Groundwater Pollution: Sources, Mechanisms, and Prevention

C Postigo, Institute of Environmental Assessment and Water Research (IDAEA-CSIC), Barcelona, Spain
DE Martinez and S Grondona, IIMyC (CONICET-Universidad Nacional de Mar del Plata) - IGCyC (CIC- UNMDP),
Argentina KSB Miglioranza, Lab. EcotoxicologÚa y Contaminación Ambiental. IIMyC, CONICET-UNMDP, Argentina

© 2018 Elsevier Inc. All rights reserved.

History of Groundwater Pollution: A Land Use-Based Perspective

Groundwater pollution, caused or induced by human activities, is a phenomenon that has occurred since the earliest Holocene, about
10,000 years ago, when mankind became sedentary and began to settle villages and farm the land. As a consequence, relevant amounts of
nitrogen were released into groundwater from farming activities, and microbial pathogens and bacteria were also spread in the aquifers
from sanitary disposal of domestic waste. Since then, agriculture and urbanization have expanded and intensified through time due to
population growth, and with them the associated groundwater pollution. Industry is another relevant human activity that impairs
groundwater quality. In this regard, ancient civilizations that mined for gemstones, gold, silver, copper, and lead were responsible for
releasing essentially inorganic compounds into groundwater bodies. After the industrial revolution and the later development of the
petrochemical and the pharmaceutical industries, wastes reaching groundwater also included organic compounds, such as tars, phenols,
oils, and complex mixtures of synthetic organic chemicals (Morris et al., 2003).
Due to population growth, groundwater pollution has dramatically increased over the past 50 years as a result of intensive and
extensive exploitation of this water resource for human consumption (drinking and sanitation) and diverse economic uses (tourism,
landscaping, agriculture, energy production, and other industrial purposes), and radical changes in land use.
Groundwater over-abstraction lowers the level of the groundwater table. This may result in reduced surface water natural discharge
flows, land subsidence, and even groundwater quality impairment. Changes in groundwater flow pattern may displace saline waters and
move the sea water–groundwater interface inland, and moreover, increase surface water infiltration. Furthermore, different quality waters
could mix in wells and boreholes, impacting even water quality of deep aquifers (Custodio, 2000).
Land-use practices have an impact on groundwater resources by increasing groundwater demand (e.g., land irrigation for agriculture or
irrigation of golf courses in arid and semi-arid areas) and changing recharge patterns. Recharge rate is reduced on sloping ground
deforested areas or re-forested areas with nondeciduous species. However, it is substantially increased in areas dedicated to irrigated
crops. Land use affects not only the recharge rate but also the recharge quality. In fact, pollutants found in a groundwater body are usually
closely related to the activity carried out on the land surface. For instance, in the case of urbanized areas, nitrogen compounds, synthetic
organic chemicals, and pathogens are likely to leach into groundwater. On the other hand, intensification of crop production will be
responsible for the release of agro-chemicals (i.e., pesticides and fertilizers) into the aquifer. Besides, in the case of irrigated cropping, an
additional hazard arises when reclaimed water is used for irrigation because persistent wastewater-derived organic contaminants may
eventually reach groundwater.

Types and Sources of Groundwater Pollution

Types of Groundwater Pollutants
Pollutants found in groundwater can be classified into two broad groups: biological and chemical, and within the latter they can be
further subclassified into two other groups: inorganic and organic.
Biological pollutants include bacteria, viruses, and parasites that are responsible for waterborne diseases, such as typhoid fever,
cholera, dysentery, polio, hepatitis, and schistosomiasis. The presence of Coliform bacteria is indicator of recent fecal pollution. This type
of contamination is exclusively attributed to human and animal waste.
Inorganic pollutants include cations and anions, most of them naturally occurring in soils, sediments, and rocks. Cations include heavy
metals, such as cadmium (Cd), chromium (Cr VI), lead (Pb), manganese (Mn), mercury (Hg), and nickel (Ni). These highly toxic
chemicals may reach groundwater after mineral dissolution with acidic waters (from mining or industrial activities) or after industrial
2
emissions. Anions of concern in groundwater include nitrate (NO 3 ), nitrite (NO2 ), sulfate (SO4 ), fluoride (F ), chloride (Cl ), arsenate
3 3
(AsO4 ), and arsenite (AsO3 ). Anthropogenic activities and naturally occurring nitrification processes are responsible for high
2
nitrate/nitrite concentrations in groundwater, whereas seawater intrusion and rock weathering increase SO 4 and Cl levels. Natural arsenic
contaminated waters have been found in Argentina, Chile, Mexico, China, Hungary, India, Bangladesh, and Vietnam, and they constitute a
public health problem in the Bengal Basin (India), where more than 40 million people are affected. This arsenic-rich groundwater is
restricted to poorly flushed aquifers located inland or in closed basins in arid or semi-arid areas or in reducing aquifers derived from
alluvium (Chakraborty et al., 2015).
Organic pollutants are those chemicals that contain carbon as a molecular backbone. The list of chemicals that most frequently leach
into groundwater include volatile organic compounds soluble in water, such as trihalomethanes (e.g., chloroform, bromodi-
chloromethane), solvents (e.g., tetrachloroethylene [PCE], trichloroethylene [TCE]), gasoline components (e.g., BTEX: benzene, toluene,
ethylbenzene, and xylene), and gasoline oxygenates (e.g., methyl-tert-butyl-ether [MTBE]); and less volatile and soluble

Encyclopedia of the Anthropocene

https://doi.org/10.1016/B978-0-12-809665-9.09880-3 87
88 Groundwater Pollution: Sources, Mechanisms, and Prevention

compounds, such as medium to highly polar pesticides (e.g., atrazines, phenylureas), and pharmaceuticals and personal care products
(e.g., caffeine, carbamazepine, sulfamethoxazole). In addition to parent compounds, some of the transformation by-products resulting
from natural break-down or biotransformation reactions may also be present in groundwater. Sometimes these metabolites are more toxic
than the original compounds.

Sources of Groundwater Pollutants

Groundwater pollution may originate from point sources and nonpoint sources. Point sources can be well identified in space, for example,
landfills, underground storage tanks, or septic systems; whereas nonpoint sources are dispersed over large areas, for example, pesticide
application in agriculture. In the first case, well-defined pollutant plumes following the hydraulic gradient of the aquifer system are
formed, whereas in the second case, pollutants spread widely into the subsurface. The latter is more difficult to identify, measure, and
control than the former.
Some of these pollutant sources are located above the ground surface and some of them are placed in the subsurface. This aspect will
affect pollutant transfer to the saturated zone.

Onsite sewage facilities: septic tanks

Septic systems are used in developed countries to treat household wastewater in those areas not connected to public sewers. In the case of
developing countries, this is the most extended practice adopted to improve sanitation conditions. They are cost-effective systems to treat
wastewater in low-density population areas (e.g., they are run by 20% of households in the United States). However, if they are not
properly placed, designed, constructed, or maintained, they constitute a source of biological and chemical (i.e., nitrates, detergents,
pharmaceuticals, personal care products, and oils) contamination into groundwater. Septic system failure causes untreated wastewater to
break out at the surface or to seep into the soils. These systems are known to be ineffective in nutrient (nitrates and phosphates) removal,
and therefore, nutrient migration into source waters is directly related to the retention capacity of the soil surrounding the leaching field of
the septic system. Moreover, some organic chemicals are resilient to the anaerobic treatment that occurs in the septic tank and therefore,
they are also susceptible to be released into the subsurface. The chemicals used to clean these systems can create additional pollutants that
may eventually end up in the groundwater.

Solid waste landfills

Landfills contribute to minimize the risks of waste disposal to public health and safety. However, it generates leachates that represent a
major threat to groundwater quality. The leachates result from the liquid waste dumped in the landfill and the decomposition of solid
waste (aided by precipitation and surface runoff events). Therefore, the improper disposal of untreated industrial and hazardous chemicals
into municipal waste landfills will increase the presence of toxic and hazardous chemicals in the leachates. The common hazardous
chemicals found in landfill leachates and their plumes are heavy metals and different classes of organic compounds (e.g., brominated
flame retardants, phenols, halogenated hydrocarbons, polychlorinated biphenyls, plasti-cizers, phthalates, dioxins). Most of them are toxic
and persistent compounds in the environment, and therefore, may cause severe contamination problems. Landfill leachates have a pH
value ranging between 6 and 9, high content of total dissolved solids and extremely high chemical oxygen demand. They also contain
elevated concentrations of common inorganic anions and cations (e.g., bicarbonate, sulfate, iron, manganese, sodium, chloride), and
dissolved organic matter (e.g., aldehydes, alcohols, short-chain sugars). Leachate composition changes through time, showing an upward
trend on the pH value from young to stabilized leachate. The contrary is observed for chemical oxygen demand, total dissolved solids, and
most chemical components of the leachate, due to natural attenuation (biodegradation, sorption, and redox reactions) occurring in the
subsoil. There is a great concern about closed landfills because if they are not properly capped with an impermeable material (e.g., clay)
before closure they may become hot spots for groundwater pollution and generate hazardous leachates after precipitation events.

Surface impoundments: liquid waste disposal

Surface impoundments are shallow lagoons or reservoirs commonly used to temporarily store or treat hazardous liquid waste. These sites
are protected with several liners (plastic/clay) at the bottom in order to prevent leaks. However, the liquid waste confined in them may
potentially enter the subsoil because these liners are not leak-free.

Land application of reclaimed water and treated sewage sludge

The use of treated wastewater and sewage sludge on agricultural lands for crop production is very beneficial in the sense that they provide
essential plant nutrients. Furthermore, the use of reclaimed water contributes to increase water resources, and land application of sludge
helps improve the soil structure. However, these practices usually represent a potential risk to groundwater quality because they may
introduce chemicals resilient to water and sludge treatments into the aquifer. In addition to inorganic chemicals, organic compounds can
also be found in treated water and sludge. The profile of the organic chemicals present in treated water is different to that found in sludge.
In this regard, medium to highly polar organic compounds are commonly found in treated wastewater, whereas more hydrophobic organic
compounds are usually present in stabilized sludge. Therefore, due to their physical– chemical properties, the compounds present
in reclaimed water are more likely to move downward up to the groundwater table than those found in sewage
sludge, which are rather sorbed onto soil particles.
 Groundwater Pollution: Sources, Mechanisms, and Prevention 89

Land application of pesticides and fertilizers

Although pesticides and fertilizers are mainly applied for crop production, they are also used for gardening, and pest control in
households, industries, and municipalities. Once released into the environment, pesticides may have different behaviors and fates. Some
of them may break down or degrade by biotic and abiotic processes; whereas others will remain unchanged for a long period of time,
becoming very persistent in the environment. The latter was observed for organochlorine pesticides, which are currently largely forbidden
in many developed countries. Pesticides such as atrazine, lindane (g-hexachlorocyclohexane), and endosulfan were frequently detected in
groundwater in countries where their use was forbidden for many years. The same situation was observed for the atrazine transformation
products desethyl atrazine and desisopropyl atrazine and for the dichlobenil metabolite BAM in several European countries where the use
of the parent compounds was also banned.
The presence of pesticides in the groundwater is a consequence of their physical–chemical properties (e.g., solubility, ionization
constant, octanol-water partition coefficient) and their transport through the vadose zone where degradation processes are scarce.
Furthermore, the misapplication of agro-chemicals, in terms of quantity and frequency, enhances the leaching potential of these products
to groundwater. As for fertilizers, nitrate pollution of groundwater is a major concern because nitrate is a highly soluble anion that behaves
conservatively in most aquifers. As a consequence, it freely moves with water through most soils without being retarded or sorbed onto
soil particles during its transport.

Chemical storage tanks

The use of underground and aboveground storage tanks to store chemicals (for industrial processes), fuels (petroleum solvents, motor
fuels, heating oil), and wastes (used oil and industrial hazardous wastes) is a common practice worldwide. Spills out of these tanks may
occur when they are overfilled. Moreover, the appearance of leaks on bare steel tanks also takes place with age due to corrosion.
Therefore, the tank content can seep out, move within the subsoil, and eventually contaminate groundwater. Improper handling and usage
of poor-quality containers are factors that lead to groundwater pollution and enhance the risks associated with storage tanks. Abandoned
underground tanks are not subject to any inspection, maintenance, or clean-up, and sometimes their locations are unknown, and
consequently the occurrence of possible leaks cannot be detected.
Storage tanks are also used for the transport of chemicals by trucks and trains. Accidental spills occurring during transport and transfer
operations constitute a relevant source of hazardous chemicals into groundwater.

Pipelines
Pipelines are used to transport any chemical stable substance (liquid or gas), such as industrial chemicals and oil brines. They have been
also set for the transport of wastes (e.g., sewer pipelines). Regardless of pipe material, leaks eventually appear in pipeline systems, leading
to a risk of groundwater contamination. This phenomenon is even more relevant if the materials transported through the pipes are
corrosive. Pollutants seeping out of the pipelines are directly linked to the material that they carry. In this regard, a high risk of biological
and chemical pollution is associated with sewer pipelines.

Mining activities
Mining activities have a big impact on the quantity and quality of water resources. Both active and abandoned mines represent a threat to
groundwater. After precipitation events, the acid mine drainages, which consist of leachates containing metals and minerals generated
from mine wastes for hundreds of years, can migrate through the unsaturated zone down to the saturated zone. The low leachate pH
(occasionally below 3) enhances heavy metal mobilization from the rocks. Moreover, groundwater can also be contaminated after spill or
leak of the chemicals used to separate a target mineral substance from the ore (e.g., cyanide or sulfuric acid).

Improperly constructed wells, abandoned wells, and injection wells

Heavy pumping modifies groundwater flow. This may result in the mixture of aged groundwater with surface water or shallow
groundwater. Thus the mixture of clean aged groundwater with polluted water could negatively affect the quality of the former. This effect
may also take place when pumping wells are not properly constructed (e.g., poor casing or inadequate cover).
Abandoned and dry wells are also a source of groundwater pollution because they are collectors of storm water runoff or they may be
used for waste disposal.
The deep injection of industrial toxic waste is in some places considered to be a safe waste disposal practice. However, the liquid
waste may occasionally travel horizontally and migrate up to ground water through neighboring abandoned wells. Injection wells are
extensively used to dispose the brines produced during hydraulic fracturing (fracking) activities.

Application of de-icing chemicals

De-icing of roadways, airports, and aircraft surfaces is a common maintenance activity in countries with severe winters. This is usually
accomplished with chemicals such as inorganic salts (NaCl, MgCl 2, CaCl2, or KCl), and alcohols and glycols (propylene glycol and
ethylene glycol). De-icing formulations also include benzotriazole and methyl-substituted benzotriazoles in order to prevent corrosion and
reduce flammability. The brines formed as the salt dissolves and after application of the de-icing formulation can be introduced into the
subsurface with precipitation events and alter groundwater quality.
90 Groundwater Pollution: Sources, Mechanisms, and Prevention

Fig. 1 Main processes involved in contaminant transport in the aquifer.

Mechanisms Involved in Groundwater Pollution: Contaminant Transport

The amount of a compound that can be found in groundwater depends on its speciation and solubility. However, its movement and its fate
into the aquifer are ruled by different processes (see Fig. 1) that may also be related to each other:
• physical processes: advection, diffusion, dispersion, evaporation, infiltration, filtration, and volatilization;
• geochemical processes: acid–base reactions, sorption–desorption, ion exchange, oxidation-–reduction, precipitation-–dissolution, and
surface complexation; and
• biochemical processes: transpiration, bacterial respiration, decay, and cell synthesis.
The movement of a chemical pollutant within an aquifer is described by the “transport equation” (see Eq. 1):
@C ¼ v @C þ D @ 2C @q (1)
@t @x 2
@x @t

where C is the concentration of the contaminant, t is time, x is the distance in the flow path, v is the average water flow velocity in the
porous media, D is the hydrodynamic dispersion coefficient, and q is a coefficient regarding to processes affecting the concentration. This
equation considers mass conservation over an elemental volume of the aquifer and it is also known as the advection –dispersion equation,
as these are the two main processes controlling solute transport in a porous media. It includes (from left to right) an advection term, a
dispersion term, and a source/sink term that describes different processes affecting the concentration. Thus this equation considers the
multiple ways in which a contaminant could move within an aquifer. Overall, advection is by far more relevant for contaminant transport
than diffusion in sedimentary aquifers, whereas diffusion is the most relevant process in aquitards (i.e., geological materials of low
hydraulic conductivity).

Physical Processes
Physical processes are the main processes involved in contaminant transport within the aquifer and consequently responsible for the
formation of the typical “contaminant plumes” caused by point contamination sources. Delineation of these plumes can be performed by
measuring the temperature (MacFarlane et al., 1983) or more usually the concentration of the pollutant in groundwater (Conant et al.,
2004).

Advection
Advection is usually the dominant process for contaminant transport in the subsurface. It refers to the transport of the contaminant caused
by the bulk movement of flowing groundwater. The advective flow velocity or the average linear groundwater velocity included in the
advection term of Eq. 1 depends on the average (bulk) properties, essentially the average permeability, of the aquifer material and the
average hydraulic gradient between two points, and can be quantified using Darcy’s law (Eq. 2):

v¼k i (2)
 Groundwater Pollution: Sources, Mechanisms, and Prevention 91

1 1
where v is the groundwater velocity (m s ), k is the hydraulic conductivity of the aquifer (m s ), and i is the hydraulic gradient. However,
this approach is too simple to evaluate contaminant transport, as it does not take into account other processes happening in the subsurface,
such as dispersion, diffusion, or sorption that also affect the groundwater flow rate within the aquifer.
The one-dimensional advective flux of a contaminant carried out by groundwater through the aquifer porous medium can be expressed
by Eq. 3:

J ¼ vx Cne (3)
2 1
where J is the mass flux per unit area per unit time (mg m s ), vx is the average linear groundwater velocity in the direction of the
1 1
groundwater flow (m s ), C is the concentration of the contaminant (mg L ), and ne is the effective porosity of the geological medium.

Molecular diffusion
While advection is the process by which a contaminant moves according to a hydraulic gradient (i.e., from areas of high hydraulic
potential to areas of low hydraulic potential), molecular diffusion is the process that makes a contaminant move following a chemical
gradient (i.e., from areas of high concentration to areas of low concentration). This process (i.e., the change in concentration over time) is
also function of the change in concentration in space in a one-dimensional system, and responds to Fick’s second law (see Eq. 4):

@C ¼ D 2 (4)
@C
dif
@t @x
2

where Ddif is the diffusion coefficient in water. Diffusion of a contaminant in a porous media is smaller than in pure water due to the
collision of the contaminant with the aquifer material and the tortuosity of the flow paths. Thus the diffusion coefficient, besides being
specific to each molecule, should be corrected for each geologic material.

Mechanical dispersion
Tortuosity of the flow paths (e.g., differences in pore size and path lengths), as well as friction with pore walls, makes groundwater
molecules and the contaminants that they may carry to move differently within the aquifer porous medium. This process, known as
mechanical dispersion, causes mechanical mixing and dilution effects along the flow path. Mechanical dispersion is longitudinal when the
mixing occurs along the direction of the groundwater flow, and transverse when the mixing takes place perpendicular to the direction of
the groundwater flow. Values for longitudinal dispersivity are usually one order of magnitude larger than those observed for transverse
dispersivity because local variations in groundwater velocity are stronger in the direction of the flow than perpendicular to it ( Schulze-
Makuch, 2009). This is the reason why contamination plumes are typically long and skinny.

Hydrodynamic dispersion
Due to the overlapping effect of the two previously described physical processes for contaminant transport in a heterogeneous porous
medium, both are combined into a parameter called the hydrodynamic dispersion coefficient, which is defined in Eq. 5:

D ¼ ax vx þ D (5)
2 1
where D is the hydrodynamic dispersion in the flow direction (m s ), ax is the longitudinal dispersivity (m), vx is the advective velocity
1 2 1
(m s ), and D is the effective diffusion coefficient for a contaminant in a porous medium (m s ) that takes into account the tortuosity
paths of a specific geological media. This parameter is considered in the dispersion-related term of Eq. 1.
The net result of the hydrodynamic dispersion, described by the aforementioned term, is an overall decrease of the contaminant
concentration and the contaminant spread to clean areas of the aquifer.

Volatilization
Volatilization of a contaminant is the partitioning of its concentration between the aqueous and vapor phases. Within an aquifer, this
process can occur in the vadose zone and at the water table. The volatility of a contaminant depends on its solubility, vapor pressure, and
Henry’s law constant. The Henry’s law constant or the air-water partition coefficient (KH) (see Eq. 6) indicates the volatility of the
contaminant:
Cair
(6)
KH ¼ CW
where Cair is the contaminant concentration in the gas phase and CW is the contaminant concentration in the aqueous phase. The higher
the KH of a contaminant is the more easily it evaporates from the aqueous phase.

Filtration
Physical filtration can also take place within the aquifer. This process retains biological organisms and particles that are larger than the
aquifer pores onto the soil.
92 Groundwater Pollution: Sources, Mechanisms, and Prevention

Geochemical Processes
The last term in Eq. 1, that is, (@q/@t), is known as the source/sink term. It involves all the geochemical and biological processes that
can modify the contaminant concentration, usually decreasing it. These reactions are usually divided into a small group of processes:
acid–base reactions, adsorption–desorption, ion exchange, oxidation–reduction, precipitation–dissolution, retardation, and complexation.

Acid–base reactions
þ
Acid–base reactions are chemical reactions that involve the proton (H ) transfer between an acid and a base. The degree of acidity of
þ
natural waters is indicated by their proton activity that is reflected in the pH value ( log H ). Groundwater pH and the presence of natural
buffers in the soil aquifer have a relevant effect in the solubility of contaminants and minerals in the aquifer (Egboka et al., 1989).

Mineral dissolution plays an important role in contaminant mobility in groundwater. On the one hand, this process may release the
contaminants sorbed onto the minerals and consequently increase the contaminant concentration in groundwater. On the other hand,
dissolution of minerals may alter the water chemistry and aid in contaminant adsorption or precipitation. This is the case for carbonate
minerals (e.g., calcite and dolomite) that are capable of neutralizing acid waters (e.g., mining leachates) according to Eq. 7.

þ 2þ (7)
CaCO3 þ H ¼ Ca þ HCO3
Carbonate minerals are good buffers for neutral and acid pH ranges. However, aluminosilicate minerals present high buffer efficiency at
pH values above 9. Therefore the aquifer materials strongly influence the mobility of contaminants in the subsurface. Groundwater pH is
also relevant for the speciation and consequently the solubility of relevant contaminants in groundwater.
In this regard, acidic waters contribute to release heavy metals from the soil, which is a natural sink for these compounds.

Sorption–desorption processes
An aquifer is formed by a solid matrix where water and dissolved substances, mostly in ionic form, move through. At pH values
commonly measured in groundwater, solid surfaces of the aquifer such as clay minerals, oxides, and organic matter are negatively
charged, and consequently, the positively charged ions are retained onto these surfaces by electrostatic forces and even covalent bonding.
This process is known as sorption and is very relevant in contaminant hydrology because it contributes to decreased contaminant
concentrations in water.
The affinity of a pollutant to sorb onto the aquifer solid phase is defined by the distribution or partition coefficient ( Kd), which is
defined as follows:
CS
K (8)
d¼ CW
where CS is the contaminant adsorbed concentration (mg/kg) and CW is the contaminant dissolved concentration (mg/L). Overall, high Kd
values indicate a high affinity of the contaminant for the solid phase. On the contrary, low Kd values indicate the preference of the
chemical to remain in the aqueous phase. The sorption–desorption behavior of a contaminant onto solid particles is described through
sorption isotherms. In a linear model, Kd is the slope of the isotherm. However, this model does not consider the limited capacity of the
solid surface for adsorption and the effects that contaminant concentration may have on adsorption. Therefore, additional adsorption
response curves were established: the Freundlich and Langmuir isotherms. These two isotherms are linear at low contaminant
concentrations. However, their slope change at high contaminant concentrations. The Freundlich isotherm does not consider a maximum
limit on adsorption; whereas the Langmuir isotherm includes an adsorption capacity term in its definition (see Fig. 2) (Deutsch, 1997).

Fig. 2 Adsorption isotherms: (A) linear isotherm, (B) Freundlich isotherm, and (C) Langmuir isotherm.
 Groundwater Pollution: Sources, Mechanisms, and Prevention 93

Heavy metals are dissolved mostly as cations and, therefore, adsorption is one of the most important mechanisms to remove them from
groundwater. Adsorption of organic contaminants onto soil particles depends on the contaminant properties and the soil properties.
Nonpolar (less soluble) compounds are more likely to sorb onto soils than highly water-soluble contaminants. Moreover, soils with high
organic matter content and/or high clay content present high sorption capacity for organic contaminants.

Adsorption is not an irreversible process; therefore, the sorbed contaminant could be released (desorbed) again into the aqueous phase.
In consequence, the contaminant moves slower through the aquifer than the groundwater. This effect is accounted for by the retardation
factor and is defined as follows (see Eq. 9):
R ¼ VX ¼ 1 þ ðKd r (9)
ð =yÞÞ
Vcont
where Vx is the average linear groundwater velocity, Vcont is the advective velocity of the contaminant, Kd is the sorption coefficient of the
contaminant, r is the soil bulk density, and y is the volumetric water content (Domenico and Schwartz, 1998). According to Eq. 9,
contaminants with high Kd values will move in groundwater very slowly. The Kd value has been used as the input for the source/sink term
in many contaminant transport models. This parameter also indicates the affinity of different metals for a specific aquifer, and
consequently, it can be used as an indicator of the aquifer contamination potential (Jakomin et al., 2015).

Ion exchange
Ion exchange reactions occur when other ions enter in contact with the aquifer material, and one ion adsorbed onto the solid phase is
replaced by another ion dissolved in the aqueous phase. This process takes place as a function of selectivity of the solid material with the
ions adsorbed onto its surface and those present in solution, the concentration and dimension of the ions in the aqueous phase and the solid
phase, and the configuration of the exchange sites at the water-solid interface. Ion exchange, in particular cation exchange, is a relevant
phenomenon that controls the fate of ionic contaminants such as heavy metals in aquifers with high content of clay minerals, metal oxides
and hydroxides, and organic matter, which are materials that present a high cation exchange capacity factor. As for cationic exchange,
divalent cations that present a high energy of adsorption tend to replace monovalent ions, so that the latter are more likely to remain in
solution.

Oxidation–reduction processes
Oxidation–reduction (redox) reactions involve the transfer of electrons between chemical species. Oxidation results in the loss of
electrons or the increase of the oxidation state by a molecule. The electrons that are lost by a molecule during oxidation are gained by a
different molecule that gets reduced in the process. Dissolved contaminants can be found in different oxidation states in the aquifer, and
the oxidation state is directly related to the contaminant speciation, mobility, degradation, and toxicity. This aspect is relevant in the case
of heavy metals. For instance, hexavalent chromium (Cr (VI)) is highly toxic and relatively mobile if compared to trivalent chromium (Cr
(III)). Uranium, selenium, arsenic, and molybdenum are less soluble (mobile) under reducing conditions than under oxidizing conditions.

Abiotic redox reactions of organic pollutants include oxidation of phenols and anilines by manganese oxides, reductive dehalogenation
of polyhalogenated alkanes, and reduction of nitroaromatic and azo compounds by reduced constituents of natural organic matter in the
presence of hydrogen sulfide, or different iron species or iron-containing minerals ( Angst and Schwarzenback, 1995). Microorganisms
usually promote redox processes in the subsurface in two different ways: by using organic matter as a substrate to build their cell mass,
and by producing suitable reactants for electron transfer in “abiotic redox reactions.”

Similarly as for pH, the redox potential of the water is expressed by the negative logarithm of the electron activity of the water (pE or
Eh). It defines the redox status of an aquifer, which contributes to predict the mobility of elements and assess the potential biodegradation
of organic contaminants in the subsurface.

Surface complexation reactions

Surface complexation reactions play a significant role in the dissolution and precipitation of minerals and consequently in the transport
and transformation of metals and organic contaminants. Complexes form by the combination of cations, anions, and sometimes molecules.
A complex is composed of a metal ion, hydrogen, or another positively charged complex, and a ligand. The ligand can be any inorganic
2 3 2
anion commonly present in groundwater (CI , F , Br , SO 4 , PO 4 , and CO 3 ). The ligand might also comprise organic molecules such as
amino acids (Domenico and Schwartz, 1998). Complexes can be positively charged, zero charged, and negatively charged. Zero charged
contaminant complexes present higher mobility than positively or negatively charged contaminant complexes because they do not interact
with other ions or materials of the aquifer (Merkel et al., 2007).

Complexation of contaminants with humic or fulvic acids reduces the contaminant’s mobility. On the contrary, the complex-ation of
heavy metals, such as cadmium, chromium, copper, lead, uranium, or plutonium with inorganic or organic ligands such as Cl , ethylene-
diamine tetraacetic acid, or nitrilotriacetic acid, increases their mobility because they are not available for adsorption or precipitation
(Egboka et al., 1989).
94 Groundwater Pollution: Sources, Mechanisms, and Prevention

Biochemical Processes
Bacterial activity can biotransform or even mineralize contaminants in the subsurface. However, this is only achieved if the bacteria
located in the immediate vicinity of the contaminant have the capacity to use it as substrate, and if the contaminant is available to these
bacteria. The redox potential determines the presence of specific bacteria populations in the aquifer, hence the biotransfor-mation of
inorganic and organic contaminants.
Aerobic bacteria are able to degrade/biotransform contaminants by using oxygen as electron acceptor (see Eq. 10), and thus aerobic
degradation only takes place in oxidizing environments (positive Eh values).
1 þ 1
þH þe ¼
(10)
4 O2 2 H2O
However, in the presence of high contaminant concentrations, bacterial respiration may deplete the oxygen in the aquifer, and
consequently anoxic conditions develop in the aquifer. Biotransformation under anoxic conditions uses different oxidized compounds as
electron acceptors. These compounds will be used sequentially according to their Eh. Firstly, after oxygen depletion, denitrifying bacteria
will overtake and will use nitrate (NO3 ), a groundwater contaminant itself, as electron acceptor (see Eq. 11).
1 5 1 1
þ e ¼ N þ (11)
6 NO3 þ H þ 6 12 2 2 H2O
After nitrate depletion, other biological reactions will sequentially take place as the reducing conditions of the aquifer increase.
4þ 3þ 2
Reduction of manganese (Mn ), iron (Fe ), sulfur (SO4 ), and finally CO2, will occur upon availability of these species in the aquifer
(Christensen et al., 2000).
The reduction of metals like iron and manganese results in the dissolution of the corresponding oxides and carbonates and the
accumulation of reduced species in the aqueous phase. Sulfur reduction causes the dissolution of sulfur minerals that are ubiquitous in
mining contaminated environments, and thereby, the release of contaminant trace metals. In highly reducing environments,
methanogenesis also takes place. This process uses carbon dioxide as electron acceptor and reduces C(þ4) into C( 4) to form methane.
Reducing conditions usually dominate in confined aquifers.
The presence of different reducing zones downgradient in a contamination plume (e.g., landfill leachate) may enhance the natural
attenuation of the contaminants in the plume.

Groundwater Protection

Groundwater protection has been addressed in most countries by issuance of different rules and regulations at national or local level that
aim at preventing aquifer contamination. In this sense, laws have been issued to regulate the use and manufacture of toxic products, and
set measures to manage the waste produced by industrial activities, and to properly place and maintain waste disposal and storage
facilities (landfills, injection wells, storage tanks). Maximum allowable concentrations for some pollutants have been established, mainly
in developed countries, to preserve a good quality of the groundwater exploited for drinking water supply. In addition, well-head
protection areas and groundwater zone protection areas have also been defined in some developed countries to prevent pollution of
drinking water sources.
Groundwater protection in developing countries, where groundwater is extensively exploited as a drinking water supply or for
agricultural purposes, is usually carried out by establishing a certain distance between waste disposal areas and groundwater supply
sources (or groundwater protected zones). That distance is sometimes arbitrarily selected due to the lack of hydrogeological technical
data. It may be as small as 5 m in densely populated areas of India or it may extend up to 200 m as in Malawi ( Hiscock, 2000). Moreover,
design and construction of wells is usually controlled by institutions in charge, so that hydrogeochem-ical characteristics of the aquifer are
taken into account and wells are properly drilled.
As a general practice, monitoring programs are usually performed (according to the available economic resources in each country in
question) in order to establish good management practices.

Groundwater Protection in Europe and in the United States

In the European Union, early groundwater protection focused at controlling emissions of substances from industrial
and urban sources (Directive 80/68/EEC). However, control of diffuse pollution from agricultural and industrial
sources was considered later (e.g., the Nitrates Directive 91/676/EEC, the Plant Protection Products Directive
91/414/EEC, the Biocides Directive 98/8/EC). Waste disposal from industrial activities is regulated by the Integrated
Pollution Prevention and Control (IPPC) Directive 96/61/EC. The Landfill Directive (99/31/EC) aims at preventing or
reducing the negative effects of landfill waste on the environment, and therefore, on groundwater. In 2006,
Directive 2006/118/EC on the protection of groundwater against pollution and deterioration was adopted. This
regulation complements the Water Framework Directive (WFD, 2000/60/EC) and aims at achieving a good
quantitative and chemical status of groundwater. The assessment of good chemical status is done based on
groundwater quality
 Groundwater Pollution: Sources, Mechanisms, and Prevention 95

standards set for nitrates (50 mg/L) and pesticides and their transformation products (0.1 mg/L for individual compounds and 0.5 mg/L for
the sum of all individual compounds), and threshold values for specific pollutants that may be established by each EU Member State. The
WFD calls the Member States for the characterization of aquifers and different groundwater masses and the establishment of safeguard
zones to protect groundwater used for abstraction of drinking water. This measure has already been adopted by many of the EU Member
States.
In the United States, several federal laws contribute to groundwater protection. The Clean Water Act regulates wastewater and
pollutant discharges into surface water, thereby protecting the groundwater connected to surface water. The Safe Drinking Water Act
(SDWA) ensures the quality of drinking water by setting limits to biological, inorganic, and organic chemical contamination in drinking
water and requiring states to develop Wellhead Protection Programs. However, private wells, not-piped irrigation systems, and agricultural
and industrial groundwater supplies lie out of the SDWA’s scope. Increased protection against microbial pathogens in public water
systems that rely on groundwater sources is provided by the Ground Water Rule. The Underground Injection Control Program (UICP) was
elaborated for waste disposal or fluid storage under the SDWA rules. Thus injection wells, including septic systems, are regulated in this
program. Generation, treatment, and disposal of solid and hazardous waste are regulated under the Resource Conservation and Recovery
Act (RCRA). It implies that groundwater has to be monitored at hazardous waste facilities and municipal solid waste landfills and
corrective measures have to be adopted if needed. Underground storage tanks are also regulated under RCRA. Pesticide use and
manufactured chemicals are regulated by the Federal Insecticide, Fungicide, and Rodenticide Act (FIFRA) and the Toxic Substances
Control Act (TSCA), respectively. Finally, the Comprehensive, Environmental Response, Com-pensation and Liability Act (CERCLA, or
Superfund) was issued to remediate abandoned waste disposal sites and clean up hazardous waste contaminated areas. Potential
groundwater pollution coming from the expanding gas extraction activities employ-ing hydraulic fracturing or “fracking” technology calls
for a review of the current valid groundwater protection rules in the different states.

Conclusions: Future Trends

Anthropogenic activities have released many contaminants into the environment. Groundwater contamination is a very important issue
because it is the most important fresh water resource from a quantitative point of view, and because the contamination events taking place
on the earth surface may also reach aquifers.
The mobility, occurrence, and fate of contaminants in groundwater are determined by the contaminant itself (e.g., molecular structure,
solubility, degradability, availability, decay rates), and the physical and biogeochemical processes that take place in the subsurface.
Contaminant transport through the aquifer from a specific point source occurs due to two main physical processes: advection and
hydrodynamic dispersion. However, there are many other chemical and biological processes simultaneously occurring in the aquifer that
have an effect on contaminant concentration and speciation. These processes depend on the aquifer matrix, but also on the pH and redox
state of the system.
The impact of anthropogenic activities or land-use practices on the quality of groundwater resources may last for decades in the
subsurface. This impact can be modulated by natural factors, such as topography, soil structure, and climate, and human factors, such as
the management and planning of the economic activity and good practices. In this respect, appropriate land-use planning appears as a
relevant tool to control and prevent groundwater pollution.
Groundwater pollution associated with urban areas is likely to increase in the future, because 70% of the world population is expected
to be urban by 2050. This problem will be intensified in less developed countries as they will experience most of the urban growth.
Therefore, it is extremely important to keep drinking water sources away from contamination sources. For this, good and smart
management practices for the disposal and treatment of waste have to be implemented. In this regard, an integrated management approach
involving experts in the fields of water engineering, hydrogeology, public health and sanitation, and the adequate design and construction
of disposal systems will contribute to avoid severe groundwater contamination events and protect people ’s health. Effective groundwater
protection from diffuse pollution sources (e.g., agriculture) needs to consider aquifer vulnerability and the delineation of groundwater
protection zones. The latter is a well-established practice in developed countries, at least for the protection of groundwater used for
abstraction of drinking water, but it is still a challenge in less developed countries, due to the lack of detailed subsurface hydrogeological
information, the lack of economic resources to compensate affected land owners, or the existence of land uses that impedes its
implementation. Particularly in developing countries, the sustainable use of groundwater requires that a sensible management program
that takes into consideration the affected communities be conducted by a regulatory agency.

Groundwater pollution from point sources can be efficiently prevented through legal instruments that limit permits for high pollution
risk activities, ban the use and production of toxic substances, and thoroughly regulate waste disposal.

Acknowledgments

J.M. Campuzano-Dominguez is acknowledged for assistance in the graphic design of Fig. 1.

96 Groundwater Pollution: Sources, Mechanisms, and Prevention

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