REMEDIATION Spring 2013

Chlorinated Hydrocarbon–Contaminated
Site Investigation With Optimized
3D-CSIA Approach

Yi Wang

An optimized “Three-Dimensional Compound Specific Isotope Analysis (3D-CSIA)” investigation

was conducted at a chlorinated hydrocarbon–contaminated site in order to (1) determine if multiple
onsite sources of groundwater contamination existed and (2) demonstrate the cost-effectiveness of
applying isotope fingerprinting at such a complex contaminated site. Previous groundwater investi-
gations identified chlorinated hydrocarbons at levels that significantly exceed drinking-water stan-
dards but failed to determine the source(s) of contamination due to the lack of vadose-zone con-
tamination and the absence of groundwater contaminants in shallow portions of the surficial aquifer.
To better understand the contaminant source(s), groundwater samples were taken and tested for
both the presence of chlorinated hydrocarbons and their isotopic signatures of 13 C/12 C, 37 Cl/35 Cl,
and 2 H/1 H. A site investigation with an optimized 3D-CSIA approach revealed multiple chlorinated
hydrocarbon releases from different sources, which was also cost-effective considering the new
lines of evidence of target contaminants obtained with the 3D-CSIA approach instead of any tradi-
tional fingerprinting approaches. In addition, the 3D-CSIA results inferred in situ bioremediation of
c 2013 Wiley Periodicals, Inc.
chlorinated hydrocarbons would be feasible at the site. O

INTRODUCTION

Chlorinated hydrocarbons, such as tetrachloroethene (PCE), trichloroethene (TCE), and

their degradation product cis-1,2-dichloroethene (c DCE), are the most frequently
detected contaminants in groundwater due to their widespread use since the early 1940s
(Morrison, 1999). Spills, leaks, and improper disposal of these compounds have resulted
in soil and water contamination to varying degrees. In many cases, the source of the
chlorinated solvent plume is unknown. Traditional molecular fingerprinting analysis, such
as gas chromatograph-mass spectrometry (GC-MS), could hardly determine their sources,
because: (1) they are often used as single compounds, unlike petroleum products as a
mixture of hydrocarbons (Z. Wang & Fingas, 2003), and (2) chlorinated hydrocarbons of
different sources are chemically identical.
Chemically identical compounds from different sources, however, may have an
isotopic difference. Compound-specific isotope analysis (CSIA) allows for the
measurement of the isotopic composition of individual compounds within a complex
sample mixture (Freeman et al., 1990; Hayes et al., 1990; Hilkert et al., 1999). The US

© 2013 Wiley Periodicals, Inc.

Published online in Wiley Online Library (wileyonlinelibrary.com). DOI: 10.1002/rem.21351 111
Chlorinated Hydrocarbon–Contaminated Site Investigation With Optimized 3D-CSIA Approach

Exhibit 1. Site map for the 3D-CSIA study; groundwater flow is generally north-northeast at the site

Environmental Protection Agency has recognized CSIA as a new advanced site diagnostic
tool, which has an array of applications for organic pollutants, contaminated site
investigation, and remediation (US EPA, 2008). CSIA measures and compares the ratios of
stable isotopes found in compounds of suspected contaminant sources or plumes as well as
the feedstock or manufacturing process of materials historically used in a site’s vicinity. It
can help discern the potential for multiple spills of the same compound based on their
different isotopic “signatures.” An isotopic signature can be used to associate a contaminant
plume with a particular spill or potentially responsible party (Hunkeler et al., 1999).
CSIA techniques have been applied to study the sources and behavior of many types of
subsurface contaminants, including mono-aromatic hydrocarbons, such as benzene,
toluene, ethylbenzene, and xylenes (Kelly et al., 1997), polycyclic aromatic hydrocarbons
(Hammer et al., 1998; Y. Wang et al., 2004), crude oils, refined hydrocarbon products
(Hostettler et al., 2007; Pond et al., 2002; Y. Wang & Huang, 2001, 2003), and
chlorinated hydrocarbons, such as TCE and PCE (Jin et al., 2011; Shouakar-Stash et al.,
2006; van Warmerdam et al., 1995).
The target investigation area for the investigation discussed is in downtown Orlando.
The site encompasses approximately eight city blocks that include various business and
residential complexes (Exhibit 1). The site is underlain by about 50 feet of fine- to
medium-grain Pliocene-Pleistocene quartz sands with an increasing percentage of clay and
silts with depth. A well-developed surficial aquifer is present within these sands, with the

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 REMEDIATION Spring 2013

average depth to water being approximately 11 feet below ground surface. The
groundwater flows toward the north-northeast.
Prior to the 3D-CSIA study, 74 monitor wells and more than a hundred screen points
were installed and sampled with nearly all of the deep groundwater samples collected at
the site reporting detectable levels of chlorinated hydrocarbons. Primary contaminants of
concern include PCE and TCE. The highest PCE and TCE concentrations were detected
near a former uniform rental service in the northwestern corner of the study area. Based
on past and current property uses, other potential sources of PCE and TCE in the target
area include former dry cleaners, print shops, and automobile repair shops. Due to the
lack of vadose-zone contamination and the absence of groundwater contaminants in
shallow portions of the surficial aquifer, the source(s) of contaminants could not be
determined.
The objectives of this study are to (1) determine if multiple onsite sources of
groundwater contamination exist at the site and (2) demonstrate the cost-effectiveness of
applying isotope fingerprinting at such a complex contaminated site. To better understand
the contaminant source, three isotope ratios, 13 C/12 C, 37 Cl/35 Cl, and 2 H/1 H, in the
primary contaminants of concern were examined.

METHODOLOGY AND QA/QC PROCEDURES

Groundwater samples from five wells at the site (Exhibit 1) were collected and analyzed The objectives of this study
for both the presence of chlorinated hydrocarbons and their 3D-CSIA signatures. In are to (1) determine if
addition, depth-discretion samples were collected in one well, MW-1, at three different multiple onsite sources of
depths: 20, 64, and 95 feet. Techniques for collecting and preserving groundwater groundwater contamin-
samples for 3D-CSIA are identical to those for volatile organic compound (VOC) analysis ation exist at the site and
using EPA Method 8260B. In this investigation, all samples were collected using standard (2) demonstrate the cost-
operating procedures for groundwater sampling, with eight replicates for each sample, effectiveness of applying
and then shipped overnight on ice to an offsite laboratory, ZymaX Forensics Isotope. isotope fingerprinting at
such a complex contami-
Upon receipt, all samples were logged into the LIMS system then stored at
nated site.
approximately 4 C in the dark until the 3D-CSIA forensics could be performed. Sample
preparation techniques and instruments that can detect chlorinated hydrocarbons at
concentrations of micrograms per liter (μg/L) were used. Chlorinated hydrocarbons were
extracted from water samples on a solid-phase micro extraction (SPME) fiber. A SPME
fiber was placed in the headspace of a vial above the water sample, which was stirred to
achieve equilibrium of the volatile compounds between the water and headspace. The
SPME fiber was inserted into the injection port of an Agilent 6890 GC linked to a furnace
and a Micromass IsoPrime IRMS (Cheadle, United Kingdom). Volatile compounds were
desorbed from the SPME fiber at high temperature in the GC injection port into the
helium (UHP 5.0 grade) carrier gas flow. Compounds, such as PCE, TCE, and c DCE,
were separated on a 30-m fused silica GC column (HP-5MS, 0.25-mm i.d., 1-μm film
thickness), flushed in the carrier gas through the furnace to convert the carbon (oxidation
at 850 C) or hydrogen (reduction at 1050 C) in each compound to CO2 or H2 , and the
carbon isotope ratio of the CO2 or the hydrogen isotope ratio of the H2 measured in the
isotope ratio mass spectrometer (IRMS).
Stable isotopes were measured as the ratio of the most abundant isotopes of a given
element (Clark & Fritz, 1997). For carbon, it is the ratio of 13 C to common 12 C, which is

© 2013 Wiley Periodicals, Inc. Remediation DOI: 10.1002/rem 113

Chlorinated Hydrocarbon–Contaminated Site Investigation With Optimized 3D-CSIA Approach
In the industrial manufac-
turing of chemicals, the
multiple isotopic signa-
tures of the final product
depend on the isotope
ratios of the feedstock
and the manufacturing
processes used to convert
the feedstock into the final
product.
114
expressed as the parts per thousand or permil (δ, ‰) difference from the reference:
δ13 Csample = [(13 C/ 12 Csample )/ (13 C/ 12 Creference ) − 1] × 1000 ‰ PDB
where PDB is the name of the reference used, in this case Pee Dee Belemnite, a carbonate
formation. A δ-‰ value that is negative, say −30‰, signifies that the sample has 30
permil or 3% less 13 C than the reference, or is depleted by 30‰. The ratios for the other
elements, such as hydrogen, are expressed in the same way relative to their specific
standards. Results of the analysis are reported as δ13 C for carbon (‰, Vienna Pee Dee
Belemnite, or VPDB), δ37 Cl for chlorine (‰, standard mean ocean chloride [SMOC]),
and δ2 H for hydrogen (‰, Vienna Standard Mean Ocean Water, or VSMOW).
Three pulses of a reference CO2 or H2 gas with known isotope composition were
injected during each GC run. The same compounds with known isotope compositions are
treated the same way as water samples and analyzed in replicates (n = 3) on GC-IRMS
during the same sequence as quality control standards. The precision of isotope analysis
has been determined by external standard runs to be better than ±0.5‰ VPDB for
carbon and ±5.0‰ VSMOW for hydrogen.
Chlorine isotope ratios were measured using the methods of Sakaguchi-Söder et al.
(2007) and Jin et al. (2011). This quick and sensitive method uses a conventional
quadrupole GC-MS (GC-qMS) instead of using a GC-IRMS (Shouakar-Stash et al., 2006).
Samples containing chlorinated compounds were introduced into a GC-MS using the
SPME fiber. The chlorine isotope ratios of target compounds PCE and TCE were
calculated from the peak areas of selected molecular ions and fragment ions of the
compounds using a set of unique mathematical equations. External chlorine isotope
standards (PCE and TCE, n = 5 for each) were prepared in the same way and injected
into an Agilent GC-qMS (Model 7890-5973, Santa Clara, California) to achieve the
similar signals relative to the samples, in order to convert the GC-qMS raw ratios to the
international SMOC scale (Bernstein et al., 2011). The precision of the method has been
demonstrated by external standard runs to be better than ±0.5‰ SMOC.
Mixed chlorinated hydrocarbon standards of PCE, TCE, and c DCE at three different
levels (10, 50, and 500 μg/L) were analyzed prior to sample analysis as calibration
standards. Duplicate sample vials were analyzed for each sample. Baseline separation for
eluted peaks on gas chromatograms was routinely examined to ensure each peak was
reported for its isotope ratio accurately without any interference from co-elution.
RESULTS AND DISCUSSION
Use of 3D-CSIA Approach
In the industrial manufacturing of chemicals, the multiple isotopic signatures of the final
product depend on the isotope ratios of the feedstock and the manufacturing processes
used to convert the feedstock into the final product. Chlorinated hydrocarbons, such as
PCE, from different manufacturers presenting similar carbon isotopic signatures may be
further differentiated using their chlorine isotopic signatures (Smith & Wang, 2010). The
less abundant 37 Cl isotope fraction in chlorinated hydrocarbons is bound more tightly to
carbon than are 35 Cl atoms (Bartholomew et al., 1954). The heavier isotopes form strong
bonds and, therefore, are less susceptible to degradation.
Remediation DOI: 10.1002/rem © 2013 Wiley Periodicals, Inc.
 REMEDIATION Spring 2013

Several investigations have documented that differences exist in the carbon, chlorine,
and hydrogen isotope ratios of TCE produced by various manufacturers in the United
States. In one case, the isotopic ratios for 13 C/12 C and 37 Cl/35 Cl were used to distinguish
among three chlorinated hydrocarbon manufacturers (van Warmerdam et al., 1995). Each
measured chlorinated hydrocarbon showed a significant range in δ37 Cl and δ13 C values. In
a similar application, CSIA test results for 13 C and 37 Cl were used to discriminate
between two different pure-phase chlorinated solvent batches obtained from various
manufacturers (Beneteau, 1996).
Poulson and Drever (1999) reported the range for multiple isotopic signatures of
manufactured TCE: δ13 C = −48.0 to −27.8‰, δ37 Cl = −2.54 to +4.08‰, and
δ2 H = −30 to +530‰. Manufactured TCE can be further distinguished from TCE
generated as a degradation product of PCE released into the environment, because the
former could have higher hydrogen isotope ratios due to the dehydrochlorination
reactions used in the industrial production of TCE. However, TCE generated as a
dechlorination product of PCE could be depleted in hydrogen isotope ratios, a result of H
atom incorporation from the groundwater (Shouakar-Stash et al., 2003).

New Lines of Evidence Obtained by 3D-CSIA Approach

The highest concentrations of PCE (1,700 to 24,000 μg/L) were detected in the three
samples from the same well MW-1 (MW-1A at a depth of 20 feet, MW-1C at a depth of
64 feet, and MW-1D at a depth of 95 feet) near the former uniform rental service
(Exhibit 2a). The PCE in the well illustrated similar δ13 C (−28.8 to −29.2‰) and δ37 Cl
(0.2 to 0.4‰) ratios, indicating a major release of PCE from a single source, which could
possibly be the former uniform rental services utilizing PCE as a dry-cleaning reagent
(Exhibit 2b). Tracing the same isotope signature back to the former uniform rental
services was impossible due to the lack of vadose-zone contamination and the absence of
groundwater contaminants in shallow portions of the surficial aquifer and any archived
PCE materials used by the former uniform rental services.
The different δ13 C (−27.2‰) and δ37 Cl (2.5‰), and positive δ2 H (+429‰) ratios
measured for TCE in sample MW-1A, supported that the TCE detected at 20 feet had a
manufacturing origin, as previously discussed, on the unique isotopic signatures of
manufactured TCE (Exhibit 2c). The lighter δ13 C (−31.2‰), similar δ37 Cl (0.2‰),
and low δ2 H (−78‰) ratios measured for TCE in sample MW-1D, however, supported
active PCE biodegradation to TCE at 95 feet. In both samples MW-1A and MW-1D,
c DCE was more abundant than trans-1,2-DCE, which was only detected at low ppb
levels. This illustrated the PCE/TCE degradation pathway (Lollar et al., 1999; Morrison,
1999). Therefore, c DCE in well MW-1 was originated as a degradation product of PCE
and TCE.
Wells DEP-19D and DEP-14D, located directly downgradient of a former dry cleaner
(Exhibit 2d), had PCE (230 and 63 μg/L) as the dominant component with similar δ13 C
ratios (−28.8 and −28.3‰). Based on their δ13 C signatures alone, PCE detected in the
two monitoring wells would have been most likely attributed to a single release. However,
the addition of the δ37 Cl isotope analysis showed significant difference (between 2.3 and
0.8‰). This suggests that multiple PCE releases from the same property seemed likely,
and such releases must have occurred over a long period of use. Tracing the same isotope

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Chlorinated Hydrocarbon–Contaminated Site Investigation With Optimized 3D-CSIA Approach

Exhibit 2. Chlorinated hydrocarbons and 3D-CSIA evidence obtained at the site

signature back to the former dry cleaner was not possible, due to the lack of vadose-zone
contamination and the absence of groundwater contaminants in shallow portions of the
surficial aquifer and any archived PCE materials used by the former dry cleaner.

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 REMEDIATION Spring 2013

Exhibit 3. Chlorinated hydrocarbon releases identified by optimized 3D-CSIA

approach at the site

Wells IS-50 and DEP-9D are located further downgradient of wells DEP-19D and
DEP-14D (Exhibit 2d). There were many historical industrial uses and groundwater
samples from the monitoring wells in this area contained higher concentrations of TCE
(860 and 313 μg/L) than PCE (30 and 37 μg/L). In this case, TCE could be a
manufactured product, a PCE degradation product, or a mixture of the both.
Here 3D-CSIA signatures played an irreplaceable role in determining TCE’s origin.
During biodegradation, PCE is degraded into TCE: the 12 C-35 Cl bond is preferentially
broken relative to 13 C-35 C and 12 C-37 Cl bonds, the residual PCE becomes isotopic
enriched in the heavy isotopes 13 C and 37 Cl, with its daughter product TCE containing
more light isotopes 12 C and 35 Cl (Slater et al., 2001; Sturchio et al., 1998). The δ13 C
(−26.9 and −28.8‰) and δ37 Cl (3.3 and 3.7‰) ratios for PCE in these wells are clearly
heavier than for TCE (carbon −35.8 and −34.8‰; chlorine 0.5 and 0.5‰) by
approximately 7‰ in δ13 C and approximately 2‰ in δ37 Cl ratios, suggesting TCE to be a
product of in situ biotic transformation of PCE (Exhibit 2e). However, heavy δ2 H ratios
(+128 and +161‰) for TCE in wells IS-50 and DEP-9D obtained in this study indicated
that manufactured TCE could have also been released to this area and commingled with
TCE derived from PCE.
Manufactured TCE with heavy δ2 H ratios entering the same area could have increased
the δ2 H ratios of TCE significantly in these wells because of the substantial difference in
hydrogen isotope ratios between manufactured TCE and degradation product TCE, and
such alteration in isotope ratios would not be applied to TCE’s carbon or chlorine isotope
ratios as substantatively as it does to TCE’s hydrogen isotope ratios (Y. Wang, 2009; Y.
Wang & Smith, 2010). Were 3D-CSIA analysis not performed on these samples, the TCE
detected in wells IS-50 and DEP-9D would most likely have been considered a
degradation product of PCE, and any potential releases of manufactured TCE would have
been overlooked. Unidentified source(s) of manufactured TCE include local print shops
and automobile repair shops, where TCE could have been used as a metal and brake
degreaser (Exhibit 3 and Exhibit 4).

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Chlorinated Hydrocarbon–Contaminated Site Investigation With Optimized 3D-CSIA Approach

Exhibit 4. Concentrations and 3D-CSIA signatures obtained for chlorinated hydrocarbons at the
site

SUMMARY

The optimized 3D-CSIA approach was cost-effective considering the new lines of
evidence obtained with this approach instead of any traditional fingerprinting approaches.
Multiple chlorinated hydrocarbon releases were identified at the studied chlorinated
hydrocarbon–contaminated site. The 3D-CSIA isotopic signatures suggested that the
former uniform rental service (northwest of the site) and the former dry cleaner
(southwest of the site) were the primary contributors to groundwater contamination at
the site; along with unidentified sources of TCE (northeast of the site). Another sampling
event is being planned to address this potential TCE source area. In addition, degradation
occurring to PCE as shown by 3D-CSIA results inferred the feasibility of in situ
bioremediation of chlorinated hydrocarbons at the site.

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Yi Wang, PhD, is the director of ZymaX Forensics Isotope, an environmental laboratory located in Escondido,
California, serving clients in all 50 states as well as numerous international locations. He has over 20 years of
experience in environmental research and development on issues related to air, soil, and water contamination. He
has a BS in environmental science, an MS in environmental chemistry, and a PhD in environmental geochemistry.
He received his training on the state-of-the-art CSIA technology at Brown and Princeton University in the United
States. Dr. Wang is a senior geochemist at DPRA who has written over 50 peer-reviewed articles and books on
air, soil, and water contamination topics and has shared this information via lectures throughout the world. He
has worked with the US EPA, the Interstate Technology & Regulatory Council (ITRC), and the State Coalition
for Remediation of Drycleaners (SCRD) on organic contaminant cases where an optimized 3D-CSIA approach
was successfully used to locate source zones, allocate responsibility, assess the viability of in situ remediation
technologies, and optimize remediation strategy. Dr. Wang can be reached at yi.wang@zymaxusa.com.

120 Remediation DOI: 10.1002/rem © 2013 Wiley Periodicals, Inc.