Journal of Contaminant Hydrology 45 2000.

6378
www.elsevier.comrlocaterjconhyd

NAPL source zone characterization and remediation

technology performance assessment: recent
developments and applications of tracer techniques
P. Suresh C. Rao a,b,) , Michael D. Annable a,c , Heonki Kim a,d
a
Inter-disciplinary Program in Hydrologic Sciences, Uniersity of Florida, Gainesille, FL 32611-0290, USA
b
School of Ciil Engineering, Purdue Uniersity, West Lafayette, IN 47907-1284, USA
c
Enironmental Engineering Sciences Department, Uniersity of Florida, Gainesille, FL 32611, USA
d
Department of Enironmental Science, Hallyum Uniersity, Chunchon, Kanwon-do, South Korea
Received 1 September 1999; received in revised form 2 February 2000; accepted 5 April 2000

Abstract

Several innovative tracer techniques have been introduced during the past 5 years for enhanced
characterization of the Asource zonesB at sites contaminated with non-aqueous phase liquid
NAPL. wastes. These tracer techniques allow for an in situ estimation of domain-averaged values
and spatial patterns for NAPL saturation Sn ., NAPLwater interfacial area a nw ., and bio-geo-
chemical reactivity k s . within the target test zone. The tracer tests can be used to evaluate the
spatial patterns in these parameters, both before and after implementing some in situ technique for
site cleanup, in order to evaluate the effectiveness of remediation achieved and the possible
impacts of the cleanup technology on hydrodynamic and bio-geochemical processes. Here, we
review the theoretical and experimental basis for these tracer methods, present selected examples
of recent field-scale applications, and examine their reliability. q 2000 Elsevier Science B.V. All
rights reserved.

Keywords: Partitioning tracers; Interfacial tracers; Geochemical tracers; Groundwater cleanup technologies;
Hazardous waste sites; Site characterization; In situ remediation techniques

1. Introduction

)
Corresponding author. School of Civil Engineering, Purdue University, West Lafayette, IN 47907-1284,
USA. Fax: q1-765-496-1107.
E-mail address: pscr@purdue.edu P.S.C. Rao..

0169-7722r00r$ - see front matter q 2000 Elsevier Science B.V. All rights reserved.
PII: S 0 1 6 9 - 7 7 2 2 0 0 . 0 0 1 1 9 - 4
64 P.S.C. Rao et al.r Journal of Contaminant Hydrology 45 (2000) 6378

Clean up of sites contaminated with non-aqueous phase liquid NAPL. wastes

requires removal of the Asource zoneB and remediation of the dissolved contaminant
plumes.. No matter what technique is used for NAPL source removal excavation,
extraction, destruction, stabilization, containment, etc.., the volume of AsoilB containing
the NAPLs must be accurately delineated the term AsoilB is used here sensu lato.. The
hydro-geochemical and microbial characteristics of the zone targeted for cleanup also
need to be adequately characterized for deploying most in situ remediation technologies.
The task of delineating and characterizing NAPL source zones using traditional
sampling methods e.g., soil cores. presents considerable difficulties to the scientific and
regulatory communities see Feenstra and Cherry, 1996.. To overcome such technical
and financial obstacles, in recent years, several innovative tracer-based methods and
advanced geophysical methods EPA, 1998. have been introduced and evaluated under
laboratory and field conditions.
In this paper, we will present an overview of new tracer techniques for NAPL source
zone characterization in support of contaminated site management. Tracer techniques are
also useful for evaluating performance of in situ remediation technologies implemented
for NAPL source zone cleanup, such that site-specific conditions influencing remedia-
tion effectiveness and efficiency can be evaluated. This information is crucial for
extrapolation of in situ remediation technologies to other sites with different geohydro-
logic and biogeochemical characteristics as well as NAPL properties. We will primarily
focus on recent laboratory studies and fieldwork conducted by our group, with appropri-
ate references made to similar work done by others.

2. Tracer techniques for NAPL source zones

Four categories of tracers have been studied: 1. non-reactive tracers used for
hydrodynamic characterization, 2. partitioning tracers that selectively partition into the
NAPL, 3. interfacial tracers that only accumulate at the NAPLwater interfaces but do
not partition into the NAPL, and 4. bio-geochemical tracers that are used to quantify
abiotic and biotic reactivity. Based on the mobile fluid phase in which they are
introduced, tracers may be classified into two broad groups: aqueous and gaseous.
Aqueous tracers are used for investigations in both saturated-zone and vadose-zone,
while the gaseous tracers are useful primarily for vadose-zone applications. Since the
use of non-reactive tracers e.g., dyes, inorganic anions, and organic acids. is well
established in environmental hydrology, we will focus on recent applications of the other
three types of tracers for site characterization and remediation assessment.

2.1. Partitioning and interfacial tracers

The volume of NAPL trapped by capillary forces in a porous medium, expressed as a

fraction of the total pore volume of the porous medium, is defined here as the residual
NAPL saturation Sn .. The area of contact between the two immiscible fluids here,
NAPL and water., distributed in a complex manner within the pore network, is defined
as the fluidfluid interfacial area a nw .. Salient features of the partitioning and interfa-
 P.S.C. Rao et al.r Journal of Contaminant Hydrology 45 (2000) 6378 65

cial tracer techniques, as they are applied in environmental hydrology, are summarized
in Table 1. Further details can be found in a recent series of papers Annable et al.,
1995, 1998a,b; Saripalli et al., 1997a,b, 1998; Kim et al., 1997, 1998, 1999a,b..
The experimental approach used for both partitioning and interfacial tracers is the
same. A small pulse of non-reactive and reactive tracers is displaced through the test
zone, and the retardation of the reactive tracers. with respect to non-reactive tracers. is
measured. The non-reactive and reactive tracers experience the same hydrodynamic
conditions during displacement through the swept zone, but the average travel time for
the reactive tracers is delayed due to specific interactions with the NAPL. The ratio of
the average travel times for the non-reactive and reactive tracers is defined as the
retardation factor R ., and is used to calculate Sn or a nw .
The mechanism responsible for retardation of partitioning tracers is fluidfluid phase
partitioning due to differential solubilities in the two fluid phases. Retardation of the
interfacial tracers is the result of accumulation at the interfaces between immiscible
fluids waterair; waterNAPL.. This difference in the retention mechanisms for the
two types of tracers is reflected in the adsorption isotherms appropriate for the two sets
of tracers see Table 1.. A linear isotherm is used for describing the reversible phase
distribution of partitioning tracers if the NAPLwater partition coefficient K n . is
constant over a significant range of tracer concentrations. Methods are available for
estimating K n for a variety of NAPLs with simple or complex compositions
Dwarakanath and Pope, 1998; Wang et al., 1998.. The issue of non-linear tracer
partitioning must be carefully considered, however, in selecting tracers and the appropri-
ate concentration range Wise, 1999; Wise et al., 1999.. While the use of n-alcohols and
methylated alcohols as aqueous partitioning tracers has been popular e.g., Jin et al.,
1995; Annable et al., 1998a., the use of natural tracers e.g., 222 Rn. has been success-
fully explored Hunkler et al., 1997; Semprini et al., 1998, 1999..
For interfacial tracers, the Gibbs model is employed to describe the non-linear
isotherm representing the reversible accumulation of interfacial tracers at fluidfluid
interfaces. The required isotherm model parameters can be surmised from the measure-
ment of the decrease in interfacial tension with increasing tracer concentration see Kim
et al., 1997.. For gaseous interfacial tracers, a linear isotherm approximation may be
valid at low concentrations commonly employed. Using published values, the linear
isotherm constants or the unit area occupied by a single tracer molecule at the interface
can be estimated see Kim et al., 1999a..
A network of multi-level samplers can be used to determine the tracer travel times at
several locations within a three-dimensional flow domain using multi-level samplers,
thus permitting determination of the spatial distribution of Sn andror anw Sillan et al.,
1998a,b; Annable et al., 1998b; Jawitz et al., 1999; James et al., 1997, 1999.. Data based
on samples collected at fully screened extraction wells provide Sn or a nw values
representing averages over the entire flow domain swept by the tracers Annable et al.,
1998a; Rao et al., 1997; Jawitz et al., 1998.. Partitioning tracer field tests have been
conducted using various flow configurations and employing different patterns of multi-
ple injection and extraction wells under forced-gradient steady fluid water or gas as the
mobile fluid. flow conditions. To date, a single filed test has been conducted to evaluate
the interfacial tracer test at a NAPL site in Utah Annable et al., 1998b.. Setarge et al.
 66
Table 1
Summary of tracer techniques
Attribute Partitioning tracers Interfacial tracers Biogeochemical tracers
Tracers used Low molecular weight; Anionic and cationic surfactants; Biologically labile

P.S.C. Rao et al.r Journal of Contaminant Hydrology 45 (2000) 6378

methyl-substituted alcohols; high molecular weight alcohols carbon compounds
Radon-222 benzoate, sugars.
Parameter estimated NAPL residual saturation Interfacial area Transformation rate
average, and spatial patterns. average, and spatial patterns. constant average,
and spatial patterns.
Applications NAPL distribution; NAPL AmorphologyB; Potential for abiotic
remediation effectiveness; interfacial mass transfer and biotic reaction
impacts of remediation rates
Mechanisms Phase partitioning Interfacial adsorption
microbial or
geochemical reaction
C dg
Isotherm model Cn s K n C w
Sn K n r Kd
G sy
2 RT dC
1 dg
/ T ,C s C 0
Cs s K d C w
R non - d
X
Retardation model R pt s1q
1y Sn .
q
uw
K i sy
2 RT dC / T ,C s C 0
, Rd s
( 1q
4v
P
X
r Kd ai K i
R ift s1q q
uw uw
Degradation model NrA NrA Zero- or first-order

K n is the NAPLwater partition coefficient; K d is soil sorption coefficient; r is soil bulk density; uw is the volumetric water content; Sn is the NAPL saturation; a i
is the NAPLwater interfacial area; K i is the interfacial adsorption coefficient; R is the retardation factor, with the subscripts pt and ift, indicating partitioning and
interfacial tracers; R is gas constant, T is absolute temperature; g is the NAPLwater interfacial tension; C and C0 are tracer concentration in the effluent and
influent solutions, respectively; v is dimensionless rate constant; P is Peclet number; R d is retardation factor for a degrading tracer; R non-d is retardation factor for a
non-degrading tracer.
 P.S.C. Rao et al.r Journal of Contaminant Hydrology 45 (2000) 6378 67

1999. conducted laboratory experiments with tar-contaminated soils, and employed

tracer techniques to estimate the NAPL volume and NAPLwater interfacial areas. The
intefacial tracer technique has also been used for estimating the airwater interfacial
areas in partially water-saturated sand columns under 1-D, steady state, water flow
conditions Kim et al., 1997, 1998, 1999a..
Most of the aggressive NAPL-remediation technologies implemented in the saturated
zone depend on extraction of the NAPL constituents generating a dissolution driving
force across the NAPL-water boundary. Thus, the ratio of NAPL volume to total
NAPLwater interfacial area accessible to mobile-water is of particular interest. Simi-
larly, some vadose-zone remediation techniques e.g., soil vapor extraction. rely on
vapor-phase mobilization of contaminants, and the mass transfer rate of the contami-
nants from soil water to soil gas is a critical parameter. The dynamics of airwater
exchange of contaminants is a strong function of specific airwater interfacial area in
the system. A new secondary parameter called a Amorphology index H N .B has been
introduced Saripalli et al., 1997a, 1998; Kim et al., 1997; Annable et al., 1998b.. H N is
defined as the ratio of NAPL or air. water interfacial area to the volumetric NAPL or
air. content u N) . expressed as a fraction of the porosity .. Brusseau et al. 1997. also
examined the significance of the airwater interfacial area morphology. Morphology
index is the specific interfacial area surface area to volume ratio of NAPL or air., and
serves as a tool to diagnose spatial patterns in NAPLor air. distribution. Tandem use of
partitioning and interfacial tracers renders a more accurate evaluation of the performance
of a remediation technique in terms of the NAPL mass removal effectiveness.

2.2. Bio-geochemical tracers

Bio-geochemical traces are used to estimate the kinetics of microbial or abiotic

reactions. Several labile or reactive compounds e.g., low-molecular weight alcohols,
benzoate, sugars, various electron donors or acceptors. can be used as bio-geochemical
tracers Chapelle, 1993; Istok et al., 1997; McCray, 1997.. The transformation rate
constant k s . can be estimated by measuring the extent of tracer losses during displace-
ment through a specified domain. The spatial variability in k s within a given flow
domain can also be determined using an appropriate spatially distributed, multi-level
monitoring network. Depending upon the nature of tracers, specific bio-geochemical
characteristics of the flow system can be elucidated.
The zero-th moment i.e., mass recovery. of a tracer concentration breakthrough
curve is evaluated and combined with the normalized, first temporal moment i.e.,
average travel time. for estimating the k s values. The apparent, normalized, first
temporal moment of the bio-geochemical tracer is calculated in the same way as that for
the non-reactive or partitioning or interfacial tracers. Because some tracer mass is lost
due to decay or transformations, both the zero-th and the normalized, first temporal
moments are smaller in comparison to those for a non-degrading tracer. Appropriate
correction can be made to correct for this see Table 1; Annable et al., 1998a..
Estimation of k s is predicated on knowledge of the appropriate rate expression
zero-th or first order; Monod kinetics, etc... More reliable estimates of k s can be
68 P.S.C. Rao et al.r Journal of Contaminant Hydrology 45 (2000) 6378

obtained if one or more products of sequential or simultaneous transformations can be

monitored in addition to the parent chemical used as the tracer. This latter version of the
tracer technique has been used frequently in laboratory experiments to measure agro-
chemical degradation rate constants e.g., Ou et al., 1986, 1988.. But this technique has
been used only to a limited extent for microbial characterization of source areas at waste
disposal sites Bouma, 1995; McCray, 1997; Istok et al., 1997; Haggerty et al., 1998;
Scroth et al., 1998..

3. Applications of tracer techniques

3.1. Laboratory experiments

The volume of NAPL in the source zones has been determined using NAPL-partition-
ing gaseous or aqueous tracers, both under laboratory and field studies Knaepen et al.,
1990; Jin et al., 1995; Whitley et al., 1995, 1999; Nelson and Brusseau, 1996; Wilson
and Mackay, 1995; Chen and Knox, 1997; Hayden and Linnemeyer, 1997; Annable et
al., 1995, 1998a; Mariner et al., 1999; Young et al., 1999.. The NAPLwater interfacial
areas were estimated using interfacial tracers Saripalli et al., 1997a; Annable et al.,
1998b.. Saripalli et al. 1997a, 1998. and Kim et al. 1997. reported on the development
of a new tracer technique for estimating the interfacial area between two immiscible
fluids NAPLwater or airwater. present at residual saturations in porous media. In
these experiments with sand and glass-bead columns, sodium dodecylbenzene sulfornate
SDBS., an anionic surfactant, was used as the interfacial tracer. Extensions and further
confirmation of this method over a larger range of residual saturations was reported by
Saripalli et al. 1997b. for NAPLwater systems, and by employing multiple interfacial
and partitioning tracers for airwater systems by Kim et al 1998, 1999a.. Based on
their data, an empirical linear relationship can be used to describe the dependence of
interfacial area on the degree of NAPL or air. saturation Kim et al., 1997, 1998;
Saripalli et al., 1997b., at least over a limited range of immiscible fluid NAPL or air.
contents.
Aqueous tracers can be used over a considerable range of Sn . However, at suffi-
ciently large Sn , the discontinuous AgangliaB of the immiscible fluid NAPL or air.
begin to join and form a continuous phase. This results in a dramatic decrease of
aqueous permeability, thus posing significant experimental difficulties e.g., long travel
times.. Increasing the hydraulic gradients to increase the flow rate during tracer
displacement experiments can compensate decrease in permeability. Alternately, gas
tracers can be used if gaseous displacement techniques akin to gas chromatography
techniques. are employed both under laboratory and field conditions.
Kim et al. 1999a. have recently demonstrated, in laboratory experiments, the use of
gaseous partitioning and interfacial tracers to determine the immiscible fluid volumetric
content and the fluidfluid contact area. Their data indicated that while the fluid water.
content estimated by gravimetric and gas-tracer techniques agree closely over the entire
range studied, the airwater interfacial areas measured using aqueous and gaseous
tracers did not display the same trends. Within a range of water contents where both
 P.S.C. Rao et al.r Journal of Contaminant Hydrology 45 (2000) 6378 69

types of tracers could be used, a i values estimated using the gaseous tracers were larger
than those estimated using the aqueous tracers see Fig. 1.. This difference increased
with decreasing water content. Kim et al. 1999a. attributed this disparity to: 1. the
differences in access to the fluidfluid interfaces for the two tracer types, 2. the
mobility of the airwater interface during aqueous tracer displacement, and 3. gaseous
tracer adsorption by the soil, especially at low water contents.

3.2. Field-scale applications

The partitioning tracer techniques have been used in the petroleum field see Jin et
al., 1995; Pope and Jackson, 1999.. During the 19951997 period, we conducted a
series of field tests to evaluate the efficacy of two in situ flushing techniques for
enhanced remediation of NAPL source zone. Pilot-scale testing of cosolvent flushing
Rao et al., 1997. and single-phase micro-emulsions flushing Jawitz et al., 1998. was
conducted in hydraulically isolated test cells that were installed within an NAPL source
zone located in a shallow, sand-gravel aquifer at Hill Air Force Base AFB., UT. These
experiments were a part of a larger, coordinated study, funded by the US Department of
Defense and the US EPA, to evaluate several in situ flushing techniques in multiple,
hydraulically isolated, test cells installed in the NAPL source zone see Wood and
Enfield, 1999.. As a part of these field experiments, we evaluated the use of partitioning
and interfacial tracers to estimate Sn and a i , for an initial site characterization, and as a
tool for performance assessment after in situ flushing to examine spatial patterns in
cleanup effectiveness Jawitz et al., 1997, 1999; Annable et al., 1998b; Sillan et al.,
1998a,b.. The tracer test results were then compared with mass removal effectiveness
assessed based on soil-core analysis and mass balance calculations for selected NAPL
constituents.

Fig. 1. Comparison of airwater interfacial areas estimated using aqueous and gaseous tracers adapted from
Kim et al., 1999a..
70 P.S.C. Rao et al.r Journal of Contaminant Hydrology 45 (2000) 6378

Spatial patterns in Sn distribution based on tracer tests, conducted before and after
cosolvent flushing, are shown in Figs. 2 and 3, while a comparison of the depth
distribution of NAPL removal effectiveness based on soil cores and tracer tests is shown
in Fig. 4 Sillan et al., 1998a.. Enclosed within each iso-surface is the volume of the
geologic formation, with Sn greater than or equal to the indicated value. The highest
initial Sn values were found just above the clay confining unit, and Sn values generally
decreased with height above the clay in the NAPL smear zone Fig. 2.. NAPL saturation
iso-surfaces based on tracer tests, after cosolvent flushing, Fig. 3. indicate that the
smallest amount of NAPL removal occurred in the low-permeability, high-Sn zone along
the clay layer, but in much of the swept zone cosolvents effectively dissolved and
flushed out the NAPL. In Fig. 4, note that: 1. the NAPL removal effectiveness
estimated by the tracer tests is slightly less than that from soil-core analysis, and 2. the
effectiveness based on soil-core data is much more variable. Spatial analysis for the in
situ microemulsion flushing study conducted at Hill AFB, based on the data from
multi-level samplers, was presented by Jawitz et al. 1999..
Cosolvent or microemulsion flushing in the test cells at Hill AFB extracted most of
the NAPL constituents, but not the high molecular weight Apitch-likeB fraction Rao et

Fig. 2. Iso-concentration surfaces of NAPL residual saturation estimated using partitioning tracer tests at Hill
AFB. a. b. are data from tracer tests during initial site characterization adapted from Sillan et al., 1998a..
 P.S.C. Rao et al.r Journal of Contaminant Hydrology 45 (2000) 6378 71

Fig. 3. Iso-concentration surfaces of NAPL residual saturation estimated using partitioning tracer tests at Hill
AFB. a. and b. show data for post-remediation tests adapted from Sillan et al., 1998a..

al., 1997; Jawitz et al., 1998.. Tracer partitioning into this ApitchB leads to the observed
partitioning tracer retardation that is incorrectly interpreted as high Sn after flushing. Lee
et al. 1998. confirmed that significant changes in a complex NAPL composition,
brought about by selective extraction during flushing, alter the alcohol tracer partition
coefficients. The estimated values of Sn and a nw from tracer tests conducted in a test
cell at Hill AFB site were combined to calculate H N s w anw rSn x, as an empirical index
of NAPL AmorphologyB. Annable et al. 1998b. reported that the tracer tests indicated
high variability about an order of magnitude range. in H N . Their data suggest that there
was high variability in NAPL distribution both at the Darcy-scale and at the test-cell
scale. In the low H N zones near the clay unit, either the interfacial area is low or the
NAPL content is high, and the opposite is true in zones above the clay with a high H N .
We also conducted a field-scale test of in situ cosolvent flushing for enhanced
extraction of a DNAPL source zone at a dry cleaner facility in Jacksonville, Florida
Jawitz et al., 2000.. Partitioning tracer tests conducted before and after alcohol flushing.
Pre-flushing tracer test provided an estimate of about 68 l of PCE in the test zone
targeted for flushing. Post-flushing tracer test indicated that after flushing with about
72 P.S.C. Rao et al.r Journal of Contaminant Hydrology 45 (2000) 6378

Fig. 4. Comparison of NAPL removal effectiveness estimated using soil-core analysis and partitioning tracer
tests adapted from Sillan et al., 1998a..

two pore volumes of alcohol, about 26 l of PCE remained in the target zone, which
suggests a PCE removal effectiveness of 63%. Mass balance calculations based on data
collected during the alcohol flood indicated that about 43 l of PCE had been extracted
62% removal effectiveness.. These results were consistent with the results from
soil-core analysis ; 67% effectiveness..
Three unique features of the study at the dry cleaner site should be noted. First, this
test was not conducted in a test cell as the Hill AFB studies discussed above. Hydraulic
containment was achieved by over-extraction at six recovery wells that surrounded the
oblong source zone 7.3 by 2.7 m.. Second, high-frequency sub-sampling of the soil
cores taken in the DNAPL source zone indicated that the DNAPL was distributed in a
few, thin 58-cm-thick. layers that did not appear to be horizontally continuous over
the areal extent of the source zone. Thus, a large fraction of the targeted DNAPL source
zone was uncontaminated. An important consequence of such highly non-uniform
DNAPL distribution is that only a small faction of the streamlines swept by the
partitioning tracers intercepts the DNAPL zones. Third, the average residual saturation
of PCE within the test zone was very low Sn s 0.004.. The combined effects of such
heterogeneous DNAPL distribution are manifested as a lack of clear separation among
the tracer breakthrough curves BTCs. measured at extraction wells. Much of the
partitioning tracer retardation had to be estimated from extrapolated tails of the BTCs.
This tracer behavior is especially problematic in interpreting tracer data from post-re-
mediation tests where the average DNAPL content is much smaller Sn s 0.0014. and
the DNAPL distribution is likely to be even more sparse Jawitz et al., 2000..
Haggerty et al. 1998. and Scroth et al. 1998. presented a method to estimate
first-order reaction rate coefficients k s . from tracer BTCs obtained from a single-well,
 P.S.C. Rao et al.r Journal of Contaminant Hydrology 45 (2000) 6378 73

Apush pullB test. The tracer mixture they used included a non-reactive, conservative
tracer and one or more reactive tracers selected to investigate a particular bio-geochem-
ical process. They also present an example application where they used this pushpull
tracer method to estimate reaction rate coefficients for microbial denitrification in a
petroleum-contaminated, unconfined, alluvial aquifer.

4. Reliability of tracer methods

For the tracer techniques to become accepted as tools for site characterization and
performance assessment, the results provided by these innovative techniques must be
compared with those from more established methods. Note that conventional methods
are available for measuring NAPL content e.g., soil coring., but in situ measurement of
bio-geochemical reactivity is much more difficult. There are no AstandardB methods for
directly measuring the NAPLwater interfacial area, and the AactualB fluidfluid
interfacial area can only be surmised from theoretical models assuming some type of
pore-network geometry and fluid saturation. Tracer technique validation must be based
not only on agreement with more traditional methods, but also based on the uncertainty
in the estimated parameter values for both types of methods.
The magnitude of deviation between the parameter values measured by different
methods depends on the extent of spatial heterogeneity in the hydrologic properties or
NAPL content, and the magnitude of the parameter values given a tracer selected. In
general, the magnitudes of such deviations as well as the uncertainties are likely to be
small for homogeneous media with uniform parameter distribution. Also, tracer tests are
expected to result in an underestimation of the actual values due to constraints in
hydrodynamic accessibility of tracers to NAPLs and non-equilibrium mass transfer. This
can be a particularly vexing problem for partitioning and interfacial tracers when used in
1. hydrologically homogeneous media with sparse NAPL distribution, 2. hydrologi-
cally heterogeneous media with non-uniform NAPL distribution, and 3. zones with high
NAPL saturation e.g., ApoolsB .. In such cases, the tracer BTCs tend to be highly
skewed with extensive tailing Jawitz et al., 2000.. Extrapolation of these tails a critical
part of estimating NAPL content or interfacial area. But such extrapolation also
introduces additional estimation errors that need to be carefully evaluated. Jin et al.
1997. used UTCHEM model simulations to estimate that the relative error associated
with underestimation of NAPL content using partitioning tracer techniques may range
from 3060% when NAPL is present both at residual saturation in a part of the flow
domain, and as pools in another part. Preliminary analysis of the data we obtained at
DNAPL sites suggests that estimation errors are likely to be larger than that estimated
based on model simulations. However, this issue merits further analysis.
The magnitude of uncertainty in the estimated parameter values is likely to vary with
the magnitude of the estimated value, but in a manner different for the conventional and
tracer methods. In heterogeneous media having low Sn values, the conventional soil-cor-
ing methods are expected to have higher uncertainty since the point measurements using
small samples may not adequately represent the spatial variability. However, as Sn
increases, the uncertainty in estimation using soil coring is likely to diminish since
74 P.S.C. Rao et al.r Journal of Contaminant Hydrology 45 (2000) 6378

NAPL is expected to be present throughout the medium., but accessibility constraints

could increase the uncertainty in tracer-based estimates. Between these extremes, the
uncertainty in parameter values estimated by tracer techniques and conventional meth-
ods is likely to be somewhat similar for intermediate values of the parameters.
However, the degree and nature of the medium heterogeneities, and the specific
tracers. chosen complicate the specification of the upper and lower bounds for these
ranges.
Jin et al. 1997. used UTCHEM model simulations of partitioning tracer displace-
ment in heterogeneous media with non-uniform NAPL distribution to evaluate the
sensitivity of the tracer methods to detect NAPLs present either as pools or at residual
saturation or both. They show that for low NAPL saturation and sparse NAPL
distribution, optimizing K n by selecting an appropriate suite of tracers can minimize the
estimation errors. Also, the mass loss of NAPL via dissolution and the associated
changes in Sn and NAPL accessibility during the tracer tests may need to be accounted
for cases where sparsely distributed NAPL has a significant aqueous solubility e.g.,
DCE or TCE..
The interference of organic matter and mineral components may be quite small for
tracer tests conducted as a part of pre-remediation site characterization Jin et al., 1997..
But in post-remediation tracer tests, estimated Sn or a nw values may be significantly
impacted Rao et al., 1997; Jawitz et al., 1998; Dai, 1997.. For example, removal of
NAPL via in situ flushing may AunmaskB sorptive domains that were otherwise
inaccessible to the tracers Dai, 1997.. A recalcitrant, insoluble fraction of the NAPL
referred to as the ApitchB component. may be left behind as thin coatings on soil
surfaces after aggressive source zone remediation. Tracer partitioning into this hy-
drophobic carbon matrix may yield a false-positive signal for presence of NAPL Rao et
al., 1997; Jawitz et al., 1998; Lee et al., 1998.. This problem is likely to be more
significant at sites contaminated with multi-component NAPLs e.g, coal and oil tars;
creosote. that have weathered on site.
Another issue with the use of tracers is that the agents used for aggressive remedia-
tion of NAPL source zones may impact tracer retardation in post-flushing tracer tests.
For example, the residual amounts of alcohol or surfactant, left behind after an in situ
flushing treatment, may alter tracer partitioning or degradation. While residual cosol-
vents or surfactants can decrease sorption of the partitioning tracers, such effects are
likely to be small unless the residual alcohol or surfactant concentration are excessively
high i.e., enough to significantly alter the aqueous solubility of the tracers.. However,
surfactants might be adsorbed on the aquifer solids, and thus increase the tracer
adsorption. Post-remediation tracer tests conducted after in situ flushing with oxidants
can also be problematic. The residual oxidant can cause abiotic degradation of the
tracers, which complicates the interpretation of the tracer data Dr Linda Lee, Purdue
University; personal communication.. Finally, microbial degradation of the tracers
during pre- or post-remediation tests can also introduce additional uncertainties in
parameter estimates. This is especially critical for tracer tests conducted in source zones
with sparse, heterogeneous distribution of the NAPL.
 P.S.C. Rao et al.r Journal of Contaminant Hydrology 45 (2000) 6378 75

5. Summary

Delineation and characterization of the NAPL source zones is an important element

of site characterization and design of remediation plans. Existing traditional methods
involving soil coring often fail to provide adequate information, and the number of
samples needed to obtain statistically reliable information may be cost-prohibitive. Also,
for bio-geochemical processes, it is desirable to develop information on the basis of in
situ measurements as opposed to data based on core samples subjected to laboratory
tests. In recent years, several innovative partitioning and interfacial tracer techniques
have been proposed and tested under lab and field conditions for in situ measurement of
the quantity and distribution of NAPLs within the source zones. Bio-geochemical tracer
techniques have been developed for an in situ characterization of the bio-geochemical
reaction rates in source zones and in dissolved plumes. The experimental and theoretical
basis for these tracer techniques is now well established, and these methods have
generated considerable interest among the practitioners and potential clients. However, a
limited extent of field-scale testing of these tracer techniques contributes to concerns
about their reliability and representativeness. Tracer techniques do provide reliable in
situ measures of the relative quantities of NAPL content and distribution and bio-geo-
chemical reactivity within the test zone hydrodynamically accessible to the mobile fluids
in the test zone targeted during the tracer test. Thus, parameter values estimated using
tracer tests should be taken as the conservative minimum. value. For example, NAPL
residing in zones with limited hydrodynamic accessibility may not be detected during a
partitioning tracer test. Similarly, highly heterogeneous distribution of the NAPL can
present additional challenges in data interpretation and introduce significant uncertain-
ties. The agents used for aggressive remediation of the NAPL source zone may also
complicate interpretation of the tracer data. Therefore, more field-scale evidence is
needed especially at DNAPL sites to establish that the tracer tests in fact provide
reliable absolute measures of NAPL content and distributions as well as NAPLwater
interfacial areas in source zones. Further evaluation of the biogeochemical tracers for
estimating the potential rates of geochemical and microbial processes is also recom-
mended.

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