South African Journal of Chemical Engineering 37 (2021) 214–226

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South African Journal of Chemical Engineering

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Treatment of arsenic sludge generated from groundwater treatment plant:

A review towards a sustainable solution
Dr. Biswajit Ruj a, *, Dr. Sankha Chakrabortty b, **, Dr. Jayato Nayak c, **, Rishyaprava Chatterjee a
a
Environmental Engineering Group, CSIR-Central Mechanical Engineering Research Institute, Durgapur 713209, India
b
School of Chemical Technology, Kalinga Institute of Industrial Technology, Bhubaneswar, 751024, Odisha, India
c
Department of Chemical Engineering, VSB Engineering College, 67, Covai Road, Karur 639111, Tamil Nadu, India

A R T I C L E I N F O A B S T R A C T

Keywords: Arsenic contamination above allowable limit in groundwater is universally been identified as a critical threat
Arsenic treatment plants with a high alarm in the African countries, Western USA and a lot of different developing countries. The
Arsenic sludge increasing numbers of arsenicosis patients with their extremely grave and fatal fates, imposes severe stringency
Safe disposal
to the treatment strategies. Though numerous types of technologies were adopted regarding the abatement of
Cementitious solidification
Stabilization
arsenic from water but as far the generated sludge from arsenic removing groundwater treatment plant is
Environmental protective strategy concerned, scanty efforts were put forward towards wise stabilization/capturing/encapsulation of arsenic sludge
to provide zero chances of leaching. Thus, arsenic with the ability of leaching back to soil and water while mixing
with surface and under-ground water, still stands as a serious and open challenge to the scientific communities
for their safe disposal. With an extensive review towards available technologies for safe arsenic sludge disposal,
this paper reviews the potential of stabilization of arsenic recalcitrant sludge employing concrete, polymer
compounds, fly ash, adding chemicals and by formation of bricks and cement blocks. Such approaches stand out
as flexible and economic strategies while permanently capturing stabilized arsenic in solid matrices while sus­
taining the strength of the building material. Thus, the requirements of coarse aggregate for the formation of
concrete blocks could also be reduced. Such a review is expected to initiate influential policies among the
research community to combat against the widespread risk of reluctant disposal practices of lethal arsenic sludge
generated from arsenic abating water purification methodologies.

1. Introduction
Throughout the globe, around 140 million human beings of different
regions are consuming water with higher arsenic concentrations more
than the prescribed permissible limit of WHO (Ravenscroft et al., 2009;
WHO, 2006). In Bangladesh alone, about 35 million of population is
under high risk of arsenic toxicity. In the Indian subcontinent, the
presence of high concentration of Arsenic has turned up to be an issue of
serious ecological concern in the current decades. Because of extremely
high human population and poverty, the Bengal delta basin is one of the
extreme red alert places in the world. Specifically, in the Bengal-Delta
Basin of Bangladesh and India, more than sixty million human popula­
tion are suffering due to consumption of arsenic containing ground
water (Sorg, 2000; Choong et al., 2007; Rajakovic et al., 2018).
Not only the from the water treatment plants but also from different
chemical and allied process industries, and metallurgical industries of
nonferrous heavy metals (eg. Cu, Pb, Zn, Sn), arsenic contaminated
sludge is produced that comes out as the waste effluent stream. In-fact,
million tons of arsenic bearing sludge generated from different process
industries, which has been shown in Table 1.
It is indeed that the most of the arsenic wastes are derived from
metallurgical industries of nonferrous heavy metals such as Cu, Pb, Zn,
Sn, etc., but, the whole thrust area of the manuscript is to nullify the
hazardous effect of arsenic sludge originated from arsenic abating water
treatment plants. In-fact, the authors have completely focused on the
stabilization/fixation/immobilization processes by different technolog­
ical means for the arsenic sludge generate from arsenic abating
groundwater treatment plants.

* Corresponding author. CSIR-Central Mechanical Engineering Research Institute, Durgapur, 713209, India.
** Corresponding author.
E-mail addresses: bruj@cmeri.res.in (Dr.B. Ruj), sankha.nit@gmail.com (Dr.S. Chakrabortty), nayak.jayato@gmail.com (Dr.J. Nayak), rishya.chatterjee@gmail.
com (R. Chatterjee).

https://doi.org/10.1016/j.sajce.2021.06.003
Received 18 August 2020; Received in revised form 16 May 2021; Accepted 7 June 2021
Available online 16 June 2021
1026-9185/© 2021 The Authors. Published by Elsevier B.V. on behalf of Institution of Chemical Engineers. This is an open access article under the CC BY-NC-ND
license (http://creativecommons.org/licenses/by-nc-nd/4.0/).
Dr.B. Ruj et al. South African Journal of Chemical Engineering 37 (2021) 214–226

Table 1
Contribution of industrial effluent in arsenic contamination. Reproduced with copyright from Li et al., 2018, “Pyrolysis of arsenic-bearing gypsum sludge being
substituted for calcium flux in smelting process” Journal of Analytical and Applied Pyrolysis, 130:19–28.
Location Cause of contamination Arsenic in effluent Reference

Behala, Kolkata Insecticide(Paris-Green) 80 – 18,750 µg/l Chatterjee et al., 1993

Peshawar, Pakistan
Peshawar, Pakistan
Peshawar, Pakistan
Peshawar, Pakistan
Peshawar, Pakistan
Peshawar, Pakistan
Peshawar, Pakistan
Yangzong lake, China
Datun Lake, China
Southwestern China
Guangxi, China
FOOD Industry 35.015 ± 4.3281 µg/l Ishaq et al., 2013
Pharmaceutical 33.569±5.6792 µg/l Ishaq et al., 2013
Textile Industry 63.242 ± 7.2321 µg/l Ishaq et al., 2013
Rubber Industry 37.026 ± 5.6621 µg/l Ishaq et al., 2013
Wool Mill 66.411±9.3218 µg/l Ishaq et al., 2013
Paper Industry 35.875 ± 8.3431 µg/l Ishaq et al., 2013
Plastic Industry 32.240±6.3241 µg/l Ishaq et al., 2013
Industrial tailing leakage accident 54.3 µg/l Chen et al., 2015
Dumping site for mineral tailings 213.5 µg/l Chen et al., 2015
Copper smelting metullurgy 10,230 mg/L Li et al., 2020
Metal smelting plant of tin, zinc and lead Arsenic oxide: 48.8 Zhang et al., 2021
Zinc arsenate: 6.86
Lead arsenate: 35.1 Elemental arsenic: 0.240
Arsenic sulfide: 7.31 (Wt%)

Understanding the widespread existence, chronic toxicity and its
massive cancer-causing ability, WHO in 1993 and USEPA in 2001 fixed
the highest allowable concentration of arsenic to be only 10 ppb in
drinking water (USEPA, 2001; WHO, 2006). Though, a wide variety of
technologies available regarding the abatement of arsenic from drinking
water but the practical implementation for the common people is still
challenging. The common technologies reported for the elimination of
arsenic for safe drinking water are adsorption, precipitation, oxidation,
coagulation-flocculation, ion-exchange, layered double hydroxides,
treatment with activated alumina, iron and manganese based oxidative
processing and membrane separation (Pal et al., 2014; Yuhui and
Qingfeng, 2016). But, eventually after a certain time period of opera­
tion, the removal efficiency of these technologies gets decreased.
Generally, regeneration or backwashing of the different removal bed of
arsenic abating water treatment plants used to be done, from where the
highly hazardous arsenic sludge comes out. The generated sludge has
high potential to leach back and again contaminated the ground water.
So, necessary treatment of these sludge has to be done for stabiliza­
tion/fixation before its disposal to bring down the potential hazard of
arsenic to the minimum/nullifying level (Paulsson et al., 2019;Eisa
et al., 2020). As suggested by USEPA in 2000, probable disposal stra­
tegies for high concentrated Arsenic wastes originated from water
clarification plants could be burial in soil with proper pretreatment and
stabilization (USEPA, 2001; Sullivan et al., 2010). But, the effective and
efficient stabilization of arsenic where no amount arsenic from the
contaminated sludge further leaches out is still a challenge. Table 2
provides an idea about the characteristic of arsenic-sludge containing
residues, produced due to the separation of arsenic-bearing
groundwater.
Thomas et al. (2007) exhibited different treatment possibilities of
arsenic affected water along with possible disposal strategies. In the
adsorption processes and ion exchange, the arsenic separating media
used to be activated alumina, oxidative iron-manganese and polymer
resins, which after separation turns highly arsenic contaminated solid
waste sludge. From membrane-based processes, liquid arsenic sludge
accumulates as the concentrated rejects while permeating clean water
and during backwashing of membranes. Moreover, arsenic rich fluid
residue used to be present in the regenerative streams or spent volume
from backwash or rinsing processes that used to be disposed by direct
discard, mixing with sanitary sewers, evaporative pond and aerated la­
goons. In case of solid waste residues containing high concentration of
arsenic, general practiced methods are mixing with sanitary sewer, land
applications and landfill. Pal et al., (2014) established a trivalent and
pentavalent arsenic rejects stabilization system post to 98% arsenic
separation from ground water using nanofiltration membranes. Chem­
ical oxidation using potassium permanganate for the transformation of
As (III) to As (V) was performed inside the stabilization stage. Though,
the authors claimed low cost (1.4 $/ 1000 L) arsenic-free water treat­
ment scheme, but, further application of stabilized sludge was not
shown.
Therefore, an extensive review has been initiated towards finding a
substantially eco-friendly solution where the high concentrated arsenic
sludge (originated from arsenic abating water treatment plants) stabi­
lization and fixation in solid concrete matrix appears to be a brighter
direction of contagious sludge handling. By the adoption of proper
method of arsenic stabilization ensures the extinction of the reactivity of
arsenic in waste sludge which could be justified by the leachability tests.
The use of such neutralized sludge could be employed for the prepara­
tion of building material by the mixing with cement. Thus, the stabilized
arsenic could be fixed in the solid matrix of concrete and losses its ability
to leachate out from it. Employing such sludge, the strength of concrete
of concrete block could be retained as like as made by the conventional
processes along with less use of naturally available coarse material.
Thus, it promises high sustainability through recycle and reuse of high
concentrated arsenic contaminated sludge generated from arsenic
mitigation ground water treatment plants, while showing a potential
direction towards making high compressive reinforce blocks. In the
backdrop of availability of very limited number of technologies, such
methodology not only supports leachable waste neutralization but also
paves a pathway towards waste to useful product formation.
2. Several types of disposal techniques for arsenic contaminated
sludge
Different properties of arsenic contaminated sludge were analysed by
Roy et al., 2018, where the reported arsenic concentrations were

Table 2
Arsenic-bearing residual characteristics (Ghurye et al., 2007).
Technology Used Residual Type Residual Volume (L/m3) Arsenic Concentration (mg/L) Solids Produced (g/m3) Arsenic in Solids (mg/Kg)

Conventional Coagulation Sludge 4.3 9.3 20 1850

Chemical Softening Sludge 9.6 4.2 200 165
Ion Exchange Liquid 3.9 10 2.3 14,250
Coagulation-Microfiltration Sludge 53 0.8 1.1 3000
NF or RO Liquid 663 0.1 NA NA

215
Dr.B. Ruj et al.
obtained in the range of 2300 PPM to 3500 PPM. pH was about 6 to 7,
and, TDS, organic acid, BOD5 level and COD concentrations were in the
ranges of about 42,000–43,000 PPM, 27–28 PPM, 11,000–12,000 PPM
and 20–373 PPM, respectively. The inorganics’ concentrations for sul­
fate were about 13 PPM, nitrate was about 0.6 PPM and iron was in the
range of 6–7 PPM. Living in the era of sustainable development, scien­
tific communities are extremely interested towards the strategic devel­
opment of safe disposal of high concentrated arsenic waste. In deficiency
of any common and established guidelines, high concentrated arsenic
sludge is often discarded in unscientific procedures. Commonly, for safe
dumping, the aim is to make the sludge less reactive or stabilized before
its disposal. In-fact, whatever be the developed technology, that must be
effective, reliable, cost effective and sustainable. Land fill disposal after
stabilization is yet the most appreciable methodology for both the
developed and developing countries (Sullivan et al., 2010).
2.1. Disposal through natural and biochemical process
2.1.1. Conventional landfill process
In the developing countries, like India, because of the lack of proper
instruction for the safe disposal hazardous sludge, landfill is the main
way to dispose the hazardous sludge. This technique is often adopted by
mining industries because there use to be higher possibilities of dilution
of the hazardous sludge with other non-arsenic containing sludge. The
arsenic rich sludge can be land filled if it contains arsenic less than 0.2 g/
m3, as suggested by USEPA (USEPA, 2001; WHO, 2006). But, in
land-filling process, arsenic and other hazardous chemicals always tend
to leach back and recontaminate the ground water again. Due to the
nonexistence of established guidelines regarding benign dumping of
arsenic sludge produced by the arsenic removal plants, a widely adopted
process used to be the discard of adsorptive screens and recovering
wastes into tiny sand shielded concreted pits of volume 1 m3. But,
without stabilization of arsenic, that process may also fail to stop the
back leaching phenomena. Before land dumping, generally air drying is
done for the sludge generated from co-precipitation and adsorption
process because of high water content in it. Tiny sand shielded
brick-lined pits are generally employed for discarding of adsorptive
filtration materials and recontaminating wastes where proper sealing of
pits is a better option in prevention of leaching out of arsenic during
flood or heavy rain. But, in-fact, in the second and third world countries
Fig. 1. Presence of Arsenic and its conversion to different forms in soil. (Shrivastava et al., 2015).
216
South African Journal of Chemical Engineering 37 (2021) 214–226
dumping pits are hardly sealed which provide supreme possibilities to
recontaminate ground water through leaching mainly during rain and
floods (Li et al., 2001). Toxicity characteristic leaching procedure
(TCLP) should be adopted for the analysis of arsenic sludge collected
from various arsenic separation plants to conclude if the planned sludge
discard technique is benign or not. Otherwise, through leaching arsenic
will potentially recontaminate the ground water environment (Erik­
sen-Hamel et al., 2003). TCLP and column leaching analyses studied on
sludge of arsenic abatement systems of Bangladesh showed insignificant
leaching capabilities of arsenic (BS EN. 12,457, 2002). Though minute
concentration of arsenic of 0.001 ppm was analyzed in the extraction
fluid, but long-term leaching can increase the leachate concentration in
the earth and ground water which could be considered to be of high risk
based on USPEA and WHO guidelines (USEPA, 2001; WHO, 2006).
Due to the different categories and properties of soil like, pH, oxi­
dation–reduction potential, presence of different inorganic and organic
matters, and concentration of sorbing species, arsenic exists in different
concentrations in the trivalent or pentavalent inorganic forms (Mas­
scheleyn et al., 1991) in soils (Vaughan 1991). Pentavalent form of
arsenic is usually present at oxidative/redox environments (Redox
potential> 200 mV; pH 5–8) but, under reductive circumstances,
trivalent for of arsenic used to be dominating (Marin et al., 1991, 1993;
Masscheleyn et al., 1991). Both the pentavalent and trivalent form of
arsenic can undergo chemical/biological and methylation processes and
may get adsorbed by the hydrous-oxide forms of iron, aluminum or
manganese (Bhumbla and Keefer, 1994); as shown in Fig. 1. Arsenic may
live in different forms in soil like: Arsenate (HAsO2− 1−
4 , HAsO4 ), Arsenite
(AsO2−3 ), Monomethyle Arsinic Acid (CH 3(AsO)(OH) 2), Dimethyle
Arsonic Acid ((CH3)2(AsO)(OH)), Dimethyle Arsine ((CH3)2(AsH)),
Trimethyle Arsine ((CH3)3(As)) and different forms of Arsenopyrite
(like: As3S3, As3S4 and FeAsS) etc. (Shrivastava et al., 2015) .
The most widely known natural mitigation for trivalent arsenic is
through formation of precipitate of Arsenic sulfide (As2S3). Though, the
trivalent form is more hazardous and mobile than the pentavalent form
of arsenic in earth, but, the methyl-arsenic complexes like, mono­
methylarsonic acid [CH3AsO(OH)2] and dimethylarsinic acid
[(CH3)2AsO(OH)] are also mobile (Bhattacharya et al., 1997, 2015).
However, these methylated forms can evaporate and used to be less
stable at oxidative environment which could be brought back to soil in
inorganic complexes (Banerjee and Chakraborty, 2005). It was reported
Dr.B. Ruj et al.
that, the adsorptivity to pentavalent form is much higher than trivalent
arsenic, while using Ferric hydroxide [Fe(OH)3] (Bhattacharya et al.,
1997, 2015), and highly oxic soils (Smith et al., 2003, 2004) as
adsorpting agents. In-fact, Fe, Al and Ca compounds present in soil, can
enhance arsenic capture (Bissen et al., 2003). Arsenic is more mobile in
sand mixed soil than that of thin-texture, because the adsorbing poten­
tial of soil depends on the surface area and clay matter content (Walsh
et al., 1977).
In-fact, the landfill process is not much appreciable as it always
possesses a tendency to leach out arsenic from the sludge volume during
rain, flood or draft. Moreover, in general, the time period to hold
arrested arsenic is also pretty less. But, being the easiest and cheapest
methodology, it is widely implemented in third world countries. It is an
extremely classical technology and not suitable for long term arrestation
of arsenic.
2.1.2. By mixing with livestock
Mixing of arsenic contaminated sludge with livestock can eliminate
hazard through the process of methylation by microbial activities. Such
methyl-arsenic complexes are like, monomethyl-arsonate [As(+V)],
monomethyl-arsonite [As(+III)], dimethyl-arsinate [As(+V)], dimethy­
larsenite [As(+III)], trimethylarsine oxide (As(+V)), and different
gaseous compounds like, mono-, di-, and tri-methyl arsines (TAMs)
(Hue, N., 2015). It was reported that, pentavalent arsenic could be
biologically reduced to trivalent form which could be further methyl­
ated through oxidation and finally converted to tri-methyl arsines
through reduction (Challenger, 1951). The possible steps could be rep­
resented by the Fig. 2 (Cullen and Reimer, 1989):
Methionine of different forms could be the contributors of methyl
groups in the Fig. 2 (Cullen and Reimer, 1989). Enzymes like, S-aden­
osine methyltransferase was recognized for such methylation activity in
the microbial species of Rhodobacter sphaeroides (Qin et al., 2006; Jie
et al., 2009). Not on bacteria, but also different fungi species Scopular­
iopsis brevicaulis, Aspergillus, Mucor, Fusarium, Peacilomyces, and Candida
humicola (Martin, 1977; Pickett et al., 1981; Madison, 1995) can take
active part in methylation to produce methylated arsenic (Cullen and
Reimer, 1989). A study was reported on the isolation of Penicillium sp.
from a cultivation evaporation aquatic pool in California, with ability to
transform methylarsonic acid and dimethylarsinic acid to trimethy­
larsine. The possible reaction scheme of biological conversion of arsenic
complexes by bacteria and fungi have been shown in Fig. 3 (Huysmans
Fig. 2. Transformation of arsenic by the interaction with livestock (Hue, N., 2015).
217
South African Journal of Chemical Engineering 37 (2021) 214–226
and Frankenberger, 1991). Fungi species of C. humicola can biologically
reduce Methylphenylarsinic acid and dimethylphenylarsine oxide to
dimethylphenylarsine, which is gaseous and could be arrested by acti­
vated carbon matrix for Arsenic mitigation from polluted water
(Frankenberger and Losi, 1995).
In India and Bangladesh, a common practice is to mix cow dung with
arsenic sludge generated from different traditional removal plants. The
bacterial species of cow dung has the potential to carry bio-reductive
reaction to transform arsenic (III) and (V) to arsine gas (AsH3) that
mixes with the atmosphere (Mudgal, 2001; Selvin et al., 2002). Gener­
ally, such kind of approach is taken in the rural and under developed
regions but it leaves high chances of recontamination of arsenic from the
cow dung blend. As a matter of fact, though arsine gas used to be less
harmful for open environment, but unscientific managing or
no-managing in open area of land enhances leachate formation during
rain, flood, draft or contact with water resources. The mixing of live­
stock for the arsenic mitigation is basically a bioremediation process, for
which, proper reaction conditions are required to be maintained. But,
due to carrying out the process in open land, none of the proper con­
ditions for aerobic or anaerobic reactions could be maintained properly.
Thus, the conversion of arsenic to non-leachate complex remains always
partial and this lives as a potential threat to further leaching, which
mixes in the ground during rain, flood, draft or contact with water
resources.
Under such circumstances, a proper technical managing of waste
mixed livestock with development of innovative techniques are highly
demanded. A proper engineering approach was shown by Roy et al.
(2018), where anaerobic microbes collected from septic tank, was used
as an inoculum to investigate the potential to stabilize arsenic rich
sludge in lab-scale batch digesters with outlets to release methane and
carbon dioxide. Sewage sludge brought from a local activated sludge
unit was the input in the bioreaction chamber to feed the microbes.
Maintaining mesophilic temperature for two and half months in
single-stage biodigester unit, it was identified that about 80% pentava­
lent arsenic mitigation (from 68 mg/L at inlet to 15 g/L at outlet) with
maximum efficacy of 1.25 mg arsenic consumption per gram of sub­
strate. In supernatant of digestion unit, arsenic concentration was only
0.04 mg/L and in sludge it was about 80 mg/kg sludge. The maximum
uptake in the reactor was found to be 1.25 mg As (V) per g of sewage
sludge input. On an average, the volatile acid concentration was about
150 mg/L with about 35% mitigation of solid contents at the outlet.
Dr.B. Ruj et al.
Fig. 3. General biointeraction for arsenic remediation by bacteria and fungae. (Hue, N., 2015).
2.2. Stabilization through chemical process
2.2.1. Stabilization through chemical encapsulation
Pyrolusite has been used as a source of a 40 to 80% of manganese
dioxide to oxidize As (III) to As (V) within a thermal range of 50 ◦ C to
100 ◦ C (Lemieux et al., 2014) in Dundee Sustainable Technology to
encapsulate arsenic. Then addition of Ca(OH)2 to form non-gaseous
calcium arsenate with high melting point. Silica, sodium carbonate,
sodium oxide, calcium oxide, alumina and feldspar of potassium used to
be mixed and with calcium arsenate while heating the mixture between
1000 ◦ C and 1200 ◦ C to generate stable arsenic oxide containing 1–20 wt
% of arsenic. This approach proposed that arsenic leaching is well below
the safety point (Lalancette et al., 2014). The overall possible reaction
describing the stabilizing of arsenic and glass formation is given as
following:
As2 O3 + 3Ca(OH)2 + MnO2 →Ca3 (AsO4 )2 + 3H2 O + MnO
Notably, this technique for arsenic stabilization involves high heat­
ing at elevated temperature which increases the overall cost of the
process. Moreover, the stabilization efficiency through this methodology
is pretty less (1%− 20% only), and, during reaction, some of the by-
products are also formed which are also discarded in the open land.
Discard of those chemical by-products could be harmful for the envi­
ronment and eco-systems. Thus, stabilization via encapsulation tech­
nology cannot be a preferred route as it affects the chemical balance of
the environment.
2.2.2. Stabilization through chemical precipitation/coagulation methods
Fly ash obtained from metal processing industrial houses often
contains arsenic content of 20% to 48% by weight along with antimony
and lead (Moon and Dermatas, 2007). Cement and pozzolanic materials
can be used to minimize the leaching ability of the target material from
discards through solidification. By proper optimization of Ca(OH)2
content, the arsenic concentration was lowered in the leachate by 99%
and up to 0.5 ppm due to the formation of CaHAsO3 (Dutre and Van­
decasteele, 1988). Arsenic sludge when treated with lime then it reduces
the mobility of dissolved arsenic and it is due to the formation of
Ca3(AsO4)2 of low solubility but till the date there is no such strong
evidence regarding the hypothesis. Calcium arsenates and the apatite
Ca5(AsO4)3OH which are precipitate under alkaline conditions and the
process which is responsible for the immobilization of arsenic with lime
(Bothe and Brown, 1999). The following equation has been indicated the
formation of calcium arsenate As3+ stabilization:
Ca(OH)2 + H3 AsO3 + H2 O→Ca3 (AsO4 )2 ⋅xH2 O
Amorphous Fe precipitates can be used to stabilize the As available
from the mine tailings. Fe addition, time and the pH has the major role
for arsenic stabilization (Kim et al., 2003; Lim et al., 2009). Fourier
transform infrared spectroscopy (FTIR), extended X-ray absorption fine
structure (EXAFS) spectroscopy are used to explore the immobilization
mechanism in which ferrous hydroxide sludge was blended with
cement. Mortar samples were prepared with various weight ratios of
blended cement to dry sludge of 2.2, 3.3,5,10 and 20. The chemical
bonding between pentavalent arsenic, Fe and Ca in unprocessed and
cement-processed sludge were analyzed by EXAFS and FTIR with (C/S
218
South African Journal of Chemical Engineering 37 (2021) 214–226
= 10) ratio of sample. From EXAFS analysis it has been found that on the
iron hydroxide surface pentavalent arsenic produced bidentate mono­
nuclear conjugates in sludge. FTIR analytics at 830 cm− 1 is due to the
adsorbed pentavalent arsenic on iron hydroxide and at 860 cm− 1 is due
to formation of calcium arsenate and 875 cm− 1 is due to the formation of
calcium carbonate (Chuanyong et al., 2003).
Different Ca/As molar ratio of Lime–As and lime–As–kaolinite slur­
ries were used for the immobilization of arsenic. Different arsenic pre­
cipitate with different oxidation states were analyzed through XRD. Ca/
As molar ratios greater than 1:1 show a significant immobilization of As
(III) and with a molar ratio of 2.5:1 shows high As (V) immobilization.
No pozzolanic reaction product has been formed and the immobilization
is only due to the precipitation which is confirmed by XRD analysis.
With the elevation of Ca:As molar ratios both the As (III) and As (V)
immobilization increases (Moon et al., 2004). Iron oxide coated cement
(IOCC) which is used for the adsorption of arsenic can be stabilized with
cement and lime. The effectiveness of the process have been observed by
leachability indices (LX) and diffusion coefficients (De). It also has been
found that the diffusion coefficients (De) are in the range of 10− 10 to
10− 12 and best result is observed when lime is used. From the XRD and
SEM data it is confirmed that the reduction of arsenic leaching is due to
the formation of calcite which inhibit the diffusion of CO2 into the
interior of the solidified waste and sealing the pore. The different
insoluble Ca–As compounds and precipitates as calcium arsenates, cal­
cium arsenite, calcium hydrogen arsenate hydrates and calcium
hydrogen arsenates are also responsible for reduction of arsenic leaching
(Kundu and Gupta, 2008). Addition of lime can reduce arsenic leaching
from water treatment residuals. Lime treated arsenic sludge residuals
are not stable in atmospheric condition as calcium-arsenic compound
decompose slowly. Hence for the long-term immobilization of arsenic
sludge residual there must be a barrier between atmospheric CO2 and
the calcium-arsenic compound. The long-term stabilization can be
achieved with the using lime and cement along with arsenic sludge re­
siduals though arsenic leaching from the residuals stabilized through
lime and ordinary Portland cement (OPC) has not been differ extremely
(Camacho et al., 2009). In another study, Beauchemin et al. (2010),
carried out a study on characterization and stability of arsenic in an
alkaline AMD sludge under prolonged anoxic conditions. A set of labo­
ratory treatments were carried out for stabilization study using 100%N2,
100%N2 + glucose and 95%N2: 5%H2 and were compared against a
control of oxidized and water saturated sludge. Based on the result of
Electron Micro Probe (EMP) analysis and spatially resolved synchrotron
X-ray fluorescence (SXRF) indicated arsenic is dominantly associated
with iron in sludge. Dissolved Manganese in N2 + Glucose treatment
increased significantly as compared to other treatments. Micro scale
SXRF and XANES (X-ray absorption near edge structure spectroscopy)
showed Mn(II) accumulated in areas which were already enriched in
iron and arsenic. Finally, it can be inferred that As(V) in AMD sludge
remains stable under prolonged anoxic condition as long as Mn(IV) is
present in sludge and negligible accumulation of organic matter.
Chemical fixation of available arsenic from organic arsenic industry
with ferric sulfate (FS), magnesium chloride (MC) and calcium hy­
droxide (CH) were evaluated through TCLP (toxicity characteristic
leaching procedure), SPLP (synthetic precipitation leaching procedure),
and SEP(sequential extraction procedure). Is has to be concluded that
Dr.B. Ruj et al.
the optimal molar ratio for the fixation is 2:1, 3:1 and 2:1 for Fe:As, Mg:
As and Ca:As respectively. Use of the FS +MC + CH shows maximum
fixation (Li-Fang et al., 2010). Arsenic containing sludge treated with
Portland cement, ferrous sulfate and lime (PFL) has been investigated
with a patented technology Terra-Bond™. For the simulation of an
organoarsenic soil material chromated copper arsenate processed
woody matters; scorodite enriched mine tailings from the La Trinidad
Mine in California; and a soil/smelter dust mixture from the Anaconda
Superfund site spiked with monosodium methyl arsenate (MSMA) have
been collected. From the XANES spectra it has been found that CCA-
containing sample shows predominant pentavalent form of arsenic
while upon treatment with PFL process the oxidation state of arsenic
does not alter. But it is very interesting that XANES spectra for the un­
treated and PFL treated scorodite-rich mine tailing shows a change in
coordination structure from a mixture of As (III / V) to predominantly As
(V). From SEM/EDS and XRD spectra it has been observed that PFL
treating sludge samples shows similarity of all three sludge materials
while Terra-Bond treated sample shows high amount of elemental sul­
fur. An epoxy material on the surface of the Terra-Bond treated sample is
responsible for arsenic encapsulation (Randall, 2012).
Cement based stabilization of arsenic bearing iron oxide sludge has
always been indicated as the pretreatment method before landfill. To
predict the mobility of arsenic from cement stabilized arsenic residues a
sample of simulated rain water (pH>8) was used that showed low
arsenic leaching of about 0.34% of the total arsenic which is very close
to the TCLP prediction value. From the XRF elemental analysis it has
been concluded that cement stabilized arsenic-bearing sludge mainly
got associated with the iron constituents. Hence cement based stabili­
zation is the most promising technique for the safe disposal of arsenic
(Clancy et al., 2015). Excellent stabilization efficiency was obtained by
mechanochemical modification of zerovalent iron using iron:manganese
molar ratio of 5:1 and forming Fe-Mn binary oxide coating on the
external area of zerovalent iron. Increasing the dosage up to 5% weight,
exhibited the increase in arsenic stabilization efficiency which turned
insignificant by the increase of dosage from 5% to 15% (Liang et al.,
2016). Arsenic leachability drastically declined from 73 ppm 0.6 ppm
using 5% dosage that is well below the threshold limit of As<5 mg/L
(USEPA,2001).
FeCl2 and FeCl3 were widely employed in stabilizing of arsenic in
mine tailings (Lin et al., 2017). The mechanism of the stabilization of
arsenic was analyzed through FTIR and XRD results. According to the
experimental result it is found that molar iron concentration than
arsenic showed leachability less than 2.5 ppm which is far below than
allowable limit for safe land fill disposal. The mechanism behind this
result has been explained as iron oxide possess positively charged sur­
face for the formation of Fe–OH2 functional groups with static
electro-affinity among the arsenate anions. At first on addition of the
iron salt the arsenic ions to the oxide external area or internal pores
through adsorption. Over the superficial area of iron oxide exchange
between the Fe–OH and Fe–OH2 ligands of the multi-core dentate
complexation ions [Fe(H2O)6]3+, [Fe2(OH)3]3+, and [Fe2(OH)2]4+
takes place and forms Fe–O–AsO(OH)–O–Fe and Fe–O–As(OH)–O–Fe
dual-core bridging inner complex and arsenic gets fixed in the double
electric layer. Even arsenic can react with ferrous or ferric salt to form a
stabilized iron-arsenic compound. FeCl3 blended solution at pH =7 and
pH =4 shows acid dissoluted arsenic was declined by 96.22% and
93.42% while FeCl2 mixed solution at pH =7 shows 96.22% decrease
respectively. The samples treated with FeCl2 and FeCl3 at different pH
are investigated in FTIR spectroscopy. Asymmetric stretching frequency
of AsO3- -1
4 revealed at 878 cm , and the stretching frequency of As–O
-1
revealed at 840 cm which indicates readily existing As–O bond post to
stabilization and energetically steadier configuration was obtained.
Fe-hydroxides can easily coagulate arsenic but the resultant products
are unstable, for which, reductive aluminum compounds could be added
to increase chemical stability of precipitates. Mello et al. (2018) re­
ported that, aluminum-iron-hydroxides could be effective for arsenic
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South African Journal of Chemical Engineering 37 (2021) 214–226
precipitation for the wastewater coming out of mines containing very
high arsenic concentrations. In presence of arsenic, different metal salts
by maintaining diversified iron to aluminum mol ratios of 1:0.0, 1:0.3,
and 1:0.7, were used for precipitation with aging periods of 90 days
(sulfate tests) or 120 days (chloride tests). Post to curing time, the
arsenic mobility significantly reduced with effective reduction of arsenic
concentration less than 10− 3 PPM. A remarkable experimentation was
performed employing mesoporous silica (SBA-15) supported
iron-manganese binary oxides (FeMnOx) (Zhou et al., 2019) to develop
an adsorbent. It was observed that further heating of that adsorbent at
350 ◦ C under inert atmosphere improved the removal efficiency of
arsenic up to 90% even by using less concentration (0.2 g/L) of adsor­
bent. The silica based iron-manganese binary oxide catalyst was found
to be reusable and having the potential of regeneration with high arsenic
adsorption performance. The possible adsorbent synthesis scheme with
adsorption mechanism is shown in Fig. 4.
The iron compounds could be employed as extremely good coagulant
for the deposition of ferric arsenate which is more insoluble than cal­
cium arsenate. Moreover, the iron ions can form potentially good ag­
gregates. The precipitation reaction is shown as below:
Fe2 (SO4 )3 + H3 AsO4 => FeAsO4 ↓(solidprecipitate)
Precipitation of extremely stable Ferric arsenate (FeAsO4•2H2O)
solubility diminishes swiftly with the increase in Fe:As ratio in solution
within the pH range of 3 to 7. Thus, by the use of iron salts for the
stabilization of arsenic, while optimizing the Fe:As molar ratio can
produce extremely good success in the solidification or stabilization
efficiency of arsenic. Table 3 represents the widely used analytical ap­
proaches for arsenic sludge stability assay.
But, while using different chemicals for stabilization process,
different chemicals are having different capacities of stabilization and
time to arrest a concentration of arsenic and time period to keep that
concentration to arrested. Different chemical species have different
chances of leaching of captured arsenic. Thus, the selection of such
stabilizing chemicals is pretty crucial to ensure safe disposal (Hartley
et al., 2004). Moreover, economics is another major factor because,
more efficient chemicals are having high cost and in some of the pro­
cesses involve several chemicals to stabilize arsenic. Lastly, there live
chances of recontamination of chemicals and by-products during
disposal after treatment which may also disturb the overall chemical
balance of the environment.
Recently, Liang et al. (2016) had used mechanochemically modified
zero valent iron in the stabilization of arsenic sludge. Modified zero
valent iron collected from commercial iron provided is co-grounded
with manganese dioxide under intensive mechanical stress. As
compared to ordinary ZVI, modified ZVI had shown better arsenic
sludge stabilization having a declination of arsenic leaching contraction
from 72.50 mg/L to 0.62 mg/L. The emergence of manganese restrains
the process of iron hydroxide crystallization performing much better in
arsenic adsorption. Based on BCR analysis, it can be inferred that un­
stable arsenic in sludge getting transformed into residual fraction with
help of amorphous iron hydroxides thereby restraining the environ­
mental availability of arsenic sludge after modified ZVI stabilization.
2.2.3. Stabilization by polymeric compounds
Stabilization of arsenic sludge also has been done by different
polymers such as polystyrene (PS) and polymetylemethacralate (PM). It
has been already reported that PS and PM were employed for stabili­
zation of hazardous and radioactive materials (Singh and Pant, 2006).
Due to their higher ability for chemical interaction these materials are
selected for solidification/stabilization but in case of (Activated alumi­
na+cement+polystyrene) at a ratio of 3:1:0.5 and (Activated alumina
(AA) +cement (C) +polymethylemethacralate (PM) at a ratio of 3:1:0.5
showed wider void space for their tubular structureed shape. Though
Activated alumina+cement+fly ash+polystyreneat a mixing ratio of
3:1:0.5:0.5 possessed bigger crystals but due to wide pore entrance
Dr.B. Ruj et al. South African Journal of Chemical Engineering 37 (2021) 214–226

Fig. 4. Adsorption o arsenic by iron oxide. Reprinted (adapted) with permission from (Zhou. J, Zhou. X, Yang K, Cao Z, Wang Z, Zhou C, Baig SA, Xu X., Adsorption
behavior and mechanism of arsenic on mesoporous silica modified by iron-manganese binary oxide (FeMnOx/SBA-15) from aqueous systems, Journal of Hazardous
Materials, 384 (2020) 121,229, doi.org/10.1016/j.jhazmat.2019.121229), Copyright (2021), Elsevier.

Table 3
Analytical practices for assay of Arsenic in variety of sludge or discards. Reprinted (adapted) with permission from “Tara M. Clancy, Kim F. Hayes, Lutgarde Raskin.
Arsenic Waste Management: A Critical Review of Testing and Disposal of Arsenic-Bearing Solid Wastes Generated during Arsenic Removal from Drinking Water, dx.
doi.org/10.1021/es401749b | Environ. Sci. Technol. 2013, 47, 10,799− 10,812′′ . Copyright (2021) American Chemical Society.
Name Use Reagent pH Time Leachant to solid Ref.
(Hour) mass ratio

Toxicity characteristic leaching Threat level detection of solid/liquid waste for CH3COOH (0.1 M) 5 18 20:1 57
procedure (TCLP) landfilling
California waste extraction test Risk level detection of solid/liquid waste for C₆H₈O₇ (0.2 M) 5 48 10:1 58
(CAL WET) landfilling
Synthetic precipitation leaching Threat level detection of solid/liquid waste for Distilled water + 4.2 Or 18 20:1 59
procedure (SPLP) leaching by rainfall HNO3 + H2SO4 5
Total available leaching procedure Categorization lethal substances Distilled water + HNO3 4&7 3 50:1 60
(TALP)
Korean waste standard test Threat level detection for soils and solid waste Heated 1:1 (w/w) + NA* 2 Not specified 61
HNO3 +HCL
German leaching test (DIN 38,414) Risk level in stabilized waste Distilled water NA* 24 10:1 62
United kingdom leaching test Hazard level in soils and solid discard Distilled water NA* 1 5:1 63
American society of Testing and Hazard level in soils and solid discard Distilled water NA* 48 4:1 64
materials (ASTM) test
BS EN 12,457 Risk level detection of solid discard for landfilling and Distilled water NA* 24 10:1 65
categorization lethal substances
Japanese standard procedure for Municipal solid waste Distilled water NA* 6 10:1 66
leaching test
Modified Dutch column test Threat level detection for soils Distilled water + HNO3 4 504 Continuous flow 67
(0.1 mM)
ASN 16.1 short term leaching Less risk level nuclear waste and stabilized waste CH3COOH (0.014 M) 3.25 2160 Semi batch 68,69

NA*: No adjustment required.

Fig. 5. TCLP and CA-WET leaching results for unencapsulated GFH, E-33 and AAFS. The line marked TC corresponds to 5 mg/L (arsenic toxicity characteristic).
Reprinted (adapted) with permission from “J.K. Shaw, S. Fathordoobadi, B.J. Zelinski, W.P. Ela, A.E. S´aez, Stabilization of arsenic-bearing solid residuals in poly­
meric matrices, Journal of Hazardous Materials. 152 (2008) 1115–1121′′ . Copyright (2021) Elsevier.

220
Dr.B. Ruj et al.
revealed more leachability. In-fact adding of polymers did not enhance
the chemical interaction of arsenic with cement matrices but increased
the pore radius of the matrix which provided more leachability to
arsenic. All the solidified waste samples are treated under semi-dynamic
leaching tests and it has been observed that the samples having
composition of AA+C+PS and AA+C+PM has high of arsenic. Arsenic
sludge which contains granular ferric oxy / hydroxide and ferric hy­
droxide amended alumina residuals can be encapsulated in a polymeric
matrix. The polymer is actually blend of polystyrene butadiene and an
epoxy resin. The polymeric waste must contains a 1:1 wt ratio of poly­
styrene–butadiene (PSB) rubber and epoxy resin, 1:10 wt ratio of sur­
factant and epoxy resin and 1:10 wt ratio of cross-linker and epoxy resin.
This polymer based formulations have ability to encapsulate with more
than 60% residues with proper mechanical properties. Commonly
available sorbents like granular ferric hydroxide (GFH), Bayoxide
(E-33), iron-amended activated alumina (AAFS) and iron-impregnated
sand all of these adsorbents contain arsenic-bearing solid residuals
(ABSRs). Based on the TCLP and CA-WET analysis, Bayoxide provided
the highest arsenic leachibility which is shows in Fig.5 (Shaw et al.,
2008).
Using precipitation polymerization technique, an arsenic grafted
polymeric adsorbent was produced prepared employing 4-vinyl pyridine
and 2-hydroxyethyl methacrylate as functional materials (Saqaf et al.,
2019). Analysis of isotherm of trivalent arsenic showed validity with
Langmuir model and pseudo-second-order kinetics model with the
highest adsorption potential of 106.3 mg/g of adsorbent. The quantified
leaching concentration was about 0.87 ppm with about 99% trivalent
arsenic abatement efficiency. The possible mechanism for capturing
trivalent arsenic by polymeric materials is shown below:
As(III) + 4 − Vinylpyridine→As − 4 − Vinylpyridine + 2 − Hydroxyethyl Methacrylate
↓
As − 4 − Vinylpyridine − 2 − Hydroxyethyl Methacrylate
But, in case of Stabilization of arsenic sludge by polymeric com­
pounds, the process suffers due to high cost due to use of several
chemicals. Moreover, the use of auxiliary chemicals increases the pos­
sibilities of recontamination, and disturb the chemical balance of the
environment.
2.3. Stabilization through solidification methods
2.3.1. Stabilization through cementation
Stabilization of arsenic sludge through cementation is not a perma­
nent solution but it is normally used as pretreatment before landfill to
assure that hazardous sludge is safe for disposal (Choong et al., 2007).
Different kinds of industrial discards used to get mixed and treated with
Portland cement for solidification. The main objectives to use the
different kind of binders are to minimize the leaching and show long
term strong structural stability. Arsenic ions can be arrested using cal­
cium silicate hydrate (C-S-H) matrix of cement by the adsorption and
co-precipitation (Halim et al., 2004). Portland cement is used in this
stabilization process the matrix fails to keep consistency during the in­
crease in pH and discharges arsenic (Paria and Yuet, 2006). Atmospheric
vapor content, periodic turns of soaking and drying and carbonation of
Ca(OH)2 present in cement are also responsible for release of arsenic
(Sanchez et al., 2002). Using Na2HAsO4•7H2O, it could be concluded
that As (V) bearing sludge can be stabilized for a longer time in cement
matrix (Mollah et al., 2004). The efficacy of stabilization for arsenic
trioxide, arsenic pentoxide, sodium arsenite and sodium arsenate at the
dosing of about 10% through consecutive batch leaching process
(Australian Standard 4439.3., 2019) were used to investigate for the
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South African Journal of Chemical Engineering 37 (2021) 214–226
effective stabilization with different binders of Portland cement, a blend
of Portland cement and iron sulfate, and another blend of Portland
cement and lime (Leist et al., 2003). It has been observed that the mass
transfer of leach-back phenomena of arsenic from cement matrix is
governed by diffusion where the presence of arsenic is inversely pro­
portional to the presence of calcium. This used to be applicable for any
kind of solidification/stabilization formulations for arsenic compounds.
Use of lime or even the high original concentration of calcium in cement
also facilitates the presence of calcium in the process of arsenic stabili­
zation. Addition of the iron also keeps positive stabilization effect in the
formation of solid matrix arresting arsenic (Leist et al., 2003). The dif­
ference between the results obtained from TCLP and TCLP (acidic)
mainly due to the formation of stronger surface complex on iron oxide
by citric acid than by acetic acid. Investigation of arsenic leachability in
the sludge using TCLP and CWET test and found 283 ppb and 7490 ppb
respectively (Jing et al., 2005). X-ray absorption near edge structure
(XANES) spectroscopy shows that the As(III) composition was reduced
from 51.1% of the total As content in the sludge to 16.3% in the cement
treated sample with 28 days of cure but if the cement treated sample was
cured for two years, the As (III) composition was found to be 7.4% only.
Trivalent arsenic oxidation rate in cement treated sludge retarded post
to a month with almost completion of cement hydration reactions. Such
retardation happens due to the inhibitory factors of minimized aqueous
volume after 4 weeks and precipitation of calcium arsenite (Dutré and
Vandecasteele, 1998). The extended TCLP showed arsenic leachability
for a long time-period for the variation of pH for unprocessed and
cement processed sludge.
Arsenic sludge can also be stabilized through briquette preparation
using cement, sand and stone chips and it has been found that upto 40%
of sludge is stabilized. TCLP of the stabilized sludge has been also carried
out and found that it is far below the permissible limit of 0.2 g/m3, as
prescribed by CPCB, India (CPCB, 1996). The mine tailing mainly
contaminated with arsenic concentration of around 88–100 mg/kg.
Solidification/stabilization of the mine tailings were done using cement
and it has been found that addition of 5% of cement is enough to pass the
unconfined compressive strength. Addition of 7.5% cement to arsenic
contaminated sludge dramatically changes the reduction of arsenic
leaching (Choi et al., 2009). Safe disposal of an adsorbent iron oxide
coated sponge post to the treatment with arsenic containing water was
performed with cement, sand, lime and fly ash. The result showed that
the leachate contained the maximum arsenic concentration of 35 ppb. It
is found that variation of cement concentration affects a little but the
mixing of calcium hydroxide gives better result. The leachability of
arsenic even after a month from the concrete samples was only
0.1–1.1%. This result proves the tremendous attraction between arsenic
and the coating of iron oxide. Fly ash was proved to be an efficient agent
in minimizing the leachability even by 300% by the formation of
insoluble fly ash–arsenic conjugate than the trials lacking the addition of
fly ash. In-fact, fly ash showed better arrest than lime (Nguyen et al.,
2009).
While using cement: sand: sediment/soil in the ratio of 19:56:25, it
was found that arsenic contamination in the leachate was lesser than
0.73 ppm (Nakwanit et al., 2011). Solidification/stabilization of arsenic
sludge with other elements such as copper, zinc and lead with ordinary
Portland cement and fly ash and it is reported that arsenic immobili­
zation in cement matrices is due to the alkaline nature and buffering
capacity provided by calcium hydroxide and C–S–H (Li et al., 2001).
Dr.B. Ruj et al.
Table 4
Composition ratio of different solid waste samples (Singh and Pant, 2006).
Composition used Weight Ratio
Mixture of activated alumina & cement 3:1
Mixture of activated alumina, cement & fly ash 3:1:0.5
Mixture of activated alumina, cement, fly ash & calcium hydroxide 3:1:0.5:0.5
Mixture of activated alumina, cement, fly ash & polystyrene 3:1:0.5:0.5
Mixture of activated alumina, cement & polystyrene 3:1:0. 5
Mixture of activated alumina, cement & polymetylemethacralate 3:1:0.5
Arsenic soil partially contained with sand can be stabilized using type I
Portland cement along with FeSO4 .7H2O. Better results were found if
the arsenic soil is treated with ferrous sulfate first then with type I
Portland cement. A good result was found due to the very low perme­
abilities of the treated soil between the range of 10− 9–10− 10 m/s.
The formed phases are due to the formation of hydrated cement. The
presence of C-S-H matrix proves that arsenic mixed soil does not affect
the matrix. There is a superposition of peaks for the silicate and
aluminate in NMR spectrum of soils which is difficult for hydrated
Portland cement (Miller et al., 2000). Addition of different proportion of
Ca(OH)2 with cement will maintain high pH for a longer time period as it
acts as a supplement of calcium. Calcite formation in the cement matrix
during carbonation reaction seals the pores which inhibits the intrusion
of atmospheric CO2 in the matrix as well as extrusion of any other
element from the matrix. The minimum amount of arsenic leaching has
been observed in the of activated alumina, cement, flyash, and calcium
hydroxide matrix (Singh and Pant, 2006). Chances of arsenic leachate
formation reduces with higher stabilization performance through the
formation of calcium arsenite and calcite, which help in sealing of pores
of solid discard. Incorporation of stabilizing polymer beads was found to
elevate arsenic leaching. Preparation of solid matrix of different binder
constituents is shown in Table 4. Decrease in arsenic mobility after
mixing with cement is also due to the development of extremely less
dissolvable calcium arsenate (Chuanyong et al., 2003).
Arsenic bearing fly ash from the copper refinery contains very high
amount of As2O3 which can be hardened using cement and calcium
hydroxide. The leachate arsenic concentration can be minimizing to 5
mg/L using a saturated solution of Ca(OH)2. In addition of Ca(OH)2 the
precipitation of As (III) is found as CaHAsO3 and it is confirmed by the
reduction of arsenic contamination in the leachate but if oxidation of the
sludge has been done before solidification/stabilization using H2O2 the
leachate arsenic concentration is found to be 0.5 mg/L, by a factor 10
than the non oxidized s/s sample. This improvement is because of the
generation of Ca3(AsO4)2 which has very low solubility product (Van­
decasteele et al., 2002). Hardening of arsenic and heavy metal con­
taining mine tailings using cement and blast furnace slag has been done
and the most optimum condition is 7:3 mixing ratio of tailings (TA) and
a 1:1 mixture of Ordinary Portland Cement (OPC) and blast furnace slag
(SG) along with 20% of water content (WC) and it is not only cost
effective but also proper strength (Kim and Jung, 2011).
Sludge from copper smelter industry contains high concentration of
heavy metals along with arsenic which can be solidified using fly ash and
lime as binder. X-ray fluorescence analysis gives data about calcium to
silicon concentration ratio, which is the main governing factor for the
strength development. It has been found that after leaching test above
99% of Cu, Ni, Pb and Zn and above 90% of As can be stabilized with
high Ca(OH)2 content. Samples with 20% of binder having 50% of lime
and 50% of fly ash met all the requirements for safe disposal. At the time
of lime addition sludge with low amount of silica does not reacts with
excess Ca(OH)2 which is responsible for decrease of Unconfined
Compressive Strength (UCS) value (Ivšić-Bajčeta et al., 2013). For the
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South African Journal of Chemical Engineering 37 (2021) 214–226
analysis of cement enhanced stabilized solidification, cement-sand
mortar cubes of 150 × 150 × 150 mm have prepared and it has been
observed that maximum leaching is found in WET test than DIN or TCLP.
Arsenic sludge content when reached to about 18% by volume with
respect to cement then it just cross the safe disposal limit of 0.2 g/m3
according to WET test hence it is observed that 10% of sludge content is
safe regarding with the entire safe disposal regulations. Replacement of
cement with fly ash using 10% sludge and different percentage of fly ash
such as 25, 50% of the volume of cement has been investigated. It has
been found that maximum 45% of cement (by volume) can be replaced
by flyash with a cement and arsenic sludge ratio of 1:3 (Banerjee and
Chakraborty, 2005).Arsenic sludge when treated with 30 wt% Portland
cement with 24 h of curing time and 50 wt% cement kiln dust with 168 h
of curing, the arsenic contamination level in lechate was found to be
lesser than the Korean Standard Test measurement value. Arsenic con­
centration in leachate got considerably minimized at pH > 3 which in­
dicates that pH has a major role on arsenic mobility. Analytical
characterization results obtained from the Portland cement and cement
kiln dust treated slurries showed that no change in arsenic speciation
and formation of calcium arsenite (Ca-As-O) and sodium calcium arse­
nate hydrate (NaCaAsO4.7•5H2O) were responsible for As(III) and As(V)
immobilization (Yoon et al., 2010).
Arsenic rich CalSiCo (patented trade name) a cement-based adsor­
bent has been used to prepare pulverized cement concrete (PCC) by the
s/s technique with cement. Leaching of As(III) and As(V) from the
CalSiCo-sludge as well as from the PCC has been depend upon the time,
pH and concentration of anions such as Cl− , NO−3 , and SO2− 4 present in
the leaching agent. The leaching tests has been performed in both the tap
water and rain water but interestingly tap water does not affect the
leaching of CalSiCo-sludge but rain water does, which is basically due to
the effect of pH. Arsenic-laden CalSiCo-sludge after treatment negligibly
small amount 0.02 mg/L of arsenic is released. Arsenic-laden CalSiCo-
sludge can replace maximum 35% of cement without hampering its
mechanical properties (Bhunia et al., 2007). Short term stabilization and
long-term stabilization of arsenic contaminated soil has been done using
coal fly ash. Addition of coal fly ash decreases the leachability of arsenic
adding up to 5 wt% and next to remove upon addition of 10 wt%
(Chuanyong et al., 2003). The observed result is because of extended
superficial area of more than 200 m2/g and occurrence of poor crystal
structures of iron and aluminum oxides. Strong adsorption of arsenic in
the form of bidentate mononuclear inner-sphere complexes has been
found on co-precipitated Fe/Al hydroxides (Masue et al., 2007). Long
term stabilization has been carried out and using 5 wt% and 10 wt% coal
fly ash and TCLP result shows arsenic concentration reduction by more
than 70% (Tsang et al., 2014).
An arsenic fixation study (Yoon et al., 2010), using portland cement,
and cement kiln dust, reported that the curing time and required content
of portland cement (24 h and 30%) is lesser than those of cement kiln
dust (168 h and 50%), to receive effective entrapment of arsenic (>3
PPM) as per Korean Standard. It was observed that higher pH (>3),
arsenic mobility and leaching tendency decrease significantly. X-ray
powder diffraction showed that the formation of calcium arsenite
(Ca-As-O) with Portland cement and sodium calcium arsenate hydrate
(NaCaAsO4, 7•5H2O) with cement kiln dust hold the pivotal re­
sponsibility for trivalent and pentavalent arsenic stabilization. The
oxidation states of arsenic had consistency and stability in the stabilized
crystal speciation, was revealed by X-ray absorption near edge structure
analysis. Extended X-ray absorption fine structure spectroscopy ana­
lysed the bonding between of arsenic and calcium, where calcium is
solely responsible for immobilization of both tri- and pentavalent forms
of arsenic. The possible overall reaction of arsenic (+III and +V) with
portland cement and cement klin dust are as follows:
Dr.B. Ruj et al.
As(+III)+NaAsO2 +Portlandcement/cementkilndust→[Ca− As− O]complex
As(+V) + Na2 HAsO4 , 7H2O + Portland cement/cement kiln dust→ NaCaAsO4 , 7.5H2 O
But, use of Portland cement cannot bring high compressive strength
of the concrete structure. Sometimes, high cost is involved for the use of
different auxiliary chemicals. Moreover, the newly formed chemical
complexes may disturb the chemical stability of the environment when
those are discharged from the stabilization process.
Cubical cement structures were developed (Roy et al., 2018) using
portland cement, river sand and stone–chip materials where curing
period of one month was provided. Arsenic sludge of 1%, 0.5%, and
0.1% (by weight) were observed to successful in developing designed
compressive perseverance of 15 N/mm2. It was found that the arsenic
sludge content used to be a principal factor to apprehend the quality of
developed structures, because, the compressive strengths of developed
cement structures get declined by elevating arsenic sludge content.
Leaching analysis by TCLP examination showed that arsenic content
(0.01 to 0.06 PPM) was much lesser than the permissible standard (5
PPM) (USEPA, 2001).
2.3.2. Stabilization through brick making
Ability of hydrosorption of brick generally used to be in negative
correlations with elevation of heating and reduction of sludge concen­
tration. But, with higher sludge concentration, the resistance to
compressive force declines for any range of heating. Sludge concentra­
tion in the range of 15% to 25% in a brick sample could be in optimum
(Rouf and Hossain, 2003). To test the solidification cum stabilization the
arsenic sludge was blended with clay and found that upto 10% of arsenic
sludge the mixing is quite safe. After TCLP analysis, arsenic content was
found to be far lesser than the allowable discharge limit of 0.2 g/m3, as
prescribed by CPCB, India (CPCB, 1996).
Arsenic contaminated sludge is also used in making ornamental brick
where it is also found that sludge content becomes the pivotal parameter
in determination of standard. Resistance to compression force declines
with increase in sludge content and the best possible concentration
could be 4% by weight for such bricks (Mahzuz et al., 2009). As the
chemical constituents of arsenic sludge closely resembles with brick
clay, the blending of these two can produce good quality product.
Hassan et al. found that by using different ratio of sludge content of 3%,
6%, 9% and 12%, primarily the resistance to the compression force
upsurges but declines afterwards with elevation of arsenic sludge con­
tent. 6% arsenic sludge concentration was found to the best for blending
with soil (Hassan et al., 2014).3%, 6%, 9% and 12% sludge mix brick
shows different leaching behavior. Arsenic Leaching increases with in­
crease sludge percentage in the prepared bricks and exceeds the maxima
of 0.05 ppm which suggests that formed bricks cannot be exposed to
acidic environment (pH=3). In basic solution, the percentage of arsenic
leaching is initially slow but for after long time period, the rate in­
creases. Hence it is understandable that rate of arsenic leaching in
alkaline medium is less than in acidic medium. In neutral medium
(pH=6.5) arsenic leaching with 3%, 6% sludge mix brick never leach
back arsenic above 0.05 ppm but with 9% and 12% sludge mix it exceeds
the permissible limit (Hassan et al., 2014). Preparation of bricks using
clay and the different adsorbing medium such as thermally treated
laterite (TTL), Acid-base treated laterite (ABTL), and Aluminum oxi­
de/hydroxide nano particles (AHNP) has been used. To reach the indian
standards brick must be prepared with a used adsorbent and clay ratio
below the 30:70 (w/w) in all the cases and shows maximum compressive
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South African Journal of Chemical Engineering 37 (2021) 214–226
strength in 30:70 (w/w) ratio. The maximum leaching of arsenic from
the bricks is 510 mg/L, which is below the permission limit of USEPA
(Rathore and Mondal, 2017).
During the production concrete block, a calcium silicate hydrate
(3CaO • 2SiO2 • 4H2O) compound gets formed which further produces a
by-product Calcium hydroxide through hydration. This not only in­
creases the strength of the solidified matrices but also potentially adsorb
or stabilize the arsenic and iron waste through the solidification process.
The possible chemical reaction is provided below:
3CaO⋅2SiO2 ⋅4H2 O + H3 AsO4 →AsSiO3 + Ca(OH)2
Though brick making is a popular method of arsenic stabilization
but, use of high concentrated arsenic sludge during the formation of
bricks generally reduce the compressive strength of bricks. Structure of
granules with less adhesion force are found in such bricks which reduce
the overall compressive force perseverance. More research should be
directed towards the development of the strength of materials for this
purpose.
Development of bricks employing about 0.4 kg of dry soil and dry
sludge of 1%− 3% varying arsenic concentrations were added to develop
bricks (Roy et al., 2018). Leaching analysis through TCLP test indicated
that leaching of arsenic from the bricks were pretty lesser than the
allowable value of 5 PPM, as per the US-EPA Standard. According to the
Indian standard, of IS 3102 (1971) and IS 1077 (1992), the essential
compressive strengths of bricks made factories and hand-made should
be 17 N/mm2 and 3–5 N/mm2, respectively. Developed bricks in this
study had compressive strengths between 3.4 to 5.2 N/mm2 (Roy et al.,
2018). Though arsenic could be effectively stabilized and the process is
efficient enough, but, more research efforts should be directed in such
techniques, to increase the mechanical strengths of the developed
materials.
Recently, Roy et al. (2019) had carried out concrete stabilization of
arsenic bearing iron sludge generated from an electrochemical arsenic
remediation plant. They carried out experiment and developed concrete
bricks of different grades (M15 and M20). Based on data from As- K edge
X-ray absorption spectroscopy (XAS) before and after stabilization in
concrete showed a decrease in As-Fe coordination after concrete stabi­
lization thereby favoring As-Ca co-ordination. The Toxicity Character­
istic Leaching procedure(TCLP) test result of the stabilized concrete
showed <15 µg/l of arsenic at the highest sludge mixture ratio(40%
sludge with respect to cement weight). XRD (X-Ray Diffraction) results
formation of calcite in concrete stabilized arsenic sludge which de­
creases the pore size contributing in low leachability of arsenic in
sludge. When sludge being mixed in specific proportion giving desired
strength, it can be employed in construction.
2.3.3. Thermal technology used for arsenic slusge treatment
Recently thermal based treatment has taken a good position for the
treatment purpose of the arsenic bearing sludge as It can achieve high
reduction rate of volume and satisfactory arsenic removal efficiency via
the formation of the environmentally stable residue and the concen­
traton of arsenic in the arsenic-bearing dust. For the most of the arsenic
solid wastes, arsenic species are in forms of As2O3, AsO3− 3 (arsenite),
AsO3−
4 (arsenate) and As2S3. They will be easily volatilized and sepa­
rated from the residue to form arsenic-bearing dust due to their low
vapor pressure at high temperatures. In a study, Xun et al. (2018), had
carried out pyrolysis of arsenic bearing gypsum sludge as a substituent
for calcium flux in smelting process. Investigatory analysis including
TG-FTIR, XRD, chemical analysis and leaching test were being
Dr.B. Ruj et al. South African Journal of Chemical Engineering 37 (2021) 214–226

Fig. 6. Schematic of the fixed bed reactor type pyrolysis used for aresnic bearing sludge tratement [Scheme adopted from Xun et al., 2018, Xun L., Xing Z., Xianjin Q.,
Kongzhai L., Yonggang W., Hua W., Jianhang H., Xinghuan H., Xin Z., Pyrolysis of arsenic-bearing gypsum sludge being substituted for calcium flflux in smelting
process, J. Anal. Appl. Pyrolysis, https://doi.org/10.1016/j.jaap.2018.02.002].

performed. High temperature (>800 ◦ C) pyrolysis was carried out in a
fixed-bed reactor (Fig. 6) where arsenic gets converted into arsenic
bearing dust having negligible arsenic concentration for further
utilization.
Recently, Hui et al. (2020) had carried out hydrothermal treatment
for the stabilization of arsenic sulfide sludge from lead and zinc smelter.
Under optimum condition i.e. temperature of 200 #x00B0;C, reaction
time of 4 h, liquid to solid ratio 1:1 and initial pH of 2, the leaching
concentration had been found to decrease to less than 5 mg/L. The outer
look ASS changed from yellow muddy to big bulk with metallic cluster.
The density of sludge found to increase, moisture content decreases and
volume contraction upto 91.67%. Thereby stabilization of As, Pb and Cd
contributed in both microstructure transformation of SS along with
speciation transformation of As, Pb and Cd.
3. A cutting-edge strategy for arsenic stabilization
Managing of As-Fe-rich sludge generated from different treatment
plants is a main issue of great concern in several developing countries.
Because of the lack of awareness, reluctance and inadequate number of
possibilities for disposal of highly concentrated arsenic rejects, direct
dumping rejected arsenic is done in the most of the arsenic removal
plants. This enhances threat level of recontamination of underground
water table through natural permeation. Moreover, generation of high-
volume iron-rich sludge increases severely along with additional dif­
ficulties in transportation. Landfill of high-volume sludge further in­
crease the crises of fresh land in the environment. Sustainable disposal
of arsenic and iron-rich sludge generated from different arsenic and
iron treatment plants is a primary issue now-a-days leading to a great

Fig. 7. Proposed scheme for sustainable arsenic sludge treatment

224
Dr.B. Ruj et al.
concern on safe disposal of the sludge in several developing countries.
In respect to recycling of the arsenic and iron-rich sludge by the
construction industries, several studies were reported. In a lot of cases,
by the supplement of about 7% sludge could be used for the production
of concrete substances (cement, mortar and concrete) and ceramics
(pottery and bricks). A conceivable and potential resolution to such
disposal issue could be through the fixation of arsenic in some solid
matrix, such as concrete blocks in which natural fine aggregates (river-
sand) have been replaced by arsenic and iron contaminated sludge.
Presence of iron-rich sludge in concrete blocks not only manages the
disposal issue but also enhances the design compressive strength of the
concrete. A major challenge for the disposal of arsenic-iron-rich sludge is
the safe disposal and/or reuse of this sludge through the fixation with
some binding material as the land requirement for the safe disposal is
drastically declining day by day. The process involving stabilization of
high amount of arsenic-rich sludge and iron sludge generated from
water treatment plants. The process is eco-friendly novel non-chemical
route for utilization of waste materials and making commercially
viable product like concrete.
Thus, a non-chemical, ecofriendly, cost effective method could be
adopted for the fixation of raw arsenic and iron-rich sludge in a concrete
block. This process possesses the potential to stabilize arsenic-rich
sludge generated from water treatment plants with the successfully
replacement of fine aggregates in concrete mix with some other waste
materials like iron sludge mixed sand renders itself a sustainable novel
non-chemical route of stabilization towards reutilization (Fig. 7). This
process could highlight the improved use in the production of concrete
blocks/bricks employing arsenic-rich sludge. Aiming towards reduction
of the consumption of naturally explored coarse aggregates and recy­
cling of materials, the use of sludge could outcast other substances as an
alternative constructive material. As an overall, the development is ex­
pected to ensure massive sustainability not only in field of waste sludge
management but also its reutilization as a strong building material
production.
4. Conclusion
Due to the lack of proper mechanism for the stabilization of arsenic
sludge, originated from arsenic mitigating ground water treatment
plants, and its safe disposal now it is an issue of threatening concern in
the era of sustainable development. However, there are some limited
research work has been done regarding the safe disposal of arsenic
bearing semi solid waste. It has been observed that cementitious so­
lidification is a reliable and cost-effective process for the arsenic sludge
stabilization, but, the use of polymeric material with cement does not
give us any encouraging result and the same has been observed for the
fly ash blending cement matrix, but certain amount of fly ash can be
mixed to decrease the cost of the process. Brick making may be the
probable solution for safe disposal of arsenic sludge but the involved
sludge content is pretty low. Addition of different stabilizing chemicals
like Ca(OH)2, CaO, FeCl2 and FeCl3 or mechanochemically modified
zerovalent iron for the safe disposal of arsenic sludge may be a good
technical option so far. But, concerning the further usability, cost,
leaching capacity and no spreading of any other contaminating species
in environment, arsenic rich sludge fixation mixed with iron for
making concrete blocks of high compressive strength could be identi­
fied as the most sustainable option. After having an extensive review,
development of such building materials employing arsenic sludge with
iron sludge generated from ground water treatment plants could be
reckoned as the most efficient, cost-effective and eco-friendly process
to nullify arsenic hazard. Such newer direction of complete stabiliza­
tion and fixation of arsenic inhibits leachate formation along with
waste to value added material formation while reducing the use of
natural coarse aggregates.
225
South African Journal of Chemical Engineering 37 (2021) 214–226
Declaration of Competing Interest
Authors declare no conflict of interest.
Acknowledgement
Authors are thankful to Department of Science & Technology, Govt.
of India, New Delhi for financial support to carry out this work and also
thankful to Director CSIR-CMERI, Durgapur for his motivation to
continue this research project.
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