Figure 5.6, Fe and Al are abundant in the
sludge and in the acidified liquid, comparing to the other metals. Figure 5.6
shows that Fe(III) and Al can start forming hydroxide precipitates at pH
values of 1.3 (Fe) and 3.5 (Al). These curves suggest that adsorption and/or
coprecipitation of Cr, Pb and Zn with Fe(OH)3 and Al(OH)3 were taking place
as the dominant factors in the removal of these metals. In this way, the
removals of Cr, Pb and Zn depend on the precipitation of Fe and Al, which
act as sorbents (Lee et al., 2002) and coprecipitants.
From Figure 5.6, it is observed that Cu(OH)2 has the lowest solubility among
Cu, Cr, Pb, and Zn hydroxides. This contradicts the extremely low removal
achieved for Cu. On the other hand, when the precipitate has low solubility
products, supersaturation is favored and consequently the nucleation rate
increases, as the particle sizes decrease (Veeken et al., 2003; Mersmann,
1999). In fact, after filtration, the liquid was a bit turbid and this is an
indication of the high nucleation rate. This might be a strong reason for the
low retention of Cu hydroxide (co)precipitate in the paper filter.
The low Cu removal by coprecipitation with Al and Fe obtained in the

present experiments are not in accordance with Lee et al. (2002) and
Martínez and McBride (2000) who found more promising results for waters
contaminated with acid mine drainage and a synthetic water, respectively.
Such differences might be due to the presence of soluble organic matter
(SOM) in the leachate (which was probably not present in the waters used by
those authors). The affinity of Cu to organic matter is discussed in Chapter
2. According to Fletcher and Beckett (1987a;b), at a pH value over 7, there is
less competition between Cu and other protons for sites on the SOM and
thus a high concentration of Cu is likely to be bound to the SOM. These Cu-
SOM complexes formed were probably at the colloidal range, which was
probably smaller than the filter pore size (12-25 µm) that was used.
92
Sulfide precipitation
When Na2S was applied at a pH value of 5, all the metals were removed at a
level of 99 %, (see Figure 5.5). Figure 5.6 confirms that at pH value below 5,
ZnS, PbS and CuS precipitates already started to form. But still, adsorption
and coprecipitation with Fe and Al might also occur also when Na2S is
applied. Lead showed the highest removal efficiency of all the metals. Figure
5.5 suggests that, at a pH value below 5, PbS was already almost totally
removed. Zinc sulfide removal was less efficient at a pH value of 7 than at a
pH value of 5. Perhaps the threshold for increasing the solubility of ZnS is at
this pH range. However, this explanation cannot be confirmed by Figure 5.6.
The residual concentrations of Zn (around 0.05 mg/L) and Cu (around 0.1
mg/L) at pH value of 8 were identical to those obtained by Bhattacharyya et
al. (1979).
According to Figure 5.6, CuS should present the highest removal efficiency
of all the other metal sulfides. But this is not observed in Figure 5.5. Despite
the relatively high range of removal, there might be some factors affecting its
increase. A possible explanation is the fact that CuS has a very low
solubility comparing with ZnS and PbS. As explained before, the low
solubility product favors the decrease in the particle sizes (Veeken et al.,
2003; Mersmann, 1999). This was confirmed by the experiments, because
the filtrated liquid was somewhat dark turbid. In addition, in the case of
sulfide precipitation, it is not possible to affirm that the formation of Cu-
SOM complexes would occur when the pH value was up to 7. Moreover, the
slight decrease in CuS removal at a pH value over 6, as shown in Figure 5.5,
could be due to the change in the solubility of CuS at this pH. However, this
explanation cannot be confirmed by Figure 5.6.
Chromium (III) sulfide is not likely to occur here, because in water this is a
very unstable form (Weast, 1979). When Na2S was applied, it seems that Cr
was still being removed by adsorption and coprecipitation with Fe(OH)3 and
Al(OH)3 that might be present in the liquid as long as the pH value
increases. Comparing both graphs of NaOH and Na2S in Figure 5.5, Cr
removal was better when NaOH was applied, since Fe(OH)3 and Al(OH)3
might be formed in larger extend than when Na2S is used.
Combined precipitation
Figure 5.7 shows the percentage of the remaining heavy metals in the
filtered liquids resulted from a precipitation process consisting of previous
93
Chapter 5
application of NaOH to achieve pH values of 4 and 5, followed by Na2S

dosing. After each precipitation step, the liquids were filtered. The initial pH
values of 4 and 5 were chosen because according to the Figure 5.5, sulfide
precipitation was already efficient at pH value of 5. The duplicate values
differed from the mean by 3.5 % at most.
With initial pH value of 4, obtained after precipitation with NaOH, metals

were removed at lower pH with Na2S than when the initial pH value was 5.
At the highest initial pH value, the removal of metals by the subsequent
sulfide precipitation was more difficult, especially for Cu and Zn.
Pb Cr Cu Zn
Initial pHNaOH= 4 Initial pHNaOH= 5

1.E+02 100.00
1.E+01 10.00
[Metal] (mg/L)
1.E+00 1.00
1.E-01 0.10
1.E-02 0.01
1.E-03 0.00
0 2 4 6 8 0 2 4 6 8
pH pH
Figure 5.7 - Heavy metals content in the remaining liquid after

combined hydroxide and sulfide precipitation followed by filtration
(at pH= 1: initial metals concentration in the leachate)
Before explaining the results shown in Figure 5.7, it is important to

understand what happened with the heavy metals when NaOH was
previously applied. From the results of single precipitation (see Figure 5.6),
all the metals, with exception of Cu, were probably adsorbed and/or
coprecipitated with Fe(OH)3 and Al(OH)3 at pH value over 5 (Zn) or below 5
(Cr and Pb). Figure 5.7 shows that at pH value of 5 Cr and Pb were better
removed than at pH value of 4. This might be due to the fact that at the
higher pH value, Fe(OH)3 and Al(OH)3 were better formed, as presented in
Figure 5.6. As observed before, Cr achieved its best removal efficiency at a
pH value of 7.
From Figure 5.7, when more Na2S was applied, as in the case when the
initial pH value was 4 (Na2S and NaOH doses are shown in Table 5.3), the
94
formation of Zn and Cu sulfide precipitates occurred at a lower pH value

than when less Na2S was applied (when the initial pH value was 5).
Comparing Figure 5.5 and Figure 5.7 with Na2S addition, it is observed that
a high removal of ZnS can be obtained at a high pH value, since in all the
three graphs the curve of ZnS is still going down at the last pH value
measured.
When Na2S was solely applied, the highest removal of Cu occurred at a pH

value of 5, whereas in the combined precipitation (with both initial pH
values of 4 and 5) the same removal efficiency was achieved only at a pH
value of 7. These differences are due to the low initial Cu removal obtained
when NaOH was applied. As mentioned before, although Cu achieved a high
removal efficiency, in theory (see Figure 5.6) this value should be even
higher. The formation of Cu-SOM complexes and the low solubility of
Cu(OH)2 and CuS are the probable reasons for this fact.
Furthermore, from Figure 5.7, when the pH value is raised to 4 or 5 by

NaOH, it should be increased another 3 pH-units by Na2S to obtain the
highest metals removal. The option with less Na2S dosage seems to be
advantageous since this chemical is at least 4 times more expensive than
NaOH (per mol) and more toxic. Comparing the chemical doses required for
single sulfide precipitation and the amount of Na2S needed for the combined
precipitation, in the second case much less precipitant is needed to achieve
the same metals removal. This can be observed in Table 5.4, where the
highest removal efficiencies obtained are displayed.
Table 5.4 - Highest heavy metal removal efficiencies achieved at different

process conditions
Situation pH Dosage (mM/L) Heavy metal
NaOH Na2S NaOH Na2S Cu Cr Pb Zn
Na2S - 5 - 150
Removal (%) 99.4 99.2 100 99.9
[Metal] (mg/L)a 0.1 0.05 0 0.03
NaOH + Na2S 4 7 260 0.81
Removal (%) 99.7 99.9 100 99.7
[Metal] (mg/L)a 0.05 0.007 0 0.1
NaOH + Na2S 5 8 270 0.72
Removal (%) 99.7 99.9 100 99.9
[Metal] (mg/L)a 0 0.06 0.008 0.07
a Heavy metal concentration remaining in the leachate after precipitation and filtration.
95
Chapter 5
From Table 5.4 it is clear the advantage of the combined hydroxide and
sulfide precipitation over the single sulfide precipitation, in terms of Na2S
dosage and removals of Cu and Cr. In accordance with Charerntanyarak
(1999) and Bhattacharyya et al. (1980), the results show that a combination
of hydroxide and sulfide precipitation is an effective alternative to remove
heavy metals from sewage sludges leachate or wastewaters.
For the main goal of this research it is appropriate to find the lowest cost
solution, where the heavy metals are removed to acceptable concentrations,
enabling the discharge of the liquid. As mentioned before, proper destination
for the metal concentrated sludge must be attended and the possibilities of
heavy metals recovery from this sludge should be also evaluated. In that
respect, the presence of aluminium and iron in the sludge leachate is a
relevant fact.
CONCLUSIONS
With the combination of hydroxide and sulfide precipitation followed by a

separation process, highly effective separation of heavy metals from the
metal-rich acidic liquid (leachate) is obtained. The leachate is resulted from
the separation with the sludge solids by centrifugation and filtration. Before
the separation step, the sludge is previously aerated and acidified in order to
promote heavy metals solubilization.
The dissolved heavy metals present in the leachate are precipitated. The
combination of NaOH (pH equal to 4 and 5) and Na2S (pH equal to 7 and 8
respectively) is able to reduce considerably the dosage of the second
precipitant, when it is solely applied.
Moreover, when iron and aluminium are present in the leachate, adsorption
and/or coprecipitation of Cr, Pb and Zn with Fe(OH)3 and Al(OH)3 might
occur at increasing pH conditions.
96
Chapter 6
General discussion
Chapter 6
INTRODUCTION
Despite the numerous studies in the field of heavy metals removal from
sewage sludges, soils and sediments over the last three decades, the
techniques applied for this purpose still remain in the laboratory and pilot
plant scale. In order to get more scientific and practical insights into this
topic, a study focusing on the removal of heavy metals from anaerobically
digested sewage sludge was performed.
This closing chapter will briefly discuss the relevant aspects found in this
research and how they may lead, together with the already available
information, to the implementation of techniques for heavy metals removal
from sewage sludges. This chapter will discuss the following issues:
Physical-chemical characterization of heavy metals in the sludge:

Physical distribution of heavy metals in the sludge;
Chemical speciation of heavy metals using sequential chemical
extraction (SCE).
Heavy metals solubilization:

Chemical leaching of heavy metals;
Bioleaching of heavy metals.
Heavy metals removal from the leachate:

Hydroxide and sulfide precipitation.
Technological aspects:
Conceptual design for a physical-chemical process to remove heavy
metals from sewage sludges;
Conceptual design for a biological-physical-chemical process to
remove heavy metals from sewage sludges.
PHYSICAL-CHEMICAL CHARACTERIZATION OF THE SLUDGE
The initial step in the investigation of technologies applied for heavy metals
removal from anaerobically digested sludge was a detailed physical-chemical
characterization of these metals in the sludge material. First, a physical
distribution of the heavy metals in the sludge was carried out, separating
the sludge into different particle-sized fractions by a wet-sieving process.
The dry matter, organic matter and heavy metals content were determined
98
General discussion
in each size class and in the total sludge sample. Second, the chemical
speciation of the heavy metals in the sludge was investigated by using three
different sequential chemical extraction (SCE) schemes.
The results demonstrated that heavy metals were mostly concentrated in the
fractions < 0.063 mm, constituting about 70 % of the total sludge mass and
contributing 78-85 % of the heavy metals present in the sludge. In all the
separated fractions, however, most of the metals concentrations exceeded
the Dutch standard (BOOM). This indicates that if land application is
considered, then the whole sludge has to be treated, without any previous
separation.
A previous physical separation of the sludge can be useful in the case when
the heavy metals concentration in a certain fraction exceeds the local limits
for land application of the sludge and when the volume of this fraction is
quite considerable compared to the total volume of the sludge. Usually, the
fraction with the lowest heavy metals content comprehends particles with
size larger than 0.5 mm. In the case of the sludge used in this research, this
fraction represented only 4-7 % of the total sludge mass, and consisted of
more than 80 % of organic matter. Still, depending on the volume of the
sludge to be treated, the 4-7 % of the total sludge mass with low heavy
metals concentrations could be separated, disposed, and contribute to a
decrease in the dimensions of the sludge treatment plant. Moreover, in case
that sludge can be separated in a relatively large fraction that is slightly
polluted and a small fraction that is strongly polluted, mild process
conditions might be sufficient to reduce metals concentration in the larger
fraction.
Chemical speciation of heavy metals using SCE (sequential chemical

extraction)
Several SCE schemes are applied as a useful assessment tool for evaluating
heavy metals mobilization in the sludge matrix and for discussing further
results obtained with sludge treatment techniques. Although there are many
SCE schemes, it is observed in literature that, in general, researchers apply
only one scheme to sludge, soil or sediment materials and use the results as
a unique speciation profile. This can be a risky procedure, especially
because of the wide variety in the nomenclature proposed for each
99
Chapter 6
extraction step of the SCE schemes. For this reason, it is wise to evaluate
the SCE schemes according to the type of chemicals used (electrolyte, weak
acid, oxidizing agent, chelating agent, reducing agent, strong acid), and not
only to the fractions names given by different authors. Moreover, the
evaluation of a SCE procedure must be always associated to the
experimental conditions applied, with respect to temperature, pH and
reaction time.
In the present research, as a tentative to investigate the causes of the

differences among the results obtained with three original SCE schemes
tested, two modified schemes were developed. In this way, some conditions
were slightly altered from original ones. The results of the application of the
three original SCE schemes and the two modified SCE schemes showed that
different procedures supply different results for the heavy metals speciation.
The experiments carried out here demonstrated that although the two
modified SCE schemes gave different results from the original schemes, they
provided valuable information for interpretation of the differences in the
results of the original SCE schemes.
Despite the uncertainty of the SCE method with respect to selectivity (metals
bound to more than one phase are solubilized) and specificity (more than
one phase is solubilized), it gives useful information concerning the
availability of the metals. The SCE results of the investigated sludge revealed
that Cr (65 - 67 %) and Cu (65 - 87 %) could be effectively released in an
oxidizing environment (85 °C, pH= 2). Zinc (78 - 86 %) could be extracted by
a reducing agent (96 °C, pH= 2), whereas Pb (62 - 81 %) could be solubilized
at strong acidic conditions at high temperature (150 °C in the microwave
oven). Furthermore, a chelating agent (20 °C, pH= 4.5) was able to release
considerable amounts of Cr (56 - 57 %), Pb (57 - 78 %) and Zn (50 - 62 %).
About 70 % of Cu could be also extracted with application of high pH (12.6)
at 20 °C.
100
General discussion
HEAVY METALS SOLUBILIZATION
In sewage sludges, heavy metals are usually so tightly incorporated or

bound to minerals and organic solids, that only at extreme acidic conditions
these metals can be sufficiently released to the liquid. Despite the high costs
of acid addition in the chemical leaching process, this technique can still be
considered as a practical step in the heavy metals removal from sewage
sludges. In fact, there is no other feasible alternative, except for bioleaching.
Particularly in the case of anaerobically digested sludges, the highest heavy

metals solubilization, especially copper, can be obtained if the oxidation-
reduction potential (ORP) of the sludge is increased, before the low pH
conditions are applied by acidification. The ORP can be raised either by
means of biological or chemical oxidation, which can be achieved through
aeration. Chemical oxidation can also occur by the addition of an oxidizing
agent like hydrogen peroxide, which in the presence of sludge can lead to
Fenton reactions.
This research evaluated the chemical leaching as an applicable technique for

the anaerobically digested sewage sludge treatment, aiming at heavy metals
removal. For this aim, several acids were tested at different conditions of pH,
reaction time and ORP. The effect of acidification was intensively tested for
liquid samples of the sludge and briefly tested for dried and crushed
samples of the sludge. The influence of the chemical oxidation on the heavy
metals solubilization was also investigated by applying aeration or adding
hydrogen peroxide.
aeration or hydrogen peroxide followed by acidification with hydrochloric
acid resulted in the highest extraction yields of almost all heavy metals.
Especially copper extraction was highly influenced by oxidation. This might
be due to its speciation in the sludge. The SCE schemes suggested that Cu
is tightly bound to organic matter and this bond might become less strong
when an oxidation step is applied. In anaerobically digested sludges, it is
likely that metal sulfides are also present. When the ORP of the sludge is
raised, the transition of the very insoluble metal sulfides (e.g., Cu2S) to the
very soluble metal sulfates (e.g., CuSO4) will occur.
101
Chapter 6
The highest extraction efficiencies achieved at different acidification and

oxidation situations for all the heavy metals studied are summarized in
Table 6.1, which is exposed in the next section.
Despite the numerous studies on bioleaching over the last two decades, the
application of this technique in the solubilization of heavy metals from
sewage sludge still prevails under laboratory and pilot plant scale. This
study was executed in order to gain more insights into the practical
application of bioleaching in the solubilization of heavy metals from
anaerobically digested sludge, its advantages and shortcomings. For that,
bioleaching using elemental sulfur and ferrous iron as substrates was
investigated and compared with chemical leaching with sulfuric acid and
aeration.
The results showed that, although the pH values achieved with bioleaching
were not as low as in the chemical leaching with sulfuric acid, Zn and Cu
extraction efficiencies were not highly different between the two methods.
Differently from Cu and Zn, bioleaching was not able to solubilize Pb and
only a small amount of Cr was released. The removal efficiencies obtained
were lower than those found in the literature (Villar and Garcia Jr., 2002;
Xiang et al., 2000) for the same type of sludge and substrate. These
differences might be due to the different sources of sludge, metals content
and speciation, total solids concentration, pH and experimental conditions.
In the case of the present research, it is possible to conclude that the

optimization of the bioleaching process requires especial attention with
respect to the substrate addition for the adequate growth of the bacteria,
temperature, and aeration conditions. Yet the results showed that the
indigenous microflora of the sludge is able to promote the heavy metals
solubilization. The bioleaching efficiency depends on how to find the best
process conditions for the microbiological activity.
To easily compare the leaching methods applied in this research, the results
are summarized in Table 6.1. The table also includes some literature
information.
Table 6.1 - Heavy metals extraction efficiency (%) from anaerobically

digested sludge using different methods
102
General discussion
Method pH Cr Cu Pb Zn
% Days % Days % Days % Days
HCla 1 72 1 49 1 96 1 89 1
Aeration + HCla 1.4 81 1+1c 94 1+1c 100 1+1c 100 1+1c
H2O2 + HCla 1.6 86 1+1c 100 1+1c 100 1+1c 100 1+1c
H2O2 + H3PO4a 1.6 92 1+1c 87 1+1c 100 1+1c 100 1+1c
Bioleaching with 2.5 25.5 15 65.5 13 d 81 11
FeSO4 + H2SO4a
Bioleaching with 2 55 10 92 10 16 10 83 10
FeSO4 + H2SO4
(Xiang et al., 2000)
Bioleaching with So 1 56 e 85 e 97 e
(Villar and Garcia
Jr., 2002)
Aeration + H2SO4a 1 65 2 68 4 51.5 2 93.5 5
HNO3b 1 72 1 56 1 87 1 66 1
HNO3b 1 81 5 74 5 90 5 77 5
HClb 1 68 1 79 1 94 1 84 1
aLiquid sludge; b Dried and crushed sludge; c Oxidation time + acidification time; d Negligible; e Not
mentioned.
Table 6.1 highlights that an oxidative step with either aeration or hydrogen
peroxide favors the extraction of the heavy metals, especially Cu. When HCl
was applied without the oxidation step, the result of Cu extraction for the
dried sludge was better than that for the liquid sludge. From a practical and
economical point of view, however, the process of drying and crushing the
sludge does not seem to be feasible.
Another important aspect shown in Table 6.1 is that, although HNO3 is an

oxidizing agent, it requires, particularly for Cu, prolonged extraction times
(about 5 days) to achieve similar extraction efficiencies as obtained with HCl
at the same pH value (around 1). Another disadvantage of HNO3 is its higher
costs (per mol) compared to HCl (factor 7). Nevertheless, different from HCl,
HNO3 has the advantage to be biodegradable.
Table 6.1 also shows that, in combination with H2O2, both HCl and H3PO4
were able to solubilize high percentages of heavy metals. However, the
dosage of H3PO4 (in mol/L) needed to decrease the pH to a proper value is at
least 2 times more than the dosage of HCl. Furthermore, H3PO4 costs (per
mol) are about 1.5 times more than the costs of HCl.
103
Chapter 6
According to Table 6.1, acidification with H2SO4 (chemically or biologically

produced) is not the best option to promote the extraction of Pb when this
metal is present in high concentrations in the sewage sludge. The formation
of the insoluble PbSO4 is the reason for that.
HEAVY METALS REMOVAL FROM THE LEACHATE
Hydroxide and sulfide precipitation
In the present research, the first step in the removal of heavy metals from
the sludge was a solubilization by chemical leaching with previous aeration.
The next treatment step was a separation of the sludge particles from the
metal-rich acidic water phase (leachate) by centrifugation. Thereafter, the
leachate was filtered (to remove remaining suspended particles) and sent to
a precipitation reactor. Hydroxide precipitation with NaOH and sulfide
precipitation with Na2S were investigated by applying both precipitating
agents separately and in combination, followed by filtration.
The results showed that, when iron and aluminium are present in the
leachate, adsorption and/or coprecipitation of Cr, Pb and Zn with Fe(OH)3
and Al(OH)3 might occur at low pH conditions, at which the heavy metals
hydroxides are still soluble. The results also demonstrated that, with the
combination of hydroxide and sulfide precipitation, highly effective removal
of heavy metals was obtained. The combination of NaOH and Na2S was able
to reduce considerably the dosage of the second precipitant, compared to
when it was solely applied. It is advantageous to reduce the dosage of Na2S,
since this chemical costs (per mol) are at least 4 times more than the costs
of NaOH and has a potential to release toxic hydrogen sulfide gas at low pH.
TECHNOLOGICAL ASPECTS
Based on the results obtained, two conceptual designs for heavy metals
removal from sewage sludge are presented and discussed. One refers to a
physical-chemical treatment (Figure 6.1) and the other to a biological-
physical-chemical treatment (Figure 6.2).
104
General discussion
Conceptual design for a physical-chemical process to remove heavy

metals from anaerobically digested sludges
Influent Wastewater treatment plant Effluent

(sludge digestor)
pH ≅ 8 Anaerobically digested sludge

+
heavy metals
HCl
pH ≅ 1
Aeration/H2O2
Leachate
Chemical pH ≅ 1 Particle + Hydroxide
leaching separation heavy metals precipitation
(pH ≅ 1)
reactor
pH ≅ 1 MeOH Particle
sludge separation
Sludge
“without”
heavy metals
Sulfide
precipitation
MeS
sludge
Particle
separation
High salinity
liquid
Figure 6.1 - Scheme of a conceptual design for a physical-chemical process

to remove heavy metals from anaerobically digested sludge
The first process step consists of heavy metals solubilization by acidification

with HCl (pH value around 1) with a previous oxidative pre-treatment (in the
same reactor) either by aeration or by H2O2.
105
Chapter 6
The second step comprises a separation of the water phase containing the
mobilized heavy metals and the sludge particles. The separator might be a
hydrocyclone, a centrifuge, a settler, a flotation tank, or a filtration device.
The sludge is removed as a concentrated sludge. After the pH correction
with lime and dewatering, the sludge can be disposed to land, perhaps used
as compost for soil improvement or as part of a material for civil
construction. It is important to realize that the quality of this sludge for
agricultural purposes might be negatively influenced by the acidification
step. As such, nutrients like phosphorus and potassium might be present in
the leachate.
The third step is the precipitation of the heavy metals and the application of
a separation unit for the removal of the obtained precipitate. The
precipitation process is first executed by adding NaOH up to a pH value of 4
to 5. This hydroxide precipitation is followed by a separation step. After
removal of the metal hydroxides flocs, a second precipitation step takes
place by using Na2S. The resulted metal sulfides flocs are separated from the
water phase in a separator. The concentrated metal hydroxides and metal
sulfides sludges should be properly disposed as hazardous waste. A process
of metals recovery from the slurry in order to reuse them as metal ore is also
possible. It might be, however, complicated and expensive. The water phase
including high concentration of NaCl and dissolved organics should be
discharged or reused in a proper way. Selective precipitation of nutrients
from the leachate should be considered as an option for the treatment.
This conceptual design of a physical-chemical process for heavy metals

removal from sewage sludge is very effective in achieving its main goal.
However, there are some drawbacks inherent to this option. The costs of the
chemicals (HCl, NaOH, Na2S) and the oxidation process (aeration or H2O2)
associated to the excess of NaCl in the final effluent constitute the major
bottlenecks. One possibility is to redirect this final effluent to the beginning
of the wastewater treatment plant, depending on the already existent
concentration of NaCl in the influent of this plant. For the costs evaluation
the required treatment time must be also considered.
106
General discussion
Conceptual design for a biological-physical-chemical process to remove

heavy metals from anaerobically digested sludges
A modification of the first conceptual design is presented in Figure 6.2. The

idea is to use the benefits of the bioleaching technique, which is mediated by
acidophilic bacteria (genus Thiobacillus) able to produce acid.
Influent Wastewater treatment plant Effluent

(sludge digestor)
Liquid
pH ≅ 8 Anaerobically digested sludge
+
heavy metals
Particle
separation
FeSO4 or S0 S0
HCl
(if necessary)
E- donor
Aerobic Liquid
+
bioreactor
Biological HS- Micro-
(bioleaching) sulfate- aerated
reducing reactor
pH ≅ 2 reactor
pH > 5
Particle Leachate
separation +
Sludge
MeSO4 precipitation
(pH ≅ 2) + MeS
pH ≅ 2 Particle sludge
separation
Sludge
“without”
heavy metals HCO3- + HS- rich effluent
Figure 6.2 - Scheme of a conceptual design for a biological-physical-

chemical process to remove heavy metals from sewage sludge
107
Chapter 6
The first step consists of an aerobic bioreactor fed with oxygen and a
reduced sulfur source (So) or ferrous iron (FeSO4 or FeS) component. These
components are oxidized by Thiobacillus and converted into sulfuric acid.
The required dosage of sulfur or ferrous iron depends on the initial pH of the
sludge, the buffering capacity and the desired final pH of the sludge. If lead
is present in the sludge, it might be necessary to apply HCl, after the pH is
decreased in the bioleaching process. This procedure, however, makes the
process more complex and its effectiveness should be investigated.
The second step is identical to that presented in the first proposed scheme.
The third step comprises the removal of the heavy metals from the leachate
in a two steps precipitation and separation unit. In this way, a sulfur cycle
can be introduced into the system (see Figure 6.2).
Due to the inorganic nature of leachate, the addition of an electron donor as

substrate in the sulfate reduction process is required. In order to be
economically feasible, the electron donor must be cheap and fully
degradable, so that no remaining pollution is generated from the
biodegradation process. Possible electron donors are: hydrogen (along with
carbon dioxide), methanol, ethanol, or acetate. The reduction of oxidized
sulfur compounds (SO42-) will generate an effluent with dissolved sulfide
(HS-) and carbonate (HCO3-). Part of this effluent will be mixed with the
leachate containing MeSO4, causing the formation of insoluble MeS and a
raise of the pH. The effluent of the sulfate-reducing reactor is partially
oxidized into elemental sulfur, which can be separated and reused as
electron donor for the Thiobacillus in the bioleaching process. This will result
in the oxidation of elemental sulfur back to sulfate, closing the sulfur cycle
inside the treatment system.
There is a necessity of a metal separation unit before the sulfate-reducing

reactor because of two reasons. First, there is a need to increase the pH of
the leachate before contacting the biomass inside the sulfate-reducing
reactor, which is pH sensitive. Second, the formation of metal precipitates
inside the sulfate-reducing reactor must be avoided, since it would result in
a poor quality metal sludge (rich in biomass). Therefore, if separated in a
previous compartment, higher quality metal slurry can be produced. This
slurry contains high concentrations of heavy metals and after being
dewatered it has to be properly disposed. The liquid fraction that is
separated from the elemental sulfur produced in the micro-aerated reactor
can be returned to the beginning of the wastewater treatment plant.
108
General discussion
From an environmental and economical point of view, the biological-

physical-chemical process seems to be more attractive than the physical-
chemical process. The final effluent generated in the biological-physical-
chemical process can be mixed with the influent of the wastewater treatment
plant, dismissing especial post-treatment. In addition, the costs of acid
addition are minimized. If elemental sulfur is chosen as substrate, the costs
with its addition can be partially surpassed by the use of biological
elemental sulfur produced in micro-aerated reactors. Disadvantages of this
process include the costs of the energy supply for aeration and the costs of
the electron donor (depending on its origin). Moreover, the formation of
PbSO4 prevents the solubilization of Pb by bioleaching process. Thus, an
additional acidification step with HCl must be considered, when a high
concentration of Pb is present in the sludge. This would, of course, make the
process more expensive. Another disadvantage is the complexity of the
operation and possibly difficult process control.
With respect to the pathogens organisms present in the sludge, it might

occur that the extreme acidic conditions applied during the bio(leaching)
process causes a considerable reduction in the concentration of such
organisms.
The goal of this research was to develop an effective process for removal of
heavy metals from sewage sludge to sufficiently low concentrations, at
acceptable costs. Definitely in the further development of the process to a
practical scale, attention has to be paid to the possibilities of reuse of the
heavy metals recovered from the sludge. Furthermore, how to deal with the
remaining liquid residues, such as those obtained after an extraction
process with HCl must be also considered.
This research was dealing with extreme low pH conditions, in order to attain
high heavy metals removal efficiencies from sewage sludges. There might be
some cases, however, that the application of milder pH conditions is
appropriate to achieve sufficient heavy metals removal efficiencies. Besides,
the results of this study may also be of interest for the removal of heavy
metals from other type of wastes, such as sediments.
109
Chapter 7
Summary
Samenvatting
Sumário
Chapter 7
SUMMARY
Removal of heavy metals from sewage sludge
Heavy metals can cause serious problems for human beings and
ecosystems. As mentioned in Chapter 1, the process of heavy metals
removal from sewage sludges is in general only feasible in the case of very
strongly polluted sludges. There are advantages of heavy metals removal
from this type of sludge. First, the possibility of sludge disposal to landfill
with reduced risk of metals being leached to surface and groundwater.
Second, sludge can be used as soil improver with less harm. Third, sludge
can be applied, with lower costs, as energy source in co-incineration. The
off-gas treatment system might be less complex and can operate at milder
process conditions than when the sludge is strongly polluted with heavy
metals. Finally, dewatered sludge or sludge fly ashes can be applied, with
lower environmental risks, as raw material in civil construction materials.
Although numerous studies have appeared in the field of heavy metals

removal from sewage sludges, several knowledge gaps still exist, which are
the reason for the less attention that has been paid to the implementation of
techniques for this purpose. Such techniques still remain in the laboratory
and pilot plant scale. The aim of this work is to contribute to the further
development of practical application of the technologies, which might be
applied in the heavy metals removal from anaerobically digested sludge.
In Chapter 2, the materials and main analytical procedures used in the

experimental part of the research are described, and the physical and
chemical characteristics of the applied sludge are evaluated. The
concentration of the heavy metals present in the sludge is emphasized and
legal standards for metals disposal on land are shown and discussed.
A physical classification scheme, based on differences in the particle size of

sludge was applied in order to determine the heavy metal content of the
various fractions of the sludge. The results demonstrated that heavy metals
were mostly concentrated in the fractions < 0.063 mm, constituting about
70 % of the total sludge mass and contributing to 78-85 % of the heavy
metals present in the sludge. In all the separated fractions, however, most of
the metals concentrations exceeded the Dutch standard (BOOM) for land
112
Summary
application. This indicates that, if land application is considered, then the

whole sludge has to be treated, without any previous separation.
An analytical approach for determining the chemical forms of heavy metals

in the sludge based on sequential chemical extraction (SCE) procedures was
executed. A sequential chemical extraction procedure consists of the
utilization of a series of chemical extractants in a sequence of reagents of
increasing harshness. For each extraction step, a specific chemical form of
the metal is expected to dissolve. Three sequential chemical extraction
schemes were tested in this research: Tessier (1979), Veeken (1998), and
Sims & Kline (1991). In addition, modified versions of Veeken and Tessier
schemes were applied as a tentative to investigate the causes of the
differences between both schemes. In these modified versions, some
conditions were slightly altered from the original ones.
Despite the uncertainty of the SCE method with respect to selectivity (metals
bound to more than one phase are solubilized) and specificity (more than
one phase is solubilized), it gives useful information concerning the
availability of the metals. The SCE results of the investigated sludge revealed
that Cr (65 - 67 %) and Cu (65 - 87 %) could be effectively released in an
oxidizing environment (85 °C, pH= 2). Zinc (78 - 86 %) could be extracted by
a reducing agent (96 °C, pH= 2), whereas Pb (62 - 81 %) could be solubilized
at strong acidic conditions at high temperature (150 °C in a microwave
oven). Furthermore, a chelating agent (20 °C, pH= 4.5) was able to release
considerable amounts of Cr (56 - 57 %), Pb (57 - 78 %) and Zn (50 - 62 %).
About 70 % of Cu could also be extracted with application of high pH (12.6)
at 20 °C. The experiments demonstrated that the two modified schemes
provided valuable information for interpretation of the differences in the
results of the original schemes.
Chapter 3 deals with the chemical leaching process applied in the crucial
step of the sludge treatment aimed at heavy metals removal: the metals
solubilization step. For this aim, organic acids (citric and oxalic) and
inorganic acids (nitric, hydrochloric and phosphoric) were tested at different
conditions of pH, reaction time, and oxidation-reduction potential (ORP). The
effect of acidification was intensively tested for liquid samples of the sludge
and briefly tested for dried and crushed sludge samples.
113
Chapter 7
It is known that a low pH value is not always enough to promote a

satisfactory metals release from anaerobic sludge particles to the liquid,
unless acidification was preceded by a rise in the sludge ORP. This increase
in the ORP of the sludge can occur by chemical oxidation or biological
oxidation. In the present work, chemical oxidation with application of
aeration or adding hydrogen peroxide were investigated. Especially copper
was highly influenced by oxidation. This was due to its speciation in the
sludge. As suggested by the SCE schemes, Cu is tightly bound to the
organic matter fraction in the sludge. Moreover, in anaerobic sludges the
heavy metals are present usually in their most reducible form. Accordingly,
Cu predominates as Cu1+. Thus, if this metal is also present as the insoluble
Cu2S in the sludge, to solubilize Cu it is necessary to oxidize Cu1+ to the
soluble form Cu2+, as CuSO4.
aeration or hydrogen peroxide followed by acidification with HCl resulted in
the highest extraction yields of most heavy metals. The best results achieved
were: Cr: 85 % with H2O2, Cu: 100 % with H2O2, Pb: 100 % with aeration
and H2O2, and Zn: 100 % with aeration and H2O2.
In Chapter 4, the effect of bioleaching on the solubilization of Cr, Cu, Pb and

Zn from anaerobically digested sludge is discussed. The principle of
bioleaching is the production of acid by specific acidophilic bacteria (genus
Thiobacillus). These bacteria can oxidize reduced sulfur or ferrous iron to
sulfuric acid. In this research, bioleaching with elemental sulfur and ferrous
iron and chemical leaching with H2SO4 were applied.
The results were compared with those found in literature and in previous
leaching experiments with HCl. It was found that bioleaching can be a
feasible alternative to promote the solubilization of Zn and Cu, especially
when ferrous iron is added as substrate. Under this condition, the
maximum extraction yield achieved for Zn was 80.8 % with a pH value of
2.7. For Cu it was 65.5 % with a pH value of 2.5. Chromium solubilization
was possible when pH was around 2.5. Less than 1 % of Pb was extracted by
bioleaching, due to the formation of the insoluble PbSO4. Chemical leaching
with HCl at a pH value of 1 solubilized almost 100 % of Pb and also provided
the best extraction yield for Cr (around 72 %). At the same pH value, HCl is
more effective than H2SO4 to solubilize all the metals studied.
114
Summary
In the present work, after solubilization of heavy metals by chemical

leaching with previous aeration, the next step was the separation of the
sludge solids from the metal-rich acidic liquid (leachate) by centrifugation
and filtration. In Chapter 5, research into the removal of heavy metals from
the leachate was carried out. For that, the obtained filtered leachate was
submitted to the application of hydroxide precipitation with NaOH and
sulfide precipitation with Na2S, both separately and in combination. These
two types of precipitation processes are the most widely applied and the
chemicals, which were chosen, are the most common ones. Each
precipitation step was followed by filtration of the precipitate.
The results showed that when iron and aluminium are present in the sludge
(as it was the case), adsorption and/or coprecipitation of the heavy metals to
a ferric or aluminium hydroxide precipitate might occur. This was especially
observed when hydroxide precipitation was solely applied. In addition, Cu
was not satisfactorily removed by hydroxide precipitation, despite the fact
that Cu(OH)2 has the lowest solubility among Cr, Pb and Zn hydroxides.
This phenomenon might be due to the high nucleation rate that occurs
when the precipitate has low solubility product. The increase in the
nucleation rate favors the particle size decrease. In the present research, the
particles passed through the filter pore size and therefore Cu was detected
in the liquid.
The combination of hydroxide and sulfide precipitation was able to promote

an effective removal of heavy metals from the leachate. Applying NaOH at a
pH value of 4-5 as a first precipitation step, followed by filtration and further
addition of Na2S to the filtered liquid at a pH value of 7-8 as a second
precipitation step, considerably decreased the dosage of the second
precipitant, when it was exclusively applied. The best removal efficiencies
obtained were: Pb: 100 %, Cr: 99.9 %, Cu: 99.7 %, and Zn: 99.9 %.
Concluding remarks
Based on the results obtained, two conceptual designs for heavy metals
removal from sewage sludge were presented and discussed in Chapter 6.
One scheme referred to a physical-chemical treatment and the other to a
biological-physical-chemical treatment. The first scheme comprises the use
of chemical leaching in the metals solubilization step and addition of NaOH
115
Chapter 7
and Na2S in combination, in the precipitation step. The second scheme

substitutes the chemical leaching step by bioleaching and, in the
precipitation step, the sulfide produced in a sulfate-reducing reactor is
utilized. The reduction of oxidized sulfur compounds (SO42-) will generate an
effluent with dissolved sulfide (HS-) and carbonate (HCO3-). Part of this
effluent will be mixed with the leachate containing MeSO4, causing the
formation of the insoluble MeS and the raise of the pH. The effluent of the
sulfate-reducing reactor is partially oxidized into elemental sulfur, which
can be separated and reused as electron donor for the Thiobacillus in the
bioleaching process.
From an environmental and economical point of view, the biological-

physical-chemical process seems to be more attractive than the physical-
chemical process. The final effluent generated in the biological-physical-
chemical process can be mixed with the influent of the wastewater treatment
plant, dismissing the special post-treatment required in the physical-
chemical process, as the remaining water in this process contains a high
concentration of NaCl. In addition, the costs of acid addition are minimized
by bioleaching.
This research had the purpose to develop an effective process for removal of
heavy metals from sewage sludge to sufficiently low concentrations, at
acceptable costs. In further development of the process to a practical scale,
attention has to be paid to the reuse possibilities of heavy metals recovered
from the sludge and how to deal with the remaining liquid residues.
Extreme low pH conditions are necessary to achieve high heavy metals

removal efficiencies from sewage sludges. Nevertheless there might be some
cases that the application of milder pH conditions is suitable to obtain
sufficient heavy metals removal efficiencies. Moreover, the results of this
study may also be applicable for the removal of heavy metals from other
wastes, such as sediments.
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Samenvatting
SAMENVATTING
Het verwijderen van zware metalen uit zuiveringsslib
Zware metalen kunnen een serieuze bedreiging vormen voor zowel mensen
als ecosystemen. In het algemeen is een proces om zware metalen te
verwijderen uit zuiveringsslib alleen technisch en economisch haalbaar
indien het slib sterk verontreinigd is. Het verwijderen van de zware metalen
uit dit soort slib heeft verscheidene voordelen. Ten eerste geeft het de
mogelijkheid om het slib na reiniging te storten met slechts een gering risico
voor uitlogen van zware metalen naar het grondwater en het
oppervlaktewater. Ten tweede is het risico bij het gebruik van het slib als
bodemverbeteraar veel minder. Ten derde kan er een besparing optreden bij
het verbranden van slib, omdat bij de rookgasreiniging minder rekening
gehouden hoeft te worden met de aanwezigheid van zware metalen, zodat
een eenvoudigere procesvoering mogelijk is. Tenslotte is het milieurisico
kleiner bij toepassing van ontwaterd slib of vliegas in civiele constructies.
Hoewel er op het gebied van zware metalenverwijdering uit rioolwaterslib

reeds vele studies verschenen zijn, zijn er nog steeds verscheidene
kennisleemtes. Dit is in feite de reden dat er nog weinig aandacht is besteed
aan de implementatie van technieken voor het verwijderen van zware
metalen. Dergelijke technieken zijn nog steeds in de fase van
laboratoriumonderzoek. Het doel van de onderhavige studie is om een
bijdrage te leveren aan de verdere ontwikkeling van de praktische toepassing
van de technologieën, die toegepast zouden kunnen worden voor de
verwijdering van zware metalen uit anaëroob vergist slib.
Slibkarakterisering
De materialen en belangrijkste analytische procedures, welke in het

experimentele onderzoek zijn gebruikt, worden beschreven in Hoofdstuk 2.
Verder worden in dit hoofdstuk de chemische en fysische karakteristieken
van het onderzochte slib beschreven. Met name worden de concentraties aan
zware metalen in het slib gegeven, en in een discussie vergeleken met de
normen voor toepassing op het land als bodemverbeteraar.
De concentraties aan zware metalen zijn experimenteel bepaald in

verschillende deeltjesgroottefracties. Het resultaat toont aan dat de zware
metalen met name geconcentreerd zijn in de fractie kleiner dan 0,063 mm,
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Chapter 7
welke ongeveer 70 % van het totale slib uitmaakt en 78-85 % van de zware
metalen die aanwezig zijn in het slib bevat. In alle deeltjesgroottefracties zijn
de concentraties aan zware metalen dermate hoog, dat ze niet voldoen aan
de Nederlandse norm voor toepassing op het land (BOOM). Dit geeft aan dat,
indien toepassing op het land wordt overwogen, het gehele slib dient te
worden behandeld, zonder voorafgaande deeltjesscheiding.
Verder is een techniek, gebaseerd op sequentiële chemische extractie (SCE),

toegepast om de verschillende chemische wijze van voorkomen van de
metalen te bepalen. Een SCE bestaat uit een serie van extracties met
extractievloeistoffen in oplopende agressiviteit. Bij iedere extractie wordt een
specifieke chemische vorm van de metalen in oplossing gebracht. Drie
verschillende extractieschema’s zijn toegepast in dit onderzoek: Tessier
(1979), Veeken (1998) en Sims & Kline (1991). Verder zijn twee aangepaste
versies van de schema’s van Veeken en Tessier uitgevoerd teneinde de
verschillen in resultaten van de beide schema’s op te helderen.
Niettegenstaande de onzekerheden in de SCE-methode met betrekking tot

selectiviteit (metalen gebonden aan meer dan een fase gaan in oplossing) en
specificiteit (meer dan een fase gaat in oplossing), geeft de methode
bruikbare informatie over de beschikbaarheid van metalen. De SCE-
resultaten van het onderzochte slib geven aan dat chroom (65 - 67 %) en
koper (65 - 87 %) in een oxiderend milieu, bij pH= 2 en 85 °C, effectief
kunnen worden gemobiliseerd. Zink (78 - 86 %) kon worden geëxtraheerd in
een reducerend milieu bij pH= 2 en 96 °C, terwijl lood (62 - 81 %) in
oplossing kan worden gebracht onder sterk zure condities bij hoge
temperatuur (150 °C in een magnetronoven). Verder was een chelator in
staat aanmerkelijke hoeveelheden chroom (56 - 57 %), lood (57 - 78 %) en
zink (50 - 62 %) van het slib los te maken. Circa 70 % van het koper kan ook
worden geëxtraheerd bij hoge pH (12.6) en 20 °C. De resultaten laten zien
dat de aangepaste SCE-schema’s waardevolle informatie verschaffen om de
verschillen in de originele schema’s te verklaren.
Chemische uitloging van zware metalen
Hoofdstuk 3 behandelt het chemische uitlogingsproces dat in de cruciale

stap van de slibbehandeling voor zware-metalenverwijdering wordt
toegepast, de solubilisatiestap. Voor dit doel werden verschillende
organische (citroenzuur en oxaalzuur) en anorganische (salpeterzuur,
zoutzuur en fosforzuur) zuren getest onder verschillende condities wat
118
Samenvatting
betreft pH, reactietijd en redoxpotentiaal. Het effect van zuurtoediening is

uitgebreid getest voor vloeibare monsters van het slib, en beperkt getest voor
gedroogde en gemalen monsters.
Het is bekend dat lage pH-waarden niet altijd voldoende zijn om de zware
metalen voldoende los te maken van de slibdeeltjes, tenzij de zuurtoediening
voorafgegaan wordt door een verhoging van de redoxpotentiaal van het slib.
Deze verhoging kan bereikt worden door of een chemische of een biologische
oxidatie. In deze studie is chemische oxidatie door middel van beluchting of
waterstofperoxidedosering onderzocht. Met name koper is zeer gevoelig voor
de redoxpotentiaal. Dit kan worden verklaard uit de speciatie van koper.
Volgens de SCE-resultaten is koper vooral gebonden aan de organische
fractie. Verder is het zo dat in anaëroob slib metalen doorgaans aanwezig
zijn in hun meest gereduceerde vorm. Derhalve is koper aanwezig als Cu+ in
onder andere het onoplosbare C2S. Het is dus noodzakelijk deze vorm te
oxideren tot het oplosbare CuSO4.
De resultaten tonen aan dat chemische oxidatie door hetzij beluchting, hetzij
waterstofperoxidedosering, gevolgd door zuurdosering in de vorm van
zoutzuur de hoogste extractierendementen opleverde. De beste resultaten
zijn gevonden voor chroom (85 %) met H2O2, koper (100 %) met H2O2, lood
(100 %) met zowel beluchting als H2O2 en zink (100 %), ook met lucht en
H2O2.
Biologische uitloging van zware metalen
In Hoofdstuk 4 wordt het effect van biologische uitloging op het oplosbaar

maken van chroom, koper , lood en zink uit anaëroob vergist slib behandeld.
Het principe van deze uitloging is de productie van zuur door bepaalde
acidofiele bacteriën (genus Thiobacillus) Deze bacteriën oxideren gereduceerd
zwavel of ijzer(II) tot zwavelzuur. Ter vergelijking werd ook chemische
uitloging met zwavelzuur toegepast.
De resultaten zijn vergeleken met literatuurgegevens en de resultaten met

zoutzuur zoals gevonden in Hoofdstuk 3. Er is gevonden dat biologische
uitloging een haalbaar alternatief is voor het oplosbaar maken van zink en
koper, met name wanneer Fe(II) als substraat wordt toegevoegd. De
maximale extractierendementen die zijn behaald zijn voor zink 80,8 % bij
een pH-waarde van 2,7 en voor koper 65,6 % bij een pH-waarde van 2,5. Het
oplossen van chroom was gedeeltelijk mogelijk bij een pH van 2,5. Minder
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Chapter 7
dan 1 % van het lood ging in oplossing vanwege de formatie van het
onoplosbare loodsulfaat. Chemische uitloging met zoutzuur bij pH= 1
resulteert in een rendement van bijna 100 % voor lood en circa 72 % voor
chroom. Bij vergelijkbare pH is zoutzuur veel effectiever dan zwavelzuur in
het oplossen van de bestudeerde zware metalen.
Het verwijderen van zware metalen uit de extractievloeistof
De volgende stap in de behandeling van het slib is het afscheiden van de

gereinigde slib deeltjes van het extractiemedium door middel van
centrifugeren of filtreren. Vervolgens dient de extractievloeistof gereinigd te
worden van zware metalen, hetgeen het onderwerp is van Hoofdstuk 5.
Hiertoe werd de gefiltreerde extractievloeistof onderworpen aan een
precipitatieproces met NaOH en Na2S, beide zowel separaat als in
combinatie. Deze procedure is gebaseerd op een veel toegepaste methode.
Iedere precipitatie werd gevolgd door het affiltreren van het precipitaat.
De resultaten gaven een indicatie dat indien ijzer of alumnium aanwezig is,
zoals in het gebruikte slib, adsorptie en coprecipitatie van zware metalen en
ijzer of aluminiumhydroxide een belangrijk mechanisme is. Dit is met name
het geval wanneer de pricipitatie met alleen natronloog wordt uitgevoerd.
Verder blijkt dat koper door precipitatie slechts in beperkte mate wordt
verwijderd, niettegenstaande het feit dat koperhydroxide in vergelijking met
chroom-, lood- en zinkhydroxide de laagste oplosbaarheid heeft. Dit
verschijnsel zou verklaard kunnen worden uit het gegeven dat een lage
oplosbaarheid gepaard kan gaan met een hoge nucleatiesnelheid. Hierdoor
is de deeltjesgrootte van koperhydroxidekristallen zeer klein, en worden ze
niet afgescheiden door het filter. Bij de analyse worden ze daardoor in feite
gemeten als opgelost koper.
De combinatie van hydroxide- en sulfideprecipitatie leidt tot een effectieve

verwijdering van zware metalen uit de extractievloeistof. Door de pH eerst op
een waarde van 4-5 te brengen met natronloog en vervolgens tot een waarde
van 7-8 met sulfide in een tweede precipitatiestap, kan de dosering van
sulfide aanzienlijk gereduceerd worden in vergelijking met het toepassen van
sulfide zonder natronloog. De beste verwijderingsrendementen die behaald
zijn bij de precipitatie zijn: Pb: 100 %, Cr: 99.9 %, Cu: 99.7 %, en
Zn: 99.9 %.
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Samenvatting
Afsluitende opmerkingen
Uitgaande van de behaalde resultaten zijn twee conceptuele

procesontwerpen voor de verwijdering van zware metalen uit zuiveringsslib
gemaakt, welke in Hoofdstuk 6 gepresenteerd worden. Eén ontwerp is
gebaseerd op een totaal fysisch-chemisch proces, het andere op een
biologisch en fysisch-chemisch proces. In het eerste processchema wordt het
slib chemisch geëxtraheerd en vervolgens de extractievloeistof van metalen
gezuiverd door middel van precipitatie met natronloog en sulfide. In het
tweede schema wordt de chemische extractie vervangen door een biologische
extractie en wordt voor de precipitatie sulfide gebruikt uit een sulfaat-
reducerende bioreactor. De reductie van geoxideerd zwavel (SO42-) resulteert
in een oplossing van sulfide en carbonaat. Deze oplossing wordt aan de
metaalsulfaathoudende extractievloeistof gedoseerd, wat leidt tot de vorming
van onoplosbare metaalsulfiden en een pH-verhoging. Het sulfaat zal
gedeeltelijk gereduceerd worden tot elementair zwavel, wat gebruikt kan
worden als elektrondonor voor de Thiobacillus in het biologische
extractieproces.
Uit milieu en economisch oogpunt bekeken lijkt het biologisch-fysisch-

chemische proces aantrekkelijker dan het fysisch-chemische proces. Het
effluent van het biologische proces kan worden toegevoegd aan het influent
van de waterzuiveringsinstallatie, waardoor een verdere nabehandeling voor
ontzouting achterwege kan blijven. Verder worden in het biologische proces
de kosten voor de aanschaf van zuur geminimaliseerd.
Het doel van het onderzoek was om tot een effectief proces te komen voor de
verwijdering van zware metalen uit zuiveringsslib, tot voldoende lage
concentraties tegen acceptabele kosten. Bij de verdere ontwikkeling van het
proces dient aandacht te worden geschonken aan hergebruikmogelijkheden
voor de teruggewonnen zware metalen en de verdere behandeling van
vloeistofresiduen.
Extreem lage pH-condities zijn noodzakelijk om een goede verwijdering van

zware metalen uit zuiveringsslib te bereiken. Nochtans kan het mogelijk zijn
dat in geval van andere metaalspeciaties mildere condities voldoende zijn.
De resultaten van dit onderzoek zijn mogelijk ook toepasbaar voor andere
afvalstromen, zoals baggerspecie.
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Chapter 7
SUMÁRIO
Remoção de metais pesados de lodo de esgoto
Os metais pesados podem causar sérios danos aos seres humanos e

ecossistemas. Conforme mencionado no Capítulo 1, o processo de remoção
de metais pesados de lodo de esgoto é, em geral, apenas viável no caso de
lodos altamente poluídos. Neste caso, a remoção dos metais pesados pode
ser bem vantajosa por várias razões. Em primeiro lugar, existe a
possibilidade de dispor o lodo em aterros sanitários com risco reduzido de
contaminação do lençol superficial e subterrâneo. Em segundo lugar, o lodo
pode ser usado como beneficiador de solos. Em terceiro lugar, o lodo pode
ser aplicado, a custos reduzidos, como fonte de energia no processo de co-
incineração. O sistema de tratamento do gás gerado neste processo seria
menos complexo e poderia operar sob condições mais amenas que no caso
de lodos altamente poluídos com metais pesados. Finalmente, o lodo tratado
desidratado ou as cinzas do lodo tratado incinerado podem ser utilizados,
com menores riscos ambientais, como matéria-prima na fabricação de
materiais de construção.
Apesar de existirem inúmeros estudos a respeito da remoção de metais

pesados de lodos de esgoto, vários são ainda os pontos não esclarecidos, os
quais são a maior razão para a deficiência na implementação das técnicas
existentes para este fim. Tais técnicas ainda prevalecem em escala de
laboratório e piloto. O objetivo deste trabalho é contribuir para o
desenvolvimento da aplicação prática de tecnologias destinadas à remoção
de metais pesados de lodos de esgoto, com ênfase nos lodos anaerobiamente
digeridos.
Caracterização do lodo
No Capítulo 2, os materiais e principais procedimentos analíticos utilizados

na parte experimental desta pesquisa são descritos e as características
físico-químicas do lodo estudado são avaliadas. As concentrações dos metais
pesados presentes no lodo, bem como as concentrações dos metais
permitida pelos limites legais de disposição de lodos no solo são mostradas e
discutidas. Um esquema de classificação física, baseado em diferenças de
tamanho de partículas do lodo foi aplicado a fim de se determinar o teor de
metais presente nas várias frações do lodo. Os resultados demonstraram
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Sumário
que os metais se concentravam principalmente nas frações < 0.063 mm,

constituindo cerca de 70 % da massa total do lodo e contribuindo 78-85 %
do total de metais presentes no lodo. Em todas as frações, entretanto, a
maioria das concentrações dos metais excedia o limite holandês (BOOM)
para aplicação do lodo no solo. Isto indica que, se a aplicação do lodo no
solo for considerada, então o lodo deve ser tratado por inteiro, sem prévia
separação de suas frações.
Para a determinação das formas químicas dos metais pesados (especiação

química) no lodo, utilizou-se um método analítico aproximado baseado em
esquemas seqüenciais de extração química (“sequential chemical
extraction”). Este método consiste em se utilizar uma série de reagentes
aplicados seqüencialmente (em ordem progressiva de “força”), tendo por
intuito solubilizar uma forma química particular dos metais. Três destes
esquemas foram testados nesta pesquisa: Tessier (1979), Veeken (1998), and
Sims & Kline (1991). Adicionalmente, versões modificadas dos esquemas
Tessier e Veeken foram aplicadas como tentativa de se investigar as causas
das diferenças entre ambos os esquemas. Nestas versões modficadas,
algumas condições foram ligeiramente alteradas das originais.
Apesar da incerteza dos métodos dos esquemas seqüenciais com respeito a

seletividade (metais ligados a mais de uma fase são solubilizados) e
especificidade (mais de uma fase é solubilizada), tais métodos fornecem
informações úteis no que tange à disponibilidade dos metais no lodo. Os
reultados dos esquemas seqüenciais investigados mostraram que o Cr (65 -
67 %) e o Cu (65 - 87 %) podem ser efetivamente solubilizados em condições
oxidativas (a 85 °C e pH= 2). O zinco (78 - 86 %) pode ser extraído do lodo
por um agente redutor (a 96 °C e pH= 2), ao passo que o Pb (62 - 81 %) pode
ser dissolvido sob condições de acidificação extrema (a 150 °C no
microondas). Além do mais, um agente quelante (a 20 °C e pH= 4.5) pode ser
capaz de solubilizar considerável concentração de Cr (56 - 57 %), Pb (57 - 78
%) and Zn (50 - 62 %). Cerca de 70 % do Cu pode também ser extraído com
a aplicação de um alto valor de pH (12.6) a 20 °C. Os experimentos
demonstraram que as duas versões modificadas dos esquemas seqüenciais
forneceram valiosas informações para a interpretação das diferenças entre
os esquemas originais testados.
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Chapter 7
Lixiviação química dos metais pesados
O Capítulo 3 se refere ao processo de lixiviação química utilizado na fase

crucial do tratamento do lodo: a solubilização dos metais. Neste sentido,
ácidos orgânicos (cítrico e oxálico) e ácidos inorgânicos (nítrico, clorídrico e
fosfórico) foram testados sob diferentes condições de pH, tempo de reação e
potencial de oxidação-redução. O efeito da acidificação foi intensamente
estudado para amostras de lodo líquidas e brevemente estudado para
amostras de lodo secas e trituradas.
Reduzir o valor do pH do lodo nem sempre é condição suficiente para

promover uma satisfatória mobilização dos metais da fase sólida para a fase
líquida. A menos que esta redução no valor do pH seja precedida de um
aumento no valor do potencial de oxidação-redução do lodo, o qual pode
ocorrer por oxidação química ou biológica. No presente trabalho, a oxidação
química por aeração e por adição de peróxido de hidrogênio foi investigada.
Verificou-se que especialmente o Cu foi influenciado pela oxidação. Isto se
deve ao fato da especiação deste metal no lodo. Conforme indicado pelos
esquemas seqüenciais de extração química, o Cu é fortemente ligado à
matéria orgânica do lodo. Ademais, em lodos anaeróbios, os metais estão
presentes em suas mais reduzidas formas. Assim, o Cu predomina como
Cu1+. Desse modo, se este metal está também presente no lodo como o
insolúvel Cu2S, para solubilizar o Cu é necessário oxidar Cu1+ à solúvel
forma Cu2+, como CuSO4.
Os resultados mostraram que a opção que inclui a oxidação química com

aeração ou peróxido de hidrogênio seguida de acidificação com HCl resultou
na mais alta porcentagem de extração da maioria dos metais pesados. Os
melhores reultados alcançados foram: Cr: 85 % com H2O2, Cu: 100 % com
H2O2, Pb: 100 % com aeração e H2O2, e Zn: 100 % com aeração e H2O2. A
extração do Cu foi particularmente influenciada pela oxidação.
Biolixiviação (“Bioleaching”) dos metais pesados
No Capítulo 4 é discutida a investigação da biolixiviação na solubilização do

Cr, Cu, Pb e Zn presentes no lodo anaeróbio. A biolixiviação tem como
princípio a produção de ácido pela bactéria acidofílica específica (genus
Thiobacillus). Tais bactérias são capazes de oxidar enxofre elementar ou
ferro ferroso a ácido sulfúrico. Nesta pesquisa, aplicou-se a biolixiviação com
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Sumário
enxofre elementar e ferro ferroso, assim como a lixiviação química com

H2SO4.
Os resultados foram comparados com os encontrados na literatura e em

experimentos anteriores com HCl. Foi observado que a biolixiviação é uma
alternativa viável para promover a solubilização do Zn e do Cu,
especialmente se o ferro ferroso for adicionado como substrato no processo.
Sob estas condições, a máxima porcentagem de extração obtida para o Zn
foi de 80.8 % com valor de pH a 2.7. Para o Cu, obteve-se 65.5 % de
extração, com valor de pH a 2.5. A solubilização do Cr foi possível somente
quando o valor do pH chegou por volta de 2.5. Menos de 1 % do Pb foi
extraído pela biolixiviação devido à formação do insolúvel PbSO4. A lixiviação
química com HCl a valor de pH por volta de 1 foi capaz de solubilizar quase
100 % do Pb e também propiciou a melhor porcentagem de extração do Cr
(ao redor de 72 %). Sob o mesmo valor de pH, o HCl é mais eficiente que o
H2SO4 para solubilizar todos os metais pesados estudados.
Remoção dos metais pesados do lixiviado
Após a solubilização dos metais pesados por lixiviação química com prévia
aeração do lodo, o próximo passo no tratamento do lodo foi a separação
física da parte sólida do lodo, do líquido acidificado rico em metais
(lixiviado), por centrifugação e filtração. O Capítulo 5 discorre sobre a
remoção dos metais pesados do lixiviado. Para tanto, o lixiviado, já filtrado,
foi submetido à aplicação separada e combinada da precipitação por
hidróxidos com NaOH e da precipitação por sulfetos com Na2S. Estes dois
tipos de precipitação são os mais aplicados atualmente e os químicos
utilizados são os mais comuns. Durante os experimentos, cada uma das
etapas de precipitação ocorreu seguida de filtração do precipitado.
Os resultados demostraram que, quando Fe e Al estão presentes no lodo

(como era o caso), adsorção e/ou coprecipitação dos metais pesados podem
ocorrer. Tais fenômenos foram especialmente observados quando a
precipitação por hidróxidos foi aplicada unicamente. Adicionalmente, este
tipo de precipitação não foi capaz de remover satisfatoriamente o Cu, apesar
de o Cu(OH)2 apresentar a mais baixa solubilidade entre os hidróxidos de
Cr, Pb e Zn. Este resultado pode ser explicado pela alta taxa de nucleação
(“nucleation”) que ocorre quando o precipitado possui baixo produto de
solubilidade. O aumento na taxa de nucleação favorece a diminuição no
tamanho das partículas. Na presente pesquisa, os precipitados formados
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Chapter 7
passaram através do poro do filtro utilizado e, por esta razão, o Cu foi

detectado na fase líquida.
A combinação das precipitações por hidróxidos e sulfetos foi capaz de

promover uma efetiva remoção dos metais pesados do lixiviado. Primeiro,
aplicando-se NaOH a um valor de pH entre 4-5 como primeira etapa de
precipitação, seguida de filtração. Depois, adicionando-se Na2S ao líquido
filtrado a um valor de pH entre 7-8 como segunda etapa de precipitação. Tal
combinação foi capaz de diminuir consideravelmente a dosagem do Na2S,
em relação à sua dosagem aplicada na precipitação única. As melhores
eficiências de remoção obtidas foram: Pb: 100 %, Cr: 99.9 %, Cu: 99.7 %, e
Zn: 99.9 %.
Aspectos importantes
Baseando-se nos resultados atingidos, dois esquemas conceituais para a

remoção de metais pesados de lodos de esgoto foram apresentados e
discutidos no Capítulo 6. Um esquema se refere a tratamento físico-químico
e o outro a tratamento biológico-físico-químico. O primeiro deles engloba o
uso da lixiviação química dos metais na fase de solubilização destes e adição
combinada de NaOH e Na2S na fase de precipitação metálica. O segundo
esquema substitui a lixiviação química pela biolixiviação e, na etapa de
precipitação, o sulfeto produzido num reator de redução de sulfato é
utilizado. A redução de compostos de enxofre oxidados (SO42-) gera um
efluente contendo sulfeto dissolvido (HS-) e carbonato (HCO3-). Parte deste
efluente deve ser misturado com o lixiviado contendo sulfato metálico,
causando a formação do insolúvel sulfeto metálico e aumentando o valor do
pH. O efluente do reator de redução de sulfato é parcialmente oxidado a
enxofre elementar, o qual pode ser separado e reusado como doador de
elétrons para o Thiobacillus no processo de biolixiviação.
Sob um ponto de vista ambiental e econômico, o processo biológico-físico-

químico é mais atraente que o processo físico-químico. O efluente final
produzido no processo biológico-físico-químico pode ser misturado ao
afluente da estação de tratamento, dispensando o pós-tratamento especial
requerido no processo físico-químico. Neste último, o efluente contém alta
concentração de NaCl. Além do mais, os custos com a adição de ácido são
minimizados na biolixiviação.
126
Sumário
Esta pesquisa teve o propósito de desenvolver um processo efetivo para a

remoção de metais pesados de lodos de esgoto a concentrações
suficientemente baixas, e custos aceitáveis. Em posteriores
desenvolvimentos do processo visando a escala prática, atenção especial
deve ser dada às possibilidades de reúso dos metais pesados removidos do
lodo, assim como ao destino final dos líquidos remanescentes.
Condições baixíssimas de pH são necessárias para se atingir elevadas

eficiências de remoção de metais pesados de lodos de esgoto. Entretanto,
haverá casos em que a aplicação de condições menos extremas serão
adequadas para se obter suficientes eficiências de remoção dos metais.
Ademais, é provável que os resultados deste estudo possam ser aplicados à
remoção de metais pesados de outros tipos de materiais residuários, como
por exemplo, sedimentos.
127
References
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135
ACKNOWLEDGEMENTS
First of all, I would like to thank my Brazilian sponsor, CNPq, to offer me this great
opportunity to conduct my PhD at Wageningen University. My recognition is infinite and I will
keep doing my best to contribute to the development of science and technology in Brazil.
A special acknowledgement goes to my promotor, Wim Rulkens. Wim, thanks to approve my
application for the PhD program in 1999! I immensely appreciate your support and effort for
clarifying my thoughts when I was writing and rewriting all the chapters. Your technological
expertise blended with your special sympathy makes you a very singular professor!
It was a gift to be daily supervised by Harry Bruning. Each meeting we had was a delightful
scientific lesson for me! Harry, many thanks for your tireless patience to teach so many theories
to this civil engineer! Especially to show how to make unexpected results attractive and
explainable. I will never forget your subtle jokes and your funny way to play with words. You
are just brilliant! Those two times we went to Schijndel for the sludge collection will last in my
memory forever. Definitely, you will be missed when I will be working in Brazil!
I must also mention that my chances to succeed in this PhD journey would be very small
without the period I was trained by my first supervisor, Marco Reali. Marco, after being your
student during my scientific initiation and MSc projects, I confess I was scared to death to do
research far from your wings… But this was also a key part to develop my PhD story… In
fact, we never lost contact and we had nice meetings during these four years! Thanks, mentor,
for your prompt support, advice, and contributions!
I am deeply grateful to Marcelo P. de Souza, Luiz A. Daniel and, of course, to the Wageningen-
enthusiast, Mario Kato, for their encouragement in the occasion of my PhD application.
I cannot forget the assistance of those who provided essential information about the Brazilian
sludges. They include: Milton Tsutiya, Luiz C. Helou, Luciana Mendonça and Fernando Fernandes.
I would like to thank everyone from Wageningen University who gave his/her valuable time,
skills and comments to make this project work. Among them, Adrie Veeken, Vinnie de Wilde,
Caroline Plugge, Tim Grotenhuis, Marc Boncz, and Erwin Temminghoff are highly acknowledged. I
thank also Johan Vermeulen for his sporadic hints, Marcel Zandvoort for reviewing Chapter 2,
and Albert Janssen for kindly providing the biogenic sulfur.
I am thankful to all the persons who helped me with the laboratory analysis and experimental
set-up. Especial thanks to: Sjoerd Hobma, Ilse Gerrits, Geert Meijer, Hillion Wegh, Katja Grolle,
Anne-Marie van den Driessche, and the ICP-guys, Arie van den Berg and Peter Nobels.
I gratefully acknowledge the impeccable assistance of the “Powerpuff Girls”: Liesbeth Kesaulÿa,
Anita van de Weerd, and Heleen Vos. Liesbeth, my first Dutch-contact, I can’t forget all those
times you rescued me from so many situations! You always brought me luck! Anita, what a
smile you have! I am very thankful for your kind friendship! I have a strong feeling that we
should have spent some more time together… Well, please, just don’t forget to include Brazil in
your touristic routes… And, Heleen, I couldn’t say anything different from the other foreigners:
you are an angel! Thousands of thanks for the three of you!!
My heartfelt thanks to two amazing girls, whose cooperation was of crucial importance to this
research: Nguyen Thi Phuong Loan and Nguyen Thi Phuoc Hien. Loan, the way we met in 2000
still intrigues me! I also think that one day we should sit together and write a book about our
unbelievable adventures in Mexico! I thank you for contributing so much with my research and
my life! Thanks also for introducing me to Hien, my second Vietnamese student. Hien, I really
enjoyed our bioleaching experience! It was also very nice to learn from you so many interesting
facts and curiosities from your history and culture.
During my PhD, I had the opportunity to meet many interesting people in conferences all over
the world. Among them, I should mention some colleagues of the “sludge association”, as the
Brazilian researcher, Cleverson Andreoli. Cleverson, thanks for your receptivity and incentive! I
felt deeply honored to visit your workplaces in Curitiba and give a lecture in your University! It
was also very nice to meet the Mexican gentlemen, Juan Manuel Méndez Contreras and José
136
Antonio Barrios. I thank you two for your friendship and, Juan M., I hope we succeed to work
in cooperation in a near future.
I am grateful for those who made a variety of contributions and shared friendly/funny
moments during my stay in Wageningen, including: Marcel Zandvoort, Bego Osuna, Jan Sipma,
Paco Cervantes and Liz Levario, Kasia Kania, Jarno Gieteling, Marc Boncz, Inge van de Poel,
Klaas de Jong, Gabor Szanto, Agnieszka Popenda, Sonja Parshina, Iemke Bisschops, Adrie Veeken,
Bas Buys, Vinnie de Wilde, Jules van Lier, Riet Rulkens, Gatze and Dora Lettinga, Marjo Lexmond,
Yang Shuo, Jurate Virkutyte, Giovanni Esposito, Sonia Lopes, Esnati Chaggu, Look Hulshoff Pol,
Willemiek Verbeek, Robin van Leerdam, Velu Muniandi, Martijn Smit, Nidal Mahmoud, Bert
Hamelers, Johan Vermeulen, Dale Rudrum, Chiel Cuypers, Adriaan Mels, Wim van Oordt, Tim
Grotenhuis, Bram Klapwijk, and, of course, some members of the Brazilian community, especially
André B. dos Santos, Renato Leitão and Gilma Chitarra.
It was a privilege to share the office with Joost van Buuren, who became one of my greatest
friends in Wageningen. Joost, I deeply appreciate our numerous talks and walks! Thanks for
teaching me so many things from the Netherlands, from the world, from the environment, and
from life. You are unique!
Talking about greatest friends… Paula Paulo!!!!! Well, I will try to resume all I want to say to
you (anyway, if something is missing, we will have plenty of time in Brazil to update it!)… I may
start saying that, “But”, you are not only a crucial character in this entire PhD story, but also in
my life story. I thank you, my precious friend, my angel, my counselor, my devil’s advocate, my
mystic sister, etc., etc., for all you did to me during these years, always unconditionally and
tirelessly. Thanks also for being so persistent with my “suspicious mind” in the very beginning.
Because of this persistence, I won a big friend forever!!
Taking the decision to live abroad for four years would be more difficult without the strong
support of my three dearest friends, Lucinha, Patty Helena and Ju. I confess I was afraid that
being on the other side of the Atlantic for so long would affect our friendship in someway…
But I am glad that this never happened! I thank you for sharing with me your experiences and
for always finding a way to send me your encouragement during all this time! I appreciate the
nice meetings we had in the meantime, too! Soon, there will be many others… Obaaa!!
There are no words that will suffice to thank my dear family, who have always been huge
supporters of anything I attempt. To make it easier, I will try some words in Portuguese: Mamã,
Mim e Mano: eu sei o quão foi difícil para vocês ouvirem pela primeira vez a minha nova idéia
de embarcar nesta viagem ao desconhecido por quatro longos anos... Mas, acreditem: mais difícil
foi encontrar palavras que pudessem lhes passar uma segurança que nem eu sabia se teria!
Porém, com o apoio que foi surgindo de vocês, e que, com o tempo, se transformou numa
verdadeira fortaleza, eu consegui me sustentar a cada dia e chegar até aqui. Conseguimos!! Sem
vocês, eu nada seria. Obrigada por tudo o que vocês são! E obrigada por todas as mensaginhas
e presentinhos que vocês me enviaram durante todo esse tempo! Eles eram como vitaminas para
mim! Também não posso deixar de agradecer o super apoio que meus tios e tias deram a mim
e aos meus pais durante esses quatro anos. Vocês são pessoinhas maravilhosas!! Muito obrigada!!
Now it is time to try to express my thankfulness to another person who means a lot to my
life: Marcus Vallero. Marcus, there is something about us that really amazes me! It is far beyond
rational explanations… What a chance we had to embark on this journey together! So many
incredible things we faced during all this time… so many landscapes, people, cultures, flavors, and
even the northern lights… Of course, as life adventurers, we could not avoid facing risks through
our way… but we survived! And here we are again! Thanks, “Mr. Life”, for always making me
smile. I thank you also for tolerating my personal eccentricities and for allowing me enough time
and space to spend with them. I do appreciate your clever suggestions for my work and your
endless patience to make me understand a bit of microbiology and related topics… Without your
presence, your unconditional support and love, my life in Wageningen would have no taste!
Finally, I would also like to thank you, the reader, for taking the time to have a look at this
thesis. Please, send me your comments!
&
137
CURRICULUM VITAE
Marina Maya Marchioretto was born in Itapira, São Paulo

State, Brazil, on September 6th, 1971. In 1996, she obtained
the Bachelor’s Degree in Civil Engineering at the São Carlos
School of Engineering, University of São Paulo. In June 1999,
she became a Master of Science on Hydraulics and Sanitation
from the São Carlos School of Engineering, University of São
Paulo. In October 1999, she started her Ph.D. research at the
Sub-department of Environmental Technology of Wageningen
University. After accomplishing her Ph.D. studies, she will
return to Brazil to resume her career.
Her address after November 2003 will be:
Av. Getulio Vargas, 887 - Jd. Sta. Marta

13976-400 Itapira - SP
Brazil
E-mail: marinamarchioretto@hotmail.com
139
This research was supported by
CNPq - “Conselho Nacional de
Desenvolvimento Científico e Tecnológico”
(Project no 200.808/98-2), an entity
from the Brazilian Government for the
development of science and technology
141
Printed by Ponsen & Looijen BV, Wageningen, the Netherlands
Cover
Idea: Marina Maya Marchioretto
Design: Ponsen & Looijen
142

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Heavy metals removal from

anaerobically digested sludge

Marina Maya Marchioretto

Heavy metals removal from

To my brother - my first friend

Marchioretto, M. M. (2003). “Heavy metals removal from anaerobically

A physical classification scheme based on wet-sieving was applied and

To assess the heavy metals solubilization, several organic and inorganic

Two conceptual designs of a treatment process to be applied in practice for

Chapter 1 - General introduction 1

Chapter 2 - Sludge characterization 17

Chapter 3 - Chemical leaching of heavy metals 37

Chapter 4 - Bioleaching of heavy metals 63

Chapter 5 - Heavy metals removal from the leachate 81

Chapter 6 - General discussion 97

Chapter 7 - Summary 112

Curriculum vitae 139

ORIGIN OF SEWAGE SLUDGE

Increasing urbanization and industrialization has culminated in a dramatic

The several levels of the municipal wastewater treatment are known as

Table 1.1 - Levels of wastewater treatment (Metcalf and Eddy, 2003)

To treat municipal wastewater streams, biological methods are usually

A conventional biological treatment process, which is worldwide used in

Grid Sand First Aeration Secondary

Figure 1.1 - Scheme of an activated sludge system

biologically at anaerobic conditions. This process is carried out in closed

COMPOSITION OF SEWAGE SLUDGE

Nitrogen, phosphorus, and organic carbon containing compounds can be

SEWAGE SLUDGE PROCESSING

Table 1.2 - Sewage sludge processing

Thickening, conditioning, dewatering, and drying are used primarily to

sludge volume should be minimized to reduce transport costs and dumping

Controlled landfill still continues to be used widely for the disposal of

The biological conversion of organic matter in aerobic digestion occurs in the

With respect to composting, this process involves aerobic degradation of

In essence, the activity of microorganisms causes both an increase in

A common possibility for sludge volume reduction is incineration. This

Wet oxidation, pyrolysis and gasification processes have attracted a lot of

SEWAGE SLUDGE MANAGEMENT POLICY WORLDWIDE

The correct management of sewage sludge and other biodegradable wastes

In developing countries, wastewater treatment hardly reaches 10 % of the

of sludge for land application, instead the use of commercial fertilizers, is an

Many countries are at many different levels of development in sludge

In Vietnam, large volumes of sludge generated in municipal wastewater

Sustainable sewage sludge treatment

Future sludge treatment should be progressively focused on an improved

Removal of colloidal and suspended particles from the influent

REMOVAL OF HEAVY METALS FROM SEWAGE SLUDGE

Basically there are three approaches (Rulkens et al., 1989) available to

The widespread use of anaerobic digestion in the treatment of sewage

The choice of the most worthwhile speciation technique to determine metals

A treatment process to remove heavy metals from (anaerobically digested)

To promote the solubilization of heavy metals it is mainly necessary to

In the case of chemical leaching, a previous oxidation step might be

A promising alternative to the chemical leaching is the microbiological

solubilization of heavy metals from sewage sludge still prevails under

SCOPE AND OUTLINE OF THIS THESIS

Although numerous studies have appeared in the field of heavy metals

characteristics of the applied sludge. The concentration of the heavy metals