Utilization of Agricultural Waste for the Removal of Organic - PowerPoint PPT Presentation

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 extraction using 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 the organic micropollutants, where the analysis had to face many different compounds o 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 on occurrence of such micropollutants in the environment was an important driving force initiating the development of modern analytical techniques e.g. SPE and procedure.

Solid Phase extraction  Adsorption – a surface phenomenon Retention of ions / molecules on the surface due to certain physical and chemical attractive forces. The surface include the outside of the adsorbent as well as pores in high surface area per unit volume.

Adsorbate Adsorbent Selective solute binding Removal of bound material is called desorption i.e. opposite of adsorption

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.

Sorbents used in solid phase extraction Synthetic Natural Activated carbon Clay/Minerals Alumina Fly ash Silica gel Agricultural waste Ion-exchange Resins XAD modified resins Coconut husk Rice husk Groundnut husk Apple residue Plant bushes Onion skin Zeolite Geolite River 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 adsorbent Low inorganic matter content Ease of activation Availability and low cost Low degradation Factors affecting adsorption Physical 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 Material Agriculture Material

Sorption using agriculture waste 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

Extraction of Cr (III) and Cr (VI) ions with Separation of chromium specie on saw dust as a function of pH Cr(III) Cr(VI) 100 80 Sorption 60 40 % 20 0 0 2 4 6 8 pH Saima, Bhanger and Khuhawar, Anal. Bioanal. Chem. 383, 619-624, 2005

Benefits  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

Sorption using Sawdust  Removal of Cd(II) ions  both treated and untreated sawdust was used  Surface area 400 cm 2  Maximum adsorption at pH 4 - 5

Figures showing uptake of Cd (II) ion on saw dust as a function of pH Treated 2.0 -1 q (metal uptake) mg g 1.5 1.0 Untreated 0.5 0.0 0 2 4 6 8 10 pH Saima, Najma, Bhanger and Khuhawar, J. Hazard. Mater. B139 116-121, 2007

Online Solid Phase Extraction of Cr(III) and Cr(VI) Motomizu et al. Talanta, 68, 388, 2005

Solid Phase Extraction of Solid Phase Extraction of Trace Organics from Water Trace Organics from Water

Lab. Methods for the Removal of Pollutant using Solid – phase extraction

80 BFA 100 BFA RB Percent sorption 60 80 APS P ercent sorption RB MOP 60 40 APS RH MOP 40 PNH 20 AH RH 20 CNS 0 PNH SW S-1 0 CC S-2 S-3 S-1(sorbents treated with doubly DS distilled deionized water and NTL dried at 283K for 8hrs) S-2(sorbents treated with 0.1M nitricacid S-3(sorbents treated with methanol) Investigation of agriculture waste Investigation of agriculture waste material as sorbents material as sorbents 0.2 g of each sorbent, 20 cm 3 of 0.2 g of each sorbent, 20 cm 3 of 1.1 î 10 -3 M toluene concentration, 1.1 î 10 -3 M toluene concentration, 30 30 min agitation time, pH 6 and min agitation time, pH 6 and 303K. 303K.

Solid phase extraction Solid phase extraction of BTEC, phenols and of BTEC, phenols and pesticides pesticides

Limit of Detection US EPA Recommended Analyte ( ì g/ml) Limit in water ( ì g/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

US EPA Limit of Detection Analyte Recommended Limit ( ì g/ml) in water ( ì g/ml) Methylparathion 0.05 0.01 Triazophos 0.05 0.01 Endosulfan 0.1 0.62 Cypermethrin 0.1 0.43 (4) (3) ( 1) = Methyl parathion (2) = Triazophos (2) (3) = Endosulfan (4) = Cypermethrin (1)

Limit of Detection Limit of Detection US EPA Recommended US EPA Recommended Analyte Analyte ( ì g/ml) ( ì g/ml) Limit in water ( ì g/ml) Limit in water ( ì g/ml) Methylparathion Methylparathion 0.05 0.05 0.01 0.01 Triazophos Triazophos 0.05 0.05 0.01 0.01 Endosulfan Endosulfan 0.1 0.1 0.62 0.62 Cypermethrin Cypermethrin 0.1 0.1 0.43 0.43 (4) (3) (2) ( 1) = Methyl parathion (2) = Triazophos (3) = Endosulfan (1) (1) (1) (1) (4) = Cypermethrin (1)

80 80 70 Percent sorption Percent sorption 60 60 50 40 40 30 20 10 20 0 25 50 75 100 125 0 25 50 75 100 125 Agitation time (min) Agitation time (min) Benzene Toluene Benzene Toluene Ethylbenzene Cumene Ethylbenzene Cumene Effect of agitation time (5-120 min) on Effect of agitation time on the the percent sorption of BTEC onto 0.1 g percent sorption of BTEC onto 0.1 g cm 3 of MOP, 25 cm 3 of 100  g/ ml sorbate RB, 25 100  g/ ml sorbate concentration of BTEC at pH 6 and 303 K. concentration of BTEC at pH 6 and 303 K.

Percent sorption and percent recovery of benzene, toluene and ethylbenzene from contaminated water by rice bran Concentration of analyte determined with spiked Concentrati sample on of % % recovery ( µg/ ml) analyte sorption Analyte determined before after ( µg/ ml) sorption sorption 0.451 10.45 0.22 98 96.2 Benzene 0.334 10.33 0.1 99 97.3 Toluene Ethylben 0.214 10.21 0.1 99 97.3 zene N.D. _ _ _ _ Cumene Mubeena, Bhanger, Hasany , J. Agric. Food Chem. 53, 8655-8662 (2005) .

Application of method on contaminated water sample using treated Moringa oleifera seeds Concentration of analyte determined in spiked % % contaminated sample (( µg/ ml) sorption recovery Analyte Before After sorption sorption 10.44 0.17 98.4 96.2 Benzene 10.33 0.1 99.03 98.3 Toluene 10.22 0.1 99.02 98.2 Ethylbenzene - - - - 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. Wastewater ( ì g/ml) Analyte Removal* (%) Recovery* (%) with 6 ml methanol ___ ___ Phenol 98 ± 0.8 96 ± 1.2 4-Chlorophenol 99 ± 0.2 99 ± 0.6 2,4-Dichlorophenol S.No Characteristics Values 1 pH 7.3 EC ( ì S cm -1 ) 2 286 3 Phenol N.D 4-CP ( ì g ml -1 ) Mubeena, Bhanger, Hasany, 4 0.4 J. Hazard. Mater. 2,4-DCP ( ì g ml -1 ) 5 1.5 B 128, 44-52 (2006)

Percent sorption and percent recoveries of MP from water samples onto RB, BFA, MOP and RH Sorbents Surface water Ground water Removal Recovery Removal Recovery 99 98 99 98 Rice bran 99 98 99 98 Bagasse fly ash 98 97 98 97 Moringa oleifera pods 97 96 97 96 Rice husk

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 ( m 2 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  SiO 2 % - 75.9  K 2 O% 2.4  0.02 -  CaO % 1.5  0.03 0.28  0.02  Fe 2 O 3 % 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 husk Moringa oleifera seed pods Scanning electron microscope pictures of natural activated adsorbents showing heterogenous surfaces Bagasse fly ash