Upload
lymien
View
243
Download
1
Embed Size (px)
Citation preview
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
Brief introduction about contaminated sites
Stable isotopes and CSIA applications
Analitical, laboratory and field results
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
Modified from EPA, 2008
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
Brief introduction about contaminated sites
Stable isotopes and CSIA applications
Analitical, laboratory and field results
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
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
Modified from EPA, 2008
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
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
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
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
Brief introduction about contaminated sites
Stable isotopes and CSIA applications
Analitical, laboratory and field results
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
CSIA knoledgew transfer
Integrated Approach to Management of
Groundwater quality In functional urban Areas