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GROUNDWATER CONTAMINATION BY
CHLORINATED SOLVENTS: HISTORY,
REMEDIATION TECHNOLOGIES AND STRATEGIES
Perry L. McCarty
1.1 INTRODUCTION
Chlorinated solvents have seen broad usage for a wide variety of purposes, from cleaning
of machinery, clothes and electronic parts to use in chemical manufacturing. However, through
general dispersal, during normal usage and also as a result of indiscriminate disposal, chlori-
nated solvents have caused a variety of environmental problems. One such problem of great
concern is the contamination of soil and groundwater. This problem became most evident
following the passage in the United States of the Comprehensive Environmental Response,
Compensation and Liability Act (CERCLA), or Superfund legislation, in 1980 and the
subsequent evaluation of chemical contamination of groundwater. It is now recognized that
there are thousands of public and private sites with chlorinated solvent related groundwater
contamination problems. Remediation of such sites has been found to be especially difficult
and costly. Many potential technical solutions have been developed and applied, often with
limited success. Time frames for remediation tend to be long, often measured in decades. It is
incumbent upon those responsible for planning, designing and overseeing the remediation of
soil and groundwater contamination with chlorinated solvents to fully understand the difficul-
ties and high costs that are likely to be involved, and to have sufficient knowledge of the uses
and limitations of the many available technologies that may be applied to a solution. It is highly
likely that several technical approaches will be needed together to reach a satisfactory solution
that will effectively reduce risks to human health and the environment.
The purpose of this introductory chapter is to provide an overview of the chlorinated
solvent problem. This includes a history of chlorinated solvent usage together with the physical,
chemical, and biological properties of chlorinated solvents that affect their movement and fate
in the environment. A brief discussion of various chemical, physical, and biological processes
that have been developed and used for site remediation is then presented. This is followed by a
discussion of goals and strategies for remediation of chlorinated solvent contaminated sites.
H.F. Stroo and C.H. Ward (eds.), In Situ Remediation of Chlorinated Solvent Plumes, 1
doi: 10.1007/978-1-4419-1401-9_1, # Springer Science+Business Media, LLC 2010
2 P.L. McCarty
to the United States were halted during the war, the U.S. chemical industry expanded rapidly,
such that by the end of the war in 1918, the United States had developed the capacity to satisfy
all of its own synthetic chemical needs. Between 1921 and 1929, the U.S. production of synthetic
organic chemicals increased from 21 million to over 633 million pounds. The trends in the U.S.
manufacture of the four solvents over the years are indicated in Figure 1.1 (Doherty, 2000a;
2000b).
Figure 1.1. United States yearly production of chlorinated solvents (after Doherty, 2000a; 2000b).
Dry cleaning fluids in the early 1900s consisted almost entirely of gasoline (Doherty,
2000a). Because of gasoline’s explosion hazard, chlorinated solvents slowly replaced hydro-
carbons, and by 1962 exceeded hydrocarbon consumption for this purpose. In the early part of
the twentieth century, CT was the first of the four chlorinated solvents to come into wide usage
for dry cleaning, but many other uses were soon found for it. Examples are use as a fire
extinguisher; to render petroleum fractions nonflammable; as a delousing agent; to extract oils
from flowers and seeds, and grease from bones and hides; in petroleum refining and pharma-
ceutical manufacturing; and as a component of floor waxes, furniture polishes, paints and
Groundwater Contamination by Chlorinated Solvents 3
varnishes. As a solvent, CT was used in liquid chromatography, for de-inking of paper, and in
the manufacture of rubber. However, its use for metal degreasing was limited because it
increased metal corrosion.
By the 1930s, concern grew over the use of CT as a fire extinguisher because of its ability to
form phosgene gas when heated in the presence of moisture (Doherty, 2000a). By the early
1940s, CT began being replaced as a dry-cleaning and degreasing agent by TCE and PCE
because of CT toxicity, better recovery methods for TCE and PCE, and the reduced corrosion
of metal containers by the latter. However, its use continued to grow for other purposes,
especially for the manufacture of chlorofluorocarbons (CFCs), which consumed 95% of the CT
produced in 1974. With the ban on the use of CFCs for aerosol products in 1978, and then
further required reductions in line with the Montreal Protocol because of stratospheric ozone
depletion, CT manufacturing declined precipitously.
PCE has been widely used in the dry-cleaning industry, which was its highest volume usage
until about 1996, with a peak usage for that purpose of about 90% in 1962 (Doherty, 2000a).
Other uses, while small by comparison, have been for aluminum cleaning, sulfur recovery,
rubber dissolution, paint removal, printing ink bleeding, soot removal, catalyst regeneration,
treatment of hookworm and some trematodes, various purposes in the textile industry, and as a
replacement for polychlorinated biphenyls (PCBs) in electrical transformers and for an inter-
mediate in CFC manufacturing. Small quantities have been used for many purposes such as in
typewriter correction fluid and shoe polish. The decline in U.S. PCE production after 1980
resulted from various factors, including improvements in dry-cleaning equipment, growing
popularity of washable fabrics, PCE imports, reduction in CFC manufacture and new environ-
mental regulations. PCE is still the solvent of choice for dry-cleaning, but efficient recovery
systems and development of alternative technologies to PCE dry cleaning have greatly reduced
demand for this chemical. It is the fourth most frequently found organic contaminant at
Superfund sites, being reported present at 924 of 1689 National Priorities List (NPL) sites in
2007 (ATSDR, 2007).
TCE has been one of the best solvents for cleaning and degreasing because of its
effectiveness, noncorrosivity, nonflammability and ease of recycling (Doherty, 2000b). It
has been used for this purpose by a wide variety of entities, including the electronics, defense,
chemical, automotive, boat, food processing, textile and dry-cleaning industries. It has also
found use as a refrigerant, a low-temperature heat transfer medium, a freezing-point depres-
sant in some fire extinguishers, an extraction agent in decaffeination of coffee, a general
human and animal anesthetic, and as an ingredient in printing inks, industrial paints, paint
strippers, lacquers, varnishes, lubricants, pesticides and adhesives. It has been contained in
many household products such as shoe polish, household cleaners, spot removers, disinfectants,
paint removers, upholstery cleaners, deodorizers, mildew preventives, typewriter correction
fluid and septic tank cleaners. However, by the 1940s the largest use of TCE was for vapor
degreasing of metals, and by 1952 about 92% of the TCE produced was used for this purpose.
In 1966, Los Angeles County, California, adopted Rule 66, which limited the emission of TCE
and several other solvents–but not PCE, CT or TCA–from industrial facilities. This state
regulation was followed by the 1970 Clean Air Act (CAA), which further controlled TCE
emissions. In 1975, the National Cancer Institute found that TCE caused cancerous tumor
growth in mice. TCE is the most frequently found organic contaminant at Superfund sites,
being reported present at 1,022 of 1,689 NPL sites in 2007 (ATSDR, 2007). The uncertain future
for TCE led to TCE-manufacturing plant closings and price increases for TCE. For these
various reasons, the usage of TCE plummeted after 1970.
TCA became a widely used replacement for CT, TCE and PCE as each ran into environ-
mental difficulties, since it is an excellent solvent and is significantly less toxic than the solvents
4 P.L. McCarty
used previously (Doherty, 2000b). Its primary uses were in cold-cleaning, vapor degreasing
and ultrasonic cleaning, with 65% used for those purposes in 1984. It was used in the aircraft,
automotive, electronic and missile industries. TCA was used in spray and solid pesticides, drain
cleaners and carpet glue. It also had many smaller usages similar to that for TCE and PCE. It
became important also as a feed stock for the manufacture of hydrochlorofluorocarbons
(HCFCs) following the phase-out of CFCs. A disadvantage of TCA is its vigorous reaction
with aluminum; stabilizers such as 1,4-dioxane are generally added at about 4% to reduce this
problem. Groundwater contamination with such stabilizers as well as with TCA is now of
considerable environmental concern. TCA’s 6% use in aerosol propellants was banned in 1978
as an early effort to protect the stratospheric ozone layer, and its use in septic tank and cesspool
cleaners was withdrawn in New York in 1979. In 1990, various regulations came into effect,
particularly the 1990 CAA Amendments, which classified TCA as a hazardous air pollutant.
The Montreal Protocol called for the complete phase-out of TCA by 2002 because of its ozone-
depleting potential. TCA usage in the 1990s decreased rapidly.
Environmental concerns were thus major factors leading to control of chlorinated solvents
and their decline in usage. By the late 1960s, the public became more aware of the environmen-
tal effects of industrial chemicals and pressures for regulation on their disposal increased
(Doherty, 2000a). The 1970 CAA Amendments began federal regulation of emissions of TCE
and PCE due to their suspected role in ground-level ozone and smog formation. As a result,
many users turned to TCA, which was not so regulated, but it was then later banned because it
caused ozone depletion in the upper atmosphere. The priority pollutant list generated by the
U.S. Environmental Protection Agency (USEPA) as a result of the 1977 Clean Water Act
specifically included CT, PCE, TCE and TCA. Proposed drinking water quality criteria for
these chemicals were published in 1979 and 1980. Wastes containing these four solvents were
also classified as hazardous in 1980 under the 1976 Resource Conservation and Recovery Act.
The 1984 Hazardous and Solid Waste Amendments required the USEPA to restrict the land
disposal of untreated solvent wastes. CERCLA, passed in 1980, established reportable quan-
tities of spills for a variety of chemicals, including the four chlorinated solvents. The four
solvents became the most widely detected contaminants at Superfund sites.
1.3.4 Superfund
The broad general concern with organic chemical contamination in groundwater began
with the report in 1978 of soil contamination in a schoolyard and neighborhood in Niagara Falls,
New York. This highly publicized contamination resulted from leaking drums of hazardous
chemicals that were dumped about 25 years previously into Love Canal, which was then covered
over and the contaminated property was sold to the city for one dollar for community use.
The outrage that resulted from discovery of such contamination led to the passage in 1980
of CERCLA or Superfund, the federal program to clean up uncontrolled hazardous waste
sites. The extensive studies that followed led to the finding of widespread groundwater
contamination, with chlorinated solvents and related compounds being the contaminants
most commonly found (Westerick et al., 1984). These findings led to the search for methods
for groundwater remediation, as well as research to better understand contaminant movement
and fate as well as to find new methods for treatment and removal.
Table 1.1. Physical and Chemical Properties of Chlorinated Solvents and Their Transformation
Products at 25 Degrees Celsius ( C) (after Yaws, 1999)
Henry’s Law Water
Density Constant, KH Solubility Octanol/Water Partition
Chlorinated Compound (g/cm3) (atm/M) (mg/L) Coefficient (log Kow)
Methanes
Carbon Tetrachloride 1.59 29 790 2.83
Trichloromethane 1.48 4.1 7,500 1.97
Dichloromethane 1.33 2.5 19,400 1.25
Chloromethane 0.92 8.2 5,900 0.91
Ethanes
1,1,1-Trichloroethane 1.34 22 1,000 2.49
1,1-Dichloroethane 1.18 5.8 5,000 1.79
1,2-Dichloroethane 1.24 1.2 8,700 1.48
Chloroethane 0.90 6.9 9,000 1.43
Ethenes
Tetrachloroethene 1.62 27 150 3.4
Trichloroethene 1.46 12 1,100 2.42
cis-1,2-Dichloroethene 1.28 7.4 3,500 1.85
trans-1,2-Dichloroethene 1.26 6.7 6,300 2.09
1,1-Dichloroethene 1.22 23 3,400 2.13
Vinyl Chloride 0.91 22 2,700 1.62
Figure 1.2. Formation of dense nonaqueous phase liquid (DNAPL) source and contamination
plume following spill of chlorinated solvents.
Since the chlorinated solvents are denser than water, the downward movement will
continue, perhaps again following a circuitous route of least resistance. Soils and aquifer solids
contain different materials. Some such as sand and gravel represent particles that are relatively
large in diameter and thus are relatively porous, allowing good passage of both water and
chlorinated solvent liquids through them. Others, such as clays, are very fine and may be
relatively impervious to water and solvents. When chlorinated solvents meet clay layers in their
downward passage, they may pool on top of the clay, or seek a downward passage around the
clay layer. Even when chlorinated solvents in their downward movement meet sand and gravel
layers that contain different diameter particles, they may be diverted into one or the other
because of different capillary forces in the different media or because of chemical properties,
such as high organic carbon content, that may be more attractive to solvents with higher
octanol-water coefficients. Thus, knowing the particular surface location where a chlorinated
solvent spill occurred is insufficient information to know where it will be found several meters
below the surface because of the many erratic paths it may follow.
The liquid solvent present in soil, subsurface solids and groundwater is termed the “source”
of the contamination. Such dense nonaqueous phase liquids are termed DNAPLs. They
generally represent the source of groundwater contamination. As groundwater moves through
10 P.L. McCarty
the permeable (sand and gravel) layers in the subsurface environment and encounters the
DNAPL, the chlorinated solvents dissolve into the groundwater up to the solubility limits noted
in Table 1.1. As the groundwater moves horizontally in response to a downward gradient in the
groundwater, the contaminated water moves with it forming a contaminated groundwater
plume, a plume which may eventually reach and contaminate a well that supplies groundwater
to surface users or may emerge into a stream or other open water source, thus contaminating it.
The two different problems that must be faced in the remediation of a chlorinated solvent
contaminated site are what to do with the DNAPL source, and how to control or remediate the
plume of contamination. Technologies have been developed to address either or both of these
problems and are briefly described in the following section.
Table 1.2. Possible Treatment Technologies for Chlorinated Solvent Contamination of Soil and
Groundwater
Conventional Pump-and-Treat Flushing
Ex situ Air Stripping Cosolvent Flushing
Ex situ Activated Carbon Adsorption Surfactant Flushing
Ex situ Catalytic Oxidation
Air Injection In Situ Thermal Technologies
Vapor Extraction Hot Fluid Injection--Air, Water, Steam
Bioventing Electrical Resistive Heating
Air Sparging Thermal Conductive Heating
Biodegradation In Situ Chemical Processes
Aerobic Cometabolism Oxidative Chemical Processes
Anaerobic Reductive Dehalogenation Reductive Chemical Processes
1.6.3 Biodegradation
In the early 1980s when the abiotic and biological transformations of chlorinated solvents
were first discovered, the interest was primarily in use of this information to help explain the
variety of chlorinated products often found in groundwater, products that were unrelated to
known chemical spills in the area. The knowledge gained helped in the determination of potentially
responsible parties. However, since transformation products known at that time were generally
also hazardous, with some such as VC being even more hazardous than the original contami-
nants, there was little to favor the use of bioremediation for chlorinated solvent spills.
Table 1.3. Possible Goals in the Remediation of Chlorinated Solvent Contamination Together with
Strategies and Applicable Treatment Technologies for Meeting Goals
Goal Strategy Possible Treatment Technologies
Slurry wall
Source Physical barrier
Sheet piling
Containment
Hydraulic barrier Groundwater extraction and reinjection
Soil removal
Contaminant Cosolvent or surfactant flushing
Source removal Steam stripping
Remediation In situ thermal desorption
Contaminant in situ In situ chemical oxidation or reduction
destruction In situ bioremediation
Chemical reduction
Reactive wall
Bioremediation
Plume Ex situ treatment
Migration
Control In situ air sparging
Hydraulic control
In situ chemical oxidation
In situ bioremediation
Pump-and-treat
Physical
Air sparging (vertical or horizontal wells)
Plume Removal Chemical Chemical oxidation
In situ bioremediation
Biological
Intrinsic bioremediation (monitored natural attenuation)
Table 1.5. Relative Performance of Alternative Technologies for Plume Remediation (after NRC,
1994)
Residual Residual Sorbed
Groundwater Concentration in
Alternative Technology Concentration Aquifer Cleanup Timea
Conventional pump-and-treat Low Medium to high Long
Vacuum extraction and bioventing NA NA NA
Air sparging (vertical or horizontal
Low to medium Low to medium Medium to long
wells)
In situ bioremediation Low to medium Low to high Medium to long
Cosolvent or surfactant flushing NA NA NA
Steam stripping NA NA NA
In situ thermal desorption NA NA NA
In situ chemical oxidation NA NA NA
In situ reactive barrier Low NA Long
Intrinsic bioremediation Low to medium Low to medium Long
Note: A “low” residual concentration and a “short” cleanup time reflect relatively good performance, while a “high”
residual concentration and a “long” cleanup time reflect much less effective performance. “NA” denotes that the
technology is not applicable to this situation.
a
Because few cases of achieving cleanup goals have been reported, these qualitative assessments reflect the judgment
of the NRC committee members.
Groundwater Contamination by Chlorinated Solvents 23
Table 1.6. Relative Performance of Alternative Technologies for Source Remediation (after
NRC, 1994)
Residual Residual Sorbed
Groundwater Concentration in
Alternative Technology Concentration Source Area Cleanup Timea
Conventional pump-and-treat Low to medium Medium to high Long
Vacuum extraction and bioventing NA Low to medium Short
Air sparging (vertical or horizontal
Low to medium Low to medium Short to medium
wells)
In situ bioremediation Low to medium Low to high Medium to long
Cosolvent or surfactant flushing Low to medium Low to medium Short to medium
Steam stripping Low to medium Low to medium Short
In situ thermal desorption Low to medium Low to medium Short
In situ chemical oxidation Medium (?) Medium (?) Medium (?)
In situ reactive barrier Low to medium Low to high Medium to high
Intrinsic bioremediation Low to medium Low to high Long
Note: A “low” residual concentration and a “short” cleanup time reflect relatively good performance, while a “high”
residual concentration and a “long” cleanup time reflect much less effective performance. “NA” denotes that the
technology is not applicable to this situation. (?) denotes a high degree of uncertainty regarding the performance of
this technology.
a
Because few cases of achieving cleanup goals have been reported, these qualitative assessments reflect the judgment
of the NRC committee members.
1.9 SUMMARY
Chlorinated solvents have been highly useful for many commercial purposes, especially for
cleaning of clothes, machine parts and electronic circuits. However, because of the many
environmental problems they have caused, their use has come under strict regulatory control,
and this has led to seeking more environmentally benign replacements for chlorinated solvents,
and closer control of their usage coupled with recycling used solvents. These changes have
resulted in a drastic reduction in chlorinated solvent production and a greatly minimized
problem with environmental contamination. Nevertheless, the legacy of soil and groundwater
contamination from past use and disposal practices constitutes one of the most difficult and
costly environmental problems yet being faced, a problem that is not likely to be resolved
satisfactorily for decades to come.
Since 1980, when the widespread contamination with chlorinated solvents became apparent,
much has been learned about their movement and fate in the environment, and many different
technical approaches to addressing their contamination of soil, air and groundwater have been
developed. Because of the cost, magnitude and difficulty of remediation of sites contaminated
with chlorinated solvents, the seeking and applying of new physical, chemical and biological
approaches has not yet ended. There is no silver bullet technology that is appropriate for every
site, each requires a detailed characterization of hydrogeology and contaminant history, setting
of realistic goals for remediation, and selection of the most appropriate technologies for
reaching that goal. Because of the great expense involved, engineers and regulators addressing
this complex problem must be familiar not only with past approaches and technologies, but also
with those that are evolving. The advantages and limitations of each, along with their relative
costs and effectiveness, need to be well understood. Only then can cost-effective solutions be
developed that satisfy both the short- and long-term needs at a given site.
24 P.L. McCarty
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