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Jarosite characteristics and its utilisation potentials

Asokan Pappua,*, Mohini Saxenaa, Shyam R. Asolekarb

aRegional Research Laboratory (CSIR), Habib Ganj Naka, Bhopal-462026, India

bCESE, Indian Institute of Technology, Bombay-400076, India

Received 22 January 2005; accepted 18 April 2005

Available online 22 June 2005

Abstract

During metallic zinc extraction from zinc sulphide or sulphide ore, huge quantity of jarosite is being released universally as

solid residues. The jarosite mainly contains iron, sulphur, zinc, calcium, lead, cadmium and aluminium. Jarosite released from

such industrial process is complex and its quality and quantity make the task more complex for safe disposal. Apart from water

contamination, jarosite already accumulated and its increasing annual production is a major source of pollution for surrounding

environment including soil, vegetation and aquatic life and hence its disposal leads to major concern because of the stringent

environmental protection regulations.

An attempt was made to evaluate the characteristics of Indian jarosite with an objectives to understand its potentials for

recycling and utilising as raw materials for developing value added products. Sand and Coal Combustion Residues (CCRs) wasused as an admixture to attain good workability and detoxify the toxic substance in the jarosite. Result revealed that jarosite is silty

clay loam in texture having 63.48% silt sized and 32.35% clay sized particles. The particle size of jarosite (D90=16.21F0.20 Am)

is finer thantheCCRs (D90=19.72F0.18 Am). The jarosite is nonuniform in structure and shape as compared to the CCRs having

spherical, hollow shaped and some of them are cenosphere in nature. The major mineral phase of jarosite is Potassium Iron

Sulphate Hydroxide {KFe3(SO4)2(OH)6}and Iron Sulphate Hydrate {2Fe2O3SO3d5H2O}. In CCRs the dominant phases are

quartz {SiO2}, mullite {3Al2O3d2SiO2} and hematite {Fe2O3}. The high electrical conductivity of jarosite (13.26F0.437 dS/m)

indicates that the presence of cations and anions are predominant over CCRs (0.498F0.007 dS/m).

The major portion of jarosite consists of iron (23.66F0.18%), sulphur (12.23F0.2%) and zinc (8.243F0.075%). But

CCRs main constituents are silicon ( 27.41F0.74%), aluminium (15.167F0.376%) and iron (4.447F0.69%). The other

constituents such as calcium, aluminium, silicon, lead, and manganese are also present in the range of 0.5 to 5%. Heavy metals

such as copper, chromium, and cadmium are found higher in jarosite as compared to the CCRs. The statistically designed

experimental trials revealed that the density, water absorption capacity and compressive strength of fired jarosite bricks are 1.51

gm/cm3, 17.46% and 43.4 kg/cm2 respectively with jarosite sand mixture in the ratio of 3:1 indicating the potentials in

developing building materials.

D 2005 Elsevier B.V. All rights reserved.

Keywords: Jarosite; Sand; Coal combustion residues; Characterisation; Recycling; Jarosite bricks; Safe management

0048-9697/$ - see front matterD 2005 Elsevier B.V. All rights reserved.

doi:10.1016/j.scitotenv.2005.04.024

* Corresponding author. Tel.: +91 755 2589827 (W), 2488767(H); fax: +91 755 2488323, 2587042.

E-mail address: [email protected] (A. Pappu).

Science of the Total Environment 359 (2006) 232243

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1. Introduction

To meet the industrial, domestic and agricultural

demand, newer processes and technologies are beingdeveloped in which huge quantity of solid and haz-

ardous wastes are released as a waste by-product.

Jarosite released during metallic zinc extraction

through hydrometallurgical process is one such ex-

ample (Asokan, 2003; Leclerc et al., 2003). Present-

ly, ~75% of the worlds zinc metal is produced

hydrometallurgically through acid leaching (Monta-

naro et al., 2001). Metallic zinc extraction process is

mainly of (a) goethite process (FeOOH), (b) jarosite

process (XFe3(SO4)2(OH6) and Hematite process and

each process has its own advantages and disadvan-tages (Bhat et al., 1987; Singh, 1996; Ismael and

Carvalho, 2003). The formation of jarosite and its

equilibrium condition is as follows:

3Fe2SO43X2SO412H2O$2XFe3SO42OH66H2SO4

whereXrepresents H3O+, Na+, K+, NH4+, Ag+, Li, or

1/ 2 Pb2+.

In the jarosite process, an Fe(3+) compound of the

type X [Fe3(SO4)2(OH)6] is precipitated by adding

alkali metal or ammonium ions (Mymrin and Vaa-

monde, 1999; Hage and Schuiling, 2000; Montanaro

et al., 2001). During these processes huge quantity of

residues in the form of mud is released and stored in

different types of closed containers or sealed reservoirs

in the premises of production unit. In European Union

about 600.000 tonnes of such zinc residues is produced

every year (Romero and Rincon, 1997). The major

quantity of jarosite is generated mainly from Spain,

Holland, Canada, France, Australia, Yugoslavia,Korea, Mexico, Norway, Finland, Germany, Argen-

tina, Belgium and Japan (Arslan and Arslan, 2003).

Apart from the corrosion and health hazards to

the operator in the tank house due to acid mist

emission in electrowinning of metals, the solid resi-

dues produced during metal extraction process

involves major environmental and ecological prob-

lem due to their disposal and storage without further

treatment (Alfantazi and Dreisinger, 2003). Safe

management of such hazardous nature of jarosite

is of paramount importance and now it has become

a global concern, to find a socio, techno-economic,

environmental friendly solution to protect a clean

and green environment. In hazardous wastes man-agement toxicity/chemical reactivity, corrosive na-

ture and ignitability are the principal characteristics

to be tackled because these constitute the real dan-

ger to environment, community health and should

therefore cause us great concern (Asokan et al.,

2003).

The toxicity in the waste is mainly due to the

presence of different metals viz., lead, cadmium,

arsenic, chromium etc. The residue released during

the process could be either recycled for further

processing or sent for safe disposal without affectingthe environment. Now concern is being expressed

by some of European Union Countries regarding the

environmental danger in avoidance of pollution for

safe storage and disposal of these residues. Efforts

are also being made to recover valuable elements/

value added material and to transform them into

other forms less harmful to the environment

(Romero and Rincon, 1997). Various remedial mea-

sures have also been proposed to recycle these

wastes as construction material, catalysts, pigments,

gypsum and refractories (Asokan, 2003; Sanjeev et

al., 1999).

1.1. Jarosite production in India

In India, Hindustan Zinc Limited (HZL) has a

multi-unit mining and smelting organization having

installed capacities of 3.49 million tonnes per year

Zinc manufacturing from four smelters located in

the states of Rajasthan, Andhra Pradesh, Bihar and

Orissa. Debari Zinc Smelter plant is one of the

largest units having ammonium jarosite process of

Electrolytic extraction method (Gupta, 1988;Acharya et al., 1992; Hindustan Zinc Limited web

site, 2003). During Zinc metal extraction process,

Dabari zinc smelter produces ~49,000 tonnes per

annum (tpa) of zinc metal and as a consequence

huge quantity of solid wastes/zinc smelter residues

namely jarosite is being released (Singh, 1996;

Raghavan and Upadhyay, 1999) waste. Presently

these wastes have been stored in the premises of

the smelter plant. The presence of toxic species

namely, lead, cadmium and zinc etc. makes this

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waste hazardous and poses serious environmental

problem.

There are several techniques that have been

developed worldwide by several researchers forremediation of hazardous wastes containing priority

toxic elements. (Lehman, 1982; Barna et al., 1997).

Solidification/stabilisation (s/s) process is one of the

techniques, now, commonly used to inhibit the

transport of heavy pollutant elements into the sur-

rounding environment and offers improvement in

the physical characteristics that reduce the leach-

ability of toxic metals. Earlier work based on the

various extensive research carried out at lab and

pilot scale levels by several researchers all over the

world showed that fly ash can be used in makingcement, concrete, bricks, in back fill/road embank-

ment, adhesives, wall board, agriculture/soil amelio-

ration, wasteland development, wood substitute,

paint and various environmental applications (Mar-

tin et al., 1990; Ferraiolo et al., 1990; Keefer, 1993;

Murarka et al., 1993; Sharma and Jain, 1993; Sikka

and Kansal, 1995; Saxena et al., 1998; Tiwari and

Saxena, 1999; Kazuo, 2000; Sumio et al., 2000;

Iyer and Scott, 2001; Sarangi et al., 2001; Asokan,

2003; Saxena and Asokan, 2003; Asokan et al.,

2005). However, some of the studies indicate that

fly ash can be used as partial replacement for Portland

cement to immobilise the toxic effect from solidified

cement fly ash binder (Wang and Vipulanandan, 1996;

Vondruska et al., 2001). Further, the regulatory stan-

dards established under the RCRA, recovery of value

added products, hazardous wastes disposal location,

design, construction, operation, final closure of the

landfill site and several other issues were discussed by

various researchers for safe hazardous waste manage-

ment (Visvanathan, 1996; Saxena and Jotshi, 1996;

Hammitt, 1989; Hazardous wastes resource center

web site, 2003).However, not much work has been published on

recycling and utilisation of jarosite. Very little work

has been cited on the treatment process for the dis-

posal of these wastes and use in tiles, ceramic pro-

ducts (Mymrin and Vaamonde, 1999; Hage and

Schuiling, 2000). Jarosite seems to be a potential

resource, which has to be recycled in a technically

feasible and environment friendly manner. In the

present work an attempt is made to evaluate the

characteristics of jarosite, its utilisation potential in

developing construction materials using CCRs for

safe and effective management.

2. Materials and method

2.1. Sample collection and processing

In the present study, the solid fine residues,

namely jarosite released during hydrometallurgical

process was obtained from Hindustan Zinc limited

(HZL), Debari Rajasthan, India. CCRs was collected

from Electro Static Precipitator, hopper number four

of Satpura Thermal Power Station, Sarni, Central

India. The samples were air-dried separately, sievedthrough 2 mm size sieve and stored in glass con-

tainer. For characterisation sampling was done from

the air-dried sample adopting conning and quarter-

ing method. Fig. 1 (a and b) shows the jarosite of

Debari Zinc Smelter, Rajasthan, India.

(a)

(b)

Fig. 1. (a and b) Jarosite of Debari Zinc Smelter, Rajasthan, India.

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2.2. Characterisation of physical and electrochemical

properties

Bulk density and particle density were measuredfollowingVeihmeyer and Hendrickson (1946)method

and porosity by Bodman (1942). Conductivity was

measured by Colonel Conductivity Meter in 1 : 2

(solid:water) ratio soil suspension and the pH values

were determined calorimetrically. The particle size dis-

tribution analysis was done using Laser Diffraction

Particle size analyser Model HELOS Laser diffraction

system, Sympatec GMBH, Germany. Total heavy

metals such as Cu, Zn, Mn, As, Se, Cr, Ni, Co, Hg,

Cd, Pb etc., were extracted from the sample by Na2CO3

digestion (Jackson, 1973) method and detected byAtomic Absorption Spectrophotometer (AAS), Z-

5000, Hitachi, Japan with flame, Graphite furnace

and hydride generator facilities.

2.3. Mineralogical and morphological characterisation

The mineralogical studies of the samples were

carried out by X-Ray Diffractometer-PW-1710 Phi-

lips, Netherland with Quasar software packages. The

micro structure characteristics was analysed by Scan-

ning Electron Micros scope-Model JOEL JSM-5600,

Japan with Energy Depressives X-ray Spectroscopy(EDS) analysis facilities.

2.4. Experimental details

A mixture of pure jarosite wastes along with me-

dium textured sand was mixed together at different

ratios (1:1 to 4:1). To attain the good workability

limited quantity of CCRs (0%, 10%, 20% and 30%)

and water were added on sand jarosite matrix. Table 1

shows the experimental details and quantity/ratio of

different matrixes used in developing s/s products.The composite matrix was kneaded well till it became

a homogeneous workable state. The tempered matrix

was then used for moulding. The well prepared jar-

osite CCRs sand matrix was moulded in rectangular

cast iron mould. The mould dimension was

7.53.53.5 cm. Moulding of the matrix wasdone in hand press with a pressure of about 20 kg/

cm2. The casted solidified matrix were then removed

Table 1

Experimental details and composition of different matrices used in developing s/s products

SI.

No.

Jarosite:

sand ratio

Sand

(gm)

Jarosite

(gm)

Jarosite-sand

weight (gm)

CCRs

(gm)

CCRs

(%)

Total weight (gm)

for 5 bricks

Water

(ml)

Experiment 1

1 1 : 1 500 500 1000 Nil Nil 1000 220

2 1 : 1 450 450 900 100 10 1000 215

3 1 : 1 400 400 800 200 20 1000 210

4 1 : 1 350 350 700 300 30 1000 200

Experiment 2

5 2 : 1 333.33 666.66 1000 Nil Nil 1000 260

6 2 : 1 300 600 900 100 10 1000 255

7 2 : 1 266.66 533.34 800 200 20 1000 250

8 2 : 1 233.33 466.67 700 300 30 1000 250

Experiment 3

9 3 : 1 250 750 1000 Nil Nil 1000 255

10 3 : 1 225 675 900 100 10 1000 250

11 3 : 1 200 600 800 200 20 1000 250

12 3 : 1 175 525 700 300 30 1000 250

Experiment 4

13 4 : 1 200 800 1000 Nil Nil 1000 265

14 4 : 1 180 720 900 100 10 1000 260

15 4 : 1 160 640 800 200 20 1000 255

16 4 : 1 140 560 700 300 30 1000 255


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from the moulds and allowed to air-dry. After air-

drying the solidified product were fired in Muffle

furnace at 950 8C for 90 min. Further, 28th days

compressive strength was tested for the fired s/s pro-

ducts using Shimadzu SERVOPULSER Material

Testing Machine (Compressive Testing Machine)

Model EHF-EG 200 KN-40L, Japan.

3. Results

3.1. Physical and electro-chemical properties

The electro-chemical properties of jarosite and

CCRs are reported in Table 2. Results revealed

that the pH of the jarosite and CCRs was almost

neutral. pH plays an important role in the solubility

of ions. The work carried out by Ding et al. (1998)

showed that the pH of jarosite was highly acidic in

nature (pH 2.7). Almost in all the jarosite based

electrolytic zinc extraction process sulphuric acid

used is as a catalyst in which jarosite begins to

precipitate at pH b1 and complete at pH 1.5 (Dutri-

zac, 1980). Further Babcan (1971) showed that

jarosite stability zone is between pH 1 to 3 at 20

and 200 8C. In this process jarosite can theoretically

contain 37% iron and 13% sulfur as sulfate and due

to its physical, chemical, mineralogical, micro struc-tural and thermal characteristic it could be recyclied

in making glass ceramic materials (Mymrin and

Vaamonde, 1999). But the jarosite released from

Debari Smelter, Hindustan Zinc Limited was neu-

Table 2

Physico-chemical properties of jarosite and CCRs

Parameters Jarosite waste CCRs

R1 R2 R3 Mean SD R1 R2 R3 Mean SD

Sand (%) 4.23 4.12 4.18 4.18 0.06 8.24 8.5 8.58 8.44 0.18

Silt (%) 63.35 63.39 63.69 63.48 0.19 74.87 74.63 74.57 74.69 0.16

Clay (%) 32.42 32.49 32.13 32.35 0.19 16.89 16.86 16.85 16.87 0.02

Texture Silty clay loam Silt loam

Bulk density (gm/cc) 0.982 0.998 0.971 0.984 0.014 1.050 1.170 1.160 1.127 0.067

Specific gravity 2.88 2.88 3.00 2.92 0.07 2.12 2.09 2.16 2.12 0.04

Porosity (%) 66.47 66.87 67.66 67.00 0.61 38.01 37.04 37.45 37.50 0.49

Water holding capacity (%) 110.13 109.86 109.89 109.96 0.148 45.50 44.66 44.79 44.98 0.45

Hydraulic conductivity (m/day) 0.035 0.033 0.044 0.037 0.006 0.529 0.485 0.499 0.504 0.0225

pH 6.70 6.80 6.85 6.78 0.08 7.08 6.98 7.03 7.03 0.05

Electrical conductivity (dS/m) 14.090 13.440 13.260 13.597 0.437 0.498 0.504 0.491 0.498 0.007

Table 3

Chemical properties of jarosite and CCRs (values are in %)

Elements Jarosite waste CCRs


Iron 23.480 23.480 23.660 23.660 0.180 5.140 3.760 4.440 4.447 0.690Sulphur 12.030 12.430 12.230 12.230 0.200 0.780 0.096 0.098 0.325 0.394

Zinc 8.170 8.320 8.240 8.243 0.075 0.004 0.004 0.004 0.004 0.000

Calcium 4.830 4.860 4.840 4.843 0.015 1.020 0.960 0.950 0.977 0.038

Aluminium 3.580 3.650 3.610 3.613 0.035 14.750 15.270 15.480 15.167 0.376

Silicon 3.370 3.430 3.400 3.400 0.030 26.670 28.150 27.420 27.413 0.740

Lead 1.890 1.890 1.930 1.903 0.023 0.003 0.004 0.004 0.004 0.000

Nitrogen 1.455 1.399 1.487 1.447 0.045 0.172 0.181 0.174 0.176 0.005

Magnesium 1.090 1.110 1.100 1.100 0.010 0.680 0.640 0.590 0.637 0.045

Sodium 0.670 0.680 0.675 0.675 0.005 0.940 1.150 1.230 1.107 0.150

Potassium 0.620 0.620 0.610 0.617 0.006 1.770 1.610 1.730 1.703 0.083

Carbon 0.142 0.172 0.151 0.155 0.0154 1.45 1.62 1.94 1.67 0.25

Manganese 0.195 0.197 0.199 0.197 0.002 0.050 0.050 0.050 0.05 0.05


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tralised using lime and hence the pH was just below

neutral (pH 6.78F0.8).

The Electrical Conductivity (EC) of jarosite was

13.597F0.437 dS/m. But CCRs was invariably lowEC (0.498 dS/m). It indicates that the presence of

both anions and cations are predominant in jarosite.

As per the international soil classification, the tex-

ture of jarosite is silty clay loam and CCRs lies

under silt loam.

The characteristic of homogenized jarosite waste

reported byRomero and Rincon (1997)showed mois-

ture content between 4447% and a mean density of

3.77 g/cm3. The present study showed that the mean

specific gravity of jarosite was 2.92 and CCRs was

relatively higher bulk density and lower specific grav-ity. As compared to CCRs, the jarosite has higher

porosity and water holding capacity due to fine textured

materials resulting from high surface area (1600 cm2/

gm). Interestingly the hydraulic conductivity of jarosite

was 0.037F0.006 m/day and which is lower than that

of CCRs. This is obvious because 90% of the CCRs

particles were 19.72F0.18 Am as against 16.21F0.2

Am size of jarosite. It is further supported by the earlier

work where the mean size (D80).of the zinc residues

particle was 23 Am having various trace elements and

heavy metals (Romero and Rincon, 1997).

3.2. Chemical properties

In hydrometallurgical process, during roasting, the

formation of zinc ferrite from zinc sulphate concen-

trates leads to considerable loss of zinc (Bhat et al.,

1987). In the present study the total contents of heavy

metals were analysed to confirm their environmental

significance for safe disposal. The results revealed

that major constituents of the jarosite were iron, sul-

phur, and zinc. However, various other elements such

Table 4

Trace and heavy metal content in jarosite and CCRs

Parameters Jarosite wastes CCRs


Copper 1015 1050 1065 1043 25.7 88.6 87.7 86.1 87 1.3

Nickel 98 76 88 87 11.0 102.4 104 99.2 102 2.4

Chromium 190 195 150 178 24.7 91.8 90.2 88.4 90 1.7

Cadmium 290 326 335 317 2 3.8 38.4 37.2 39.1 38 1.0

Cobalt 46 35 32 38 7.4 58.9 59.9 58.5 59 0.7

All the values are expressed in ppm.

(a)

(b)

(c)

Fig. 2. (a) SEM microstructure of jarosite particles showing irreg-

ular shape. (b) SEM microstructure of CCRs showing spherical and

cenosphere particles. (c) SEM microstructure of sand showing

angular shape with solid structure.


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as Al, Pb, Mg, Na, K, Mn etc., were also present in

jarosite (Table 3). Similar results were reported by

earlier researchers that the fine particles of zinc resi-

dues contain various elements such as Fe-, Zn, Pb, Si,

Ca, Cu, K, Ti, Sn and Al (Hage and Schuiling, 2000;

Bhat et al., 1987).

The heavy metals content such as Cu, Ni, Cd, Cr,

and Co in jarosite and CCRs is shown inTable 4andit is revealed that the concentration of these metals

ions were higher in jarosite as compared to the

CCRs except Ni and Co. As per the Hazardous

Waste (Management and Handling) Amendment

Rules, 2003, the primary or secondary production

of Zn including jarosite is categorized as hazardous

wastes (Ministry of Environment and Forest website,

2003). Further, the concentration of cadmium (50

mg/kg), lead (5000 mg/kg), zinc (20,000 mg/kg)

and sulphur (50,000 mg/kg) were exceeded theabove regulatory limits of Schedule 2 of rule 3

(14) b of Class A, B, C and D (Ministry of Envi-

P Potassium Iron Sulphate Hydroxide- KFe3(SO4)2(OH)6

I Iron Sulphate Hydrate- 2Fe2O3SO3 5H2O

P

II

I

PI

P

P PPI

P I

10000

8100

6400

4900

3600

2500

1600

900

400

100

0

[ counts ]

0 20 40 60 [

Fig. 3. X-Ray diffractogram of jarosite showing phase constituents.

Q - Quartz SiO2M Mullite 3Al2O3 2SiO2H Hematite Fe2O3A Amorphous (Glassy phase)

Q

M

HAQ

Q

H

HM

M

A

M

4900

3600

2500

1600

900

400

100

00 20 40 60 [

[ counts ]

Fig. 4. X-Ray diffractogram of CCRs showing phase constituents.


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ronment and Forest website, 2003). The present

study further confirmed that, based on the character-

istics, as per the US Regulatory frame work, jarosites

released from hydrometallurgical process of HZL,Debari India is hazardous in nature.

3.3. Morphological and mineralogical studies

The microstructure analysis of jarosite reveals that

most of the particles are irregular in shape with

multiple humps. Fig. 2 (a, b, and c) shows the

microstructure of jarosite, CCRs and sand respec-

tively. It reveals from the results that most of the

jarosite particles surface is smooth and irregular in

shape. CCRs particles are almost regular in shapeand most of them are spherical and some of them are

cenospheric in nature. However, the microstructure

of medium textured sand showed crystal structure,

angular shape and solid state. Figs. 3 and 4 shows

the phase constituents of jarosite and CCRs respec-

tively. The typical X-ray diffractogram of jarosite

indicates that the major mineral phase in jarosite is

(KFe3(SO4)2(OH)6 and Iron sulphate hydrate

(2Fe2O3SO35H2O). But in CCRs, the major phase

is Quartz and mullite (Aluminium silicate). It also

shows the presence of iron oxide (Hematite).

4. Discussion

The jarosite was s/s with the bulking agent CCRs

and sand and produced solid structure.Fig. 5(a and b)

shows solidified products before firing and after firing.

Keeping in view of potential application of these s/s

products as building construction materials, the densi-

ty, water absorption and compressive strength of the

solidified fired products developed from jarosite were

assessed. The density of solidified matrix/productsusing different ratios of jarosite waste is shown in

Fig. 6. It is apparent from the results that increase in

concentration of jarosite waste decreased the density,

which is obvious because the density of jarosite is very

low. Further by increasing CCRs concentration as a

partial substitute for sand the density decreased as

compared to the jarosite and sand alone. Moreover,

the unfired and fired s/s products are smooth in sur-

face. It shows the potentiality in using it for light

weight applications in the construction sector. The

water absorption capacity of the s/s products varies

from 16.727.2% and with application of CCRs the

water absorption capacity increased due to the mor-

phological properties (Fig. 7). But minimum water

absorption was obtained when 50% jarosite was

used. Also it is expected that during firing process at

950 8C under solid state reaction, the toxic substance/

elements were to be detoxified/immobilised through

complexing in silicate matrix. The studies carried out

on s/s of toxic metal wastes using coke and coal

combustion by-products revealed that alkaline wastes

could retain low concentration of toxic metal ions andsolidification and sorption of metals were significant

due to the presence of CaO and CaSO4 in CCRs

(Vempati et al., 1995).

The effect of jarosite waste, CCRs and sand on the

compressive strength of s/s products are shown in Table

5. The stress stroke curve indicates that maximum

compressive strength of the fired s/s products was

found optimum (43.4 kg/cm2) when jarosite was used

three times of the total mass(Fig. 8).However, CCRs

substitution did not show any positive impact in terms

(a)

(b)

Fig. 5. (a) Unfired jarosite s/sproducts.(b) Fired jarosite s/sproducts.


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1.40

1.44

1.48

1.52

1.56

1.60

1.64

0 1 2 3 4 5

Jarosite: Sand

Density(gm/cm

3)

0 10 20 30 CCRs (%)

Fig. 6. Effect of jarosite, sand and CCRs on density of fired solidified products.

15.00

17.00

19.00

21.00

23.00

25.00

27.00

29.00

0 1 2 3 4 5

Jarosite : Sand

Water

absorptioncapacity(%)

0 10 20 30 CCRs (%)

Fig. 7. Effect of jarosite, sand and CCRs on water absorption capacity of fired solidified products.


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of increase in strength of the s/s products. Earlier study

showed that when CCRs was substituted as portland

cement, strength was maintained at constant level and it

increased when active silica was higher than that ofcement (Papadakis, 2000). The work carried out by

Constantino et al. (2001) and Jang and Kim (2000)

showed that CCRs can be used as raw materials and

main binder for s/s of electric arc furnace dust and mine

wastes containing hazardous metals such as Pb, Cd, Cr,

Zn and Cu and confirmed that the leachate/mobility of

heavy metal pollutant is pH dependent. In the present

study, jarosite pH was just below neutral (pH=6.78)

and hence the concentration of toxic elements such as

Zn, Cd, Pb, Cr etc., might probably stabilise with

CCRs-jarosite matrix. The fixation of toxic elementsin this process can reduce the contamination potential

of jarosite. The work carried out earlier by Montanaro

et al. (2001) showed that at high temperature, the heavy

metal oxide contents in the densified products become

low soluble crystalline phase or glassy phase. This

could help to reduce the heavy metal leaching. The

specific surface area of jarosite powder has significant

effect on the compacting behaviour and kinetics of

firing oxidation of powder by atmospheric oxygen(Hewaidy et al., 1979).For supporting this hypothesis

and confidence building further studies on leachability

of toxic elements from the solidified products are need

to be assessed to use these fired s/s products in envi-

ronmental friendly applications in construction indus-

tries and the outcome of the research is expected to be

one of the major solution for safely recycling the

hazardous jarosite.

Table 5

Effect of jarosite, sand and CCRs on compressive strength of fired solidified products

SI. No. Experiments Jarosite : Sand CCRs (%) Compressive strength kg/cm2

R1 R2 R3 Mean SD

Experiment 1

1 T1 1 : 1 Nil 10.99 9.79 10.99 10.59 0.69

2 T2 1 : 1 10 9.10 9.42 9.16 9.23 0.17

3 T3 1 : 1 20 23.21 22.83 22.57 22.87 0.32

4 T4 1 : 1 30 10.87 11.29 11.29 11.15 0.24

Experiment 2

5 T1 2 : 1 Nil 26.76 26.69 26.42 26.62 0.18

6 T2 2 : 1 10 15.07 14.42 14.31 14.60 0.41

7 T3 2 : 1 20 11.55 11.93 11.67 11.72 0.19

8 T4 2 : 1 30 10.57 11.68 11.02 11.09 0.56

Experiment 3

9 T1 3 : 1 Nil 42.86 43.52 43.81 43.40 0.49

10 T2 3 : 1 10 15.35 13.87 14.24 14.49 0.77

11 T3 3 : 1 20 11.3 11.8 12.61 11.90 0.66

12 T4 3 : 1 30 12.04 12.72 12.42 12.39 0.34

Experiment 4

13 T1 4 : 1 Nil 14.12 14.32 14.55 14.33 0.22

14 T2 4 : 1 10 9.26 9.82 9.65 9.58 0.29

15 T3 4 : 1 20 10.08 9.56 10.17 9.94 0.33

16 T4 4 : 1 30 10.37 9.94 9.91 10.07 0.26

Fig. 8. Stress stroke curve indicating the breaking load of the fired

solidified jarosite sand (3:1) products.


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5. Conclusion

Jarosite wastes generated from the hydrometallurgi-

cal process contain significant quantity of compoundsof iron, zinc, sulphur, lead, cadmium, manganese etc.

The presence of toxic substances make these wastes

hazardous and possess serious problem for their dis-

posal. However, due to weathering/bacterial action

there is a release of toxic elements in soluble form

which ultimately contaminate the soil, ground water

and aquatic life due to improper management of such

hazardous wastes. Work carried out by various

researchers so far focused primarily on the recovery

of zinc from the process wastes, leaching of toxic

metals and utilisation of zinc wastes in glass ceramicproducts. The result revealed from the present study

that the compressive strength of s/s products reached

43.4 kg/cm2 at 3:1 ratio of jarosite sand mixture in

which the water absorption capacity and density was

17.46% and 1.51 gm/cm3 respectively. This is also

confirming the quality as per the Indian standard spec-

ification (IS 2248:1992) for its use in construction

sector. Further the physico-chemical characterisation

indicates that there is a utilisation potential as building

materials like bricks, blocks, cement, tiles, composites.

Acknowledgement

Authors are thankful to Dr. N. Ramakrishnan, Di-

rector, Regional Research Laboratory Bhopal, India

for the permission to publish this paper. Authors are

also grateful to the officials of Debari Smelter, HZL,

Rajasthan and Satpura Thermal Power Station, Sarni,

Madhya Pradesh for the support in providing samples

and Shri S.P.Singh Chauhan, Former Director, Statis-

tics and Economic Department, Madhya Pradesh,

India for fruitful discussion and correction of themanuscript.

References

Alfantazi AM, Dreisinger DB. Foaming behavior of surfactants for

acid mist control in zinc electrolysis processes. Hydrometallurgy

2003;69:5772.

Acharya S, Anand S, Das RP. Iron rejection through jarosite pre-

cipitation during acid pressure leaching of zinc leach residue.

Hydrometallurgy 1992;31:101 10.

Arslan C, Arslan F. Thermochemical review of jarosite and goethite

stability regions at 25 and 95 8C. Turk J Eng Environ Sci 2003;

27:4552.

Asokan, P., 2003 Application of coal combustion residues in haz-

ardous waste management. Ph.D., 2nd Annual Progress Report.

Indian Institute of Technology, Bombay, India.

Asokan P, Saxena M, Asolekar SR. Hazardous waste disposal and

recycling-regulatory strategies and issues. Centre for rural

development and environment. Proc. National Workshop on

Implementation of Environmental Legislations Protection and

Conservation of Environment, 1216 Oct., Bhopal, India;

2003. p. 24351.

Asokan P, Saxena M, Asolekar SR. Coal combustion residues

environmental implications and recycling potentials. Resour

Conserv Recycl 2005;43(4):23952.

Babcan J. Synthesis of jarosite KFe3(SO4)2(OH)6. Goel Zb 1971;

22(2):299304.

Barna R, Sanchez F, Moszkowicz P, Mehu J. Leaching behaviour ofpollutants in stabilised/solidified wastes. J Hazard Mater 1997;

52:287310.

Bhat KL, Natarajan KA, Ramachandran T. Electroleaching of zinc

leach residues. Hydrometallurgy 1987;18:287 303.

Bodman GB. Nomogrammes for rapid calculations of soil density,

water content and total porosity relationships. Am Soc Agron

1942;34:88393.

Constantino, Periera F, Rodriguez-Pinero Miguel, Vale J. Solidifi-

cation/stabilisation of electric arc furnace dust using coal fly ash

analysis of the stabilisation process. J Hazard Waste Mater

2001;B82:18395.

Ding M, Geusebroek M, Sloot HA. Interfacial precipitation affects

the resistance to transport in layered jarosite/fly ash. J Geochem

Explor 1998;62:31923.Dutrizac JE. The physical chemistry of iron precipitation in the zinc

industry. In: Cigan JM, Mackey TS, Okeefe TJ, editors. Lead

zinctin 80. New York7 AIME; 1980. p. 53264.

Ferraiolo G, Zilli M, Converti A. Fly ash disposal and utilisation.

Chem Biotech 1990;47:281 305.

Gupta SC. Zinc ion solubility in polluted groundwater of Udai-

pur District, Rajasthan. Indian J Environ Health 1988;30(4):

3915.

Hage JLT, Schuiling RD. Comparative column elution of jarosite

waste and its autoclaved product-evidence for the immobiliza-

tion of deleterious elements in jarosite. Miner Eng 2000;13(3)

28796.

Hammitt JK. Illegal hazardous-waste disposal and enforcement in

the United States: a preliminary assessment. J Hazard Mater

1989;22:10119.

Hazardous wastes resource center web site. http://www.etc.org/

Technological and environmental issues/treatment technologies/

landfills/index.cfm.August 2003.

Hewaidy IF, Sabra HO, Nassif EH. Characteristics of electrolytic

zinc powder produced from zinc dross. Powder Technol

1979;24:24550.

Hindustan Zinc Limited web site. http://www.hzlindia.com, http://

www.hzlmetals.com. August 2003.

Ismael MRC, Carvalho JMR. Iron recovery from sulphate leach

liquors in zinc hydrometallurgy. Miner Eng 2003;16:31 9.

http://www.etc.org/technologicalandenvironmentalissues/treatmenttechnologies/landfills/index.cfm.http://www.hzlindia.com/http://www.hzlindia.com/http://www.hzlmetals.com/http://www.hzlmetals.com/http://www.hzlindia.com/http://www.etc.org/technologicalandenvironmentalissues/treatmenttechnologies/landfills/index.cfm.

7/25/2019 1-s2.0-S0048969705003207-main

12/12

Iyer RS, Scott JA. Power station fly ash A review of value-added

utilisation outside of the construction industry. Resour Conserv

Recycl 2001;31:21728.

Jackson ML. Soil chemical analysis. New Delhi7 Prentice Hall of

India pvt. Ltd.; 1973.

Jang A, Kim INS. Solidification and stabilization of Pb, Zn, Cd, and

Cu in tailing wastes using cement and fly ash. Miner Eng

2000;13(1415):659 1662.

Kazuo O. Present situation of effective use of coal ash in Japan and

new Japanese industrial standard of fly ash. In: Verma CVJ, Rao

SVR, Vimal Kumar, Krishnamoorthy R, editors. Fly ash dispos-

al and utilisation, vol. (I2). Proc 2nd Int Conf on Fly Ash

Disposal and Utilisation, 2-4 February 2000, New Delhi, India;

2000. p. 1028.

Keefer RF. Coal ashes-industrial wastes or beneficial by-products.

In: Keefer RF, Sajwan K, editors. Trace element in coal and coal

combustion residues. Advances in trace substances research.

Florida: Lewis Publishers, CRC Press; 1993. 3-9 pp.Leclerc N, Meux E, Lecuire JM. Hydrometallurgical extraction of

zinc from zinc ferrites. Hydrometallurgy 2003;70:17583.

Lehman JP. Hazardous waste disposal. NewYork7 Plenum Press;

1982. 396 pp.

Martin JP, Collins RA, Browning JS, Biehl FJ. Properties and use of

fly ashes for embankments. Energy Eng 1990;116(2):71 86.

Ministry of Environment and Forests web site. Hazardous Wastes

(Management and Handling) Amendment Rules, 2000-Draft

Notification. 2003.http://envfor.nic.in/.

Montanaro L, Bianchini N, Rincon J Ma, Romero M. Sintering

behaviour of pressed red mud wastes from zinc hydrometallur-

gy. Ceram Int 2001;27:2937.

Murarka JP, Mattigod SV, Keefer RF. An overview of electric power

research institute (EPRI) research related to effective manage-ment of coal combustion residues. In: Keefer RF, Sajwan K,

editors. Trace element in coal and coal combustion residues.

Advances in Trace Substances Research. Florida7 Lewis Pub-

lishers, CRC Press; 1993. 145-149 pp.

Mymrin V, Vaamonde VA. Technical note new construction materi-

als from Spanish jarosite processing wastes. Miner Eng 1999;

12(11):1399402.

Papadakis VG. Effect of fly ash on Portland cement systems: Part II.

High-calcium fly ash. Cem Concr Res 2000;30:164754.

Raghavan R, Upadhyay RN. Innovative hydrometallurgical proces-

sing technique for industrial zinc and manganese process resi-

dues. Hydrometallurgy 1999;51:207 26.

Romero M, Rincon J Ma. Micro structural characterisation of a

goethite waste from zinc hydrometallurgical process. Mater Lett

1997;31:6773.

Sanjeev B, Amritphale SS, Chandra N. Utilisation of toxic solid

waste generated in a nonferrous metal industry for making frit/

glazing material and its application for glazing of ceramics. In:

Rao PR, Kumar R, Srikanth S, Goswami NG, editors. Proc

Nonferrous Extractive Metallurgy in the New Millenium. Jam-

shedpur, India7 NML; 1999. p. 37584.

Sarangi PK, Mahakur D, Mishra PC. Soil biochemical activity and

growth response of rice Oryza sativa in fly ash amended soil.

Bioresour Technol 2001;76:199 205.

Saxena M, Asokan P. Alternative building construction materials.

In: Mittal HK, Dash PK, Mohan C, editors. Science tech entre-

preneur, centre for entrepreneurship development Madhya Pra-

desh, India; 2003. p. 3 6.

Saxena SC, Jotshi CK. Management and combustion of hazardous

wastes. Pror Energy Combust Sci 1996;22:40125.

Saxena M, Asokan P, Mandal S, Chauhan A. Impact of fly ash

phase constituents on wasteland soils. Environ Energy Conserv

1998;4(4):22934.Sharma RC, Jain NK. An Indian fly ash with high percentage of

cenospheres. Cem Concr Res 1993;23(1):23940.

Sikka R, Kansal BD. Effect of fly-ash application on yield and

nutrient composition of rice, wheat and on ph and available

nutrient status of soils. Bioresour Technol 1995;51:199 203.

Singh V. Technological innovation in the zinc electrolyte purification

process of a hydrometallurgical zinc plant through reduction in

zinc dust consumption. Hydrometallurgy 1996;40:247 62.

Sumio H, Kawaguchi M, Yasuhara K. Effective use of fly ash slurry

as fill materials. Hazard Mater 2000;76:301 37.

Tiwari S, Saxena M. Use of fly ash in high performance industrial

coatings. Br Corros J 1999;3(34):18491.

Veihmeyer FJ, Hendrickson AH. Soil density as a factor in determin-

ing the permanent wilting percentage. Soil Sci 1946;62:4516.Vempati KR, Mullah AY, Chinthala A, Cocke LD, Beeghly HJ.

Solidification and stabilization of toxic metal wastes using coke

and coal combustion by products. Waste Manag 1995;15(5/6):

43340.

Visvanathan. Hazardous waste disposal. Resour Conserv Recycl

1996;16:20112.

Vondruska M, Bednarik V, Sild M. Solidification and stabilisa-

tion of waste ferrous sulphate from titanium dioxide produc-

tion by fluidised bed combustion product. Waste Manag

2001;21:116.

Wang SY, Vipulanandan C. Leachability of lead from solidified

cement fly ash binder. Cem Concr Res 1996;26(6):895905.

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