STUDIES ON REMOVAL OF HEAVY METALS FROM ENVIRONMENT USING BIOSORBENTS

INTRODUCTION
USAGE

OF HEAVY METALS IN MANY INDUSTRIES CHROMIUM,THE MAJOR APPLICATION IS IN FERTLISER AND LEATHER TANNING RESPECTIVELY . WASTEWATER CONTAMINATED WITH HEAVY METALS IS A SERIOUS ENVIRONMENTAL PROBLEM.

TRADITIONAL TECHNIQUES
PRECIPITATION

OXIDATION/REDUCTION
ION

EXCHANGE FILTRATION ELECTROCHEMICAL PROCESSES MEMBRANE SEPARATIONS EVAPORATION

DISADVANTAGES OF TRADITIONAL TECHNIQUES

HIGH

COST INCOMPLETE REMOVAL LOW SELECTIVITY HIGH ENERGY CONSUMPTION GENERATION OF TOXIC SLURRIES

BIOSORPTION

THE ABILITY OF BIOLOGICAL MATERIALS TO ACCUMULATE HEAVY METALS FROM WASTEWATER THROUGH METABOLICALLY MEDIATED OR PHYSICO-CHEMICAL PATHWAYS OF UPTAKE. PROCESS INVOLVES A SOLID PHASE (SORBENT OR BIOSORBENT; BIOLOGICAL MATERIAL) AND A LIQUID PHASE (SOLVENT, NORMALLY WATER) CONTAINING A DISSOLVED SPECIES TO BE SORBED (SORBATE, METAL IONS).

ADVANTAGES
LOW

COST HIGH EFFICIENCY MINIMISATION OF CHEMICAL AND BIOLOGICAL SLUDGE NO ADDITIONAL NUTRIENT REQUIREMENT REGENERATION OF BIOSORBENT POSSIBILITY OF METAL RECOVERY.

PASSIVE BIOSORPTION

METABOLICALLY INACTIVE, DEAD, MICROBIAL BIOMASS METAL UPTAKE IS BY PHYSICO-CHEMICAL INTERACTION BETWEEN THE METAL AND THE FUNCTIONAL GROUPS PRESENT ON THE MICROBIAL CELL SURFACE THIS IS BASED ON PHYSICAL ADSORPTION, ION EXCHANGE AND CHEMICAL SORPTION CELL WALLS OF MICROBIAL BIOMASS, MAINLY COMPOSED OF POLYSACCHARIDES, PROTEINS AND LIPIDS HAVE ABUNDANT METAL BINDING GROUPS SUCH AS CARBOXYL, SULPHATE, PHOSPHATE AND AMINO GROUPS.

 PHYSICAL

ADSORPTION: TAKES PLACE WITH THE HELP OF VAN DER Waals' forces.AND ELECTROSTATIC INTERACTIONS.

ION

EXCHANGE: Cell walls of microorganisms contain polysaccharides and bivalent metal ions exchange with the counter ions of the polysaccharides.

ACTIVE BIOSORPTION
ACTIVE,

LIVE CELLS, METABOLICALLY

DRIVEN.
TWO

STEPS 1. PASSIVE BIOSORPTION 2. INTRACELLULAR UPTAKE

INTRACELLULAR UPTAKE

METAL SEQUESTERING BY LOW MOLECULAR WEIGHT METABOLIC PRODUCTS (E.G. OXALIC AND CITRIC ACIDS) COMPLEXATION AND CHELATION OF METALS BY SULFIDE AND SIDEROPHORES, ENZYMATICALLY MEDIATED METAL DEPOSITION (E.G. PHOSPHATASE) INFLUX OF METALS TROUGH THE CELL MEMBRANE METAL BINDING BY LOW MOLECULAR WEIGHT PROTEINS (METALLOTHIONEINS) METAL COMPARTMENTALIZATION IN VACUOLES

IMPORTANT FACTORS
CHOICE

OF BIOSORBENT CHOICE OF ELUANT EXPERIMENTAL CONDITIONS INITIAL pH INITIAL METAL CONCENTRATION TEMPERATURE

MATERIALS USED
METAL

REMOVED Cr III IONS ( CrCl3 HEXAHYDRATE)

BIOSORBENT

SACCHAROMYCES CEREVISIAE
ELUANTS

H2SO4, HCl AND CH3COOH OF 0.1, 0.5 AND 1.0 M

YEAST INNOCULUM

(YPD) MEDIUM IS USED FOR REVIVAL AND DEVELOPMENT OF THE INNOCULUM. ABOUT 5G OF YEAST PELLETS ARE USED FOR THE REVIVAL AND IT IS INOCULATED IN 100ML MEDIUM AND KEPT IN A SHAKER FOR ABOUT TWO DAYS.

CONSTITUENTS OF YPD MEDIUM COMPONENTS AMOUNT YEAST EXTRACT 10 G PEPTONE 20 G DEXTROSE 20 G AGAR 20 G DISTILLED WATER 1000ML

EXPERIMENT

BIOMASS WASHED THREE TIMES WITH DISTILLED WATER FOLLWED BY CENTRIFUGATION 50 g OF WET YEAST IS SUSPENDED IN 100ml OF DISTILLED WATER. 25ml OF YEAST SUSPENSION IS ADDED WITH 250ml OF METAL SOLUTION and 50 ml OF THAT SOLUTION IS CENTRIFUGED ( 3 MIN, 3000 RPM ) AND THE YEAST IS REMOVED AND DRIED AT 105 C , UNTIL CONSTANT WEIGHT IS REACHED.

PROCEDURE

250ML OF CR(III) SOLUTIONS WERE PREPARED IN 500MLFLASKS, WITH INITIAL CONCENTRATION OF 10, 25 AND 50 MG CR(III)/L. METAL SOLUTIONS WERE MIXED WITH 25ML OF YEAST SUSPENSION AND INCUBATED AT 30C WITH ORBITAL SHAKING (150 RPM). AFTER 0.25, 0.5, 2 AND 24 H EXPOSURE, 50ML SAMPLES WERE COLLECTED AND BIOMASS, LOADED WITH METAL, WAS SEPARATED BY CENTRIFUGATION (3 MIN, 3000 RPM) AND MIXED WITH ELUANT. THE ELUANT VOLUME USED WAS HALF THE VOLUME OF TREATED METAL SOLUTION, CORRESPONDING TO AN S/L RATIO OF 8 G/L. AFTER 30 MIN OF ELUTION, 10ML SAMPLES WERE CENTRIFUGED TO EVALUATE CHROMIUM RECOVERY.

METAL UPTAKE q = (Ci Cf) V / m

(mg Cr 3+ /g)

RECOVERY Cr recovery = CFEL (VEL /m)/ q * 100 (%)

q is the metal uptake (mg/g) Ci is the Cr(III) initial concentration (mg/L) Cf is the Cr(III) final concentration (mg/L) V is the solution volume (L) m is the biosorbent dry weight (g) CFEL is the Cr(III) final concentration in eluant (mg/L) VEL is the eluant volume (L)

ANALYSIS
UV

spectrophotometer Diphenyl carbazide CrCl3 + 2 KMnO4 + 2 HCl -----------> K2Cr2O7 + 2 MnCl2 + 2 Cl2 +H2O STANDARD CHART

Calibration chart
standard calibration chart
1.8 1.6 1.4 1.2 1 0.8 0.6 0.4 0.2 0 0 0.5 1 ppm

y = 0.791x

absorbance

1.5

2.5

RESULTS AND DISCUSSIONS

EFFECT EFFECT

OF INITIAL pH

OF INITIAL METAL CONCENTRATION OF SORPTION TIME

EFFECT

BIOMASS

ELUANT CONTACT TIME SELECTION AND METAL RECOVERY

EFFECT OF INITIAL pH
EFFECT OF INITIAL pH ON METAL ION SORPTION
SORPTION EFFICIENCY %

60 50 40 30 20 10 0 3 4 pH 5 6

EFFECT OF INITIAL METAL CONCENTRATION

EFFECT OF INITIAL METAL ION CONCENTRATION ON SORPTION
62 60 58 56 54 52 50 48 46 50 25 10 Cr ION INITIAL CONCENTRATION mg/L
SORPTION EFFICIENCY %

EFFECT OF SORPTION TIME

CHROMIUM UPTAKE FOR DIFFERENT METAL INITIAL CONCENTRATION WITH TIME
7
Cr UPTAKE q mg/g

6 5 4 3 2 1 0 0 10 TIME h 20 30 50 mg/L 25 mg/L 10 mg/L

ADSORPTION ISOTHERMS
FREUNDLICH

ADSORPTION ISOTHERM LANGMUIR ADSORPTION ISOTHERM FREUNDLICH ISOTHERM BASED ON HETEROGENEOUS SURFACE q = K Cf ^(1/N) K SORPTION CAPACITY N SORPTION INTENSITY

LINEARISED FORM OF FREUNDLICH ISOTHERM

ln q = 1/n ln Cf + ln K N = 1.9029 K = 1.105 R = 0.946

FREUNDLICH ISOTHERM
3.5 3 2.5
ln q

y = 0.5309x + 0.086 R2 = 0.8964

2 1.5 1 0.5 0 0 1 2 3 ln Cf 4 5 6

LANGMUIR ISOTHERM
MONOLAYER

COVERAGE q = (qmax) (b) ( Cf ) / (1+ b Cf ) (Cf /q) = (1/ qmax ) + ( Cf /qmax)

q max = 20.20 mg b = 0.01895

LANGMUIR ISOTHERM
16 14 12 10 8 6 4 2 0 0 50 100 cf y = 0.0495x + 2.6003 R2 = 0.9978

cf / q

150

200

250

LANGMUIR ISOTHERM
18 16 14 12 10 8 6 4 2 0 0 50 100 150 200 250 Cf FINAL CONCENTRATION

q METAL UPTAKE

BIOMASS ELUANT CONTACT TIME

SELECTION AND METAL RECOVERY
RECOVERY OF Cr FOR INITIAL CONCENTRATION 50 mg/L BY DIFFERENT ELUANTS OF VARYING MOLARITIES
90 80
RECOVERY %
0.1 M H2SO4 1.0 M HCl 0.5 M HCl 0.1 M HCl 1.0 M CH3COOH 0.5 M CH3COOH 0.1 M CH3COOH

1.0 M H2SO4 0.5 M H2SO4

70 60 50 40 30 20 10 0 0.083 0.25 TIME h 0.5 1

RECOVERY OF Cr FOR INITIAL CONCENTRATION 25 mg/L BY DIFFERENT ELUANTS OF VARYING MOLARITIES

70 60
RECOVERY %

1.0 M H2SO4 0.5 M H2SO4 0.1 M H2S04 1.0 M HCl 0.5 HCl 0.1 M HCl 1.0 M CH3COOH 0.5 M CH3COOH 0.1 M CH3COOH 0.083 0.25 TIME h 0.5 1

50 40 30 20 10 0

RECOVERY OF Cr FOR INITIAL CONCENTRATION 10 mg/L BY DIFFERENT ELUANTS OF VARYING MOLARITIES 80 70 60 1.0 M H2SO4 0.5 M H2SO4 0.1 M H2SO4 1.0 M HCl 0.5 M HCl 0.1 M HCl 1.0 M CH3COOH 0.5 M CH3COOH 0.1 M CH3COOH

RECOVERY %

50 40 30 20 10 0 0.083 0.25 TIME h 0.5 1

CONCLUSIONS

SORPTION EFFICIENCY IS 52 % AT THE OPTIMUM PH 5 AND LOWER AT OTHER PH VALUES. SORPTION EFFICIENCY % DECREASED AS THE INITIAL METAL CONCENTRATION WAS INCREASED AND FOUND TO BE 60 , 57 AND 52 FOR 10 , 25 AND 50 MG/L RESPECTIVELY. METAL UPTAKE INCREASED WITH THE INCREASE IN THE SORPTION TIME. METAL RECOVERY INCREASED FOR ACETIC ACID WITH RESPECT TO THE BIOMASS AND ELUANT CONTACT TIME.

FUTURE WORK

TAMARINDUS INDICA SEEDS, BACILLUS SPECIES, PAPAYA WOOD BARKS , CONE BIOMASS OF PINUS SYLVESTRIS, WHEAT SHELL, RICE BARN, PAPER MILL WASTES, FRUIT JUICE JUICE WASTES, THIOBACILLUS FERROOXIDANS, CHLORELLA VULGARIS ETC. TAMARINDUS INDICA SEEDS HAS THE METAL REMOVAL PERCENTAGE OF ABOUT 80. HENCE OF REMOVAL OF CR USING TAMARINDUS INDICA SEEDS IS TO BE DONE.

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