How to Resolve Unresolved Complex Mixture

Transcription

1 Seminar and Workshop: Environmental Protection Prevention, Monitoring and Remediation - Worldwide and Our Experiences How to Resolve Unresolved Complex Mixture Vladimir P. Beškoski Department of Biochemistry, Faculty of Chemistry University of Belgrade, Belgrade, Serbia vbeskoski@chem.bg.ac.rs Institut Vinča

2 ENVIRONMENT IN SERBIA Europe ~ 1,800,000 potentially contaminated sites/240,000 sites require remediation! Official data from Serbia heavy polluted sites! 2

3 Locations of known illegal dumps in the territory of the Republic of Serbia, REPORT ON THE STATE OF THE ENVIRONMENT IN SERBIA 2009, Ministry of Environment and Spatial Planning 3 3

4 THE ESSENCE OF BIOREMEDIATION HARMFUL SUBSTANCES BIOLOGICAL AGENT MICROORGANISMS SUBSTANCES WITHOUT HARMFUL EFFECT ON THE ENVIRONMENT AND HUMANS + BIOMASS GREEN BIO/TECHNOLOGY!!! 4

5 BIOREMEDIATION FROM LABORATORY VIA PILOT 150m 3 of soil in Oil Refinery Pančevo TO INDUSTRIAL SCALE m 3 of soil, JKP BE

6 BIOREMEDIATION FROM LABORATORY TO INDUSTRIAL SCALE Methods Biochemical Microbiological Chemical 6

7 LABORATORY LEVEL Reduction of Total Petroleum Hydrocarbons (TPH) in experiments on the laboratory shaker (Erlenmeyer flasks) - gravimetric method No. Sample 1. 3NST8 TPH (g/kg) 0 days 120 days Reduction of TPH (%) 48, NST8-SG* 103,2 38, NST8-BS* 14, NS Sludge 221, NS Sludge-SG 412,5 88, NS Sludge-BS 47, The degradation rate was from 1,8 6,4 g/kg/day. *Surface active substances 7

8 log No. of microorganisms (CFU/g) LABORATORY LEVEL BASIC MICROBIOLOGICAL DATA TIME (days) TC ANA HD YM Ps. Bac. 8 TC-Total Chemoorganoheterotrophs; ANA Anaerobic microorganisms; HD Hydrocarbon degraders; YM Yeast and Molds; Ps. Pseudomonas spp.; Bac. Bacillus spp. Milic et al., J Serb Chem Soc 2009;74:455-60

9 Graphical representation of the dynamics of pilot bioremediation in the function of time 0-60 days 173 mg/kg/day ~30 g/kg days 292 mg/kg/day 21,5 Total: 151 mg/kg/day days 64 mg/kg/day 7,8 2,2 g/kg (~93%) 9 Jovančićević et al., Water Air and Soil Pollution 2008; 190:

10 Comparative gas chromatograms of TPH at the beginning (Start) and after the completed bioremediation (End) at the pilot biopile Start End (180 days) 10 Miletić et al., CLEAN Soil, Air, Water 2014;42:

11 GAS CHROMATOGRAPHY IN Reduction of TPH 5,2 BIOREMEDIATION UCM Unresolved Complex Mixture GC-FID 2,1 1,3 0,3 11 Average rate of biodegradation 0-50 days: 62 mg/kg/day days: 16 mg/kg/day days: 20 mg/kg/day Beškoski et al., Chemosphere 2011;83:34-40

12 GC-MS analysis - SIM mode Fragmentograms of the isoprenoids (SIM, m/z 183) of the alkane fractions in the samples S-0 and S Beškoski et al., J Serb Chem Soc 2010;75:

13 GC-MS analysis - SIM mode Fragmentograms of terpanes (SIM, m/z 191) of alkane fractions in samples S-0 and S-150. Fragmentograms of steranes (SIM, m/z 217) of alkane fractions in samples S-0 and S Novaković et al., Environ Chem Lett 2012;10:287 94

14 Comprehensive GCxGC-MS analysis Faculty of Chemistry, University of Belgrade

15 Comprehensive GCxGC-MS analysis UCM finally resolved!

16 BIOCHEMICAL PROFILING OF MICROORGANISMS USING COMPREHENSIVE GCxGC-MS The fatty acid methyl ester profile of Brachybacterium sp. CH-KOV3 a) GC MS; b) 2D GCxGC MS. 16 Djurić et al., Int J Biol Macromol 2017;104: Izrael-Živković et al., Journal of Molecular Catalysis. B, Enzymatic 2017; in press

17 Comprehensive GCxGC-MS posibilities TPH (>1000) PAHs (>16) PCBs (209) Pesticides (>100) Lignin Metabolite profiling (metabolomics) Biodegradation products non targeted analysis Natural products (plant extracts, propolis, honey ) 17 Lama et al., ACS Sustainable Chemistry & Engineering 2017;5: Beškoski et al., CLEAN Soil, Air, Water 2017;45: Kannan et al., Environ Sci Pollut R 2015, in press

18 Thank you for your attention