
Environmental Encyclopedia 3
Chlorination
aromatic organochlorine compounds are resistant to micro-
bial degradation; the aliphatic chlorinated solvents have cer-
tain anesthetic properties (e.g., chloroform); some are known
for their antiseptic properties (e.g., hexachloraphene). The
presence of chlorine imparts toxicity to many organochlorine
compounds (e.g., chlorinated pesticides).
Chlorinated hydrocarbons have many uses, including
chlorinated solvents, organochlorine pesticides, and indus-
trial compounds. Common chlorinated solvents are dichlo-
romethane (methylene chloride), chloroform, carbon tetra-
chloride, trichloroethane, trichloroethylene,
tetrachloroethane,
tetrachloroethylene
. These compounds
are used in drycleaning solvents, degreasing agents for ma-
chinery and vehicles, paint thinners and removers, laboratory
solvents, and in manufacturing processes, such as coffee
decaffeination. These solvents are hazardous to human
health and exposures are regulated in the workplace. Some
are being phased out for their toxicity to humans and the
environment
, as molecules have the potential to react with
and destroy stratospheric
ozone
.
The organochlorine pesticides include several sub-
groups, including the cyclodiene insecticides (e.g.,
chlor-
dane
, heptachlor, dieldrin), the DDT family of compounds
and its analogs, and the hexachlorocyclohexanes (often in-
correctly referred to as BHCs, or benzene hexachlorides).
These insecticides were developed and marketed extensively
after World War II, but due to their toxicity, persistence,
widespread environmental contamination, and adverse eco-
logical impacts, most were banned or restricted for use in
the United States in the 1970s and 80s. These insecticides
generally have low water solubilities, a high affinity for or-
ganic matter, readily bioaccumulate in plants and animals,
particularly aquatic organisms, and have long environmental
half-lives compared to the currently-used insecticides.
There are many chlorinated industrial products and
reagent materials. Examples include
vinyl chloride
, which
is used to make PVC (
polyvinyl chloride
)
plastics
; chlori-
nated benzenes, including hexachlorobenzene; PCB (poly-
chlorinated biphenyl), used extensively in electrical trans-
formers and capacitors; chlorinated phenols, including
pentachlorophenol
(PCP); chlorinated naphthalenes; and
chlorinated diphenylethers. They represent a diversity of
applications, and are valued for their low reactivity and high
insulating properties.
There are also chlorinated byproducts of environmen-
tal concern, particularly the polychlorinated dibenzo-p-diox-
ins (PCDDs) and the polychlorinated dibenzofurans
(PCDFs). These families of compounds are products of
incomplete
combustion
of organochlorine-containing ma-
terials, and are primarily found in the
fly ash
of
municipal
solid waste
incinerators. The most toxic component of
PCDDs, 2,3,7,8-tetrachlorodibenzo-p-dioxin (2,3,7,8-
242
TCDD), was a trace contaminant in the production of the
herbicide 2,4,5-T
and is found in trace amounts in 2,4,5-
trichlorophenol and technical grade pentachlorophenol.
PCDDs and PCDFs can also be formed in the chlorine
bleaching process of
pulp and paper mills
, and have been
found in their
effluent
and in trace amounts in some paper
products.
[Deborah L. Swackhammer]
F
URTHER
R
EADING
Brooks, G. T. Chlorinated Insecticides. Cleveland, OH: CRC Press, 1974.
Chau, A. S. Y., and B. K. Afghan. Analysis of Pesticides in Water, Vol. II.
Boca Raton, FL: CRC Press, 1982.
Fleming, W. J., D. R. Clark, Jr. and C. J. Henny. Organochlorine Pesticides
and PCBs: A Continuing Problem for the 1980s. Washington, DC: U. S.
Fish and Wildlife Service, 1985.
Manahan, S. E. Environmental Chemistry, 5th ed. Ann Arbor, MI: Lewis
Publishers, 1991.
Chlorination
Chlorination refers to the application of
chlorine
for the
purposes of oxidation. The forms of chlorine used for chlori-
nation include: chlorine gas, hypochlorous
acid
(HOCl),
hypochlorite
ion
(OCl), and chloramines or combined chlo-
rine (Mono-, di-, and tri-chloramines). The first three forms
of chlorine are known as free chlorine.
Chlorine (Cl) has three valences under normal envi-
ronmental conditions, -1, 0 and +1. Environmental scientists
often refer only to the chlorine forms having 0 and +1
valences as chlorine; they refer to the -1 form as chloride.
Chlorine with a valence of 0 (Cl
2
) and chlorine with a valence
of +1 (HOCl) both have the ability to oxidize materials,
whereas chlorine at a -1 valence, chloride, is already at its
lowest oxidation state and has no oxidizing power.
The functions of chlorination are to disinfect water or
wastewater
, decolorize waters or fabrics, sanitize and clean
surfaces, remove iron and manganese, and reduce odors. The
fundamental principle of each application is that due to its
oxidizing potential, chlorine is able to effect many types of
chemical reactions. Chlorine can cause alterations in DNA,
cell-membrane porosity,
enzyme
configurations, and other
biochemicals; the oxidative process can also lead to the death
of a cell or
virus
. Chemical bonds, such as those in certain
dyes, can be oxidized, causing a change in the color of
a substance. Textile companies sometimes use chlorine to
decolorize fabrics or process waters. In some cases, odors
can be reduced or eliminated through oxidation. However,
the odor of certain compounds, such as some phenolics, is
aggravated through a reaction with chlorine. Certain soluble
metals can be made insoluble through oxidation by chlorine