8.IJAEST Vol No 7 Issue No 1 Removal of as (III) From Groundwater by Iron Impregnated Potato Peels 054 064

8/6/2019 8.IJAEST Vol No 7 Issue No 1 Removal of as (III) From Groundwater by Iron Impregnated Potato Peels 054 064

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Removal of As (III) From Groundwater by

Iron Impregnated Potato Peels

(IIPP): Batch Study

Buddharatna.J.Godboley R.M. DhobleM.Tech. student, IV sem. Environmental Engg. Associate Prof. Civil Engg.

G.H.Raisoni College of Engg. Nagpur India. G. H. Raisoni College of Engg. Nagpur India

E mail:- [email protected] E mail:- rmdhoble@ rediffmil.com

Abstract:

The presence of arsenic in ground water is major problem as it causes adverse effects on human body

if the concentration is more than 10g/L and drink arsenic contaminated water for longer period. In

present study the efforts have been taken to remove As (III) from drinking water using IronImpregnated Potato Peels (IIPP). From the experimental data of batch study it was found that at 1.0

mg/L concentration of As (III) the Langmuir adsorption capacity in batch study was found 0.1039

mg/g at the adsorbent dose (IIPP) of 20 g/L at pH 7.0. The adsorption process is exothermic in nature.

The IIPP was also used in field water with the same conditions of simulated water and found that all

the physicochemical parameters of drinking water were in the permissible limits. No leaching of iron

was found in the water after treatment. Kinetic study was also carried out and found that the values

of correlation coefficient (R2) for the pseudo-second-order kinetic model fitted well as

compared to pseudo first-order model. The cost of IIPP was found Rs. 69 /Kg.Key word: Arsenic (III) removal, adsorption, iron impregnated potato peel

-------------------------------------------------------------------------------------------------------------------------

1.0 IntroductionArsenic (As) is considered a contaminant

of major concern due to its high toxicity at

small concentrations and its ability to go

undetected (L.M.Camacho et al., 2011). It

is naturally present in the environment due

to geological formations, such as lacustre

sediments and volcanic rocks. The highest

arsenic concentrations (20-200 mg/kg) are

typically found in organic-rich and

sulphide-rich shales, sedimentary

ironstones, phosphatic rocks, and somecoals (D, Chakraborti et al., 2002). The

common valencies of geogenic arsenic in

ground water sources are As(III) (arsenite)

and As(V)(arsenate).The inorganic

hydrolysed species are present as H3AsO3,

H2AsO3--, HAsO3

2-, AsO3

3--and H3AsO4,

H2AsO4--

HAsO42--

andAsO43-

(A.Gupta,

et al., 1997). Under reducing

conditions, Arsenite (As (III)) is the

dominant form; arsenate (As (V)) is

generally the stable form in oxygenatedenvironments. Arsenic and its compounds

occur in crystalline, powder, amorphous or

vitreous forms. They usually occur in trace

quantities in all rock, soil, water and air.

However, concentrations may be higher in

certain areas as a result of weathering and

anthropogenic activities including metal

mining and smelting, fossil

fuel combustion and pesticide use. Arsenic

is a geogenic water menace affecting

millions of people all over the world and is

regarded as the largest mass poisoning inhistory. Permanent arsenic intake leads to

chronic intoxication, and prolonged arsenic

exposure can damage the central nervous

system, liver, skin and results in the

appearance of diverse types of cancer, such

as hyperkeratosis, lung and skin cancer (D.

Mohan, et al., 2007).

In India after West-Bengal and the

bordering districts of Bangladesh, arsenic

in groundwater was detected in part of

Assam, Arunachal Pradesh, Manipur,Nagaland and Tripura, Jharkhand, Bihar

Buddharatna.J.Godboley* et al. / (IJAEST) INTERNATIONAL JOURNAL OF ADVANCED ENGINEERING SCIENCES AND TECHNOLOGIESVol No. 7, Issue No. 1, 054 - 064

ISSN: 2230-7818 @ 2011 http://www.ijaest.iserp.org. All rights Reserved. Page 54

ngg.gg.

rediffmil.c

es adverse effects on human bod cts on

aminated water for longer periodm longer

(III) from drinking water usiner usinta of batch study it was found tt

n capacity in batch study was fca batch s

. The adsorption process is exothdsorption process is

e conditions of simulated watere co of s at

er were in the permissible limits.e ts

ic study was also carried out anic e

e pseudo-second-order kinete pse c ne

el. The cost of IIPP was found Re cost o I ndsorption, iron impregnated potaon imp t

--------------------------------------------------- --

ed a contaminanta con

to its high toxicity ati h toxicity

s and its ability to goo go

.Camacho et al., 2011). It.C .,

esent in the environment dueesent i

cal formations, such as lacusation

ts and volcanic rocks. The hinic ro h

ic concentrations (20-200 mc (20-2

pically found in organicically gani

hide-rich shales,e-rich

ones, phosphatic r, pho r, Chakrabortihakra

alenciescies

sour

ccuc

vi


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Chhattisgarh, and Utter Pradesh. Elevated

arsenic concentration has been found in

Taiwan, Argentina, Mexico, Chile, Chin,

Thailand, USA, South Africa, New

Zealand Bangladesh and India (R.M.

Dhoble et al., 2010; S. Bang et al., 2005).Arsenic concentration in rural area

averaged between 0.6 and 0.9 mg/L and in

between 3.2 and 5.6 mg/L for the rivers

influenced by industrial discharges (C.

Neal et al., 2000).

In West Bengal most frequent arsenic

concentration value range from 0.3 to 0.7

mg/L with occasionally higher value of

1.86 and 5.0 mg/L reported from two

places in the district of Murshidabad(A.Gupta et al., 1997). High concentration

of arsenic (10 - 3200 g/L) in groundwater

of West Bengal has been encountered in

Nadia, Murshidabad, Malda, Barddhaman,

Hooghly, North & South 24- Paragnas

districts of West Bengal. According to a

survey conducted by WHO in 2006, the

number of people poisoned by arsenic in

India and Bangladesh alone were 70

million (C.Niu et al., 2007). WHO

provisional guideline value for arsenic indrinking water is 10 g/l (WHO, 2004).

Permissible limit of arsenic in drinking

water is less than 10g/L (WHO. 1993).

2.0 Materials and Methods

2.1 Materials

All the chemicals used in the present study

were analytical grade. Standards for

calibration were prepared from As (III)

standard reference sodium (Meta) arsenite.Stock solution (1000mg/L) was prepared

from sodium (Meta) arsenite (Merck India)

A.R.grade and frozen to prevent oxidation.

Solutions of As (III) of 100 mg/L were

prepared in every fortnight and working

solutions of As (III) were prepared

according to experiment requirements. pH

was adjusted by standard acid and base

solutions of 0.1 N HCl and 0.1 N NaOH

respectively.

2.2 Methods

The synthesized material was subjected to

detailed characterization by using different

techniques like X-ray diffraction, scanning

electron microscopy (SEM) and Wave

length energy dispersive analysis of X-ray(WDAX). XRD patterns have been

recorded at Vishwesharaya National

institute of Technology (VNIT), Nagpur

using X- Ray diffractometer, (Model

Phillips: PW-1830). The SEM analysis of

the synthesized adsorbents was carried out

at VNIT, Nagpur using Scanning Electron

Microscopy (Jeol, JXA-840 A, Electron

probe micro-analyzer, Japan) with different

magnification. Chemical composition of

the adsorption materials was carried onWave length Dispersive X-Ray

Fluorescence Spectrophotometer

(WDXRFS) equipment from Indian Bureau

of Mines at Nagpur (PW 2403 magix,

Philips Netherlands).

3.0 Characterisation of Material.

3.1 X-ray Powder Diffraction (XRD)

In this test samples were scanned for 2

range from 5 to 60.The X-ray diffraction

spectrum pattern of the IIPP did not showany significant change in sharp peak

(Fig.1), thereby indicating the amorphous

nature of the product.

Fig 1: -Characterisation of IIPP by

XRD

3.2 Scanning Electrons Microscopes

(SEM)

Scanning electrons microscopes analysis

was performed to understand the

morphology of IIPP.From Fig.2. it is

observed that the pore size of adsorbent is

bigger before adsorption and then filledby the arsenic ions after adsorption.



aa

, thethe

senic in

were 70

07). WHO

e for arsenic inforg/l (WHO, 2004).WHO, 2

f arsenic in drinkingrinking

10g/L (WHO. 1993).. 3

s and Methodsnd M

als

e chemicals used in the presee in the

ere analytical grade. Staere ana Sta

ibration were prepared ftion

rd reference sodiumeferen iumlution (1000on (1

(Meta)eta

fror

e SEe

rbents wasrb

using Scanningsing

eol, JXA-840 A, Elee A-84

-analyzer, Japan) with differeal an) w

ation. Chemical compositiotio ompo

sorption materials was carrcar ve length Dispersive

luorescence Spectrre ce

(WDXRFS) equipment froRFS) e nt

f Mines at Nagpur

Philips Netherlands)..

.0 Characteris.0 c

.1 X-ray Pow- Po

In this testI s

range frran r

spectrpectan


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a) Before adsorption b) After adsorption

Fig 2: Characterisation of IIPP by SEM

3.3 Chemical composition of IIPP was

carried out on WDAX. Table 1 shows the

composition of material (IIPP)

Table 1: Chemical composition of IIPP

4.0 Batch study

In the adsorption study a temperature

controlled orbital shaker (Remi

Instruments, Mumbai), was used for the

batch adsorption study. The temperature

range for the studies was from 293 to

313K. All the batch studies were

performed at the shaking rate of 150

revolutions per minute (rpm). For each

experimental run, 50 ml aqueous solutionof the known concentration of arsenic (III)

was taken in 100 ml capacity plastic

bottles containing 50 ml of arsenic (III)

solution and known mass of the adsorbent.

These bottles were agitated at a constant

shaking rate of 150 rpm in a temperature

controlled orbital shaker maintained at a

constant temperature. The pH of the

adsorbate solution was adjusted using 0.1

N HCl or 0.1 N NaOH aqueous solutions

without any further adjustment during the

sorption process. To check whether the

equilibrium has been attained, the samples

were withdrawn from the flasks at

different time intervals. Remaining

Arsenic (III) was measured by Atomic

absorption spectrometer (Hydride Vapors

Generator, HVGAAS). The comparison

was made between synthesis and field

water.

5.0 Adsorption model5.1 Langmuir Isotherm

Langmuir isotherm is based on the

assumption that points of valency exist on

the surface of the adsorbent and that each

of these sites is capable of adsorbing one

molecule; thus, the adsorbed layer will be

one molecule thick. Furthermore, it is

assumed that all the adsorption sites have

equal affinities for molecules of theadsorbate and that the presence of

Element Fe Si Mg Al P Ca

Percentage 61.7 2.28 0.77 0.73 0.55 0.27



ff r adsorptionsorpt

M

study a temperatureature

bital shaker (Remii

umbai), was used for theumba d

rption study. The temperatstudy.

or the studies was from 2es wa 2

. All the batch studie. ch s

rformed at the shaking rarforme g ra

olutions per minute (rpions

imental run, 50 mltal ru lown concentrconc

in 100100

in

Mg Al

2.28 0.77 0.70.77 .7


4/11

adsorbed molecules at one site will not

affect the adsorption of molecules at an

adjacent site. The Langmuir equation is

commonly written as follows (I.

Langmuir.1916).

qe= ---- (1)

Where qe is the amount adsorbed (mg/g);

Ce is the equilibrium concentration of

adsorbate (mg/l); qmax indicates the

monolayer adsorption capacity of

adsorbent (mg/g) and the Langmuir

constant b (L/mg) is related to the energy

of adsorption. The linear form of the

Langmuir isotherm can be expressed asequation 2.

= ( ---- (2)

When is plotted against , a straight

with slope is obtained which shows

the adsorption follow the Langmuir

isotherm. The Langmuir constants b and

qmax are calculated from the slope and

intercept with Y- axis. The essential

characteristics of a Langmuir isotherm can

be expressed in terms of a dimensionless

separation factor, r (T.Weber et al., 1974)

which describes the type of isotherm and is

defined by

r= ---- (3)

Where b and Co are the terms appearing in

the Langmuir isotherm. The parameter

indicates the shape of the isotherm

accordingly.

5.2 Freundlich Isotherm

The equation that describes such isotherm

is the Freundlich Isotherm, given as

neFe

CKQ1

= --- (4)

Where,F

K and n are the constants.e

C= the

concentration of adsorbate solution at

equilibrium by taking logarithm on both

sides, this equation is converted into a

linear form: (S.Kandu et al., 2006)

log qe= log kf+1/n log Ce ---- (5)

Thus a plot between ln q e and ln eC is a

straight line. The Freundlich equation is

most useful for dilute solutions over small

concentration ranges. The values of the

constants nand kf can be determined

from the plot. Larger Kf indicates larger

the adsorption capacity. The intercept is

roughly an indicator of sorption capacity

and the slope, 1/n, of adsorption capacity.The parameter 1/n measures the strength of

adsorption. A high KF and high n value

is an indication of high adsorption

throughout the concentration range. A low

KF and high n indicates a low adsorption

throughout the concentration range. A low

n value indicates high adsorption at

strong solute concentration.

if

1/n < 1, bond energies increases withsurface density

1/n > 1, bond energies decreases with

surface density

1/n = 1, all surface sites are equivalent

6.0 Kinetic study

In order to estimate equilibrium adsorption

rate for the uptake of As (III) by

impregnated potato peels (IIPP), time

dependent sorption studies were

conducted. Adsorption kinetics was

monitored by adding known weight of

IIPP into 50 ml of at 1mg/L arsenic

solution at 293 K, 303K and 313K stirred

at 150 rpm. A portion of solution was

withdrawn from the vessel at

predetermined time intervals was filtered

and analyzed for residual concentration of

As (III) using Atomic absorption

spectrophotometer hydride vapour

generator.



ghtht

showss

Langmuir

onstants b and

the slope andthe s

axis. The essentiale essent

Langmuir isotherm cans can

terms of a dimensionlesste

tor, r (T.Weber et al., 1974)tor, r a

ribes the type of isotherm andhe typ

y

and Co are thed Co a

uir isothisot

l

olutiono

s. The valus.

k ff can be dete ca

. Larger K. Kff indicates lain

on capacity. The interceptc The

an indicator of sorption capn tion

e slope, 1/n, of adsorption can c parameter 1/n measures the s

dsorption. A high Krpt n. A high KFF and hi

is an indication of hiindica of

hroughout the concentrtr

KF and high n indic

hroughout the conh co

n value indin

strong solutete

ifif

1/n/nsur


5/11

For adsorption, simplified approach given

by Lagergren can often be applied with

success especially in the first phase of the

sorption. The Lagergren first-order rate

model is given by the following

expression. (J. Baig et al., 2010)Log (qe-qt) = log qe t ----- (6)

where qe and qt (mg/g) are the amounts of

As adsorbed at equilibrium (mg/g) and t

(min), respectively, while K1 is the rate

constant of the equation (min1). The

Lagergren second-order rate model is

given by the following expression [ Baig

etal., 2010]:

= ----- (7)

whereK2 (g/mol/min) is the rate constant

of the second-order equation, qt (mol/g) is

the amount of adsorption at time t (min)

and qe is the amount of adsorption

equilibrium (mol/g). In order to be able to

estimate maximum capacities of

adsorbents, it is necessary to know the

quantity of adsorbed metal as a function of

metal concentration in solution.

7.0 Results and discussion

7.1 Optimum dose of adsorbent

The optimum dose experiments

were carried by adding different amount of

adsorbent doses 1.0, 2.0, 3.0, 5.0, 10.0,

20.0 and 25 g/L into the 1.0 mg/l known

amount of As (III) concentration. This was

put inside the 100 ml capacity glass bottles

containing 50 ml of Arsenic (III) solution.The bottles with arsenic mixture were then

being put into the incubator shaker which

operated at 150 rpm and with constant

temperature 303K up to 24 hrs.From Fig. 3

shows that as the dose of adsorbent

increased the adsorption of as (III) also

increased upto from 1 to 20 g/L and

found at the dose of 20 g/L the remaining

As (III) was less than 10 g/L ( less than

permissible limit WHO 2007).After this

removal was not significantly reduced.Hence the IIPP dose of 20g/L was

finalized and used for further study. This is

also noted that as the dose of adsorbent

increased the adsorption capacity also

increased. This may be due to the more

number of active sites available.

Fig.3 : Effect of dose of adsorbent for As(III) removal on adsorption by IIPP

Condition: Co- 1mg/L, pH -7.0, Temp.

303K. rpm 150.

7.2 Effect of pH

The sorption of As (III) by the

adsorbent was studied over a pH of 2-12 at

303K and over a contact time of 24 h.

concentration of 1.0 mg/L As (III) was

used. From the Fig. 4 it is observed that

the adsorption of As (III) was less in acidiczone and increased as the pH increased

upto 7.0 pH and then decreased. For the

drinking purpose the pH should be in the

range of 6.5-8.5 (BIS 10500-1991) and in

the present study it was found that pH is in

permissible limit

Fig.4: Effect of pH for As (III) removal on

adsorption by IIPP.

(Condition: Co- 1mg/L, Dose of

adsorbent: 20 g/L., Temp. 303K. rpm

150.)



onon

ble toto

es of

know the

s a function of

ution.ion.

cussion

e of adsorbente

ptimum dose experimentsptimu p

d by adding different amountdding

t doses 1.0, 2.0, 3.0, 5.0,0, 2.0, ,

and 25 g/L into the 1.0 mg/lan the 1.

ount of As (III) concentrationount o tratio

t inside the 100 ml capacityide th ty

ining 50 ml of Arsen50 rsentles with arsenicwith a

into the inthe i

150

ffect of dose of adsorbent ft rbent(III) removal on adsorptiono

ondition:d Co- 1mg/L, pH -o- 1m

303K. rpm 150.. rpm 150.

.2 Effect of pH

The sorptioso

adsorbent was studs t

303K and ovo

oncentratioi

used. Fruse

he adhe azo


6/11


7/11


8/11

Table 2: Langmuir Adsorption isotherm parameters for As (III) adsorption by IIPP

Temperature qmax ( mg/g) r R2

293K 0.1177 0.007 0.951

303K 0.1039 0.010 0.947

313K 0.0798 0.0062 0.919

Table 3: Freundlich adsorption isotherm parameters for As (III) adsorption by IIPP

Table 4: Variouskinetic and diffusion parameters for As (III) adsorption by IIPP

Table 5: Physicochemical parameters of field water before and after treatment with IIPP

Sr.No Parameter UnitBefore

Treatment

After

Treatment

Permissible limit

BIS 10500-1991

1 pH - 7.18 7.33 6.5-8. 5

2 Turbidity NTU BDL BDL


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Table 6: Comparison of IIPP with existing adsorbents reported in literature

Adsorbent pH

Concent

ration

(mg/L)

Removal

efficiency of

( As III ) in %

Reference

Giridih bituminouscoal (GBC). 5-9 1.0 20-30

S.Guha et al.,

1990

Lignite 7.5 1.0 6-14

crush coconut shell, 7.5 1.0 15-33

Illite 7.5 1.0 7-12

Kaolinite clay, 7.5 1.0 5-8

Rice husk, 7.5 1.0 0-19

Fly ash 7.5 1.0 Not detectable

Charcoal 7.5 1.0 5-18

Yamuna sand 7.5 1.0 26-29

Partially activated coconut

shell6.2 1.0 72

S.Prasad

et al., 1995

Powder activated alumina(PAA) and kimberlite tailing

7.0-8.0 1.0 90-94

K.

Pallamreddy etal., 1996

Zero- Valent iron 7.1-8.0 1.0 95J. Lackovic

etal., 2000

Iron oxide impregnated

activated alumina12 1.1 96.7

S. Kuriakose

etal.,2004

Iron oxide coated sand 7.5 0.1 99V. Gupta et

al.,2005

Activated charcoal 8.0

0.05,0.1,

0.5 &1.0 72.71, 68 & 63.

A. Quaff etal., 2005

Activated tea waste 8.0 0.05,0.1,

0.5 &1.048, 47, 45 & 43.

IIPP 7.0 1.0 99.27 Present study



S.Guh

1990

- 8

0-0-19

N t detectable

. 5-. 5-1818

1.0 2 - 29

.2 1.0 72

ling7.0-8.0 1.0

n 7.1-8.0.

impregnatedated

d alumina12

on oxide coated sandxide c

harcoalcoal


10/11

12.0 Comparison of IIPP with alreadyexisting adsorbents.

Comparison was made with few reported

adsorbents on percentage removal basis

and found that IIPP has good percentageremoval capacity of As (III) than others.

(Ref. Table 6)

13.0 Cost analysisCost of IIPP was worked out by

considering loss and impurities in batch

and found Rs. 68.67/kg (Rs.69/kg) which

could be low cost of adsorbent to remove

as As(III) from drinking water.

Conclusion Pre-treatment was required to raw

material before using for removal of As

(III).

Optimum dose of IIPP was found 20g/Lfor removal of As (III) of 1 mg/L

concentration.

Adsorption capacity was more in thepH range of 6-8.

Optimum time of contact was found 24hrs.

Adsorption capacity of IIPP onLangmuir model and Freundlich model

was 0.1039 mg/g and 0.385 mg/g

respectively at 303K.

Freundlich model was best fitted thenLangmuir model.

It is apparent from the values ofcorrelation coefficients fort the pseudo-

second-order kinetic model fitted well

as compared to pseudo first-order

model. All the physicochemical parameter of

drinking water was within permissible

limits (BIS 10500 -1991) after

treatment.

The cost of IIPP was found Rs 69/Kg.References

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