stable isotopes application for contaminated site ... · stable isotopes application for...

Stable isotopes application for

contaminated site characterization and

remediation

Dr. Massimo Marchesi (PIF)

Massimo Marchesi

Brief introduction about contaminated sites

Stable isotopes and CSIA applications

Analitical, laboratory and field results

Perspectives

Massimo Marchesi

Importance

• 2,5 milions of contaminated sites in EU

• > 340.000 to be remediated

Menagement costs

€ 2.4-17.3 billions /year

~ 50% Public Expediture

(€10 per capita)

https://www.nap.edu/read/14668/chapter/

4

Massimo Marchesi

Importance

• > 700.000 Ha, (>2% land - Italy)

• water quality loss

Progetto Plumes

Progetto Plumes

Massimo Marchesi

What stable isotopes and CSIA can do?

• Fingerprinting – tracking responsabilities (Pulluter pays principle)

Progetto Plumes

Massimo Marchesi

What stable isotopes and CSIA can do?

• Remediation assesmentISCO

Enhanced bioremediation

P&T

PRBPHISICAL BARRIERS

https://clu-in.org/products/newsltrs/tnandt/view_new.cfm?issue=1212.cfm

Massimo Marchesi

Monitored natural attenuation (MNA)

http://www.premiercorp.ca/old/ricker-plume-stability-method.html

http://www.environmentalrestoration.wiki/index.php?title=Monitored_Natural_Attenuation_(MNA)

Massimo Marchesi




Perspectives

Massimo Marchesi

From greeck greco ἴσος (isos) τόπος

(topos) means «same place") atom

with same atomic number but differnt

masses (different number of

neutrons)

ISOTOPES

Massimo Marchesi

Notation

TCE

13C

13C

13

12 12

12

12

12

13

13

13

12

13

Molecules with light isotope

Molecules with heavy isotope

12C 98.93 13C 1.07%

2H 99.99 1H 0.01%

12

12

12

12

12

12

12

12

12

12

12

R = 0.010867

δ = -80 ‰

Element Relative ab. (%) Standard Abbreviat. Abund. ratio

Hydrogen 1H 99.985 2H 0.015 Vienna standard Mean Ocean water VSMOW 1.5575 x10-4

Carbon 12C 98.89 13C 1.11% Carbonate from Vienna Pee Dee

Belemnite

VPDB 0.011237

Chlorine 35Cl 75.8 37Cl 24.2 Chloride ion in ocean water Standard

Mean Ocean Chloride

SMOC 0.324

Massimo Marchesi

http://www.cefns.nau.edu/geology/naml/Meteorite/Book-GlossaryC.html

VP

DB

+8 ‰-33 ‰-80 ‰

δ = +8 ‰

δ = -33 ‰δ = -80 ‰

+0 ‰

δ = +0 ‰R = 0.011327

R = 0.010867R = 0.010338

R = 0.011237

Isotope ratio (relative) Isotope ratio (absolute) Abondance

1,12 98,88

1,07 98,931,02 98,98

1,11 98,89

13C (%) 12C (%)

Enrichm

ent D

eple

tion

Enrichm

ent D

eple

tion

Differences

Massimo Marchesi

from Shouakar-Stash et al. 2003

Modified from EPA, 2008

Differences in VOCs: fingerprinting

Massimo Marchesi

13

12 12

12

12

12

13

13

13

13

12

12

12 12

13

TCE released

1313

1313

12

TCE remaining

12

12

12

12

13

cis-DCE produced

12

13

Molecules with light isotope

Molecules with heavy isotope

Conce

ntr

atio

n

TCE remaining

cis-DCE produced

Isoto

pic

com

posi

tion [‰

]

d13

CTCE

Time (or Distance)

Biodegradation: isotope fractionation


Massimo Marchesi

d13Cr,0= -18.5‰

in the focus

e (-1.7 to -8.8 ‰)

Biodegradation

5 - 25%

40 – 75%

Biodegradation: isotope fractionation

Massimo Marchesi

....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

Biodegradation & isotopic fractionation

Massimo Marchesi




Perspectives

Massimo Marchesi

OBJECTIVES

CSIA

To develop a tool-box

CSIA

MBTs

Modeling

1999 13C-CSIA (UW)

2005 PoliMi (Dr. Alberti)

2006 37Cl-CSIA (UW) 2013 2H-CSIA (UW)

2013-2019 Fingerprinting/AMIIGA (Dr. Alberti)

Massimo Marchesi

TEAM

Luca Alberti, Ilaria Pietrini & Massimo Marchesi

IST. DONEGANI - TEAMB:

Francesca de Ferra

Giovanna Carpani

GEOLAB (E&P)

Corrado Barbieri

Roberto Galimberti

SYNDIAL

Danilo Antonellini

Luciano Zaninetta

Andrea Franzetti, Tatiana Stella

Prof. Ramon AravenaProf. Orfan Shouakar-Stash

MASSIMO MARCHESI

Massimo Marchesi

APPROACH

Massimo Marchesi

MCB and CSIA

37Cl/35Cl

2H/1H

13C/12C

AEROBIC C6H5Cl (O2) → CO2

no 13C enrichment

DEHALOGENATION C6H5Cl → C6H6 (benzene)13C enrichment approx. -5 ‰

from Shouakar-Stash et al. 2003

SOURCE DIFFERENTIATION


NATURAL ATTENUATIONPROCESSES DISTINGUISHAL

Zwank et al, 2005

MASSIMO MARCHESI

Massimo Marchesi

13C-CSIA development (Milano)

10 - 20 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

Massimo Marchesi

RESULTS (1): Aerobic biodegradation

pure cultureSphingomonas

groundwater(A) O2 only / (B) O2 + nutrients

soil slurry(A) O2 only / (B) O2 + nutrients

(A) O2 only

(A) O2 only

MASSIMO MARCHESI

Massimo Marchesi

RESULTS (2): Anaerobic biodegradation

pure cultureDehalococcoides

groundwater(A) anoxic / (B) nutrients / (C) AF

soil slurry(A) anoxic / (B) nutrients / (C) AF

nutrients nutrients

nutrients

nutrients

MASSIMO MARCHESI

AF AF

Massimo Marchesi

ANALYTICAL ADVANCEMENTS

2) 37Cl\35Cl – CSIA for MCB

at IT2 (CANADA)

3) A continuous-flow method was developed for 2H–CSIA; δ2H values were measured with an

analytical error of ± 4 ‰ (similar method as for

Shouakar-Stash and Drimmie, 2013).

AEROBIC C6H5Cl (O2) → CO2 no 13C enrichment

ANAEROBIC no 13C enrichment

No infos about:37Cl or 2H

Massimo Marchesi

37 Cl CSIA method development (Waterloo, Canada)

MASSIMO MARCHESI

Massimo Marchesi

Ɛ in between 0.6 – 0.7 ‰

37 Cl results for aerobic

ln R

/R0

MASSIMO MARCHESI

Massimo Marchesi

37 Cl and 13 C (dual isotope approach)

AE

RO

BIC

MASSIMO MARCHESI

Massimo Marchesi

LABORATORY RESULTS

Potential for aerobic biodegradation

Potential for anaerobic biodegradation

BUT No dehalogenation processes

Potential for using δ 37Cl to

evaluate natural attenuation

Potential for using δ37Cl/δ13C for

processes distinguishal

MASSIMO MARCHESI

Massimo Marchesi

-40,4 δ 13C ‰

FIELD RESULTS

10 – 100 ug/L

100 – 1000 ug/L

> 1000 ug/L

MASSIMO MARCHESI

I---------------------I500 m

Massimo Marchesi

13C-CSIA results

Massimo Marchesi

37Cl-CSIA results

Massimo Marchesi

SOURCE 2

SOURCE 1

att

en

ua

tio

n

MASSIMO MARCHESI

P-1

P-5

P-6P-10

P-3

P-2

P-9

P-8B-28

P-86B-27

B-53

P-84

37Cl-CSIA results

Massimo Marchesi

CSIA results

Massimo Marchesi

CONCLUSIONS

1) Analytical facility for 13C CSIA

was implemented in Milan, Italy

2) 37Cl and 2H CSIA methodology

was developed

3) measurable ε for 37Cl were estimated for

aerobic biodegradation of MCB

4) 37Cl coupled with 13C and 2H was applied for sources

apportionment and natural attenuation evaluation at a

contaminated field site

MASSIMO MARCHESI

5) Additonal tools such BMTs, modeling, multilevel

sampling were also developed

Massimo Marchesi




Perspectives

Massimo Marchesi

MULTIDISCIPLINARY APPROACH

37Cl, 13C e 2H – CSIA for chlorinated solvents

DGGE, qPCE ecc. – MBTs in different conditions, aerobic, anaerobic…

Numerical modeling

Innovative sampling techniques

1,00E+00

1,00E+02

1,00E+04

1,00E+06

1,00E+08

1,00E+10

T0 sedT2 sed+NT2

n°copyg-1

PZ9_916S

tod

Massimo Marchesi

MULTILEVELS

Massimo Marchesi

MODELING

P9

P10

Massimo Marchesi

CSIA knoledgew transfer

Integrated Approach to Management of

Groundwater quality In functional urban Areas

Massimo Marchesi

Acknowledgements

Pietrini, Antelmi, Colombo e tutto il gruppo di Geoscienze

Andrea Franzetti, Tatiana Stella

Prof. Ramon AravenaProf. Orfan Shouakar-Stash

MASSIMO MARCHESI

Dr. Luca Alberti

Prof. Giampaolo Rosati

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