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Procedia Environmental Sciences 35 (2016) 943 949

International Conference on Solid Waste Management, 5IconSWM 2015

Disposal Problem of Arsenic Sludge Generated During Arsenic

Removal from Drinking Water
Prasanta Mandal, S.R.Debbarma, Arup Saha, Biswajit Ruj*
CSIR-Central Mechanical Engineering Research Institute (CMERI), M.G.Avenue, Durgapur, WB, India

Abstract

Arsenic (As) causes acute and chronic toxicity, it harm the skin and associated with increase risk of cancer in the skin,
bladder and kidney. It is very difficult to diagnose the early symptoms of arsenicosis so it depends largely on awareness with
improving the quality of drinking water. There are several methods are available for removal of As from water. The most
commonly used technologies are oxidation, co-precipitation, adsorption, absorption, coagulation, ion-exchange resin, lime
treatment and membrane techniques. Now today the safe disposal of large quantity of As contaminated sludge generated from As
removal water treatment plant which contain about 5-7 kg of arsenic per cubic meter due to risk of underground water
contamination as arsenic has very high leaching potential. For safe disposal of solid hazardous waste of As requires treatment. A
long term solution appears to solidification/stabilization (s/s) of As-sludge and using it for beneficial purposes like bricks and
concretes etc. In the field of active research, this paper identifies the gap between the implementation of process as well as new
technologies for safe disposal of arsenic sludge.
2016The
2016 TheAuthors.
Authors. Published
Published by Elsevier
by Elsevier B.V.B.V.
This is an open access article under the CC BY-NC-ND license
(http://creativecommons.org/licenses/by-nc-nd/4.0/).
Peer-review under responsibility ofthe organizing committee of 5IconSWM 2015.
Peer-review under responsibility of the organizing committee of 5IconSWM 2015
Keywords:Arsenic Sludge, Arsenic Removal, Drinking Water

Introduction

Arsenic is a naturally occurring semi-metal element present in the environment in both inorganic and organic
forms. Inorganic arsenic is considered to be the most toxic form of the element and is found in groundwater and
surface water [1].Now elevated concentrations of arsenic 50-100 g/l are found in groundwater in some areas of
India, Bangladesh, Chile, China, Argentina, Mexico, Hungary, Taiwan, Vietnam, Japan, New Zealand, Germany

* Corresponding author.
E-mail address:biswajitruj@yahoo.co.in, bruj@cmeri.res.in

1878-0296 2016 The Authors. Published by Elsevier B.V. This is an open access article under the CC BY-NC-ND license
(http://creativecommons.org/licenses/by-nc-nd/4.0/).
Peer-review under responsibility of the organizing committee of 5IconSWM 2015
doi:10.1016/j.proenv.2016.07.084
944 Prasanta Mandal et al. / Procedia Environmental Sciences 35 (2016) 943 949

and the United States due to naturally occurring arsenic in the aquifer sediment where as new guideline
recommended by WHO is 10g/l [2,3,4]. In humans, inorganic arsenic is readily absorbed from the gastrointestinal
tract and is primarily transported in the blood bound to sulfhydryl groups in proteins and low-molecular-weight
compounds, such as amino acids and peptides[5,6].A 2007 study found that over 137 million people in more than 70
countries are probably affected by arsenic poisoning of drinking water[7].

Current Standards (MCL) for Arsenic in Drinking Water

World Health Organization 10 ppb
Environmental Protection Agency 10ppb
USA 10ppb
European Union 10 ppb
Australia 7 ppb
Bangladesh 50 ppb
India 50 ppb
New Jersey 5 ppb

Activated alumina as adsobent has been used in most of the arsenic removal plants for removal of arsenic. After
long use, efficiency of those plants are decreased and needs regeneration of the activated alumina for its further use.
For several numbers of arsenic removal plants there is a regenerating unit around this area. During regeneration, a
large quantity of solid waste residue (SWR) As-sludge is produced which is highly rich in arsenic and dumped into a
concrete chamber near the regenerating unit which contains about 5-7 kg of arsenic per cubic meter of
sludge[8,9,31]. This sludge is hazardous as per the Resource Conservancy and Recovery Act (RCRA) of USEPA
(1986) and is much above the permissible standard (0.2 g/m3) for its direct disposal into the inland water
environment (CPCB-MEF, GOI 19951996)[10]. As environmental regulations become more stringent and volume
of generated sludge continues to increase, traditional sludge (SWR) disposal methods are not suitable and require
changes. So, disposal and solidification/stabilization (s/s) of arsenic contaminated sludge using practicable and
economical methods is a great challenge for the engineers and researchers.

Natural Source of Arsenic Contamination in Ground Water:

Arsenic is a semimetal or metalloid a natural constituent of earths crust. Its present in several stable oxidation
states III, -I, 0, +III, +V but the +III and +V states are most common in natural system and also dominates in
aqueous medium,specifically As (III) is 2560 times more toxic than As (V) [11].Arsenic containing pyrites
disperse and contaminate the ground water,arsenopyrite (FeAsS) is probably the most common mineral source of
arsenic [12,13,14].

FeAsS+O2+H2O AsO43-+ Fe3+ + SO42-+ H+

Important factors controlling the dissolution of Arsenic are:

x pH
x Temperature
x Moisture (hydrolysis)
x Redox character of the species
x Reactivity of the species towards CO2& H2O.
x Solubility

Indian Scenario:

Investigations by Central Ground Water Board (CGWB) reveals that arsenic contamination (>0.05 mg/L) is
affecting the states of West Bengal, Bihar, Uttar Pradesh, Assam, Chhattisgarh. The Bengal Delta Plain (BDP)
covering Bangladesh and West Bengal in India is the most severe case of groundwater arsenic contamination [15].
 Prasanta Mandal et al. / Procedia Environmental Sciences 35 (2016) 943 949 945

Global Scenario:

Arsenic level beyond permissible limits in drinking water is the main cause of arsenic toxicity in the world.
Taiwan, China, Chile, Argentina, Mexico, India, Hungary Bangladesh, USA and Thailand Reported such type of
contamination [2].The summary of the current global scenario of arsenic contamination is shown in Figure.

Fig. 1.

Global scenario of arsenic contamination of ground water

Health Effect:

Arsenic is a substance that is carcinogenic capable of causing cancer. Chronic arsenic toxicity (arsenicosis)
due to drinking of arsenic contaminated ground water is a major environmental health hazard throughout the world
including India. Long-term exposure to arsenic in drinking water can cause cancer in the skin, lungs, bladder and
kidney. It can also cause other skin changes such as thickening and pigmentation. Black foot disease, (BFD) a form
of peripheral vascular disease, has been reported to be one of the important complication of chronic arsenic
toxicity(CAT) in Taiwan. [16,17].Exposure to arsenic in the workplace by inhalation can also cause lung cancer
Non-malignant skin alterations, such as keratosis and hypo- and hyper-pigmentation, have been linked to arsenic
ingestion.

Removal technologies for Arsenic Contaminated Drinking water:

There are several methods available for removal of arsenic from water in large conventional treatment plants.
The most commonly used processes of arsenic removal from water have been described by Cheng and others
(1994), Hering and others (1996), Hering and others (1997), Kartinen and Martin (1995), Shen (1973), and Joshi and
Chaudhuri (1996)[18].
946 Prasanta Mandal et al. / Procedia Environmental Sciences 35 (2016) 943 949

Fig. 2.A keratosis victim

The basic principles of arsenic removal from water are based on conventional techniques of oxidation,
coprecipitation and adsorption on coagulated flocs, adsorption onto sorptive media, ion exchange, and membrane
filtration[19]. Oxidation of As(III) to As(V) is needed for effective removal of arsenic from groundwater by most
treatment methods[20]. The most common arsenic removal technologies can be grouped into the following four
categories:

x Oxidation and sedimentation

x Coagulation and filtration
x Sorptive filtration
x Membrane filtration

The existing and emerging arsenic removal technologies are available including:

x Sorption on activated alumina

x Sorption on iron oxide coated sand
x Sand with zero-valent iron
x Cation exchange resins
x Anion exchange resins
x Coagulation with ferric ion
x Granulated iron oxide
x Nanomagnetite particles
x Reverse osmosis

Characteristics of Arsenic contaminated sludge:

The physical characteristics of wastes generated by traditional As removal processes has been done by scanning
electron microscopy equipped with energy dispersive X-ray spectrometer (SEM-EDX).

Physical properties of sludge: Density of oven dried(105oC) sludge = 0.9 g/cc.

Arsenic contain within sludge almost 4.2 kg/m3,and pH of the sludge variable from 5 to 8.
 Prasanta Mandal et al. / Procedia Environmental Sciences 35 (2016) 943 949 947

Table 1: Some chemical and physical characteristics of the sludge

Al2O3 SiO2 Fe2O3 CaSiO3 As

Chemical composition of Arsenic sludge (wt.%) 71.85 13.08 11.46 3.19 0.42

Fig. 3.SEM photographs of Arsenic sludge

Fig. 4. EDAX of Sludge

Disposal methods:

Regeneration of activated alumina and ion exchange resins results in various semi liquid wastes that may be
acidic, caustic, saline, and too arsenic rich for simple disposal. Hence, environmentally safe disposal of sludge,
saturated media, and liquid wastes rich in arsenic is a concern. The EPA has developed a toxic characteristic
leaching procedure (TCLP) test to identify wastes likely to leach toxic chemicals into groundwater[21,22]. The
permissible level for TCLP leachate is generally 100 times higher than the maximum contaminant level in drinking
water. Wastes with high concentration of arsenic may need solidification or confinement before final disposal.
Arsenic rich sludge may be disposed by the following methods:
948 Prasanta Mandal et al. / Procedia Environmental Sciences 35 (2016) 943 949

x Disposal in on-site sanitation pits/ landfill.

x Mixing with concrete in a controlled ratio.
x Mixing with clay for burning for brick manufacturing.

Disposal in on-site sanitation pits/ landfill:

Groundwater constitutes 97% of all freshwater that is potentially available for human use. Groundwater is
therefore of fundamental importance to human life. On-site sanitation systems can lead to contamination of
groundwater sources. The contamination takes place in the event of a pathway existing between a source i.e. on-site
sanitation system and a receptor[23].

Mixing with concrete in a controlled ratio:

Another commonly used treatment is cement based solidification and stabilization (s/s). Cement is used to treat
a large range of hazardous wastes by improving physical characteristics and decreasing the toxicity and transmission
of contaminants.This process involves mixing the waste, either in form of sludge, liquid or solid, into a cementitious
binder system[24]. However the effectiveness of As sludge treatment through s/s was strongly influenced by the
type of As compound present. Arsenate has the lowest mobility[25]. It was found that Ca of cement influenced the
leaching and immobilized As. With higher Ca:As molar ratio generally results in lower As leaching[26]. The
enormous reduction of As concentration in cement-based immobilization was due to the formation of calcium bi-
arsenate (CaHAsO3), which possesses a binding/cementing property, in the presence of Ca(OH)2[27,28]. The
solidification and stabilization (S/S) technique with lime and Ordinary Portland cement (OPC) was successfully
applied for the stabilization and environmentally safe disposal of arsenic contaminated sludge.

Mixing with clay for brick manufacturing:

The physical property requirements in most specifications are water absorption capacity, Saturation coefficient,
Specific gravity, Specific Surface Area (SSA), optimum moisture content (OMC), Toxicity Characteristics Leaching
Procedure (TCLP) using USEPA Method 131. It was observed that, with increase in percentage of sludge the
compressive strength of the bricks decreases with all firing temperatures[29,30]. Stabilization of As-sludge using
clay it was observed that up to 10% of clay (volume) was found to be safe[31]. As contaminated sludge could be
used safely up to 4% only for making ornamental bricks and tiles [29].
Conclusions:

Arsenic-contaminated water is a massive problem in the developing world. But, even when you filter it, the
toxic sludge that the process produces often gets dumped right back into the water supply.Effective and reliable
method for environmental safe disposal of arsenic contaminated sludge is a gigantic problem. U.S Environmental
Protection Agency (USEPA) recognizes cementitious solidification as the best demonstrated available technology
(BDAT) for land disposal of most toxic elements. Arsenic sludge technologies have improved significantly over
the last few years but many of the technologies do not work satisfactorily. Reliable, cost-effective, and sustainable
treatment technologies are yet to be identified and further developed.

Acknowledgement:

Authors are thankful to Director-CSIR-CMERI, Durgapur for supporting this work.

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