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Utilization of Agricultural Waste for the Removal of Organic Pollutants from
Aqueous Media
Muhammad Iqbal Bhanger
National Center of Excellence in Analytical Chemistry,University of Sindh, Jamshoro, Pakistan
This presentation is focused on :
a preview about the preconcentration /enrichment, determination and removal of various organic pollutants by solid phase extractionusing natural material (e.g. agriculture waste)
Common sources of organic pollutants in our environment
Industrial effluents
Pesticides applications
Municipal discharge
Power plants
Oil spillage
Environmental trace organic analysis
Several problem were encountered in theorganic micropollutants, where the analysishad to face many different compoundso c c u r r i n g a t t r a c e c o n c e n t r a t i o n s .
Therefore, the need of a reliable data onoccurrence of such micropollutants in theenvironment was an important driving forceini t iat ing the development of modernanalytical techniques e.g. SPE and procedure.
Solid Phase extraction
Adsorption � a surface phenomenon
Retention of ions / molecules on thesurface due to certain physical andchemical attractive forces. The surfaceinclude the outside of the adsorbent aswell as pores in high surface area perunit volume.
Adsorbent
Adsorbate
Removal of bound material is called desorption i.e. opposite of adsorption
Selective solute binding
SPE - an increasingly popular technique in comparison to the classical solvent �solvent extraction because of :
high enrichment factor, high recovery, rapid phase separation, low cost, low consumption of organic solvents the ability of combination with other
detection techniques in the form of on-line or off-line mode.
Synthetic Natural
Sorbents used in solid phase extraction
Activated carbon Clay/MineralsAlumina Fly ashSilica gel Agricultural waste Ion-exchange Resins XAD modified resins Coconut husk
Rice huskGroundnut huskApple residuePlant bushesOnion skin ZeoliteGeoliteRiver sand
Advantages of Natural Sorbent
Inexpensive
Environmental friendly
Freely Available
Active
Stable
Accessible
Easy to reuse
Lab. Set-up for the Removal of Pollutant using
Solid �phase extraction
Materials commonly used for extraction chemical substances from water
Ion-imprinted polymers Immunoaffinity based sorbents Nano-composite materials Functionalized chelating polymers /
Inorganic material Agriculture wastes Sand, Clay, industrial waste Microbial biosorbents e.g. algae, fungi,
bacteria
Choice of adsorbentLow inorganic matter contentEase of activationAvailability and low costLow degradation
Factors affecting adsorptionPhysical nature of the adsorbent �pore structure, functional groups, polarity, molecular weight, size and Solution conditions e.g. pH, ionic strength and the adsorbate concentration
Scheme for the preparation of palladium Ion imprinted material.
Daniel, Babu and Rao, Talanta (65) 441, 2005
Agriculture MaterialAgriculture Material
Solid phase Extraction and separation of
(a) Cr(III) and Cr(VI)
(b) Cd(II) using sawdust as an adsorbent (relatively abundant and inexpensive material)
Green Chemistry
Sorption using agriculture waste material
Extraction of Cr (III) and Cr (VI) ions with Separation of chromium specie on saw dust as a function of pH
0
20
40
60
80
100
0 2 4 6 8
pH
% S
orpt
ion
Cr(III) Cr(VI)
Saima, Bhanger and Khuhawar,Anal. Bioanal. Chem. 383, 619-624, 2005
Easy, simple and economical
Both specie of Cr can be adsorbed without the need of oxidation / reduction.
Rapid and sensitive
Can be designed on a large scale
Benefits
Removal of Cd(II) ions both treated and untreated
sawdust was used Surface area 400 cm2
Maximum adsorption at pH 4 - 5
Sorption using Sawdust
Saima, Najma, Bhanger and Khuhawar,
J. Hazard. Mater. B139 116-121, 2007
Figures showing uptake of Cd (II) ion on saw dust as a function of pH
Untreated
Treated
0.0
0.5
1.0
1.5
2.0
0 2 4 6 8 10pH
q (m
etal
upt
ake)
mg
g-1
Online Solid Phase Extraction of Cr(III)and Cr(VI)
Motomizu et al. Talanta, 68, 388, 2005
Solid Phase Extraction of Trace Organics from WaterSolid Phase Extraction of
Trace Organics from Water
Lab. Methods for the Removal of Pollutant using Solid �
phase extraction
S-1(sorbents treated with doubly distilled deionized water and
dried at 283K for 8hrs)
0
20
40
60
80
S-1
Per
cen
t so
rpti
on
BFA
RB
APS
MOP
RH
PNH
AH
CNS
SW
CC
DS
NTL
0
20
40
60
80
100
S-2 S-3
S-2(sorbents treated with 0.1M nitricacid S-3(sorbents treated with methanol)
Per
cen
t so
rpti
on
BFA
RB
APS
MOP
RH
PNH
0.2 g of each sorbent, 20 cm3 of1.1î10-3 M toluene concentration,30 min agitation time, pH 6 and303K.
0.2 g of each sorbent, 20 cm3 of1.1î10-3 M toluene concentration, 30min agitation time, pH 6 and 303K.
Investigation of agriculture waste Investigation of agriculture waste material as sorbentsmaterial as sorbents
Solid phase extraction of BTEC, phenols and
pesticides
Solid phase extraction of BTEC, phenols and
pesticides
AnalyteLimit of Detection
(ìg/ml)US EPA Recommended Limit in water (ìg/ml)
Phenol 0.1 0.21
4-Chlorophenol 0.08 0.7
2,4-Dichlorophenol 0.08 0.8
1 = Phenol
2 = 4-Chlorophenol
3 = 2,4-Dichlorophenol
AnalyteLimit of Detection
(ìg/ml)
US EPA Recommended Limit
in water (ìg/ml) Methylparathion 0.05 0.01
Triazophos 0.05 0.01
Endosulfan 0.1 0.62
Cypermethrin 0.1 0.43
(1)
(2)
(3)
(4)
(1) = Methyl parathion
(2) = Triazophos
(3) = Endosulfan
(4) = Cypermethrin
AnalyteAnalyteLimit of DetectionLimit of Detection
(ìg/ml)(ìg/ml)US EPA Recommended US EPA Recommended Limit in water (ìg/ml) Limit in water (ìg/ml)
MethylparathionMethylparathion 0.050.05 0.010.01
TriazophosTriazophos 0.050.05 0.010.01
EndosulfanEndosulfan 0.10.1 0.620.62
CypermethrinCypermethrin 0.10.1 0.430.43
(1)(1)(1)
(1)(1)
(2)
(3)(4)
(1) = Methyl parathion
(2) = Triazophos
(3) = Endosulfan
(4) = Cypermethrin
20
40
60
80
0 25 50 75 100 125Agitation time (min)
Per
cen
t so
rpti
on
Benzene TolueneEthylbenzene Cumene
10
20
30
40
50
60
70
80
0 25 50 75 100 125
Agitation time (min)
Per
cen
t so
rpti
on
Benzene TolueneEthylbenzene Cumene
Effect of agitation time (5-120 min) onthe percent sorption of BTEC onto 0.1 gRB, 25 cm3 of 100 g/ ml sorbateconcentration of BTEC at pH 6 and 303 K.
Effect of agitation time on thepercent sorption of BTEC onto 0.1 gMOP, 25 cm3 of 100 g/ ml sorbateconcentration of BTEC at pH 6 and303 K.
Percent sorption and percent recovery of benzene, toluene and ethylbenzene from
contaminated water by rice bran
Analyte
Concentration of analyte determined(µg/ ml)
Concentration of analyte determined with spiked
sample (µg/ ml)
%sorption % recovery
before sorption
after sorption
Benzene 0.451 10.45 0.22 98 96.2 Toluene 0.334 10.33 0.1 99 97.3 Ethylbenzene 0.214 10.21 0.1 99 97.3
Cumene N.D. _ _ _ _
Mubeena, Bhanger, Hasany , J. Agric. Food Chem. 53, 8655-8662 (2005).
Application of method on contaminated water sample using treated Moringa oleifera seeds
Analyte
Concentration of analyte determined in spiked
contaminated sample ((µg/ ml) % sorption
% recovery
Before sorption
After sorption
Benzene 10.44 0.17 98.4 96.2
Toluene 10.33 0.1 99.03 98.3
Ethylbenzene 10.22 0.1 99.02 98.2
Cumene - - - -
Mubeena, Bhanger, Hasany, J. Hazard. Mater. 141, 546-556 (2007)
Percent sorption and percent recoveries of 4-CP and 2,4-DCP from industrial wastewater sample onto rice husk.
Analyte Wastewater (ìg/ml)Removal* (%) Recovery* (%)
with 6 ml methanol
Phenol ___ ___
4-Chlorophenol 98 ± 0.8 96 ±1.2
2,4-Dichlorophenol 99 ± 0.2 99 ± 0.6
S.No Characteristics Values
1 pH 7.3
2 EC (ìS cm-1) 286
3 Phenol N.D
4 4-CP (ìg ml-1) 0.4
5 2,4-DCP (ìg ml-1) 1.5
Mubeena, Bhanger, Hasany, J. Hazard. Mater.
B 128, 44-52 (2006)
Sorbents Surface water Ground water
Removal Recovery Removal Recovery
Rice bran 99 98 99 98
Bagasse fly ash 99 98 99 98
Moringa oleifera pods 98 97 98 97
Rice husk 97 96 97 96
Percent sorption and percent recoveries of MP from water samples onto RB, BFA,
MOP and RH
Surface Characteristics of treated agriculture waste sorbents
Parameters MOP Rice husk
Total intrusion volume (ml/g) 0.72 0.01 0.694 0.046 Total pore area (m2 g-1) 27 0.8 17 0.6 Average pore diameter (nm) 86 1.3 51 1.5
Carbon % 97.6 0.02 24.1 0.05
SiO2% - 75.9 K2O% 2.4 0.02 - CaO % 1.5 0.03 0.28 0.02 Fe2O3 % 1.1 0.01 0.3 0.03 Cellulose weight % 15.6 0.05 0.4 0.04 Hemicellulose % 11.1 0.07 0.6 0.02 Lignin % 10.7 0.08 0.5 0.01 Crude fibre % 13.8 0.06 0.8 0.02
Rice huskMoringa oleifera seed pods
Bagasse fly ash
Scanning electron microscope pictures of natural activated adsorbents showing heterogenous surfaces
SEM image of the rice bran activated chemically and thermally.
Proposed Mechanism of Sorption
� The sorption mechanism may be deduced from the involvement ofdifferent functional groups present on the sorbents surfaces such as−OH, NH2 metal oxides (via ash content i.e. Si−O−Si) and fibrecarbonaceous CxOH. These functional groups may be dissociated atdifferent pH values as per their acidic dissociation constants andconsequently take part in surface complexation / exchange of sorbatespecies.
� The surfaces are expected to be negatively charged, which mayfacilitate the sorption of positively charged species at low pH ontothese active groups via surface complexation.
.00� −OH = −O− + H+
.00
� CxOH = −CxO− + H- NH2 = - NH3
+
Conclusion
Adsorption of trace organics on solid surface from the aqueous solutions present the most wide spread use of natural material. The use of agriculture waste also add on to the Green Chemistry.
Molecular size, molecular structure, steric form of sorbatealso influences the sorption. More soluble a substance is inwater; its low sorption is likely to occur on the sorbentsurface e.g. phenol as compared to nitrophenol.
The equilibrium uptake and adsorption yield were highestfor the treated materials, which was expected, because ofthe greater specific surface area and the microporousstructure of treated materials as compared with untreatedmaterials.
The results of surface characterization indicate thatrice bran, rice husk, and Moringa oleifera pods arecomposed of substantial amount of cellulose,hemicellulose, lignin and protein besides ash. Theseactive sites may display different affinities for varioussorbed species.
Therefore, the quantity and nature of active sites inthe cells of such biomaterials may be a major factorin the binding behavior of sorbed species at a givenpH in sorptive solution. The lignin content mayincrease the sorption of organics on the sorbentssurfaces of botanical origin.
My co-workers
Dr. Mubeena Akhter, Dr. Saima Q. Memon
and
Organizers of Pak-Turk Bilateral Workshop on Chemical Sciences especially
Prof. M.Yilmaz, Prof. Mustafa Ersoz and Dr. Shahabuddin Memon.
Acknowledgment
A view of NCEAC, Jamshoro, Pakistanvisit us www.ceacsu.edu.pk
A view of NCEAC, Jamshoro, Pakistanvisit us www.ceacsu.edu.pk