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Chloride

S S Kaushal, University of Maryland Center for Environmental Science, Solomons, MD, USA
ã 2009 Elsevier Inc. All rights reserved.

Introduction: Chloride and Salinization increases in salinity up to 1 g l1 have been shown to
have lethal and sublethal effects on some aquatic
Salinization of inland waters has been recognized as an
plants and invertebrates in freshwater. Other work
environmental problem in arid and semiarid environ-
has also reported that acute toxicity levels for stream
ments in the United States and throughout the world
macroinvertebrates ranges from 1 to 13 g l1, which
and its temporal and spatial extent because of land use
are similar to concentrations reported recently in some
and land cover change have also now been documen-
urban streams of the United States by Kaushal et al. and
ted in humid regions. Salinization describes an increase
other areas of the world reported by Williams. Chronic
in the sum concentration of all the ionic constituents
concentrations of chloride as low as 250 mg l1 have
dissolved in inland waters, and salinities are typically
been recommended for the protection of some sensitive
described in units of milligrams per liter or millequiva-
taxa of freshwater life and human drinking water by
lents per liter. Chloride, an important anion in many
federal agencies in the United States and Canada,
salts, can comprise 5–17% of total solids in river
although there are no formal regulations for chloride
waters globally with highest relative contributions to
concentrations in inland waters.
total solids in river waters in Australia. Chloride typi-
cally comprises 1.9% the mass of sea water, where it
is most abundant in the Earth’s surface waters. It is the Natural and Anthropogenic Sources of
dominant natural form of the element chlorine with
Chloride to Inland Waters
atomic number 17, which is formed when the element
chlorine picks up an electron to form an anion, and is Under conditions of minimal anthropogenic distur-
necessary to most forms of life. bance, chloride is typically not the dominant anion
The salinity of inland waters has a world average in streams and lakes. Streams and lakes near marine
concentration of 120 mg l1, according to synthetic environments can receive substantial inputs of chlo-
work by Wetzel, and this is thought to be slightly ride from atmospheric deposition from marine
elevated above a natural range because of human sources. Similarly, a major source of salinity and
activities. Salinity in inland waters is dominated by chloride to many dilute inland waters of arid regions
the four major anions: bicarbonate (HCO 3 ), carbonate can be the ionic content of atmospheric precipitation

(CO 3 ), sulfate (SO 2
4 ), and chloride (Cl ). In inland and particulate deposition. Continental rain contains
waters that are experiencing minimal anthropogenic typically more sulfate as an anion than chloride, but
disturbance, concentrations of chloride are generally chloride ion concentrations tend to increase with
no more than a few milligrams per liter, with some proximity to the sea. Other natural sources of chlo-
local or regional variations of higher salinity. The low ride to freshwaters can include weathering of rocks
salinity and chloride concentrations of many fresh- and ion exchange in soils. Chloride-containing miner-
waters have influenced the distribution of organisms, als are usually only found in greater abundance in dry
and a long history and evolutionary adaptation to the climates or deep underground because chloride is
osmotic conditions of low salinity. soluble in water. Some of the common chloride-
High chloride concentrations as a result of saliniza- containing minerals include halite (sodium chloride),
tion can negatively influence freshwater life at the sylvite (potassium chloride), and carnallite (potas-
cellular level either from lack of water or an excess of sium magnesium chloride hexahydrate). The effects
ions (or both) that can result in a range of toxic effects, of these environmental factors can produce some
however. Cells of plants and animals can suffer from temporal and spatial variability in chloride concen-
water deficit because of difficulty in extracting water trations in streams, rivers, and lakes because of
from the surrounding environment. Microbial com- changes in hydrology and geologic setting. It has
munities are capable of adjusting their osmotic poten- been demonstrated that substantial amounts of chlo-
tial through the production of solutes within cells, but ride can also be contained in vegetation and in roots
also may show salt stress and community shifts in in watersheds, and that it can be re-released from
response to changes in increased chloride concentra- decaying plant biomass into forest soils and even-
tions and salinity. tually streams. In many soft waters, sodium (Na)
In soils, chloride concentrations above 30 mg l1 and chloride (Cl) typically occur in approximately
have been shown to damage land plants. Acute equivalent concentrations. The equivalency may be

23
24 Inorganic Chemicals _ Chloride

disrupted in streams and rivers experiencing differ- increasingly prevalent. It is now known that increas-
ences in anthropogenic sources though (Figure 1). ing land use/land cover change can increase chloride
In arid environments, salts and chloride in fresh- concentrations and contribute to salinization of fresh-
water ecosystems are primarily concentrated by evap- water in humid environments. Jobbagy and Jackson
oration of irrigation water used in agricultural reported increasing salinization and chloride concen-
practices, which ultimately leach into soils and trations because of evapotranspiration by plants and
groundwater. In areas with limited rainfall, an accu- alterations in groundwater levels as a result of
mulation of sodium and chloride may also occur. increasing tree plantations in Argentina. There have
When salinity reaches threshold concentrations of also been recent documented increases in chloride
1 g l1, freshwater resources of inland waters become concentrations in freshwaters of the Amazon River
largely useless for agriculture. Water with high solute basin because of rapid population growth, urban
concentrations can travel to streams and rivers con- expansion, and increases in wastewater and septic
tributing to further salinization of freshwater discharges.
resources and high chloride concentrations. In 2001, Road salt represents a considerable source of chlor-
Williams estimated that the annual economic costs of ide to many inland waters in colder regions (Figure 2),
salinization in Australia attributed to loss of agricul- although road salt can lose its melting ability at
tural production were $50 million, and another US temperatures below 15 to 20  C. Approximately
$90 million loss arising from degradation of infra- 51% of the world output of salt production is now
structure and loss of freshwater resources. Williams used by cold countries to deice roads in winter both
predicted that salinized landscapes will increase in grit bins and spread by winter service vehicles.
approximately sixfold within the first few decades of Benbow and Merritt estimate that some 10–15 mil-
the twenty-first century in Australia, although predi- lion tons of road salt (predominantly halite or ‘rock
cted changes in drought intensity and frequency could salt’) are used each year in the United States. Road
enhance increased chloride and salt concentrations. salt melts ice because it forms a eutectic mixture, or
It was previously thought that anthropogenic salin- mixture at such proportions that the melting point is
ization of freshwater was not significant in humid and as low as possible, and that all the constituents crys-
temperate climatic regions, where a majority of the tallize simultaneously at this temperature from liquid
global population lives and where land use change is solution.

Gunpowder/patapsco drainages
10000

1000 POBR (forest)


Sodium concentration (mg/L)

DRKR (urban)
GFCP (urban)
GFGL (suburb)

100 GFGB (suburb)


GFVN (suburb)
MAWI (urban)
GFGR (urban)
10 MCDN (ag)
BARN (low resident)

R2 = 0.0536
1
1 10 100 1000 10 000
Chloride concentration (mg/L)

Figure 1 Relationships between sodium and chloride in streams of the Gunpowder and Patapsco River watersheds in Baltimore, MD,
USA, draining differing land uses. Most ratios of sodium and chloride in steams are equivalent to halite or NaCl, but data from the
circled streams suggests differences in sources of salt to other streams due to other human sources of salt in the watersheds.
Data collection supported by Maryland Water Resources Research Center.
Inorganic Chemicals _ Chloride 25

Previous work has shown that there have been increased threefold over 50 years, with 70% of the
sharp increases in concentrations of sodium and chlor- chloride inputs estimated from industrial sources,
ide in aquatic systems of the rural northeastern and runoff from road salt, and municipal wastewaters.
Midwestern United States over decades because of Jackson and Jobbagy estimated that the amount of
road salt use. Concentrations of chloride have been Na and Cl in road salt surpassed the importance of
rapidly increasing in tributaries of the Hudson River Na and Cl deposition for the continental United States
since the 1950s because of road salt, and concentra- some time in the early 1960s. Long-term concentra-
tions of chloride have increased by over an order of tions of chloride in rural areas in the northeast are
magnitude in a mountain lake in the Hubbard Brook presently lower than in the suburban and urban areas
Experimental Forest of New Hampshire after the and other more developed areas of the eastern United
opening of highways in the 1970s. Bubeck et al. States; suburban and urban areas with greater road
showed that chloride concentrations increased at density and impervious surface coverage may be
least fivefold in Irondequoit Bay over a two-decade showing advanced stages of salinization of inland
period. The chloride concentration in Lake Erie waters. Surprisingly, long-term concentrations of
chloride are also increasing in areas of the United
States where urbanization and deicer use has roughly
remained the same possibly because of groundwater
storage over decades.
Kaushal et al. demonstrated an empirical relation-
ship between increasing impervious surface coverage
in the mid-Atlantic United States and increasing mean
annual chloride concentration found in stream water
(Figure 3). Not only small streams have been affected
by increased chloride concentrations because of land
use change, larger rivers that serve as important habi-
tat for aquatic life and drinking water supplies for
humans in metropolitan areas of the eastern United
States have also shown marked increases in chloride
concentrations since the 1950s. Recent long-term
records from drinking water intakes compiled by the
U.S. Geological Survey and U.S. Environmental Pro-
Figure 2 Road salt crystals near a storm drain entering a major tection Agency have demonstrated chloride concen-
drinking water supply in Baltimore, MD, USA. (Photo courtesy trations have increased markedly from the early
of Ken Belt.) twentieth century, suggesting that major supplies of

600
1998 1999 2000
500 2001 2002
Mean annual chloride
concentration (mg/L)

400
R2 = 0.81
300
Chronic toxicity to freshwater life

200

100
Damage to land plants

0
0 10 20 30 40 50
Rural Suburban Urban
Percent impervious surface in watershed

Figure 3 Relationship between impervious surface and mean annual concentration of chloride in streams of the Baltimore Long Term
Ecological Research site during a 5-year period (R2 = 0.81). Sites are located along a gradient of urbanization. Dashed lines indicate
thresholds for damage to some land plants and for chronic toxicity to sensitive freshwater life (Kaushal et al., 2005).
26 Inorganic Chemicals _ Chloride

drinking water in the eastern United States are con- and indirectly influence broader ecosystem processes
taminated from road salt. Kaushal et al. similarly in inland waters related to primary productivity,
reported that chloride concentrations in major drink- decomposition, nutrient spiraling and cycling, nutri-
ing water supplies of Baltimore, MD, USA, have ent recycling in lakes because of changes in mixing
increased fourfold over the last several decades regime, and the trophic complexity of food webs.
(Figure 4). Long-term increases in chloride may be The effects of salinization on these ecosystem level
indicative of regional increases in the importance properties in inland water are surprisingly less
of roadway chemicals on aquatic ecosystems and known in both arid and humid environments, but
salinization of drinking water supplies. are under current investigation.
In addition to the consistently elevated concentra-
tions of chloride, extreme fluctuations in concentra-
Ecological Implications of Increased
tions of chloride over intraannual periods due to
Chloride Concentrations
drought or deicer inputs may also provide a harsh
Increased salinization and chloride concentrations environment for many freshwater organisms and dis-
can induce a variety of ecological effects within both rupt ecosystem functions. Drought may concentrate
aquatic and terrestrial ecosystems. It can lead to the salt concentrations in groundwater and surface
acidification of streams, mobilize toxic metals from waters. The runoff of salts and other deicing com-
soils through ion exchange, affect mortality and repro- pounds containing chloride applied to roads can
duction of aquatic plants and animals, alter community also undergo large seasonal fluctuations and large
composition of plants in riparian areas and wetlands, variations preceding and following the snow events
facilitate the invasion of saltwater species into previ- (Figure 4). Fluctuations in chloride concentrations
ously freshwater ecosystems, and interfere with the may have compounded effects on biota in addition
natural mixing of lakes. At relatively low concentra- to elevated concentrations because of difficulties in
tions, salt has also been shown to alter the structure regulation of osmotic balance. Previous work has
of microbial communities. It can also inhibit the documented changes in fish assemblages in prairie
process of denitrification, a microbial process critical streams, where variations in salinity are greatest.
for removing nitrate and maintaining water quality, Previous work has also shown that monovalent Cl
in inland waters that are receiving inputs of salt for is more toxic to aquatic animals than to other forms,
the first time. Previous work has also shown that and minimum tolerance by organisms decreases as
increased chloride can inhibit nitrification and respi- fluctuations in its concentration increase. Salt toxicity
ration of organic matter. Undesirable effects of is directly related to water temperature, and its effects
increasing salinity to particular taxa may directly may be pronounced in suburban and urban streams

Drinking water supply to Baltimore, Maryland


60
LMR0015
MDE0026 R2 = 0.74
Chloride concentration (mg/L)

50
BEA
40

30
R2 = 0.44
20
R2 = 0.65
10

0
M- A- M- F- J- D- N- O- S- A- J- J- M- A- M-
79 81 83 85 87 88 90 92 94 96 98 00 02 04 06
Date

Figure 4 Examples of significant, long-term increases in baseline concentration of chloride in streams in Baltimore, MD, USA.
The R2 values are given for linear regressions. Streams are located in rural areas, but contain roads within their watersheds. LMR0015
(Little Morgan Run), MDE0026 (Middle Run), and BEA (Beaver Run) are sampling stations for tributaries to Liberty Reservoir, a major
drinking water supply for Baltimore, MD.
Inorganic Chemicals _ Chloride 27

receiving warm runoff from pavements or in arid compared with other anions of concern in pollutant
environments experiencing a greater intensity and studies (relative importance of storage in deep ground-
frequency of warmer temperatures. water, shallow groundwater, soils and sediments, or
organic transformations and vegetative uptake), accu-
mulation of salt and chloride in close proximity to
hydrological flow paths to streams, rivers, and lakes
Retention of Chloride within Watersheds
may contribute to increasing long-term salinity in
and Inland Waters
streams, rivers, and lakes. There also maybe storage
As previously noted, concentrations of chloride have and flushing of chloride during variability in hydro-
increased in inland waters of many arid environments logic conditions as reported for other mobile anions
because of agricultural practices, and inputs of with implications for interannual variations in both
sodium and chloride have also steadily increased in mass transport and concentrations.
many watersheds of the United States as a result of
increasing land use change and road deicer use. Other
work has shown that a relatively large fraction of
Conclusions
chloride entering watersheds is surprisingly retained
by soils, soil water, and groundwater. It has been Salinization of inland waters represents a major envi-
estimated that over 50% of anthropogenic salt inputs ronmental problem. Chloride is the dominant natural
from deicer use to a watershed can be retained in form of the element chlorine, and is a constituent of
shallow groundwater within watersheds, and others many salts in the environment. Long-term concentra-
have predicted the flushing of chloride to freshwater tions of chloride have increased substantially in many
ecosystems can take up to half a century. In addition, regions of the world as a result of land use and land
average annual ionic budgets estimated by Likens in a cover change. Large amounts of chloride entering
lake in New Hampshire receiving road salt inputs watersheds and inland waters can be retained within
showed considerable higher retention of chloride rela- biota and abiotically in sediments and groundwater.
tive to other ions such as Ca, Mg, Na, K, and Hþ In particular, road salt applications and accumulation
during a 6-year monitoring period. Further, work in in humid environments may now be contributing to
the same research area in the Hubbard Brook Experi- increased salinization of important drinking water
mental Forest of New Hampshire hypothesized that supplies for humans and habitat for aquatic organ-
substantial amounts of chloride can be retained in isms. Further research on factors related to the reten-
organic plant biomass and re-released following tion of chloride in inland waters may be useful in
clear-cutting of trees. elucidating mechanisms explaining long-term
The abiotic and biotic retention and storage of increases in baseline concentrations of chloride in
chloride may be of additional importance for consid- surface waters, and it may be useful in ecosystem
eration in hydrologic and ecosystem studies, where restoration and reclamation of inland waters from
chloride is typically used as a conservative tracer to anthropogenic salinization.
delineate hydrologic flow paths and biogeochemical
processing in watersheds and inland waters.
A conservative tracer is a solute that is not readily
Knowledge Gaps
used by the biota or otherwise transformed from state
to state by physical and chemical processes and pass An elucidation of the relationship between increasing
unaltered through inland water ecosystems. Given the land use/land cover change and dynamics of chloride
growing body of work demonstrating chloride reten- in inland waters are necessary in forecasting the time
tion in watersheds (e.g., increased chloride concentra- periods of salinization of many freshwater resources
tions during summer months in watersheds receiving and/or potential trajectories of recovery from salini-
road salt applications in winter months, increased zation. In addition, interactive effects between land
chloride in groundwater wells, potential organic use/land cover change and climate variability (particu-
transformations of chlorine in watersheds of New larly increased frequency and severity of drought) will
Hampshire and Sweden, etc.), it may be necessary to become increasingly important in influencing regional
further understand the abiotic and biotic mechanisms patterns of salinity and chloride in inland waters of
contributing to hindering the downstream passage of both arid and humid environments. In addition, loss
chloride due to potential uptake or temporary of vegetation can lead to the process of desertification
storage. in dry lakebeds and may influence the quantity and
Although factors and mechanisms influencing chemical composition of regional groundwater inputs
watershed storage of chloride are less known to inland waters.
28 Inorganic Chemicals _ Chloride

More work is needed to investigate factors influen- chloride dynamics and stream channel geomorphol-
cing retention of chloride, using input–ouput budgets ogy may be important in predicting solute storage and
and mass balances of chloride in watersheds of differ- residence time in streams and rivers. This can be
ing land use, topography, and watershed size. Infor- accomplished through use of chloride injection
mation on increasing chloride inputs from natural experiments in streams or it can be investigated
and anthropogenic sources (e.g., atmospheric deposi- using transects of wells placed along hydrologic flow-
tion, numbers of septic systems, water softeners, fer- paths from groundwater to streams and lakes. This is
tilizer application rates, and road salt use) can be particularly important given that stream and river
compared with hydrologic outputs in streams and restoration is an important industry and strategies to
rivers. Net retention can be determined from the dif- increase hydrologic exchange between stream chan-
ference between inputs and outputs. Work using mass nels and rivers may also lead to the accumulation of
balance has suggested that, surprisingly, chloride can road salt in banks.
be retained biologically by plants and soils in the Although further work is needed to understand the
Hubbard Brook Experimental Forest, and other dynamics of chloride, there is no doubt that it is
research on chloride dynamics in Swedish watersheds increasing in many inland waters due to anthropo-
have also suggested the importance of organic trans- genic activities. Future work should elucidate the
formations of chlorine and chloride. fluxes, flow paths, and stores of salt in the environ-
Because chloride is typically used as a hydrologic ment as a result of anthropogenic activities and the
tracer of water and human wastewater inputs, deter- biological effects of increased chloride concentrations
mining sources, ages, and hydrologic flow paths of and their variability in inland waters.
chloride is an active area of research and uses a com-
bination of stoichiometric (elemental ratios) and iso-
topic tracer approaches. It can also be used to identify
different anthropogenic sources of chloride to aqui- Further Reading
fers and inland waters. Current work uses ratios of
Naþ, Cl, Br, and I to infer sources of salt to Benbow M and Merritt RW (2005) Road salt – WQ-831. In: Lehr
JH and Keeley J (eds.) Water Encyclopedia. New York: Wiley.
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Godwin KS, Hafner SD, and Buff MF (2003) Long-term trends in
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Inorganic Chemicals _ Chloride 29

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