1 STUDIES OF BIOSORPTION HEAVY METALS IONS BY Spirogyra subsalsa sp. BIOMASS Mawardi 1) , Edison Munaf 2) , Soleh Kosela 3) , Riwandi Sihombing 3), Rahmiana Zein 2) 1) Laboratory of Analytical Chemistry, Faculty of Mathematics and Science, State University Padang, Padang 25131, Indonesia 2) Laboratory of Analytical Environmental Chemistry, Faculty of Mathematics and Science, Andalas University, Padang 25163, Indonesia 3) Laboratory of Chemistry, Faculty of Mathematics and Science, Indonesia University, Depok 16424, Indonesia METHODS In this research was learned about function of functional group in algae S. subsalsa sp biomass in course of biosorption each Pb2+, Cu2+, Cd2+, Zn2+, Cr3+ and Cr6+ cations, by treating biomass by chemical modification of carboxyl, carbonyl and amino groups, that is methanol 99%, glycol, and mixture formaldehyde and formic acid, influence of immobilization of biomass within polysilicate matrix to absorption capacities. Optimation condition of regeneration column by nitrate acid, HNO3, and recovery column and application of column to remove and preconcentration trace element from waste waters.
RESULTS • •
•
Treating of biomass by chemical modification, that is methanol 99%, glicol, and mixture formaldehyde and formic acid to cause decrease in cation sorption capacity of biomassa for Pb2+, Cd2+, Zn2+, and Cr3+ cations. The exemption for Cu2+, which the biomass treated by methanol, and Cr6+, which the biomass treated by glicol, and mixture formaldehyde and formic acid increasingly in cation sorption capacity of biomassa, 10,46%; 116,50% and 41,78%, respectively. The biomass was treated by mixture formaldehyde and formic acid showing very keen sorption capacity degradation to each Pb2+, Cd2+, Zn2+, and Cr3+, that are 91,27; 85,39; 79,96; 91,30 and 55,91% respectively, except to Cr6+, what is in condensation of there are in species Cr2O72- anion, sorption capacities increase 41,78%.
Generally, immobilization biomass by sodium silicate cause to increase sorpsion capacity of biomass, specially Cr6+, sorption improvement more than 100%, that is 2,27 mg/g for pure biomassa and 5,77 mg/g for
2 immobilized biomass. The increase of sorption capacity immobilized biomass each Pb2+, Cd2+, Zn2+, and Cr3+ cations are 4,25; 15,95; 8,84 and 3,49%. While for metal Cr6+ absorbtion increase to 153,74 %. Desorption of the adsorption Pb2+ significantly proportional with used nitrate acid concentration, that is more 89% at 0,5 M HNO3, while for Cu2+ at 0,05 M HNO3 have desorbed about 60%. While desorbed Cd2+ and Zn2+ cations were washed once with HNO3 0,5 M more than 80%. The biosrption process of cations by immobilized biomass was a rapid process, wherein more than 50% of the final uptake value occur at rate flow 50 drops/minute.
Effect of metals concentration on biosorption of modification carboxyl group of Spyrogira subsalsa sp by methanol 99%. 10 9
Metal Uptake (mg/g)
Pb(II)
8 7
Cu(II)
6
Zn(II)
5
Cr (III)
4
Cr (VI)
Cd(II)
3 2 1 0 0
100
200
Solution of Concentration
300
3
FTIR Spectrum of modification and unmodification of spirogyra subsalsa sp fungsional group by methanol 99%
2 7.8 2 7 2 6 2 3 5 8533 2 806 3 4 743 2 3 2 2 2 1 2 %T 0 1 9 1 8 1 7 1 6 1 5 1 4 1 3 1 2.04000. 3 0 600
617 15 42 1651
2 3 3 200
2 800
2 400
2 000
1 800 cm1
1 600
1 400
1052 1 200
1 000
80 0
60 0
450. 0
Effect of metals concentration on biosorption of modification carbonyl group of Spyrogira subsalsa sp by glycol 10
M etal Up ta ke (mg/g)
9 8
Pb(II)
7 6
Cu(II)
5
Cd(II)
4
Zn(II)
3
Cr (III)
2
Cr (VI)
1 0 0
100
200
300
Solution of Concentration
400
%T
4 FTIR Spectrum of modification and unmodification of spirogyra subsalsa sp fungsional group by glycol 2 7.8 2 7 2 6 2 5 2 4
3 853 3 806 3 743
2 3
617
2 2 2 1 2 0
1408
1 9 1 8
1542
2928
1 7 1 6
10521
1 5
1651
1 4
3406
1 3 1 2.0
4000. 0
3 600
3 200
2 800
2 400
2 000
1 800
cm1
1 600
1 400
1 200
1 000
80 0
60 0
450. 0
5
Metal Uptake (mg/g)
Effect of metals concentration on biosorption of modification amine group of Spyrogira subsalsa sp by mixture of formic acid and formaldehide
4 3.5 3 2.5 2 1.5 1 0.5 0
Pb(II) Cu(II) Cd(II) Zn(II) Cr (III) Cr (VI)
0
50
100
150
200
250
300
Solution of Concentration FTIR Spectrum of modification and unmodification of spirogyra subsalsa sp fungsional group by mixture of formic acid and formaldehide
2 7.8 2 7 2 6 2 3 5 8533 2 8063 4 743 2 3 2 2 2 1 2 %T 0 1 9 1 8 1 7 1 6 1 5 1 4 1 3 1 2.04000. 3 0 600
617 1 1
2 928 3 406 3 200
2 800
1052
1 651 2 400
2 000
1 800 cm1
1 600
1 400
1 200
1 000
80 0
60 0
450. 0
6 Biosorption capacities of modification and unmodification biomass to Pb(II) and Cu(II)
16
Pb (II)ad s (mg/g)
14
11.23 19,33%
12
Unmodification biomass
12.15 37,45%
9.06
91,27%
Modification biomass
7.8
10
6.07
8 6 4
0.84
2 0
carboxyl
carbonyl
Amine
Functi onal Group
Cd(II) ads (mg/g)
Biosorption capacities of modification and unmodification biomass to Cd(II) and Zn(II) Unmodification Biomass
7 6 5
Modification Biomass
5.39
5.15
5.15 4.09
3.75
4 3 2
1.08
1 0 CarboxylCarbonyl Amine Fungsional Group
Cromi um(III) ads (mg/g)
7
7 6
Unmodification Biopmass
5.04
5.04
5
Modification Biomass
3.93
4 2.5
3
2.325
2
1.025
1 0 Carboxyl
Carbonyl
Amine
Fungsional Group
Biosorption capacities of modification and unmodification biomass to Cr(II) and Cr(VI)