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Encyclopedia of Physical Science and Technology en015j-696 August 2, 2001
Soil and Groundwater Pollution
Michael J. Barcelona
University of Michigan
I. Nature of the Subsurface Environment
II. Sources of Subsurface Contamination
III. Subsurface Processes Which Govern
Contaminant Behavior
IV. Remediation of Soil and Water Contamination
V. Concluding Comments
GLOSSARY
Advection The movement of ground water in the satu-
rated zone in response to differences in groundwater
elevation, hydraulic head or pressure differences.
Dispersion A hydrologic process which affects mixing of
solutes at the grain scale owing to differences in flow
path, and rates, which tend to elongate and broaden
contaminant plume dimensions.
Redox Reactions Oxidation and reduction processes
which affects the stability and persistence of electron
acceptors (e.g., oxygen, ferric iron, nitrate, etc.) and
donors (e.g., organic matter, ferrous iron, sulfide, etc.)
often mediated by microbial activity.
Saturated Zone The subsurface environment where the
void space in rock or soil is filled with ground
water.
Sorption A physicochemical phenomenon which retards
the movement of solutes due to adsorptive and absorp-
tive partitioning on aquifer sediments.
Unsaturated (Vadose) Zone The subsurface environ-
ment from the surface soil zone to the capillary fringe
above the zone of saturation.
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Gary A. Robbins
University of Connecticut
THE CONTAMINATION of soil and groundwater with
organic, inorganic, and microbial constituents has oc-
curred for many centuries due to improper handling of
waste materials ranging from septic wastes to those arising
from products of commerce. In the last century, the rise of
industrial manufacturing complexes, synthetic chemical/
petrochemical, metal working and mining processes have
led to the release of complex mixtures of contaminants.
Chemical contamination of shallow soil and groundwa-
ter by petrochemical, pesticides, radionuclides, metals,
and agricultural chemicals is recognized as a major po-
tential human and environmental health risk due primar-
ily to ground water use for drinking water. The reduc-
tion of groundwater supply from over use and degrada-
tion of groundwater quality by contamination in many
countries have become major issues bearing on public
health and socioeconomic development. Water resource
development and protection programs have responded to
these challenges over the past 2 decades with the applica-
tion of a diverse array of options to ameliorate long-term
impacts.
The subsurface is a dynamic environment extending
downward from the earth’s surface. It is composed of soils
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50
or sediments overlying bedrock. It forms the framework
for physical, chemical, and biological processes that in-
fluence the fate and transport of contaminants. A multi-
tude of surface and near-surface sources of contamination
exist which vary in extent, frequency, and magnitude of
potential human or environmental risk that may persist
for years to many decades. Contaminant mixtures ranging
from soluble compounds and biochemical transformation
products are transported in the subsurface by ground wa-
ter. During their transport, contaminants are attenuated or
transformed into other constituents by hydrogeochemical
processes. Scientific and engineering approaches to sub-
surface contamination have matured from initial detection
and assessment efforts to current programs, which incor-
porate integrated hydrogeochemical and microbial reme-
diation approaches in the context of the three-dimensional
nature of geologic conditions and contamination.
I. NATURE OF THE SUBSURFACE
ENVIRONMENT
A. Soils and Sediments
Soils are the in-situ products of physical and chemical
weathering of rocks or preexisting soils. The type of soil
and its thickness are largely functions of the parent ma-
terial and the climate (whether humid or arid). As shown
in Fig. 1, soils are aggregates composed of solid materi-
als (rock fragments, minerals, or organic matter) and void
space that may be filled partially or wholly with water.
Sediments are soils that have been transported away from
their source and deposited. Sediments may be transported
by gravity movement down slope, surface water, such as
streams or rivers, wind, or glacial ice. In pollution inves-
tigations, soils and sediments are typically classified us-
ing the Unified Soil Classification System. In this system
soils are classified on the basis of grain size and grain size
distribution. From a pollution standpoint the most critical
properties of soils are listed in Table I. These properties in-
fluence the migration of water and contaminants in the soil.
FIGURE 1 Soil phases.
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Soil and Groundwater Pollution
TABLE I Properties of Soils and Sediments that
Influence Subsurface Pollution Migration
Properties
Mineralogy
Grain shape
Grain size and distribution
Density
Porosity (amount of void space)
Soil moisture
Organic content
Degree of cementation or compaction
Anisotropy
Heterogeneity
B. Rocks
When soils or sediments are compacted or cemented they
form a type of rock called a sedimentary rock. Sedimen-
tary rocks also include rocks formed by chemical precipi-
tation (e.g., limestone) and organic deposition (e.g., coal).
If these rocks are exposed to high temperatures and pres-
sures resulting from large-scale earth processes, they can
be recrystallized into metamorphic rocks (e.g., slate, mar-
ble). If rocks are subject to melting and then cooling, they
form igneous rocks (e.g., granite).
C. Geologic Setting/Conceptual Model
The geologic setting includes the types of soils, sediments
and rocks, their properties, and their three-dimensional
distribution in space. In evaluating the migration of pol-
lutants in groundwater, the geologic setting is analogous
to the plumbing in a house. It controls the direction of
groundwater and contaminant movement. A key objec-
tive in conducting site investigations of pollution entails
obtaining information on subsurface geologic conditions.
This information aids in the development of a concep-
tual model used in evaluating contaminant conditions and
developing a remedial strategy. Historically, the scope of
geologic investigations conducted at contamination sites
was an extension of the type of investigation conducted
for construction purposes. We have since learned to apply
new techniques and methods to help expedite site investi-
gations and reduce their costs. Significant advances have
also been made in investigating fracture conditions in rock.
D. Hydrogeologic Settings
Figure 2 shows an idealized profile of the subsurface.
From the surface down to the water table, the soil void
space is partially filled with water and is termed the un-
saturated zone. Below the water table, the soil void space
is completely filled with water. This zone is termed the
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Soil and Groundwater Pollution
FIGURE 2 Subsurface profile.
saturated zone and the water in the saturated zone is called
ground water. Just above the water table, the pore space
may be completely filled with water but the water is held
by capillarity. This zone is called the capillary fringe. Wa-
ter infiltrates down into the soil to the water table under
gravity and capillarity and then continues to migrate as
groundwater. The groundwater environment is dynamic
and ground water is always moving. In general, ground
water moves from areas of high elevation to areas of low
elevation. The exact path that the groundwater and pol-
lution will take is dependent on how groundwater eleva-
tion changes and the geologic setting. For example, in
igneous and metamorphic rocks, ground water flow is re-
stricted to fractures and faults in the rock (see Fig. 3).
The movement of the groundwater is then dependent on
the orientation and aperture (opening) width of fractures,
fracture continuity, and the spatial variation in ground wa-
ter elevation (hydraulic gradient). In soils, sediments, and
sedimentary rocks groundwater and pollution move pre-
dominately through the pore spaces between grains. In
some cases these materials may also be fractured and flow
through both fractures and pore space occurs simultane-
ously. In recent years, we have learned that if soils or
rocks are exposed for long periods of time to pollution,
FIGURE 3 Ground water flow restricted to fractures in crystalline
rock.
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51
the pollutants can become trapped in dead-end pore (or
fracture) spaces by diffusion. Remedial efforts may be re-
quired for a long period to allow pollutants to diffuse out
of the dead-end pore spaces.
Typically, groundwater pollution is characterized
through the installation and sampling of wells. We have
since learned that wells may provide misleading informa-
tion owing to vertical concentration averaging. In eval-
uating the hydrogeologic setting we have learned that a
three-dimensional point of view is required to understand
the flow of groundwater and migration of pollution in the
subsurface. This requires installing multilevel samplers in
soil or sediments and conducting packer testing in wells
in fractured rock.
II. SOURCES OF SUBSURFACE
CONTAMINATION
A. Source Type and Magnitude
Subsurface contamination can occur due to releases of
chemical and microbial constituents from both natural
and anthropogenic sources. Contaminant sources there-
fore vary in extent and magnitude by virtue of their ori-
gin. Natural sources may be exemplified by point releases
from economic mineral deposits (e.g., petroleum seeps)
or trace elements contained in regional geologic materi-
als (e.g., release of arsenic due to natural reduction pro-
cesses). Similarly, anthropogenic sources include point re-
leases from underground fuel or solvent storage tanks as
well as local to regional sources, such as waste impound-
ments, landfills, mining activities, or excessive ground wa-
ter withdrawals resulting in the intrusion of saline waters
or brines. It should be recognized that due to the interplay
between hydrologic processes and the nature of contami-
nant releases, the demarcation between point and nonpoint
sources may be indistinct, particularly in historical areas
of commercial, industrial, and human activity.
A number of authors have provided detailed lists of
contaminant sources based on the origin as well as the
scale of consequences. The focus of the present treatment
is on anthropogenic sources, which range over multiple
scales of source extent and contaminant impacts (Johnson
et al., 2000; Westrick, 1990).
Table II contains a categorization of sources of con-
tamination developed by the USEPA (1976) and Of-
fice of Technology Assessment (1984) as referenced by
Canter et al. (1988). The categories are based on a func-
tional classification of various activities. It is evident from
the previously cited categorization that many engineered
systems designed to contain potentially toxic or hazardous
products and wastes need to be considered in the inventory
of sources. This point is borne out by the detailed listing
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TABLE II Sources of Groundwater Contamination
Category Type of source (example)
I. Sources designed to discharge substances (Injection wells,
land applications)
II. Sources designed to store, treat, and/or dispose of substances,
discharge through planned release (landfills, impoundments,
tanks)
III. Sources designed to retain substances during transport or
transmission (pipelines, motor transportation)
IV. Sources discharging substances as consequences of other
planned activities
V. Sources providing a conduit or inducing discharge through
altered flow patterns (oil, gas, or water wells)
VI. Naturally occurring sources whose discharge is created and/or
exacerbated by human activity (natural leaching, saltwater
intrusion, ground water–surface water interactions)
of sources with the estimated amount of material involved
contained in Table III.
It should be noted that the number of facilities and the
approximate amounts of material involved are subject to
considerable uncertainty, which is common to both data
sources. In any one category, the specific design, age,
release characteristics, and the resident hydrogeologic
setting all exert influence on the duration and extent of
potential releases to soil or groundwater. It is entirely pos-
sible that some of the sources represent little or no con-
tinuing threat to the environment or human health since
regulations have been passed requiring upgrading or re-
placement of critical components. An example of this view
is the status of underground storage tanks for fuels which
were to be removed or upgraded by the fall of 1998 by
regulation (USEPA, 1976).
Certain sources were identified as “important” in the
Office of Technology Assessment report due to their num-
ber, diversity, areal extent and toxicity. These sources have
been designated by a star (*) preceding their place in the ta-
ble. In general, these sources represent those which are nu-
merous, widespread, with multiple types of contaminants
which may pose a threat to human or environmental health.
Sources can only be generally linked to specific chem-
ical or microbial contaminants and their potential effects
on human and environmental health. The picture at local,
regional, and national scales may be blurred by chemical
contaminants, which appear in several categories (e.g.,
benzene or trichloroethylene which have been associated
both with landfill leachates and leaking storage tanks).
Also, natural biodegradation processes act on primary
contaminants to yield transformation products (e.g., vinyl
chloride and dichloroethylene from trichloroethylene or
perchloroethylene).
The correspondence of sources and the potential threat
from specific contaminants can be better appreciated by
Soil and Groundwater Pollution
considering sources as a function of scale, i.e., either point
or nonpoint sources. Point sources are those which are
confined or generally release contaminants in a single,
geographic area. Example of point sources are septic or
underground storage tanks, landfills, or surface impound-
ments. Nonpoint sources may affect large geographic
areas by the nature of their release characteristics. The
principal examples of nonpoint sources are agricultural
applications of fertilizers and pesticides in rural areas. In
this case, millions of acres dedicated to selected crops
(e.g., cotton, corn, soybeans, wheat, etc.) receive annual
applications of pesticides or nutrients (i.e., nitrate, urea,
phosphates). These substances may infiltrate with ground-
water recharge, resulting in widespread contamination.
Table IV contains a selective review of contaminants
from point and nonpoint sources with a general estimate
of persistence and risk to human environmental health.
The persistence and risk estimates are generalized on the
basis of subsurface transport and fate and risks to surface
water environments or drinking water.
Identification of contaminant source types and major
contaminants are really the initial steps in the evaluation
of the potential for soil and groundwater contamination.
From this point, a number of factors having to do with the
hydrogeologic settings, pollutant fate, and transport and
potential exposure points (i.e., sensitive aquatic environ-
ments and drinking water sources) should be considered.
A number of source and site prioritization methods have
been proposed for use in assessment of pollution poten-
tial (Aller et al., 1985; Canter, 1985; Canter et al., 1988)
for product and waste management activities. The end re-
sult of these applications of these methods is a composite
score, usually based on a conceptual model of pollution
potential with which to select sites or prioritize further
assessment efforts.
B. Extent of Subsurface Contamination
The extent and magnitude of subsurface contamination
are largely dependent on source characteristics, contami-
nant properties, and the influence of hydrologic and bio-
geochemical processes on their transport and fate. Con-
taminants of concern to human or environmental health
may originate from diverse sources and be transported
differentially. For example, benzene and trichloroethy-
lene detected in groundwater due to storage tank releases
or landfills are soluble contaminants with major differ-
ences in contaminant behavior. Benzene, irrespective of
source characteristics, may migrate in ground water but
is known to be microbially degraded, particularly under
aerobic conditions, to organic acids and other less harmful
metabolites. Trichloroethylene on the other hand, is trans-
formed by microbial reductive dechlorination processes to
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Soil and Groundwater Pollution 53

TABLE III Ground Water/Contamination Sources Categories and Extent

Approximate number Approximate amount
Source of facilities of materiala

Category I
∗ Subsurface percolation ∼16 to 20 M >800 bgy
Injection wells >0.5 M ∼450 to 600 bgy
∗ Land applications sites >3,000 ∼4 Mtons/yr
Category II
∗ Landfills >95,000 >280 Mtons/yr
Open dumps ∼2,400 ∼10 bgy
∗ Surface impoundments >180,000 >800 bgy
∗ Waste tailings ? ∼580 Mtons/yr
∗ Underground storage tanks >2.5 M >35 bgy
∗ Radioactive disposal sites ∼31 ∼3.7 Myd3
Category III
Pipelines >900,000 miles >280 bgy
∗ Materials transport/transfer >16,000 spills ∼14 Mtons/yr
Category IV
∗ Irrigation practices ∼50–60 M acres2 ∼169 M acre-ft
∗ Pesticide applications ∼280 M acres2 ∼0.3 Mtons/yr
∗ Fertilizer applications ∼229 M acres2 ∼42 Mtons/yr
∗ Urban runoff ∼21–33 M acres ?
∗ Mining/mine drainage >80,000 active on >4 M acres ∼108 bgy
Animal feeding ∼1935 sites ∼8 Mtons/yr
Category V
Oil production wells ∼548,000 active >2 M abandoned ?
∗ Other wells ? ?
Category VI ? ?
Ground water–surface water interactions ? ?
∗ Natural leaching ? ?
Saltwater intrusion ? ?

a Units: bgy, billions of gallons/yr; bg, billion gallons; Mtons/yr, millions of tons/yr; Myd3 , millions of yd3 .

dichloroethylene and vinyl chloride, which are far more
mobile and potentially toxic contaminants.
The dimensions of subsurface transport and transfor-
mation coupled with the properties of intermediate by-
products further complicate risk assessments as well as the
application of technologies to manage potential health or
environmental impacts. For example, contaminant charac-
teristics as well as associated risks differ significantly be-
tween source areas and the dissolved plume. Fortunately,
predictive models incorporating fate and transport consid-
erations have been developed to cope with these complica-
tions given adequate source and site characterization data.
These models are widely distributed and are discussed in
depth in Section III.
Over the past 2 decades, local discoveries of impaired
soil or groundwater quality conditions have led to
national, regional, and state contaminant assessment
programs (Council on Environmental Quality, 1981).
Assessment programs initially focused on drinking water
quality and organic contaminant detection frequency.
They were later directed at the extent of contamination of
the subsurface using both public water supply wells and
those installed for monitoring purposes at known sites of
contamination. Early drinking water quality assessment
programs should not be interpreted solely as indicative
of the quality of the resource, since finished rather than
raw drinking water quality was measured. In this respect,
they also included the effects of drinking water treatment
and disinfection. Disinfection of drinking water by either
chlorine compounds or ozone has been shown to result in
the production of disinfection by-products from reactions
with natural organic matter including haloform com-
pounds (e.g., chloroform, bromoform, dichloromethane
etc.).
Assessment results directed toward the contamination
of the resource have been conducted in increasing numbers
at the national, regional, and state levels. Selected exam-
ples of the results of resource contamination assessment
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54 Soil and Groundwater Pollution

TABLE IV Major Contaminants from Selected Point and Nonpoint Sources with General Estimates of Per-
sistence and Risk

Generala
Source type Selected major contaminants Persistence Risk

Point
Septic tanks Ammonia (NH3 )-N L M
[Nitrate (NO− −
3 ); Nitrite (NO2 )] [H;L] [M;L]
Underground storage tanks Fuels; petroleum hydrocarbons M M
[benzene, methyl-t-butyl ether] [M;H] [H;M]
Chlorinated solvents H H
[percholoroethylene; trichloroethylene] [H;H] [H;H]
Breakdown products [H;M] [M;H]
[dichloroethylene, vinyl chloride]
Landfills/hazardous waste sites Fuels, solvents (M;H) (M;H)
Trace metals [Chromium, Cadmium, Lead] [M;H;H] [M;H;H]
[Arsenic, Copper, Mercury] [M;H;H] [M-H;M;H]
Organic constituents
[polychlorinated biphenyls, phenols, polycyclic [H;M;H] [H;M;M]
aromatic hydrocarbons]
Inorganic constituents
[HCN] [H] [H]
Surface wastewater impoundments Inorganic and organic constituents (as above) (as above) (as above)
Nonpoint
Agricultural chemicals Insecticides
[Chlordane; Diazinon] [H;L] [M;L]
Herbicides
[Atrazine; 2-4D] [M;L] [M;L]
Fertilizers
[NO− 3 , NH3 ] [H;L] [M;L]
Natural soil/sediment constituents Arsenic, Selenium [M;M] [M-H;M-H]
Radon [H] [M-H]
a Risk Designations: [H]—high, [M]—medium, [L]—low.

methods from nonpoint sources are detailed in the fol-
lowing with an emphasis on contaminants of concern.
It is important to recognize that land use (both past and
present) and hydrogeology exert major effects on the oc-
currence of contaminants as well as their spatial distri-
butions. For example, nitrate and boron concentrations
in groundwater were evaluated by Eckhardt et al. (1989)
for undeveloped, developed (sewered and unsewered), and
agricultural land uses. They found that nitrate concentra-
tions were not significantly different among the various
uses. Boron concentrations on the other hand were signif-
icantly higher in recently sewered and agricultural areas
than in unsewered areas but not from long-term sewered
areas. The results suggest little difference between nitrate
and boron concentrations in shallow groundwater in ar-
eas with agricultural or septic tank uses. (Other studies
have shown significantly higher nitrate concentrations in
both areas of high-density septic tank uses compared to
undeveloped areas (Bicki et al., 1984), as well as in shal-
low groundwater aquifers in agricultural areas (Hallberg,
1986).)
In general, shallow groundwater resources are con-
sidered more vulnerable to surface sources of con-
tamination, particularly water table aquifers which are
overlain by transmissive soils and thin permeable un-
saturated zones. Soil properties or the presence of
macropores have been linked to higher pesticide leach-
ing potential and groundwater contamination by DBCP
(1,2 dibromochloropropane) in agricultural regions of
California (Teso et al., 1988). The conditions in the
Netherlands’ shallow groundwater resources underscore
the vulnerability of these formations particularly in urban
and agriculturally intensive areas. In this summary, ni-
trate, pesticides, and selected trace metals (e.g. Zn, Pb, Cu,
and Cd) were found to be significantly higher in shallow
groundwater in areas of intensive development or agricul-
tural use. An example of this correspondence for nitrate
is shown in Figs. 4a and b, where shallow aquifers with
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Soil and Groundwater Pollution 55

permeable overburden, consistently, showed the highest
levels of nitrate. This type of pattern of agricultural land
use, groundwater vulnerability, and contamination by sep-
tic, fertilizer, and pesticide contamination has been noted
in a number of studies (Goetsch et al., 1992; Mason et al.,
1987; USEPA, 1982).
Volatile organic compounds, most often associated with
fuel and solvent sources (e.g., storage tanks, spills, waste
landfills, and abandoned waste sites) have been the sub-
ject of a number of groundwater and drinking water in-
vestigations (Johnson et al., 2000; Squillace et al., 1996;
Westrick, 1990). Here again, the coincidence of high lev-
els of contaminants in shallow ground water and intensive
human activities is a clear result.
In the Groundwater Supply Survey reviewed by
Westrick (1990), approximately 340 large (i.e., >10,000
people) and 600 small (i.e., <10,000 people) systems
were sampled. Sampling was done in both a random and
nonrandom fashion. The most frequently observed com-
pounds were chlorinated solvents (e.g., tetrachloroethy-
lene, trichloroethylene, trichloroethane, dichloroethylene,
carbon tetrachloride, etc.) and aromatic hydrocarbons
(e.g., benzene, toluene, ethyl benzene, and xylenes). Pos-
itive results for contamination detection were found in
28% (random) and 37% of (nonrandom) large system
samples. Small systems’ positives were 17 and 22%, re-
spectively. About half of the water supplies were posi-
tive for more than one volatile compound and multiple
chlorinated compounds often were often detected in in-
dividual samples. This at least in part reflects the break-
down of higher chlorinated compounds to intermediate
products like dichloroethylene. The presence of aromatic

FIGURE 4a Major hydrologic and soil conditions in The Netherlands: (A) higher zone with bedrock close to the land
surface; (B) higher freely draining areas with predominantly sandy soils at the land surface; (C) low artificially drained
polder areas with mainly clayey and peaty deposits; and (D) higher freely draining sandy coastal dune belt. (From
“Regional Ground Water Quality,” Copyright 1993, Van Nostrand Reinhold, New York. Reprinted by permission of
John Wiley & Sons, Inc.)
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FIGURE 4b Nitrate concentration in shallow ground water based
in 1989 data (mg/L nitrate-N). (From “Regional Ground Wa-
ter Quality,” Copyright 1993, Van Nostrand Reinhold, New York.
Reprinted with permission of John Wiley & Sons, Inc.)
hydrocarbons seemed to point to contributions from un-
derground storage tanks at service stations in developed
areas.
A more recent U.S. Geological Survey-Nation Water
Quality Assessment program study of the occurrence of
the fuel additive MTBE in shallow groundwater supports
this view. Urban areas had positive MTBE results in
27% of the samples while the frequency in agricultural
areas was only 1.3%. MTBE was not necessarily found
with the aromatic fuel hydrocarbons. This in part can be
explained by the greater stability and mobility of MTBE
relative to the aromatics. Johnson et al. (2000) brought up
the question of just how many water supply wells have yet
to be contaminated by MTBE given that it has only been
in widespread use for the last 2 decades. The fact that the
results of these surveys are similar supports the contention
that ground water quality, especially where groundwater
use and intensive development coincide, needs to be pro-
tected if the resource is to continue to yield potable water
for a large fraction of our population.
Two major types of contamination of concern are as-
sociated with microbial pathogens (e.g., bacteria, virus,
cryptospiridium) and chemical or radiogenic elements na-
tive to the subsurface environments. Microbial contamina-
tion of water supply is a worldwide problem which has far
more damaging immediate consequences in causing water
Soil and Groundwater Pollution
borne disease than those arising from chemical sources.
Groundwater supplies have traditionally been considered
safe from pathogens owing to their limited persistence and
mobility in the subsurface. More recent work has shown
that viable bacterial and viral mobility can be quite signif-
icant and water supply operators should exercise care in
well-head protection from septic influences as well as in
disinfection practices.
Natural distributions of elements in subsurface geologic
formations can give rise to ground water or soil zone con-
tamination. Two examples of note are the generation of
radioactive decay products (e.g., radon gas, radium) from
natural thorium and uranium, and the release of naturally
occurring arsenic or selenium from earth materials.
Wanty and Nordstrom (1993) have reviewed the origins
and occurrence of natural radionuclides in ground water
and soil gas. They recommend monitoring vigilance par-
ticularly for radium and radon gas, which undergo fur-
ther decay via emission of (beta) and (alpha) radiation. A
number of field studies have identified areas in the United
States with potentially significant problems with these ra-
dionuclides (Gundersen and Wanty, 1993). In many cases,
more active ventilation of the subfloors or basements of
buildings can minimize radon exposures, while radium
problems may require water supply treatment at the plant
or the use of alternative supply.
Chemical contamination resulting from the natural oc-
currence of selected elements in subsurface materials has
been recognized as a potentially broad problem in certain
areas. For example, under reducing conditions, arsenic III
is soluble in the H3 AsO3 and H2 AsO3 forms in natural
waters. Results from leaching of arsenic minerals within
areas of the United States and the world which have natu-
rally high aquifer sediment levels of arsenic levels may be
high enough to cause neurological damage, liver damage,
and cancers via drinking water. Most of the U.S. reports of
elevated arsenic levels in groundwater have been limited
to regional studies with relatively small sample sizes. It is
notable that, owing to the differential mobility of oxidized
versus reduced arsenic and selenium (the opposite trend
holds in that reduced Se forms are far less soluble or mo-
bile than oxidized forms), evaluations of contamination
must pay careful attention to groundwater age, depth, and
geochemistry.
The main questions that need to be considered for
many intensive agricultural and urban areas are: How do
we confront current contaminated conditions and protect
that portion of the resource which has yet to be compro-
mised? The answer to both questions lies in public pol-
icy to support the reasoned stewardship of the resource
and bringing to bear the best available technologies to
protect and remediate known contamination sources and
plumes.
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Soil and Groundwater Pollution
III. SUBSURFACE PROCESSES WHICH
GOVERN CONTAMINANT BEHAVIOR
A. Transport
In the unsaturated zone, dissolved contaminants migrate
in conjunction with infiltrating water. As such, they mi-
grate under the influence of gravity and capillarity. The
migration of contaminants in the unsaturated zone is
largely controlled by the amounts of precipitation and the
unsaturated permeability of the soils and sediments. An-
other mechanism for the transport of volatile contaminants
in the unsaturated zone is vapor diffusion. Chemicals with
low boiling points (fuels and organic solvents) can read-
ily volatilize into soil air. Through gaseous diffusion these
chemicals can spread in the unsaturated zone and partition
into soil pore water or the groundwater. The ultimate fate
of volatile organic chemicals will depend on their origin
and extent as free-phase liquids (e.g., LNAPL—lighter
than aqueous phase, or DNAPL—more dense than aque-
ous phase) and to which they are involved in chemical or
microbial processes. Examples of various release scenar-
ios are shown in Figs. 5a through e.
Once in the saturated zone, dissolved contaminants mi-
grate from their source principally by advection and dis-
FIGURE 5 Organic contaminant distribution resulting from inter-
actions between geologic heterogeneities and types of sources.
Stippling represents dissolved or vapor phase contaminants. Solid
black represents nonaqueous phase liquids (NAPLs).
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57
persion. Advection refers to the movement of groundwater
and contaminants owing to spatial or temporal variations
in hydraulic head (water level elevation). Advection is de-
scribed by Darcy’s law. Variations in hydraulic head may
be caused by surface elevation differences, spatial varia-
tions in recharge or discharge locations, or be induced by
well pumpage.
Dispersion refers to the spreading of contaminants ow-
ing to velocity variations. Although contaminant spread-
ing can occur by diffusion this is generally not important,
except under low permeable conditions where the ground
water velocity is very low. Dispersion acts to spread con-
tamination in three dimensions along the ground water
flow path. As such contaminant concentrations are re-
duced with distance from the source. Despite much re-
search on dispersion since the 1950s, capability to quantify
dispersion remains illusive. Difficulties stem from appar-
ent scaling of dispersion with contaminant travel distance
due to heterogeneities, concentration averaging in wells,
or not accounting for the three-dimensional nature of con-
taminant spreading.
Advection and dispersion of contaminants can be mod-
eled using analytical and numerical methods. Advance-
ment of computer technology now permits the use of
complex numerical computational methods on portable
computers. Modeling is helpful in evaluating factors that
control contaminant migration, assessing the extent of
contamination, and evaluating the effectiveness of reme-
dial measures.
B. Reactivity
1. Chemical
Chemicals that migrate in groundwater which are not at-
tenuated by chemical and biological processes are said to
be conservative. Conservative chemicals move at the rate
of the ground water. Reactive chemicals are those that are
attenuated in velocity or are mass dissipated. Table V lists
pertinent reactions that can influence contaminant migra-
tion. Whether a given reaction is important depends on
the chemistry of the contaminant, redox conditions, and
the nature of the solids that make up the soil or rock. For
example, organic contaminants such as benzene may be
velocity attenuated by adsorption on to organic matter in
the soil. The extent of adsorption is, among other factors,
dependent on the amount of organic matter present. The
migration of chromium depends on oxidation-reduction
conditions and pH.
These factors control the speciation of chromium.
Under oxidizing conditions and low pH, the stable
chromium species is hexavalent chromium(+6). Hexava-
lent chromium binds with oxygen to form a negatively
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58 Soil and Groundwater Pollution

TABLE V Soil and Vadose Zone Treatment Methods

Method category Target contaminants Residual

Excavation-incineration Organic compounds metals, inorganic compounds, Ash to appropriate landfill

Excavation-fixation or Stabilization
Excavation-vitrification
Slurry walls or grout curtains (constructed
in place)
Soil thermal treating via injection of steam,
inductive heating, etc. . .
Soil vapor extraction and/or venting
(introduction of air)
miscellaneous contaminants
All of the above
Long–lived radionuclides
Many types of contaminant sources
Volatile organic compounds
Volatile organic compounds and aerobically
degraded nonvolatile organic compounds
Landfilling of residue
Appropriate repository
Isolation of contaminants from vadose zone
and upper saturated zone. Requires monitoring
Vacuum capture and treatment of all gases
Treatment of off gases

charged chromate ion that is highly mobile in groundwater.
Under reduced conditions trivalent chromium (+3) is
stable and can precipitate out of solution as an oxy-
hydroxide or adsorb readily on to minerals or organic
matter.
The velocity of contaminants may also be influenced
by the diffusion of contaminants into dead space pores or
fractures (where the ground water velocity is essentially
negligible) or within grains. These processes may become
significant in attenuating the movement of contaminants
at sites where soil and rocks have been exposed to con-
tamination for long periods.
Radioactive substances migrating in ground water
undergo radioactive decay. If decay rates are high
(half-lives are short) relative to the groundwater veloc-
ity, radioactive decay is an effective mass attenuation
mechanism.
2. Biological
Bacteria can have a significant influence on the mass at-
tenuation of organic and inorganic chemicals. Bacteria
in the subsurface can utilize organic contaminants as a
food source, particularly hydrocarbons in fuels. Bacteria
are known to play a major role in attenuating the aro-
matic hydrocarbons from gasoline releases. The oxida-
tion of organic chemicals by bacteria requires electron
acceptors. Under aerobic conditions, oxygen is the elec-
tron acceptor. Under anaerobic conditions, iron (Fe III),
manganese (Mn IV), nitrogen (Nitrate), and sulfur (Sul-
fate) act as electron acceptors. Under highly reduced con-
ditions, methanogens can utilize organic contaminants in
the production of methane. The utilization of organic con-
taminants by bacteria generally results in changes to the
overall water quality (e.g., increase in pH, decrease in Eh,
increases in total dissolved solids, reduced metal species,
alkalinity). Although biological degradation of contami-
nants is complex in detail, it is often simulated as a first-
order process (Domenico, 1987).
IV. REMEDIATION OF SOIL
AND WATER CONTAMINATION
Groundwater resources provide approximately one half
of the nation’s water supply as well as a major fraction
of water used for self-supplied industry. Since both the
consequences of human activities and the natural leach-
ing processes may compromise the quality of water, treat-
ment is frequently necessary prior to use. Preferably, the
treatment would be accomplished by engineered treatment
plants prior to distribution to the consumer. However, this
is not always possible, particularly in cases where con-
sumers are geographically distant from the resource or
where distribution system treatment other than at the point
of use is too expensive.
In this sense, impaired water quality can exert a major
influence on quantity. In addition further resource damage
must be minimized to ensure the quality of future water
supply. Treatment of contaminated public resources has
been required by statute when the responsible party(ies)
are known or the USEPA assumes responsibility for
cleanup when the sites of sources have been abandoned.
Over the past 2 decades, numerous approaches have been
developed to contain contaminated groundwater plumes,
treat or destroy contaminants in the subsurface (i.e.,
in situ) or above ground, or manage risk to human or en-
vironmental health by active monitoring of ongoing natu-
ral processes which diminish contaminant concentrations.
These approaches range from those which are technology
based such as soil venting, vapor extraction, groundwater
pumping with treatment above ground, or in-situ meth-
ods; to those based on observed plume behavior relative
to known exposure points. In the latter case, called natural
attenuation, model predictions are made for the outcome
of natural processes such as advection/dispersion induced
dilution, sorption on aquifer sediments, volatilization, and
biodegradation. Natural attenuation remedies require ac-
tive monitoring as well as periodic reviews of progress
toward cleanup or risk management goods. It is implied
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Soil and Groundwater Pollution 59

in regulatory guidance for natural attenuation remedies tions which are sand sized or greater. The in-situ thermal
that steps will be taken to isolate or remove contaminant methods have been used successfully in pilot-scale to mo-
sources, particularly in cases where dissolved plumes are bilize organic compounds with boiling points less than
expanding. 150◦ C even when the contaminants are in a nonaqueous
Remediation of near-surface contamination sources fre- phase liquid.
quently requires consideration of vadose zone residuals as One category of the vadose zone treatment technologies
well as nonaqueous phase liquids in the capillary fringe which has been applied in relatively numerous instances
or fully saturated environment of groundwater. Though is soil vapor extraction (SVE) (with or without the intro-
cleanup technologies directed at the vadose and saturated duction of air) (Hutzler et al., 1989; Johnson et al., 1990,
zones are discussed separately here, it should be empha- 1994). The most effective applications of SVE employ
sized that thorough cleanup of the subsurface requires a careful control of applied vacuum through designed
combined approach. Also, with the exception of pump extraction points about which are arrayed air introduction
and treat technologies, the track records of many exist- points to ensure airflow through the most contaminated
ing or developing treatment technologies are limited to 10 zones. Figure 6a shows a typical SVE process diagram
to 20 years at most. Many of these methods have been (NRC, 1994). Success with SVE methods has been more
found to have limited effectiveness, though research and difficult to achieve where toxic nonvolatile compounds
development efforts are progressing. are present in the source, or where permeability of the
subsurface limits the zone influence of gas flow.
Vadose zone treatment methods focused on source areas
A. Soil (Vadose) Zone Methods can effectively limit the long-term release of contaminants
Many of the sources of soil and groundwater contamina-
tion occur at or near the land surface. With this in mind,
source removal implies the removal, destruction, or iso-
lation of contaminated soil which would otherwise repre-
sent a long-term source of contaminants to groundwater.
Where these approaches are feasible and cost effective,
they are clearly preferable to attempt to destroy contami-
nants in-place. Table VI provides a selective summary of
soil and vadose zone treatment methods ranging from ex-
cavation and removal to contaminant treatment in place.
Above-ground treatments favor total contaminant destruc-
tion rather than isolation of contaminants except in the
cases of radionuclides for which only time will cause to
dissipate the radiation.
In-situ methods are generally less effective than above-
ground remedies. However, they minimize surface disrup-
tion of utilities, infrastructure, etc., and may extend well
below the depth of excavation capability. The construction
of grout (clay) curtains or slurry walls has been shown to
be effective in source control efforts particularly in forma-

TABLE VI Chemical and Microbial Processes Influencing

Contaminant Attenuation

Velocity attenuation Adsorption, ion exchange

Dead space diffusion
Intragranular diffusion
Mass attenuation Radioactive decay
Biodegradation (coupled with reduction of FIGURE 6 Process control diagram for (a) SVE, (b) air sparging,
oxygen, iron, manganese, sulfur, nitrogen or (c) direct chemical injection, (d) geochemical enhancement for
methanogenous) bioremediation. [Reprinted with permission from “Alternatvies for
Groundwater Cleanup,” 1994, by the National Academy of Sci-
Precipitation (resulting from pH or redox
ences. Courtesy of the National Academy Press, Washington,
changes)
D.C.]
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60 Soil and Groundwater Pollution

to soil gas or ground water. As such, their operation in con-
cert with plume control technologies has shown promise
for many mobile, persistent contaminants. Above-ground
treatments of off-gases from SVE systems include thermal
or catalytic oxidation, combustion in internal combustion
engines, and activated carbon adsorption prior to release
to the atmosphere.
B. Groundwater (Saturated) Zone Methods
The transport of contaminants in soil gas and groundwater
represent major pathways of contaminant exposure to hu-
mans or sensitive ecosystems. The vadose zone treatment
methods discussed previously exert control over fur-
ther contaminant release to soil gas when applied and
monitored carefully.
Effective treatment or containment of dissolved con-
taminant plumes and NAPL phases in the capillary fringe
or saturated zones represent a continuing challenge to
remediation technologies. Effective source control mea-
sures depend on careful delineation (in three dimensions)
of contaminants, and characterization efforts may limit the
success of saturated zone contaminant treatment or control
measures. Selected treatment or containment methods for
the saturated zone are provided in Table VII. Flow barriers
constructed by slurry wall, grout injection, or sheet pile
methods have been used in some instances to channel or
contain contaminated groundwater usually in combination
with pumping control methods.
Among the first saturated zone treatment and contain-
ment methods applied for LNAPL contaminants (i.e.,
lighter than aqueous phase liquids) were interceptor
trenches that penetrated the upper portion of the near
source saturated zone. In these cases, the trench provides
a collection point for hydrocarbon contaminants by skim-
ming, discrete liquid pumping, or sorption for subsequent
treatment or re-use.
Pump and treat systems were employed early in the de-
velopment of groundwater remediation approaches. Pump
and treat methods frequently involve pumping ground-
water from contaminated portions of the plume to the
surface for treatment by air-stripping volatile organic
compounds. Off-gases can be treated as in SVE treat-
ment streams. Though they frequently failed to remove
significant contaminant mass, these systems often suc-
ceeded in controlling plume migration to off-site bound-
aries or potential exposure points. Plume control and a
more rapid approach to groundwater cleanup goals may be
achievable when pumping and treatment are followed by
reinjection.
Air sparging technologies seek to introduce air (or O2 )
bubbles into the upper saturated zone to strip volatile or-
ganics from the plume to be captured in the vadose zone,
add O2 to stimulate degradation processes, and influence
water flow patterns for enhanced extraction or reinjection.
A process diagram for air sparging is shown in Fig. 6b
(NRC, 1994). Research has shown that the formation of
gas stream tubes for escaping sparged air limited the zone
of influence of these systems (Pankow and Cherry, 1996).
It is clear that the technology is best suited for degrad-
able organic compounds in plume rather than source
areas.
The realization that contaminant mass removal was lim-
ited in many instances where the preceding technologies
were employed led to the development of more aggres-
sive treatment approaches. In many cases, the newer tech-
nologies incorporated the more successful flow control
and plume containment advantages of previous work. It
should be recognized that continuing improvements in
site characterization monitoring approaches enabled better

TABLE VII Saturated Zone Treatment Methods

Method category Target contaminants Residual

Slurry wall/grout curtain/sheet pile Flow control None

Interceptor trenches
Pump and treat (with or without reinjection)
Air sparging with or without soil vapor
extraction or control pumping
Reactive permeable barriers
Injection of surfactants, direct chemical
reductants, or oxidants with or without
control pumping
In-situ enhanced bioremediation injection of
electron acceptors, donors, and nutrients
In-situ bioaugmentation introduction of
microorganisms, nutrients, cosubstrates,
electron donor/acceptors
Lighter than aqueous phase Liquids–LNAPLs
Dissolved contaminants
Volatile organic compounds
Organic compounds and selected trace metals
Organic compounds and selected trace metals
Solubilized mobilized or degradable organic
compounds and selected trace metals
Degradable organic compounds and selected
trace metals
Oil/H2 O separation sorption
Air stripping and/or carbon sorption for organic
compounds off-gas treatment
Off-gas treatment and carbon sorption
Various polishing treatments as necessary
Treatment of pumped effluent
Treatment of pumped effluent
Treatment of pumped effluent
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Soil and Groundwater Pollution
resolution of contaminant source and plume dimensions
by the late 1980s.
Reactive barrier plume treatment methods represent a
standard of comparison for in-situ treatment of contami-
nants that are recalcitrant to other mitigation methods. The
initial work in North America issued from observations
that zero-valent iron (Fe0 filings) could cause the
dechlorination of dissolved tetrachloroethylene and
trichloroethylene.
The placement of these materials in the path of con-
taminant plumes as permeable reactive barriers followed
logically. The technology has been employed at numerous
locations in the United States and Canada for chlorinated
solvents as well as for toxic oxidized trace metals (e.g.,
Cr VI). Many of these systems have achieved sustained
dechlorination and reductive capacity after 10 years of
service.
Further in-situ treatments have been developed to sol-
ubilize or mobilize contaminants, particularly NAPLs by
the use of surfactants, or to oxidize or reduce contaminants
directly. All of these technologies require reagent injec-
tion and extraction flow control and may demand above-
ground polishing treatments to assure success. These tech-
niques are emerging from pilot scale to field applications
with rather encouraging results (Bedient et al., 1999; Bjerg
et al., 2000; Sabatini et al., 1995).
The injection of chemicals into the subsurface to di-
rectly treat subsurface contamination often occurs with
significant local changes in subsurface geochemistry. For
example, oxidant injection (e.g., magnesium peroxide or
hydrogen peroxide) can result in increased oxygen con-
centrations, which may stimulate natural aerobic micro-
bial activity. The enhancement of conditions for microbial
degradation of contaminants supports microbial restora-
tion of the subsurface resource. Process diagrams for di-
rect chemical introduction and geochemical enhancement
approaches for bioremediation are shown in Figs. 6c and
6d, respectively.
More recent refinements of biostimulation technolo-
gies have led to the introduction of microorganisms ca-
pable of contaminant degradation along with engineered
geochemical adjustments. The organisms introduced in
these schemes have been isolated from previously con-
taminated sites or waste-water treatment plants and are not
genetically modified bacteria. Although currently at the
research stage, bioaugmentation techniques have shown
promise for contaminants, which either fail to degrade
or undergo transformation to more mobile and toxic by-
products under natural conditions. Working in concert
with natural flow conditions, the success of these technolo-
gies rests on the use of low-maintenance injection methods
to sustain favorable degradation conditions and microbial
viability.
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61
V. CONCLUDING COMMENTS
The field of contaminant hydrogeology in the last 2
decades has incorporated new concepts in mathemati-
cal geology, geostatistics, subsurface microbiology, toxi-
cology, biogeochemistry, and environmental engineering.
Exciting developments have been made in the detection,
assessment, mitigation, and elimination of subsurface con-
tamination, largely in response to the need to meet chal-
lenges posed by expedient chemical waste and product
handling methods. While significant challenges remain to
be met, the tools exist to avoid further contamination of
soil and groundwater and minimize risk to human and
environmental health.
In the near future, scientists and engineers will be drawn
further into advanced resource protection efforts particu-
larly where water quantity and quality concerns clash with
the demands of population and economic growth across
the globe.
SEE ALSO THE FOLLOWING ARTICLES
DRINKING WATER QUALITY AND TREATMENT • ENVIRON-
MENTAL GEOCHEMISTRY • ENVIRONMENTAL MEASURE-
MENTS • ENVIRONMENTAL OBSERVATION AND FORE-
CASTING SYSTEMS • POLLUTION, AIR • POLLUTION
CONTROL • POLLUTION, ENVIRONMENTAL • SOIL
MECHANICS • SOIL PHYSICS • TRANSPORT AND FATE
OF CHEMICALS IN THE ENVIRONMENT • WATER POLLU-
TION • WATER RESOURCES
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