Stable isotopes application for contaminated site characterization and remediation. Dr. Massimo Marchesi (PIF)

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1 Stable isotopes application for contaminated site characterization and remediation Dr. (PIF)

2 Brief introduction about contaminated sites Stable isotopes and CSIA applications Analitical, laboratory and field results Perspectives

3 Importance 2,5 milions of contaminated sites in EU > to be remediated 4 Menagement costs billions /year ~ 50% Public Expediture ( 10 per capita)

4 Importance > Ha, (>2% land - Italy) Progetto Plumes water quality loss Progetto Plumes

5 What stable isotopes and CSIA can do? Fingerprinting tracking responsabilities (Pulluter pays principle) Progetto Plumes

6 What stable isotopes and CSIA can do? ISCO Remediation assesment Enhanced bioremediation P&T PRB PHISICAL BARRIERS

7 Monitored natural attenuation (MNA)

8 Brief introduction about contaminated sites Stable isotopes and CSIA applications Analitical, laboratory and field results Perspectives

9 ISOTOPES From greeck greco ἴσος (isos) τόπος (topos) means «same place") atom with same atomic number but differnt masses (different number of neutrons)

10 Notation C TCE C C 1.07% 2 H H 0.01% R = C Molecules with light isotope Molecules with heavy isotope δ = -80 Element Relative ab. (%) Standard Abbreviat. Abund. ratio Hydrogen 1 H H Vienna standard Mean Ocean water VSMOW x10-4 Carbon C C 1.11% Carbonate from Vienna Pee Dee Belemnite Chlorine 35 Cl Cl 24.2 Chloride ion in ocean water Standard Mean Ocean Chloride VPDB SMOC 0.324

11 Enrichment Enrichment VPDB Differences Isotope ratio (relative) Isotope ratio (absolute) Abondance C (%) C (%) δ = +8 δ = +0 δ = -33 δ = -80 Depletion R = 0.07 R = R = R = , 98,88 1,11 98,89 1,07 98,93 1,02 98,98 Depletion

12 Differences in VOCs: fingerprinting Modified from EPA, 2008 from Shouakar-Stash et al. 2003

13 Concentration Biodegradation: isotope fractionation Modified from EPA, 2008 TCE released cis-dce produced TCE remaining cis-dce produced Isotopic composition [ ] d C TCE TCE remaining Molecules with light isotope Molecules with heavy isotope Time (or Distance)

14 Biodegradation: isotope fractionation d C r,0 = in the focus e (-1.7 to -8.8 ) Biodegradation 5-25% 40 75%

15 Biodegradation & isotopic fractionation...the traditional approach of monitoring a reduction in the concentrations of contaminants at sites often does not offer compelling documentation that the contaminants are actually being degraded. When data on concentrations are the only data available, it is difficult or impossible to exclude the possibility that the reduction in contaminant concentrations are caused by some other process such as dilution or dispersion, or that the monitoring wells failed to adequately sample the plume of contaminated ground water. Stable isotope analyses can provide unequivocal documentation that biodegradation or abiotic transformation processes actually destroyed the contaminant. from EPA, 2008

16 Brief introduction about contaminated sites Stable isotopes and CSIA applications Analitical, laboratory and field results Perspectives

17 OBJECTIVES 1999 C-CSIA (UW) Cl-CSIA (UW) 20 2 H-CSIA (UW) 2005 PoliMi (Dr. Alberti) CSIA Fingerprinting/AMIIGA (Dr. Alberti) To develop a tool-box CSIA MBTs Modeling

18 TEAM Luca Alberti, Ilaria Pietrini & IST. DONEGANI - TEAMB: Francesca de Ferra Giovanna Carpani GEOLAB (E&P) Corrado Barbieri Roberto Galimberti Andrea Franzetti, Tatiana Stella SYNDIAL Danilo Antonellini Luciano Zaninetta Prof. Ramon Aravena Prof. Orfan Shouakar-Stash MASSIMO Massimo MARCHESI Marchesi

19 APPROACH

20 MCB and CSIA 37 Cl/ 35 Cl PROCESSES SOURCE NATURAL DIFFERENTIATION ATTENUATION DISTINGUISHAL 2 H/ 1 H from Shouakar-Stash et al Modified from EPA, 2008 C/ C Zwank et al, 2005 AEROBIC C 6 H 5 Cl (O 2 ) CO 2 no C enrichment DEHALOGENATION C 6 H 5 Cl C 6 H 6 (benzene) C enrichment approx. -5 MASSIMO Massimo MARCHESI Marchesi

21 C-CSIA development (Milano) µg/l Set-up for MCB, Benzene, 1,2- DCA e 1,1,2- TCA. Low error 0,1 a 0,4 Good detection limits

22 RESULTS (1): Aerobic biodegradation pure culture Sphingomonas groundwater (A) O 2 only / (B) O 2 + nutrients (A) O 2 only soil slurry (A) O 2 only / (B) O 2 + nutrients (A) O 2 only MASSIMO Massimo MARCHESI Marchesi

23 RESULTS (2): Anaerobic biodegradation pure culture Dehalococcoides nutrients AF nutrients AF groundwater (A) anoxic / (B) nutrients / (C) AF nutrients nutrients soil slurry (A) anoxic / (B) nutrients / (C) AF MASSIMO Massimo MARCHESI Marchesi

24 ANALYTICAL ADVANCEMENTS AEROBIC C 6 H 5 Cl (O 2 ) CO 2 no C enrichment ANAEROBIC no C enrichment No infos about: 37 Cl or 2 H 2) 37 Cl\ 35 Cl CSIA for MCB at IT 2 (CANADA) 3) A continuous-flow method was developed for 2 H CSIA; δ 2 H values were measured with an analytical error of ± 4 (similar method as for Shouakar-Stash and Drimmie, 20).

25 37 Cl CSIA method development (Waterloo, Canada) MASSIMO Massimo MARCHESI Marchesi

26 37 Cl results for aerobic ln R/R0 Ɛ in between MASSIMO Massimo MARCHESI Marchesi

27 37 Cl and C (dual isotope approach) AEROBIC MASSIMO Massimo MARCHESI Marchesi

28 LABORATORY RESULTS Potential for aerobic biodegradation Potential for anaerobic biodegradation BUT No dehalogenation processes Potential for using δ 37 Cl to evaluate natural attenuation Potential for using δ 37 Cl/δ C for processes distinguishal MASSIMO Massimo MARCHESI Marchesi

29 FIELD RESULTS > 1000 ug/l ug/l ug/l -40,4 δ C 500 m I I MASSIMO Massimo MARCHESI Marchesi

30 C-CSIA results

31 C-CSIA results

32 37 Cl-CSIA results

33 37 Cl-CSIA results attenuation P-6 P-10 P-5 P-3 SOURCE 2 P-2 P-1 P-84 P-86 P-8 P-9 B-27 B-28 B-53 SOURCE 1 MASSIMO Massimo MARCHESI Marchesi

34 CSIA results

35 CONCLUSIONS 1) Analytical facility for C CSIA was implemented in Milan, Italy 2) 37 Cl and 2 H CSIA methodology was developed 3) measurable ε for 37 Cl were estimated for aerobic biodegradation of MCB 4) 37 Cl coupled with C and 2 H was applied for sources apportionment and natural attenuation evaluation at a contaminated field site 5) Additonal tools such BMTs, modeling, multilevel sampling were also developed MASSIMO Massimo MARCHESI Marchesi

36 Brief introduction about contaminated sites Stable isotopes and CSIA applications Analitical, laboratory and field results Perspectives

37 MULTIDISCIPLINARY APPROACH 1,00E+10 1,00E+08 16S tod PZ9_9 n copy g -1 1,00E+06 1,00E+04 1,00E+02 1,00E+00 T0 sed T2 sed+n T2 37 Cl, C e 2 H CSIA for chlorinated solvents DGGE, qpce ecc. MBTs in different conditions, aerobic, anaerobic Numerical modeling Innovative sampling techniques

38 MULTILEVELS

39 MODELING P9 P10

40 CSIA knoledgew transfer Integrated Approach to Management of Groundwater quality In functional urban Areas

41 Acknowledgements Pietrini, Antelmi, Colombo e tutto il gruppo di Geoscienze Dr. Luca Alberti Prof. Giampaolo Rosati Andrea Franzetti, Tatiana Stella Prof. Ramon Aravena Prof. Orfan Shouakar-Stash MASSIMO Massimo MARCHESI Marchesi