Journal of Contaminant Hydrology 245 (2022) 103940

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Journal of Contaminant Hydrology

journal homepage: www.elsevier.com/locate/jconhyd

Hydrogeochemical and isotopic evaluation of VOC commingled plumes in a

weathered fractured bedrock aquifer treated with thermal
and bioremediation
SashaT. Hart a, *, Reginaldo A. Bertolo a, Maria S. Agostini b, Roland Feig c, Paulo Lojkasek-Lima a,
José C.R. Gouvea Jr a, Fernanda S. Barreto a, Ramon Aravena d
a
CEPAS Groundwater Research Center, University of Sao Paulo, Rua do Lago, 562, 05508-080 Sao Paulo, SP, Brazil
b
BASF S.A., Av. Brasil, 791, Building E 250, 12521-140 Guaratingueta, SP, Brazil
c
BASF SE, Carl-Bosch-Strasse 38, 67056 Ludwigshafen am Rhein, Germany
d
Department of Earth and Environmental Sciences, University of Waterloo, 200 University Avenue West, N2L 3G1 Waterloo, Ontario, Canada

A R T I C L E I N F O A B S T R A C T

Keywords: Chlorinated ethanes and ethenes isotopic analyses in groundwater and hydrogeochemical results from a former
Commingled plumes industrial area in Sao Paulo (Brazil) were used to confirm the existence and allow further characterization of
Isotopic fingerprinting source areas and their commingled plumes, both before and after thermal and bioremediation treatments. Prior
Chlorinated ethanes and ethenes
to full scale remediation, a recently identified off-site source area with unknown history and limited access for
Thermal remediation
Bioremediation
further intrusive works presented lower δ13C values (− 6.5‰ to − 1.8‰ for 1,2-DCA) than the downgradient on-
site source area (+8.6‰ to +20.0‰). Intermediate δ13C values for 1,2-DCA were identified further downgradient
from the sources, within commingled plumes patterns. The isotope and concentration results show the typical
degradation patterns associated with biotic reductive dechlorination for chlorinated ethenes and dihaloelimi­
nation for 1,2-DCA. Results following remediation treatments show further levels of isotopic enrichment, for
chlorinated ethenes and chlorinated ethanes in the tropically weathered and deeper fractured bedrock (gneisses)
groundwater. Hydrogeochemical results, isotopic mass balance and Carbon-Chlorine isotope slopes data are
coherent with remediation treatment and a complex commingled plume setting. The results of this study
confirmed the Temporal Conceptual Model proposed by Hart et al. (2021) and identified the need for further
studies to evaluate isotopic dynamics under thermal remediation, including thermal-induced hydrolysis
processes.

1. Introduction (Parker, 2007; L'Apiccirella, 2009; Lojkasek-Lima et al., 2012; Bertolo,

Chlorinated ethenes and ethanes are some of the most frequent
contaminants detected in groundwater systems. They have typically
been used as solvents within industrial production processes and, mainly
during the second half of the last century, they infiltrated the ground due
to spills or improper residue disposal. Characteristics, such as high
density and solubility, favoured them being mobilized to deep levels and
transported with groundwater over long distances, making remediation
very challenging (Parker, 2007; Hunkeler et al., 2011; Barbosa, 2019;
Murray et al., 2019). Multiple source areas with plumes under pumping
influence of supply wells often exist at industrial regions, which add
complexity to the characterization of chlorinated compounds plumes
2017). Furthermore, groundwater may be contaminated within a com­
mingled plume configuration, mixing contaminants from more than one
source area, potentially including unidentified polluters. Management
of such complex scenarios, including remediation strategies, requires
investigation using multiple lines of evidence and a setup of robust
conceptual models (Kresic and Mikszewski, 2013; ITRC, 2017; Hart
et al., 2021).
Traditional contaminant composition and concentration data, when
evaluated alone, can be of limited use for the forensic determination of
chlorinated ethenes and ethanes sources, due to the effect of other
processes such as dilution and degradation (Nijenhuis et al., 2013). In
addition, complex areas typically present higher levels of uncertainties,

* Corresponding author.
E-mail address: sasha.hart@usp.br (SashaT. Hart).

https://doi.org/10.1016/j.jconhyd.2021.103940
Received 27 April 2021; Received in revised form 15 December 2021; Accepted 24 December 2021
Available online 4 January 2022
0169-7722/© 2022 Elsevier B.V. All rights reserved.
SashaT. Hart et al.
for example within a commingled plume scenario (ITRC, 2017). Various
other tools may be employed together, such as high resolution drilling,
tracer testing, microbial evaluation and compound specific isotopic
analysis (Hunkeler et al., 2004; Blessing et al., 2009; Eccarius et al.,
2012; Lojkasek-Lima et al., 2012; Nijenhuis et al., 2013; Kaown et al.,
2016; NJDEP - New Jersey Department of Environmental Protection,
2017). The potential to fingerprint chlorinated organic compounds in
source areas was first suggested by van Warmerdam et al. (1995) based
on the isotopic analysis of specific synthetic chlorinated organic values
for different producers. The number of publications on forensic studies
using the isotope tool in contaminated areas is increasing however often
limited by legal aspects and confidentiality agreements (Philp, 2015;
Teixeira and Abreu, 2018).
The isotopic signatures can change over time due to natural or
induced degradation processes; however isotopic analyses and mass
balances can assist in recognizing the fractionation patterns and path­
ways of degradation. A guide for assessing biodegradation with single or
multiple isotopes, including several studies, was published by USEPA
(2008) and confirms its vast potential. In recent years, the database for
the application of the dual and triple isotope approach has continuously
expanded including a large amount of contaminants, degradation
pathways and other complexity factors (Shouakar-Stash et al., 2011;
Palau et al., 2014; Palau et al., 2017a; Palau et al., 2017b; Gafni et al.,
2018; Torrentó et al., 2021). Regarding the evaluation of thermal
remediation processes by using isotope tools there is a limited amount of
publications. Badin et al. (2016) and Murray et al. (2019) evaluated
their effects at a site in Denmark based on the evolution of isotopes for
tetrachloroethylene (PCE) degradation pathways.
The Metropolitan Region of Sao Paulo, Brazil, presents a high po­
tential for the existence of unidentified commingled plumes in its
aquifers mainly in the historic extensive industrial neighbourhoods. The
public water supply system uses surface water reservoirs however it is
supplemented by private wells, which are estimated to be beyond
12.000 (FUSP, 2009). Comprehensive analytical monitoring data of the
supply wells is limited, however contamination with chlorinated sol­
vents compounds and several management challenges have been iden­
tified and characterized (Hart et al., 2007; L'Apiccirella, 2009; Fanti
et al., 2017; Bertolo, 2017; Lojkasek-Lima, 2018; Barbosa, 2019; Hart
et al., 2021).
The study area of this paper is located in the Metropolitan Region of
Sao Paulo and presents a long industrial history and intensive ground­
water use of the fractured crystalline bedrock aquifer until impacts by
organic compounds were identified in bedrock wells. For approximately
15 years it was understood this was related to an on-site source (where
chlorinated ethanes predominated, with lower content of chlorinated
ethenes). Then an off-site source area (where chlorinated ethenes pre­
dominated, with lower content of ethanes) was initially identified with a
limited number of boreholes near the upgradient boundary of the
adjacent industry. The source area extent, history and plumes were
unknown and access was restricted due to existing infra structure and
activities. This indicated there was potential for commingling with on-
site plumes in addition to limitations for further intrusive works.
The main objectives of this study were to further confirm chlorinated
ethane and ethene source areas and characterize commingled plumes
distribution and degradation, before and after thermal and bioremedi­
ation treatment at the on-site source area. Hydrogeochemical ap­
proaches, including compound specific stable isotope analyses (CSIA) of
chlorinated ethenes and ethanes, were selected and applied. A dual
Carbon-Chlorine isotope approach was also used to contribute to a
better understanding of the chlorinated compounds degradation
pathways.
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Journal of Contaminant Hydrology 245 (2022) 103940
2. Study site description
2.1. Hydrogeology and temporal conceptual site
The study area was a former chemical industry within the Metro­
politan Region of Sao Paulo, Brazil (see Fig. 1). Over almost a century,
the region was mainly of industrial use, but within the last two decades it
is transforming into a more commercial and residential use. The
research area is in the alluvial plain of a river, which is historically
subject to flooding. The total annual precipitation rate is around 1400
mm, with the highest monthly precipitation rate up to 300 mm in
January. Historic annual average temperature is approximately 20 ◦ C.
Groundwater was extracted for the industrial process from the deep
fractured bedrock aquifer by the operation of two on-site groundwater
supply wells PP-02 and PP-05 (open borehole in the fresh rock and with
a total depth of 250 m). When traces of chlorinated solvents were
identified, these wells were operated within a pump & treat remediation
strategy and, more recently, turned into discrete multilevel wells
(named by the supply well name followed by the screen maximum
depth) as part of the monitoring network.
A Temporal Conceptual Model was developed by Hart et al. (2021)
after a review of the long-term management results and contamination
behaviour that occurred over time at this study site, which is presented
in Fig. 2.
All the geological data were classified based on humid tropical soils
and presented in Hart et al. (2021). The following units were identified
(from top to bottom): Fill Materials; Alluvial Sediments; Weathered
Rock Soil; and Bedrock Gneissic Rock (this unit was subdivided into Soft
Weathered Rock; Hard Weathered Rock; and Fresh Rock).
This region presents two main aquifers units (Hirata and Ferreira,
2001): the Cenozoic sedimentary deposits of the Sao Paulo Basin (with
supply wells presenting a specific capacity of 0.48m3/h/m) and the
underlying crystalline bedrock (with supply wells presenting a specific
capacity of 0.91 m3/h/m). The crystalline bedrock aquifer is subdivided
into two highly heterogeneous and anisotropic horizons: the weathered
rock, with dual porosity, and the fresh rock, with fracture porosity. The
phreatic groundwater surface is typically identified within 2 m below
ground surface in the study area, presenting a hydraulic gradient of
approximately 1%. Groundwater flow velocities and directions were
calculated for all the geological units above the bedrock, and they range
from less than 1 m to 11 m/year with predominance towards south and
southeast (Fig. 1). Within the bedrock, groundwater flow velocity and
direction were found to be highly heterogeneous and dependent on
specific fracture setups, recharge processes and eventual influence of
pumping.
2.2. Investigation and remediation
Since 2000, the area has been subjected to various contaminated
land investigation and remediation actions (mainly excavation works
and a pump & treat system at PP-02 and PP-05 and shallower wells,
including near PMI-02 area, Fig. 1). One chlorinated solvent source area
was identified on-site, with a high predominance of 1,2 dichloroethane
(1,2-DCA, a compound that was previously used on-site as pure product
for industrial purposes) and lower concentrations of several chloro­
ethane and chloroethene compounds. By 2014, soil and groundwater
quality had improved due to the above-mentioned remediation actions,
mainly within the fill material unit. Concentrations at some deeper wells
had not achieved remediation targets, while a high resolution investi­
gation (including Membrane Interface Probe - MIP) confirmed persis­
tence of anomalies in the on-site source area at that time, within the
underlying sedimentary dark organic clay unit (Fig. 2). Its highest
concentrations were typically detected near the later installed moni­
toring well PMG-01 (Fig. 1) within soil and groundwater (approximately
75 mg/L for total volatile organic compounds, VOC, and 32 mg/L for 1,2
DCA). Therefore the management strategy was revised to incorporate
SashaT. Hart et al.
Fig. 1. Location map, phreatic groundwater main flow directions (in 2016) and the monitoring wells selected for isotopic sampling (full monitoring network and the
remediation wells includes more than 100 other locations).
further investigations to diminish uncertainties, an evaluation of new
available technologies and a revision of the conceptual model.
In 2015 and 2016, new investigations and a localized bio remedia­
tion test (beside PM-044 and PM-045, which can be identified in Fig. 1)
were performed. An off-site area near the upgradient boundary of an off-
site active industrial area with restricted access presented unexpected
high concentrations in soil (between 2.4 m and 11.8 m deep, mainly in
Fill Materials and Weathered Rock Soils) and the associated ground­
water. These anomalies were not fully delineated laterally or further
upgradient and the impact origin was considered unknown. This area
was located approximately 40 m northeast from the main on-site source
area well (PMG-01) and in between them no major impacts were iden­
tified during MIP, soil and groundwater investigations. The new in­
vestigations found the upgradient well (PM-060F, in the Weathered
Rock Soil unit) presented the highest VOC concentrations and a high
predominance of PCE, with lower concentrations of several chloro­
ethane and chloroethene compounds. The high concentrations in soil
and groundwater (approximately 150 mg/L for total VOC and 60 mg/L
for PCE), within approximately 30% of PCE solubility concentration
limit, suggested the potential existence of dense non-aqueous phase
liquid (DNAPL) in this area. This, together with other lines of evidence
(such as spatial apparent discontinuity, depths, estimated flows, high
resolution investigation and geochemical signatures), was considered
indicative of the existence of a nearby unknown off-site source area and
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Journal of Contaminant Hydrology 245 (2022) 103940
a commingled plume configuration. In order to further evaluate this
understanding, without new intrusive off-site works, the investigations
followed with the isotopic studies carried out before and after new full
scale remediation works discussed later on in this paper.
A new remediation strategy was defined and implemented on-site
between 2016 and the first semester of 2018 (Fig. 3). Electro-thermal
remediation was applied between October 2016 and May 2017 to
treat the whole on-site source area (delineated based on detailed soil and
groundwater analytical results within the organic clay level of the Al­
luvial Sediments unit). Temperatures were increased and stabilized
around 100 ◦ C over approximately 4 months in order to mobilize
contaminant via solubilisation and volatilization processes, followed by
liquid and vapour phase recovery via negatively pressurized systems.
Temperature variation can potentially enhance or limit bioremedi­
ation. Temperatures in the mesophilic range (between 25 and 40 ◦ C)
have found to result in higher contaminant bioavailability and biode­
gradability, with very limited bacterial populations above 60 ◦C (Leite
et al., 2021). Heating also induces hydrolysis, which is a process of direct
destruction of the compounds. For the thermal hydrolysis process of 1,2-
DCA, the expected equation is presented below (Palau et al., 2017a)
resulting in production of ethylene glycol and chloride, with pH
decrease:
C2 H4 Cl2 + 2H2 O→C2 H6 O2 + 2H+ + 2Cl−
Monitoring of the applied thermal remediation indicated that targets
SashaT. Hart et al.
Fig. 2. Temporal Conceptual Model (for vertical scale consider 20 m from surface to Fresh Rock-Gneiss): 1) Baseline before contamination, with upward ground­
water flow; 2) During industrial use, with on-site supply well, commingled plume due to on-site known and off-site unknown source areas; 3) After on-site reme­
diation, remaining off-site source area plume and pumping (Hart et al., 2021).
were achieved and 176 kg of chlorinated solvents were recovered
(99.5% in vapour phase and the remaining as liquid phase). It was also
estimated (based on initial/final mass calculations, temperatures mea­
surements and theoretical assumptions) that thermal works had induced
the degradation of additional 491 kg via hydrolysis pathway (mainly for
1,2-DCA, followed by 1,1 DCA).
The new remediation strategy also included Bioremediation, that
was applied mainly between 2017 and the first semester of 2018 to treat
the on-site source area associated plumes, identified mainly within the
Eluvial Soil and Weathered Soil geological units. The process was based
on the promotion of biotic reductive dechlorination via injection of a
carbon source (molasses) into a network of dedicated remediation wells.
During thermal treatment, this substrate was injected at further down­
gradient areas and once heating ceased injections took place throughout
the study area, including beneath the heated horizon. The bedrock
levels, typically less impacted, were not subject to direct heating or in­
jections however indirect positive effects related to the remediation at
shallower levels were expected.
3. Materials and methods
3.1. Sampling strategy
The site monitoring well network included more than 100 sampling
locations and were sampled every semester (or more intensively during
some remediation works at specific locations) for groundwater chemical
analyses. A group of selected wells were sampled for groundwater iso­
topic analyses in 2016 (after the 2015 localized bio remediation pilot
test and prior to the thermal and full scale bio remediation) and in 2019
(two years after the end of the thermal remediation and one year after
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Journal of Contaminant Hydrology 245 (2022) 103940
the last molasses injection). The wells were selected (Fig. 1) in order to
include spatially representative locations, source areas and the plumes
along the groundwater flow system. In total, 28 different wells were
sampled in both or either in the first or the second campaigns. Some
wells were sampled for isotopes only in the 2019 because they were
installed after the 2016 campaign and others removed due to the ther­
mal treatment.
The groundwater sampling procedures followed the low-flow
method protocols (USEPA, 2017). Due to the thermal remediation, an
additional procedure was performed in the 2019 campaign, when
groundwater temperature was identified more than 10 ◦ C above initial
background levels. In these cases, a cooling system was added externally
(without contact) to the low flow closed lines, in order to reduce tem­
peratures to initial background levels before groundwater samples
collection.
Samples were stored and preserved following laboratories in­
structions, then immediately labelled, refrigerated within ice boxes and
sent with chain of custodies for analyses. Samples were followed to
guarantee minimum possible transport time (3days in the case of the
international laboratory).
In order to facilitate data interpretation, the wells were classified
within two major groups. Porous group, related to locations where
intergranular porosity dominates, which included wells installed in the
Fill Material, Alluvial Sediments and Weathered Rock Soil geological
units. Groundwater in most of these wells, including the on-site source
area (around PMG-01, Fig. 3), was targeted for remediation. The off-site
main source well (PM-060F, Fig. 3) is also part of this group but is
located up gradient and was not a remediation target. The second type,
Bedrock group, is related to locations where fracture porosity may
predominate and included those wells installed in the deeper geological
SashaT. Hart et al.
Fig. 3. Thermal and bio remediation pilot test, target areas and regions with low influence (where, respectively, temperatures and methane measurements were
identified above baseline but below remediation target levels). Bio remediation was also conducted in the thermal target area, after heating period.
units Soft Weathered Rock, Hard Weathered Rock or Fresh Rock.
3.2. Analyses
Groundwater chemical analyses were conducted for approximately
70 standard chlorinated VOC plus degradation products ethene and
ethane. The following hydrogeochemical parameters were analysed as
part of the thermal and bioremediation evaluation: Oxidation-Reduction
Potential (ORP), temperature, electrical conductivity, pH, dissolved
oxygen, sulphate, total organic carbon (TOC), sulphide, total alkalinity,
chloride and methane. Some parameters, such as ORP, were not always
monitored at wells that presented high temperatures due to the risk of
damaging the equipment. Some wells samples were also eventually
analysed for dissolved iron, dissolved manganese, nitrate and ammo­
nium nitrogen. All analyses were conducted following United States of
America standard analytical and quality control/assurance procedures
and methods (e.g. EPA 8260C for VOC) in the laboratories located in Sao
Paulo of the international company Merieux NutriSciences.
Isotopic analysis were conducted for the chlorinated compounds and
degradation products most typically identified at the site: PCE, tri­
chloroethene (TCE), cis 1,2-dichloroethene (cis-1,2-DCE), Vinyl Chlo­
ride (VC), 1,1,2,2-Tetrachloroethane (1,1,2,2-TeCA), 1,1,2-
5
Journal of Contaminant Hydrology 245 (2022) 103940
Trichloroethane (1,1,2-TCA), 1,2-DCA, 1,1-Dichloroethene (1,1-DCE),
1,1-Dichloroethane (1,1-DCA), ethene and ethane. Chloroethane is also
a potential chlorinated ethane degradation product of 1,2-DCA however
was not isotopically analysed due to none detectable or low
concentrations.
During the first and second sampling campaigns, Carbon isotopes
were analysed at the Organic Geochemistry Laboratory of the University
of Oklahoma (USA). During the second campaign, Chlorine isotopic
analyses for chlorinated ethenes were added to the analytical plan and
were performed at the same laboratory. Quality control and assurance
measures were applied, including sample custody, traceability controls,
control samples and duplicates analyses. The analytical precision was
calculated as ±0.5‰ or lower for all carbon and chlorine isotope ana­
lyses. Detection limit was typically 1 μg/L, depending on compound
response for each sample. Results were reported in standard delta no­
tation, following methods described by USEPA (2008) and laboratory
internal procedures. Standards were reported to be commercially ob­
tained calibrated to the appropriate international isotope scale (VPDB,
VSMOW or SMOC) or developed using high purity (e.g. ACS-grade)
specimens, based on off-line isotope ratio analysis. National or inter­
national certifications systems specifically for compound specific iso­
topic analyses did not exist that could be applied to certify the
SashaT. Hart et al.
laboratory.
The laboratory internal procedures for isotopic analyses indicate that
volatile compounds were extracted from water using a purge and trap
apparatus (PT) and then transferred to a gas chromatograph (GC) and a
mass spectrometer. For low molecular weight compounds, including
chlorinated ethenes, the PT transfer line is connected to a polar-phase
column. Analytes eluting from the transfer line are trapped using a
cryogenic focuser prior to being transferred to a main GC column for
target compound separation. For carbon, the separated analytes are
directed through a thermal conversion reactor and converted individu­
ally to pulses of surrogate gas product (CO2) for isotope ratio determi­
nation via an isotope ratio-monitoring mass spectrometer (IRMS). The
chlorine ratios are determined without thermal conversion, using a
standard quadrupole mass spectrometer (qMS) operated within a single
ion mode. The ratio of 37Cl/35Cl is calculated with the results of
scanning two Cl-bearing mass fragments with identical structure: first
one containing 35Cl and no 37Cl and the second containing a single
37Cl.
3.3. Isotopic mass balance
Isotopic mass balances were applied for total chlorinated ethanes
and ethenes to further evaluate the complete sequential degradation
pathways and influence of multiple sources (Hunkeler et al., 1999;
Nijenhuis et al., 2013; Badin et al., 2016; Murray et al., 2019). This was
applied for each sampling point and taking into account sequential
degradation substances for which both isotope and concentrations
values were available. The isotopic values of the total chlorinated eth­
enes (δ13CCE; PCE, TCE, Cis-DCE and VC) and chlorinated ethanes
(δ13CCa; 1,1,2-TCA, 1,2-DCA) was calculated by multiplying the molar
concentration of each compound (Ci) with its respective carbon isotope
signature (δ13Ci), adding all contributions and dividing by the total
molar concentration (CCE) (Eq. (1)) (Nijenhuis et al., 2013).
[ ] ∑(C *δ13 C )
(1)
i i
δ13 CCE ◦/◦ ◦ =
CCE
The error associated with the isotopic mass balance can be calculated
by error propagation (Badin et al., 2016) however uncertainties include
several factors: analytical errors, limited amount of analysis, multiple
sources, different hydrogeological units and multiple degradation
pathways towards ethene and ethane (therefore not included in the
isotope mass balance).
4. Results and discussions
4.1. Evolution of hydrogeochemical conditions
The hydrogeochemical results for the campaigns that included iso­
topic analyses (2016 and 2019) are presented as supplementary material
(Table 1 of SI). The hydrogeochemical results prior to remediation for
the Porous and Bedrock group wells presented, in general, reducing
anaerobic conditions. Results after remediation typically did not indi­
cate major changes in ORP however, mainly for the Porous group wells,
sulphate decreased and methane increased. For example, at the on-site
source well PMG-01 between 2016 and 2019 ORP changed from
− 107.1 to − 109.0 mV; sulphate decreased from 110.0 to below 5.0 mg/
L; methane increased from 7.4 to 30.5 mg/L. In 2019, two years after the
thermal treatment, both Porous and Bedrock group wells typically pre­
sented temperatures more than 3 ◦ C higher than in 2016, with most
different measurements identified at Porous well PM-044F (from 21.8 to
32.0 ◦ C) and Bedrock PP-02-79.3 m (from 19.8 to 25.4 ◦ C). More steady
conditions for all of these parameters were identified at the off-site
source area well PM-60F, which was not targeted for remediation. The
Bedrock group wells were also not directly targeted for remediation
however hydrogeochemical changes were identified (such as
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Journal of Contaminant Hydrology 245 (2022) 103940
temperature and methane increases, sulphate decreases; Table 1 of SI)
and confirmed the influence of thermal and bioremediation. This was
possibly enhanced by the groundwater downwards vertical flow pattern
and aquifer high connectivity previously that were noted during
hydrogeological tests (Hart et al., 2021). The overall hydrogeochemical
results indicate that the thermal and bioremediation treatment pro­
moted a long-term lasting effect in the targeted and underlying areas,
including temperature increase and enhancement of sulphate reducing
and methanogenesis conditions.
An example of groundwater time series measurements during the
thermal treatment is presented in Fig. 4. The well PMG-01 was screened
in the sedimentary dark organic clay level and located approximately 2
m from an electro-heating device. During the heating period, VOC total
mass (calculated adding all detectable VOC, not ethane or ethane)
decreased, likely due to both hydrolysis and volatilization processes.
Chloride increased and pH decreased as expected for the hydrolysis
process. TOC concentrations increased possibly due to a solubilisation
process of natural carbon, mainly from the organic clay layer. In addi­
tion, it is noticeable that methane concentrations decreased during this
period, possible due to volatilization and ceasing of natural biodegra­
dation activity. Sulphate presented slight increase, which also suggests
that limited biodegradation activity was taking place. After the heating
treatment period, temperature gradually decreased and the trend of
decreasing VOC continued at slower rate. Sulphate decreased and
methane increased, which supports that biodegradation of, respectively,
VOC and TOC returned, possibly stimulated by residual temperature
nearer microbial optimum levels around 40 ◦ C (Horst et al., 2018; Leite
et al., 2021).
An example of groundwater time series of measurements, during the
localized bioremediation pilot test is presented in Fig. 5. This test was
conducted in 2015, followed by the isotopic 2016 sampling campaign
and after by the full scale bio and thermal remediation works. The well
PM-048F (Fig. 3) was screened in the Weathered Soil unit. ORP was not
included in this figure as the available data suggested limited changes
around − 155.0mv. This well initially presented some of the highest
contaminant concentrations of the on-site source area and was located
approximately 1 m from an injection well (later removed together with
well PM-048F due to the thermal works). Results indicated that
approximately 3 months after the molasses injection event, VOC, TOC,
sulphate concentrations and pH decreased, while methane concentra­
tion increased. Chloride concentrations initially slightly increased, fol­
lowed by a decreasing tendency period. Temperature remained fairly
stable. During the last monitoring events methane, TOC and pH returned
to levels similar to baseline. These results are all consistent with the
expected biotic reductive dechlorination reactions.
4.2. Chlorinated ethene and ethane concentrations
Molar mass fractions of all main compounds, together with Total
VOC concentrations only for chlorinated compounds, in order to eval­
uate remediation effects on the most toxic compounds), of the selected
28 monitoring wells are presented in Fig. 6A and B for, respectively,
Porous and Bedrock Wells. VOC concentrations are presented in Table 2
of SI.
The highest total VOC concentrations in the on-site source area was
detected in PMG-01 (within the organic clay unit) with 1,2-DCA
showing the highest concentration, followed by 1,1-DCA, VC, cis-1,2-
DCE and a very low content of TCE (Fig. 6A; Table 1 of SI). These re­
sults suggest a distinct signature of mixed compounds (chlorinated
ethanes and, to less degree, ethenes) and that biodegradation had
already intensively occurred in the on-site source area. Post remedial
results indicate a significant decrease in total VOC concentration (up to
99%) and the predominance of ethane and ethene. This is a clear indi­
cation that the intensive treatment and post-thermal biodegradation had
been performed extremely well in the attenuation and transformation of
VOC to ethene and ethane (Fig. 6A; Table 2 of SI). Nearby on-site
SashaT. Hart et al.
Fig. 4. Groundwater monitoring evolution from well PMG-01 before, during and after the 2016/2017 thermal treatment. The first isotopic sampling campaign
occurred in 2016, before heating commence.
monitoring wells (PMG-002, PMG-004, PM-027FA, PM-031FA, PM-
044F and PM-062F; Fig. 3) presented similar patterns to well PMG-01.
The 2019 results for PM-045F, also in this region, collected after the
pilot remediation test showed a large amount of ethene (5820 μg/L,
Table 2 of SI) indicating an almost complete transformation of VOC to
final products of biodegradation. The 2019 data showed ethene is not
present and small amount of TCE, 1.1-DCA and 1,1,2 TCA and a small
increase in VC and 1,1 DCA (Fig. 6A, Table 1, SI). This pattern is possibly
due to a minor rebound and/or side effect of the thermal and biore­
mediation treatments.
The molar fraction data from the groundwater of wells located
directly downgradient from the off-site source well PM-060F (for
example, PM-051F, PM-058F, PM-062F, PMI-09, PMI-010, PM-032F,
PMI-07) presents mixtures with variable compositions of chloroethene
and chloroethane compounds, together with ethene and ethane (Fig. 6A
and B; Table 2 of SI). These results suggest the existence of degradation
processes and an evidence of a commingled plume situation. A signifi­
cant reduction in VOC mass is observed in wells PM-058F and PM-062F
in the 2019 data with proportional increase of the final product ethane,
which is likely to be related to the effect of the nearby thermal and
bioremediation.
Concerning the wells located further downgradient from both source
zones (for example, PM-041F, PMI-02, PMI-04, PM-052F, PM-53F, PMP-
08, PP-02 and PP-05), they presented variable VOC composition with
predominance of a mixture of chlorinated ethane and ethene by-
products (Fig. 6A and B). These signatures suggest that potentially
they could have originated from off-site and/or on-site sources and were
also under the influence of biodegradation. This may have been further
induced previously by the operation of the pump and treat system at
several locations throughout this region. After thermal and bio reme­
diation, typically the concentrations decreased and proportions of
breakdown products increased, mainly in the wells located in the
7
Journal of Contaminant Hydrology 245 (2022) 103940
Weathered Rock Soil (targeted by bio remediation) and the Soft
Weathered Rock geological unit, such as PM-041F, PMI-04 and PM-053F
(Fig. 3, Fig. 6A and B). No appreciable changes in concentration and
molar fraction composition were observed between 2016 and 2019 data
(Fig. 6B) in the shallowest and deepest port of the monitoring nest PP-02
located in the underlying Fresh Rock geological unit and further
downgradient from the VOC sources (Fig. 1). It is possible it will take a
longer period of time to see the effect of remediation treatment due to
the distance or this also could be explained with the potential existence
of areas in the bedrock with less connectivity to the remediated areas or
the possible existence of another source area.
The mixed compound sources and generalized pattern of intensively
biodegraded compounds hampered the interpretation of single com­
pound distributions. PCE, a chlorinated ethene parent compound,
identified predominantly only in the off-site groundwater at well PM-
60F had extremely limited presence in all downgradient wells, despite
wide occurrence of its biodegradation products. 1,2-DCA was identified
throughout the whole study area, including at both source areas most
impacted wells, and it was previously used on-site. Therefore, 1,2-DCA
could have been a chlorinated ethane parent compound, however it
could have been produced by the degradation of other products, such as
1,1,2-TCA, that was identified only as a minor compound at specific
wells. The plumes of 1,2-DCA, identified in the 2016 and 2019 cam­
paigns are presented, respectively, in Fig. 7A and B. The 2016 plume
does not clearly distinguish the source areas however the 1,2-DCA dis­
tribution indicates the contribution of the off-site and on-site to the
downgradient areas. The 2019 plumes present a strong reduction in size
and concentrations of 1,2-DCA with no indications of plume displace­
ment or rebound effects, mainly in the on-site source area targeted by
thermal and bioremediation treatments, indicating this source is no
longer contributing 1,2 DCA to the downgradient groundwater.
The study area included complexity issues posed by the close
SashaT. Hart et al.
Fig. 5. Groundwater monitoring evolution from well PM-048F before, during and after the 2015 bioremediation localized pilot test (substrate injected in another
well, located 1 m away). The first isotopic sampling campaign occurred later, in 2016, and was followed by full scale bioremediation.
location (less than 40 m) of the source areas and limited information
about the off-site source area. In addition, the direction of groundwater
flow was previously probably influenced by the former pump & treat
system, that operated at PP-02, PP-05 and shallower levels (including
near PMI-02). This configuration (see conceptual model in Fig. 2) plus
the VOC distribution and signatures (Fig. 6) suggest that a mixing zone
existed downgradient from both source areas. This mixing area created
commingled plumes among compounds present at one or both source
areas such as, PCE and 1,2-DCA, in addition to a mixture of several
degraded chlorinated ethane and ethene compounds. The fraction
related to each source varied throughout the commingled plumes
however the 2019 results indicated that the on-site source was inten­
sively treated. Therefore it is expected that the on-site contribution to
the commingled plumes was reduced and possibly ceased. This was also
confirmed later in 2019 and 2020 by several monitoring campaigns of
the expanded well network, in addition to soil and vapour sampling
studies, which are not described in this paper.
4.3. VOC isotopic characterization
The carbon and chlorine isotopic results (in δ ‰) are presented,
respectively, in Tables 1 and 2.
The baseline (2016) δ13C isotope results in groundwater present δ13C
values of − 17.5 and − 1.8 ‰ for PCE and 1,2-DCA, respectively in the
off-site source well PM-60F (Table 1). In the on-site source groundwater
of well PMG-01 a δ13C value of +10.3 ‰ was observed for 1,2-DCA,
while PCE was not analysed due to low detection of this compound
(1.1 μg/L; Table 2 of SI). These δ13C values are systematically more
enriched isotopically compared with the values reported for commercial
products that range between − 23‰ and − 33‰ for PCE (Beneteau et al.,
1999) and between − 26.5‰ and − 29.5‰ for 1,2 DCA (Palau et al.,
2014; Schmidt et al., 2014; Franke et al., 2017). These isotopic patterns
8
Journal of Contaminant Hydrology 245 (2022) 103940
plus the presence of by-products indicated that biodegradation has been
an active attenuation process for chlorinated compounds in the source
areas, prior to thermal and full-scale bioremediation. The δ13C results
for potential parent compounds 1,1,2,2-TeCA and 1,1,2-TCA are avail­
able for a limited number of wells (mainly near the off-site source area)
but are all lower than values identified in the same wells for 1,2-DCA,
which is another evidence 1,2-DCA is not a product of their degradation.
A wide range in isotopic baseline (2016) composition is observed for
PCE near or downgradient the off-site source area, with δ13C results
varying between − 20.7 and − 7.9‰, and its potential by-products range
between − 26.5 and − 3.9‰ for TCE, − 24.1 and − 9.8‰ for 1,2-DCE,
− 31.3 and − 5.5‰ for VC, − 22.7 and +4.6‰ for ethene and − 16.6
and − 9.6‰ for ethane (Table 1). The results are, in general, coherent
with a reductive dechlorination pathway for PCE (Hunkeler et al., 1999;
Abe et al., 2009). For 1,2-DCA during the 2016 campaign, a wide range
of enriched δ13C values of − 6.5 and +20‰ is observed near and
downgradient from both sources indicating this compound has been
affected by a high degree of enrichment, with different potential
degradation pathways and origins as discussed later on in this chapter.
The data collected in 2019 indicate δ13C isotopic results with further
enriched values, mainly in groundwater located in the area of influence
of bioremediation and thermal treatment, as further discussed at the end
of this chapter. For example well PMG-004, located near the area of the
on-site source (Fig. 3), presented δ13C values of − 14.5‰ for TCE, − 3.1‰
for cis-DCE, +0.7‰ for VC, +45.2‰ for 1,2-DCA, − 10.9 for ethane, and
+2‰ for ethene (Table 1).
In 2019, chlorine isotopes for PCE and its degradation products were
sampled for the first time. The δ37Cl results for PCE, coherently with
δ13C results, indicate lower values near the off-site source area (between
− 1.8 and − 0.9‰) and further enriched values (between +2.8 and
+4.6‰) in downgradient wells under the influence of remediation.
Isotopic mass balance results over distance from the most upgradient
SashaT. Hart et al. Journal of Contaminant Hydrology 245 (2022) 103940

(caption on next page)

9
SashaT. Hart et al. Journal of Contaminant Hydrology 245 (2022) 103940

Fig. 6. Molar mass fraction for all compounds (chlorinated compound plus ethene and ethane) and total concentration only for chlorinated compounds of: (A) Porous
and (B) Bedrock group wells. In order related to distance from the most upgradient well (PM-060F). “D.L.” means detection limit. Green and pink stars beside the
years indicate wells that were under influence of, respectively, thermal treatment or bioremediation (including the 2015 pilot test; Fig. 3).
The results prior remediation (2016) shows that the upgradient off-site groundwater in well PM-060F presented the highest total VOC concentrations of the off-site
source area (126,279 μg/L) and of the whole study area (Fig. 6A and B; Table 2 of SI). It had a clear predominance of PCE followed by its by-products of
biodegradation (TCE, cis 1,2-DCE, VC, ethene and ethane), 1,2-DCA, 1,1-DCA and ethane. This suggests this source presented a mixture of compounds (chlorinated
ethenes and, to less degree, chlorinated ethanes) and biodegradation is an active process, despite the high total VOCs concentration and potential nearby presence of
DNAPL. In 2019 was observed a decrease in Total VOCs (57,692 μg/L), molar fractions of TCE, cis 1,2-DCE and 1,2-DCA together with an molar fraction increase of
PCE and ethane The groundwater in the nearby off-site well PM-051F (Fig. 1), which is in a shallower unit (shallow sands overlaid by organic clay favourable to
biodegradation), presented in 2016 a total VOC concentration of (85,197 μg/L) composed of a greater proportion of vinyl chloride, 1,2-DCA and ethene. In 2019,
total VOCs also decreased (41,255 μg/L), followed by a molar increase of ethene. This also indicated that biodegradation is an active process in the nearby areas of
well PM-051F. The decrease in concentration in wells PM-060F and PM-051F could also be related to unknown recharge conditions or activities in the up-gradient
areas. (For interpretation of the references to colour in this figure legend, the reader is referred to the web version of this article.)

well (PM-60F), near the offsite source area, are presented in Fig. 8
(Tables 3 and 4 of SI). The results for 2016 (Fig. 8a) indicate high var­
iations both for chlorinated ethenes (δ13Cce, between − 28.7 and
− 5.7‰) and ethanes (δ13Cca, between − 10.8 and +20.0‰). Higher
enriched values are identified mainly near the onsite source area (30 to
40 m) and intermediate values further downgradient (within the com­
mingled plume). This suggests potential mixture of source signatures
and/or further degradation (from both chlorinated ethenes and ethanes)
towards none chlorinated compounds (such as ethene and ethane) and/
or other degradation pathways and/or variations related to the different
hydrogeological units. The results for 2019 (Fig. 8b) indicate similar
results, with increases noted at a closer distance (approximately 20 m)
and higher ranges for δ13Cce (between − 29.3 and +2.9‰) and δ13Cca
(between − 4.3 and +40.9‰). These changes are likely to be related to
remediation effects which enhanced degradation and isotopic
enrichment.
4.3.1. 1,2-DCA biodegradation pathways
The by-products of biodegradation of 1,2-DCA potentially can
include VC (via dehydrohalogenation), ethene (via dihaloelimination)
and chloroethane (via hydrogenolysis), followed by ethane (Hunkeler
et al., 2002; Palau et al., 2017a and 2017b). The 2016 and 2019 results
indicate chloroethane was identified near detections limits or not
detected, excepting well PMG-03 in 2019 which presented a concen­
tration of 2190 μg/L (Table 2 of SI). These results tend to discard
chloroethane production as the main degradation pathway for 1,2-DCA.
A further insight about the origin of VC, ethene and ethane can be
done analysing the baseline (2016, Tables 1 and 2 of SI) concentration
and isotope data for the groundwater representative of the off-site and
in-situ source areas. For example, the groundwater in the off-site well
PM-60F is characterized by a 1,2-DCA concentration of 4640 μg/L, VC at
3210 μg/L, ethene at 2090 μg/L and ethane at 798 μg/L. δ13C results
values indicate 1,2-DCA values of − 1.8‰, VC at − 18.3‰, ethene at
− 22.7‰ and ethane − 16.6‰. The enriched isotopic values observed for
ethene and ethane suggests both gases have been affected by biodeg­
radation and the non-presence of chloroethane indicated that ethane is a
by-product of biodegradation of ethene. . As discussed previously, this is
a well were VC is likely to have originated from the degradation of the
parent compound PCE and its by-products. The highly enriched δ13C for
1,2-DCA and the high concentration of ethene suggests that 1,2 DCA was
biodegrading to ethene. The groundwater in the in-situ-source well
PMG-01, is characterized by a 1,2-DCA concentration of 32,500 μg/L,
VC at 8900 μg/L, ethene at 23700 μg/L and ethane at <5 μg/L. δ13C
results show values for 1,2-DCA of +10.3‰, VC at − 31.3‰, ethene at
+2.5‰ and ethane not analysed due to none detectable concentrations.
These results indicated that VC has been accumulating and has not been
transformed to ethene, which is likely to be a direct biodegradation
product of 1,2-DCA. Ethane was not detected in this groundwater,
confirming it was not a main biodegradation product of 1,2-DCA.
Concerning the fate of the gases, the isotopic mass balance results
(Fig. 8) and the range with highly enriched δ13C values observed in 2016
(Table 1) for ethene (− 22.7‰ to 4.6‰) and ethane (− 16.6 to − 9.6‰)
indicate that further transformation of the parent compounds to non-
toxic compounds have occurred and these gases have also been
affected by biodegradation.
4.3.2. Carbon isotope data for 1,2-DCA prior and post remediation
Since 1.2-DCA is one of the main compounds present in the on-site
and off-site VOC source areas, its carbon isotope data will be used to
evaluate the signatures throughout the study area including at the
comingling plume located downgradient from the sources. 1.2-DCA is
also considered a potential parent compound, as suggested by the on-site
history and isotopes results (Table 1), which simplifies the interpretation
of the isotopic signatures as their values shall not be influenced by
fractionation during previous degradation steps. Fig. 9A and B presents
the isotopic results on map and proposes general plume zonings based
on the combination of the lines of evidence presented in this paper
(hydrogeology, geochemistry, VOC and isotopic signatures). A large
isotopic difference is observed in 1,2-DCA 2016 results (Fig. 9A) in the
sources areas, which are characterized by a δ13C value of − 1.8‰ in well
PM-060F, representing the off-site source, compared to a δ13C value of
+10.3‰ in well PMG-01 representing the on-site source. A lower δ13C
value of − 6.5‰ than the 1,2-DCA at well PM-060F (located in the
Weathered Rock Soil unit) was observed in the nearby well PM-51F
(located in the shallower Sandy Deposit unit), possibly due to source
and/or degradation heterogeneities. Highly enriched δ13C values of
+8.6‰ (PM-031FA), +15.1‰ (PM-027FA), +14.9‰ (PMG-002) and +
20.0‰ (PMG-003) are also observed in 1,2-DCA in groundwater of other
wells tapping the organic clay and the sand unit located most near the
on-site source area most impacted well (PMG-01). Then, groundwater in
wells tapping the soft weathered rocks located east (perpendicular to
recorded groundwater flow directions) of the on-site source and down­
gradient from the off-site source show lower δ13C values of, +2.5‰ (PM-
058F), +3.0‰ (PM-062F) and − 2.8‰ (PM-032F) for 1,2-DCA (Fig. 9A).
These results (at least 5.6‰ below the minimum value mentioned above
for the on-site nearby source area wells) suggest none or less on-site
source influence over an off-site plume that presents progressive iso­
topic enrichment due to degradation as it moves downgradient. Further
downgradient from the two sources areas, all δ13C 1,2–DCA values
(Fig. 9A) are within the range of − 2.8‰ to 3.0‰ (apart from +4.0‰ and
+7.0‰ at PP-05 55.7 m and PP-05 82.5 m, which are respectively 4.6‰
and 1.6‰ lower than the minimum value identified at the on-site most
nearby source area wells). This suggests mixing of plumes of both
sources, in a comingled plume configuration, with predominance of δ13C
values that are more like the signature of the off-site source most
impacted wells (PM-060F and PM-051F) and their downgradient wells
(PM-058F, PM-060F and PM-032F).
Because of the high rate of degradation caused by the thermal and
bioremediation, the δ13C 1,2-DCA in the treatment areas presented
further enrichment in 2019 compared to 2016. The 2019 isotope data in
groundwater in the treatment area (Fig. 3) show δ13C values ranging
between +24.7‰ (PMI-09) and + 45.2‰ (PMG-04). At the off-site
source area wells, that were not targeted by thermal or bioremedia­
tion, the δ13C 1,2-DCA presented a lower level of enrichment (+7.4‰ at

10
SashaT. Hart et al. Journal of Contaminant Hydrology 245 (2022) 103940

(A) 2016

(B) 2019

Fig. 7. 1,2-DCA plume in: (A) 2016 and (B) 2019, considering results of all hydrogeological units (overlapped plumes of Porous and Bedrock wells) and full
monitoring well network and high resolution works (not presented here).

11
 SashaT. Hart et al.
Table 1
Carbon isotopic results (δ13C, in ‰) for 2016 and 2019.
Well PCE TCE cis 1,2 DCE VC Ethene Ethane 1,2 DCA 1,1,2 TCA 1,1,2,2 TeCA 1,1 DCE 1,1 DCA

Year 2016 2019 2016 2019 2016 2019 2016 2019 2016 2019 2016 2019 2016 2019 2016 2019 2016 2019 2016 2019 2016 2019

PM-027FA NA NA NA NA − 13.1 NA − 24.5 NA 4.6 NA − 13.5 NA 15.1 NA NA NA NA NA NA NA NA NA

PM-031FA NA NA NA NA − 15.2 − 10.3 − 22.2 − 20.4 − 6.1 NA NA − 16 8.6 NA NA NA NA NA NA NA NA − 10.9
PM-032F NA NA NA NA NA NA − 24.6 NA NA NA NA NA − 2.8 NA − 28.5 NA NA NA NA NA NA NA
PM-041F NA NA − 3.9 − 15.7 − 21.5 − 15.1 − 26.8 − 13.7 − 6 NA NA − 10.5 1.3 14.7 − 21.6 NA NA NA − 19 NA NA − 25.6
PM-044F NA NA NA NA NA NA NA − 6.5 NA NA NA − 7.8 NA 38 NA NA NA NA NA NA NA − 10.6
PM-045F NA NA NA − 5.75 NA 2.2 NA − 9.5 NA NA NA − 8.9 NA NA NA NA NA NA NA NA NA − 10.1
PM-051F − 20.7 − 24.3 − 26.5 − 28.8 − 24.1 − 18.1 − 26 − 27.7 − 15.6 − 15.8 NA NA − 6.5 − 3.7 − 13.4 NA NA NA − 18.2 NA NA − 28.2
PM-052F NA − 14.6 NA − 18 NA − 14.2 NA − 17.9 NA NA NA − 9.3 NA 3.3 NA NA NA NA NA NA NA − 25.9
PM-053F − 13.6 NA − 22.6 NA − 21.5 NA − 26.2 NA − 4.7 NA − 11.4 NA 1 NA − 29.8 NA NA NA NA NA NA NA
PM-058F − 8.1 NA − 16.6 − 3 − 20.7 − 3.2 − 24.6 − 7.3 − 6.6 − 1.9 − 9.6 − 10.2 2.5 18 − 28.3 NA − 22.4 NA − 18.5 NA NA − 20.9
PM-060F − 17.5 − 18.2 − 21.3 − 19.3 − 16.3 − 16.2 − 18.3 − 16.6 − 22.7 − 21.7 − 16.6 − 16.3 − 1.8 7.4 − 29.8 NA − 33.3 NA − 29.4 NA NA − 28.1
PM-062F − 7.9 − 14.9 − 14.8 NA − 19.2 NA − 26.9 − 16.3 − 6.4 NA − 10.7 − 4.3 3 NA − 29.1 NA − 17 NA − 24 NA NA − 21.2
12

PMG-001 NA NA − 21 NA − 21 NA − 31.3 NA 2.5 NA NA NA 10.3 NA − 16.9 NA NA NA NA NA NA NA

PMG-002 NA NA NA NA NA NA − 22.5 NA − 9.3 NA − 15 NA 14.9 NA NA NA NA NA NA NA NA NA
PMG-003 NA NA NA NA − 9.8 NA − 5.5 NA − 5.5 NA NA NA 20 NA NA NA NA NA NA NA NA NA
PMG-004 * NA NA NA − 14.5 NA − 3.1 NA 0.7 NA 2.0 NA − 10.9 NA 45.2 NA NA NA NA NA NA NA − 17.4
PMI-02 NA − 6.95 NA − 14.3 NA − 17.9 NA − 26.7 NA − 6.3 NA − 7.8 NA 1.3 NA NA NA NA NA NA NA − 27.5
PMI-04 NA − 14.3 NA − 21.4 NA − 18.3 NA − 22.7 NA − 0.5 NA − 4.3 NA 6.4 NA NA NA NA NA NA NA − 25.4
PMI-07 * NA NA NA − 31.1 NA − 24.9 NA − 30.2 NA NA NA NA NA − 4.1 NA NA NA NA NA NA NA − 27.5
PMI-09 * NA NA NA − 16.3 NA − 5.5 NA 4.9 NA − 2.5 NA − 8 NA 24.7 NA NA NA NA NA NA NA − 18
PMI-10 * NA − 25.1 NA − 27.2 NA − 19.5 NA − 20.7 NA − 20.8 NA − 18.3 NA − 4.8 NA NA NA NA NA NA NA − 27.1
PMP-008 NA − 10.5 NA − 18.3 NA − 21.6 NA − 28.8 NA − 6.6 NA − 9.5 NA 3.2 NA NA NA NA NA NA NA − 26.8
PP-02-42,0 m NA − 13.6 − 25.9 − 25.1 − 23.2 − 20.9 − 27.4 − 24.7 NA NA NA − 7.4 − 0.8 0.2 NA NA NA NA NA NA NA − 27.6
PP-02-61,0 m NA NA − 25.7 NA − 22.9 NA − 26 NA NA NA NA NA − 0.8 NA NA NA NA NA NA NA NA NA
PP-02-79.3 m NA NA NA − 20.8 NA − 18.1 − 21.2 − 23.5 NA − 8.9 NA NA 0 1.8 NA NA NA NA NA NA NA − 28

Journal of Contaminant Hydrology 245 (2022) 103940

PP-05-30.8 m NA − 15 NA − 24 NA − 17.9 NA NA NA NA NA NA 2.3 4.3 NA NA NA NA NA NA NA − 25.9
PP-05-55.7 m NA NA NA NA − 16.5 − 21.1 NA NA NA NA NA NA 4 7 NA NA NA NA NA NA NA NA
PP-05-82.5 m NA NA NA NA − 21.1 NA NA NA NA NA NA NA 7 NA NA NA NA NA NA NA NA NA

Those identified with “*” were installed in 2017. “NA” means not analysed (due to date of installation or low concentrations).
SashaT. Hart et al. Journal of Contaminant Hydrology 245 (2022) 103940

Table 2 The downgradient groundwater from both sources along the com­
Chlorine isotopic results (δ37Cl, in ‰) sampled in 2019. ingled plume show similar isotopic pattern than in 2016, apart from
Well PCE TCE cis 1,2 DCE VC increases at Bedrock wells PM-041F (from +1.3 to +14.7‰) and less
significantly at PP-05 30.8 m (from +2.3 to +4.3‰) and PP-02-79.3 m
Year 2019 2019 2019 2019
(from 0.0 to +1.8‰). As groundwater flow presents high velocity in the
PM-31FA NA NA 0.3 1 fractured rock aquifer, this isotopic variation may be related to the δ13C
PM-41F NA 3.5 0.1 1.6
PM-44F NA NA NA 7.9
enrichment observed in the area of the on-site source thermal treatment
PM-45F NA 4.2 3.6 4 and nearby bioremediation activities. This is also supported by the
PM-51F NA − 1.9 − 4.2 − 1.9 geochemical variations evidences (see section 4.1) and hydrogeological
PM-52F 1.3 2.7 0.9 1.6 testing (Hart et al., 2021). The 2019 carbon isotope data, similarly to the
PM-58F NA NA 4.3 5.9
2016 campaign, indicates the downgradient commingle plume presents
PM-60F − 0.7 2.8 3.5 5.1
PM-62F − 0.6 NA NA 2.7 predominance of values that are more similar to the off-site source
PMG-04 NA 0.3 − 2.6 − 0.6 signature, reinforced by the on-site source thermal intensive treatment
PMI-02 4.6 4.7 1.6 1.9 and isotopic enrichment.
PMI-04 − 0.3 1.8 0.5 0.6
PMI-07 NA − 1.3 − 4 2.3
PMI-09 NA 2.8 2 12
4.3.3. Dual carbon and chlorine isotope patterns
PMI-10 − 1.8 − 0.9 − 2.7 − 1.7 Dual Carbon-Chlorine isotope results for chlorinated ethenes of the
PMP-08 2.8 3.1 0.2 − 0.1 2019 campaign are plotted in Fig. 10, together with plotted average
PP-02-42 m 0.2 2.5 − 1.1 2.8 lines and equations, including slopes, calculated for the data. They can
PP-02-79.3 m NA 2.7 0.5 2.7
be used to support differentiation between processes governing PCE
PP-05-30.8 m − 0.6 1.7 − 1 NA
degradation (Kuder et al., 2013; Badin et al., 2016). It is important to
“NA” means not analysed (due to low concentrations). highlight that PCE was identified as a major compound only in the off-
site source area near well PM-060F however cannot be discarded that
PM-060F and − 3.7‰ at PM-051F). The first well (PM-058F) located at other PCE sources exist, mainly in the off-site areas that were not
east of the on-site source also shows a highly enriched δ13C value of investigated. This could be an explanation for PMI-10 lower δ13C and
+18‰ (Fig. 9B), which is correlated with a large reduction in 1,2 DCA δ37Cl PCE results (Tables 1 and 2 and Fig. 10) as wells as source and/or
concentration (Fig. 6A; Table 2 of SI). These δ13C 1,2-DCA enrichments, degradation heterogeneities. The groundwater with the highest tem­
out of the targeted treatment areas, are probably related to positive perature (indicative of thermal treatment) and methane (indicative of
degradation side effects of the nearby thermal and bioremediation bio remediation) detections were highlighted in order to support eval­
(related to influence of temperature and TOC increases). The δ13C 1,2- uation of eventual processes induced by remediation. The wells that
DCA in the groundwater further east of the on-site source area pre­ presented higher δ13C and δ37Cl values correlate to those with higher
sents values of − 4.1‰ (well PMI-07) and − 4.8‰ (PMI-10) which are methane concentrations, suggesting higher degradation levels. There
close to that detected in the 2016 campaign for the nearby well (− 2.8‰ are some isotope data in groundwater (such as wells PMG-04 and PM-
at PM-032F). This confirms this part of the study area was not targeted 045F, locate near the on-site source and thermal remediation area)
neither intensively affected by the thermal and bioremediation treat­ that are out of the general linear pattern shown by the other wells and
ments. In addition, the values detected in this region are again most like present more intensive carbon enrichment. Their distribution poten­
the off-site source area wells signatures (PM-060F and PM-051F). tially is related to a different pattern and could be explained if existed

Fig. 8. Isotopic mass balance for chlorinated ethenes (δ13Cce) and ethanes (δ13Cca) in 2016 (a) and 2019 (b, after remediation). Related to distance between screens
from the most upgradient well (PM-060F), within the offsite source area. Note the onsite source area is located at approximately 30 m to 40 m and correlates to
higher values.

13
SashaT. Hart et al. Journal of Contaminant Hydrology 245 (2022) 103940

Fig. 9. 1,2-DCA carbon δ13C isotopic results and overlapped Porous and Bedrock wells plume zoning (above 0.1 ppm) for: (A) 2016, and (B) 2019.

another PCE source, not identified, with different original signature expected to cause high δ13C fractionation according to Slater et al.,
(Carbon enriched). Another potential explanation could be a thermal- 2000) and hydrolysis (to be further researched and characterized for
induced degradation pathway related to this type of heating which isotopic fractionation). The evaluation of these hypothesis is restricted
caused, in addition to inducing bio degradation, volatilization (not due to uncertainties related to the initial sources content, off-site source

14
SashaT. Hart et al. Journal of Contaminant Hydrology 245 (2022) 103940

Fig. 10. Dual C-Cl isotope slopes for PCE, TCE, cis 1,2-DCE and VC. Wells highlighted in yellow and orange presented, respectively, temperatures between 30 and
40 ◦ C and 60–100 ◦ C during thermal remediation. Dots highlighted in green are wells that presented concentrations of methane above 20 mg/L. (For interpretation of
the references to colour in this figure legend, the reader is referred to the web version of this article.)

area investigation, lack of pre remediation chlorine isotopic results and
limited references concerning isotopic fractionation associated with
thermal-induced degradation (Badin et al., 2016; Murray et al., 2019).
Nonetheless, the overall results confirm that carbon and chlorine iso­
topic fractionation occurred due to both bio remediation and thermal
treatment (by stimulating bio degradation and potentially via another
process, such as hydrolysis, to be further investigated).
In order to further evaluate isotopic fractionation trends, the ob­
tained dual C-Cl slopes values for the combined data set were compared
to other field studies and laboratory experiments results (compiled and
complemented by Murray et al. (2019). Data have been reported for
oxidation and reductive dechlorination pathways, both biotic and
abiotic, however non for combined thermal and bio remediation. For
PCE, the slope obtained in the current study (2.1) falls within the range
widely reported for biotic reductive dechlorination (0.7 to 3.8). For TCE,
the obtained slope (2.5) also falls within the range widely reported for
biotic reductive dechlorination (2.3–4.8). For cis 1,2-DCE, the identified
slope (1.6) is significantly lower than the ranges reported for biotic
reductive dechlorination (4.5 to 17.8) and abiotic degradation (3.1 to
5.0) however fits within the range of 1.5 to 3.0 reported for combined
biotic and abiotic degradation processes. For VC, references were not
identified and therefore comparison was not possible. This overall
evaluation is another evidence that isotopic fractionation occurred due
to biotic reductive dechlorination. It also suggests there is a need for
further studies characterizing isotopic fractionation during VOCs
degradation by thermally-induced processes (mainly hydrolysis) to
assess potential specific characteristics of this degradation pathway.
5. Conclusions
Chlorinated ethanes and ethenes isotopic analyses in groundwater
and hydrogeochemical results from a former industrial area in Sao Paulo
(Brazil) were used to evaluate source areas and commingled plumes,
both before and after thermal and bioremediation treatments in
weathered fractured bedrock.
The δ13C groundwater baseline isotopic results (2016) indicated

15
SashaT. Hart et al.
clear differences for chlorinated ethanes and ethenes signatures and
mass balances throughout the study area. The main well of the recently
identified off-site source area (well PM-60F) was dominated by chlori­
nated ethenes and presented the typical reductive dichlorination trend
with δ13C values of − 17.5‰ for PCE, − 21.3‰ for TCE, − 16.3‰ for cis-
DCE and − 18.3‰ for VC. A relative high concentration of 1,2-DCA is
found in this groundwater characterized by a δ13C of − 1.8‰. A δ13C
value of − 6.2‰ for 1,2-DCA was found in a nearby well PM-51F which is
characterized by much lower concentration of chlorinated ethenes and
higher concentration of 1,2-DCA, VC and ethene. The on-site source area
wells were dominated by chlorinated ethanes and much more enriched
δ13C values, +8.6‰ to +20.0‰, for 1,2-DCA than the off-site source
area wells. The observed 1,2-DCA large isotope difference between
source areas and its presence throughout the study were favourable
conditions to evaluate the hypothesis of the existence commingled
plumes. Intermediate δ13C values for 1,2-DCA and mixed VOC concen­
trations were identified in wells downgradient from both source areas,
consistent with commingled plumes formation. The wells downgradient
from the source areas presented variable content of degradation prod­
ucts under favourable hydrogeochemical conditions for biotic reductive
dechlorination of chlorinated ethanes and dihaloelimination for 1,2-
DCA. The existence of commingled plumes were also supported by the
proximity of the source areas (less than 40 m) and hydrogeological
characteristics, including high connectivity between geological units
and potential past groundwater converging flow directions when
pumping activities occurred (Hart et al., 2021).
The δ13C isotopic results from the post remediation campaign (2019)
were consistent with the baseline results however presented additional
isotopic enrichments, mainly near the treatment areas. The hydro­
geochemical evaluation confirmed that the biotic reductive dechlori­
nation conditions were enhanced by both the bio remediation and
thermal treatment. The temperature increases induced natural carbon
solubilisation and temporally reached microbial optimum levels around
40 ◦ C (Horst et al., 2018; Leite et al., 2021). This was also evaluated with
dual Carbon-Chlorine isotope slopes for the chlorinated ethenes which
indicated that most enriched values were identified at wells with higher
methane concentrations (indicative of TOC bio degradation) and,
mainly for δ13C, at wells where temperature had increased (due to
thermal treatment). The slopes were compared with available reference
values and were typically coherent with ranges reported for biotic
reductive dechlorination pathway (Kuder et al., 2013; Badin et al.,
2016). Degradation products were also detected, both for biotic reduc­
tive dechlorination and hydrolysis pathways (chloride increase and pH
decrease), matching VOC concentrations reductions.
The results of this study allowed further characterization of the
chlorinated ethane and ethene source areas and confirm the formation of
commingled plumes in a complex setting. They were consistent with the
Temporal Conceptual Model proposed by Hart et al. (2021) and also
suggest there is a need for further studies characterizing isotopic frac­
tionation during VOC degradation by thermally-induced processes
(mainly hydrolysis) to assess potential specific characteristics of this
degradation pathway. These results and conclusions potentially can be
used as a scientific basis for other studies in areas with similar charac­
teristics, such as tropically weathered bedrock aquifers, undefined
sources, commingled plumes, thermal and bioremediation activities.
Funding
This work was supported by BASF S.A..
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
16
Journal of Contaminant Hydrology 245 (2022) 103940
Acknowledgements
The authors express special thanks to Raoni Zeitune, Jordi Palau, all
reviewers, BASF, Seequent, amid others, for their valuable support.
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.jconhyd.2021.103940.
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