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Chapter 7

WATER POLLUTION

Environmental Chemistry, 9th Edition

Stanley E. Manahan
Taylor and Francis/CRC Press
2010

For questions, contact:

Stanley E. Manahan
manahans@missouri.edu

7.1 Nature and Types of Water Pollutants

See list in Table 7.1
Markers of water pollution that show presence of pollution
sources
Herbicides indicate agricultural runoff
Fecal coliform bacteria indicate sewage sources
Pharmaceutical metabolites in domestic wastewater
Biomarkers of water pollution are organisms that indicate
pollution
May accumulate pollutants that appear in analysis
May show effects from pollutant exposure
Fish lipid tissue accumulates persistent organic pollutants
Osprey at top of aquatic food web is a good biomarker

7.2 Elemental Pollutants

Trace elements (harmful at a few parts per million or less)
See list in Table 7.2
Heavy metals are among most harmful
Cadmium Mercury Lead
Most are sulfur seekers
Metalloids may be significant water pollutants
Most important is arsenic
Selenium and antimony can also be harmful

7.3 Heavy Metals

Cadmium
Highly toxic
Chemically very similar to zinc
From mining and industrial wastes (especially metal
plating
Lead
Widely used and distributed in the past
Plumbing (lead pipe, solder) used to be a major source
Uses (such as in gasoline) have been greatly curtailed
Mercury
Highly toxic
Minimata Bay incident
Mobilized by bacterial methylationHgCH3+, Hg(CH3) 2

7.4 Metalloids
Arsenic is the most significant
From coal combustion
Occurs with phosphate minerals
Byproduct of copper, gold, lead refining
Natural occurrence in some groundwaters
Formerly in pesticides: Pb3(AsO4)2, Na3AsO3, Cu3(AsO3)2
Bangladesh tube well poisonings may have affected
millions

7.5 Organically Bound Metals and Metalloids

Have metal (metalloid) bonded to carbon
Alkyl groups such as ethyl in Pb(C2H5)4
p (pi) electron donors such as ethylene, C2H4
Carbonyls with bound CO
Tetraethyllead, C2H4, in gasoline introduced large quantities
of lead into the environment until it was banned
Methylation of mercury by anoxic bacteria mobilized
otherwise insoluble inorganic mercury
Organotin compounds were widely used as marine biocides
in ship and boat paints
Tributyltin chloride commonly used industrial biocide
Endocrine disruption in shellfish and oysters
Uses now being phased out

7.6 Inorganic Species

Cyanide (HCN, CN-)
Extremely toxic
Industrial uses including metal cleaning, electroplating
Produced by coke ovens
Water pollution and fish kills from mineral processing
Concern for terrorist attacks on water supplies
Ammonia
Generally as NH4+, NH3 at high pH
Added to drinking water for residual disinfection from
chlorination
Free carbon dioxide, CO2
In water from decay of organic matter, geochemical
sources
Makes water corrosive, harmful to aquatic life

Hydrogen sulfide, H2S

From industrial sources, decay of organosulfur
compounds, geochemical sources
Foul odor, very detrimental to water quality, very toxic
Precipitates heavy metals
Nitrite ion, NO2-, intermediate in reduction of NO3 Very toxic, but rare water pollutant
Sulfite ion, SO32 Added to water as O2 scavenger
Perchlorate ion, ClO4 Industrial pollutant in some cases
Recognized as a pollutant fairly recently
Asbestos
Causes cancer when inhaled, but unknown effects in water
Asbestos-like fibers in Lake Superior, Reserve Mining

7.7 Algal Nutrients and Eutrophication

Eutrophication means well nourished
Eutrophication in excess is detrimental causing heavy
growth of biomass followed by decay
Consumes O2
Fills shallow water bodies
Of numerous algal nutrients (Table 7.3) phosphorus is
generally limiting and is controlled to control eutrophication

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7.8 Acidity, Alkalinity, and Salinity

Acid
Pollutant acids generally strong acids
One of the most common is acid mine water (H2SO4)
Potential industrial sources of pollution
Alkalinity
Generally due to NaHCO3
From natural geological sources
Can be worsened by irrigation practices
Salinity
Salts such as NaCl and Na2SO4
Increased in municipal water systems
Increased by irrigation
Major problem, especially in heavily irrigated areas

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7.9 Oxygen, Oxidants, and Reductants

Dissolved oxygen, DO, is important in water
Depleted by oxidation of NH4+, Fe2+, SO32-, and especially
biodegradation of biomass, {CH2O}
{CH2O} + O2 CO2 + H2O
Biochemical oxygen demand, BOD, refers to amount of
oxygen consumed in a volume of water by the
biodegradable organic matter in it
Total organic carbon, TOC, is often substituted for BOD

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Figure 7.3 Oxygen sag curve resulting from the

addition of oxidizable pollutant to a stream

7.10 Organic Pollutants

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Bioaccumulation of Organic Pollutants

Bioconcentration factor (BCF):
Substance concentration in organism
Substance concentration in water
Bioaccumulation factor, BAF, considers pollutant
concentration in food as well as water
Sewage
Contains many pollutants including pathogenic
microorganisms, detergents, salts, solids (Table 7.4)
Most significant pollutant in sewage is biodegradable
organic material ({CH2O}) manifested as biochemical
oxygen demand (BOD)
Main objective of wastewater treatment is elimination of
BOD (Chapter 8)

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Figure 7.4 Settling of solids from an ocean-floor

sewage discharge

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Soaps, Detergents, and Detergent Builders

Soaps are salts of long-chain fatty acids
Sodium stearate: C17H35CO2-Na+
Soaps form spherical micelles which
may entrain water-insoluble grease and
oil particles (right)
Soap lowers water surface tension
which aids its cleaning action
Soaps are biodegradable
Soaps produce insoluble salts with divalent metal ions,
predominantly calcium, which removes them from water,
but reduces their effectiveness as cleaning agents in hard
water
Calcium stearate: Ca2+(C17H35CO2-)2(s)

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Detergents
Synthetic detergents lower water surface tension and
enable its cleaning action
Do not form precipitates with hardness ions
Amphiphilic structure with ionic head and hydrocarbon
tail
Detergent surfactants concentrate at interfaces of water
with air, solids (dirt), and immiscible greases and oils
Poorly biodegradable ABS surfactants formerly used

Biodegradable LAS
surfactants now used

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Alkyl polyethoxylate surfactants (structural formula below)

Used as detergents, dispersing agents, emulsifiers,

solubilizers, wetting agents
Resist biodegradation
Xenoestrogens of health concern
Detergent formulations have numerous components
Examples: Alkalies, anticorrosive silicates
Builders added to improve performance have caused
problems
Polyphosphates used in builders hydrolyze to phosphates
that cause eutrophication

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Naturally Occurring Chlorinated and Brominated

Compounds
Produced mostly by marine organisms
Chemical defense agents
Detected in arctic samples
Air Fish Seabird eggs Marine mammals Human milk
Example below

Microbial Toxins in Water

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Toxins from aquatic bacteria and protozoa

Many, such as
Cylindrospermopsin from
cyanobacteria
Protozoal dinoflagellata toxins cause many maladies
Gastrointestinal, respiratory, skin disorders in humans
Mass kills of marine mammals
Sometimes fatal paralytic conditions from eating infested
shellfish
Red tides from explosive growth of dinoflagellates
Turn water red, yellow, olive-green
Kill marine organisms
Make sea spray very irritating to humans

7.11 Pesticides in Water

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Numerous kinds of compounds added to soil and plants

Insecticides Herbicides Molluscicides
Fungicides Bactericides Slimicides Avicides (birds)
Piscicides (fish) Plant growth regulators
Plant defoliants Plant desiccants
Insecticides and fungicides most important for human
exposure because of application near harvest time
Herbicides most important water pollutants because of
widespread application directly onto soil
Table 7.4 lists numerous pesticides that may be
encountered as water pollutants

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Pesticides and Other Chemicals of Concern for

Water Pollution
1. Highly biodegradation resistant compounds
2. Known or probable carcinogens
3. Substances with adverse reproductive or developmental
effects
4. Neurotoxins including cholinesterase inhibitors
5. Acutely toxic substances
6. Known groundwater contaminants

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Natural Product Insecticides

Nicotine from tobacco
Rotenone from some legume roots
Pyrethrins
Products such as pyrethrum I from chrysanthum varieties
grown in Kenya
Used in China 2000 years ago
Pyrethroids are synthetic analogs of pyrethrins
Allethrin Fenvalerate Cypermethrin

Figure 7.6. Common botanical insecticides and synthetic

analogs of the pyrethrins.

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DDT and Organochlorine Insecticides (Figure 7.7)

Organochlorine insecticides have been mostly phased out

of use because of persistence, harm to birds
Endosulfan one of the last to be eliminated

Organophosphate insecticides (Figure 7.8)

Though biodegradable and not generally
environmentally harmful, some very toxic effects
(acetycholinesterase inhibitors)

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Malathion is a commonly used organophosphate because

mammals can hydrolyze it to non-toxic products

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Carbamates: Esters of Carbamic Acid (Figure 7.9)

Biodegradable
Acetylcholinesterase inhibitors but not unduly toxic

Fungicides

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Figure 7.10 Examples of widely used fungicides that can be

water pollutants

Herbicides
Herbicides applied to millions of acres of cropland
worldwide to control weeds
Herbicides commonly occur in surface water and
groundwater, especially in intensely cropped areas
Especially common are atrazine, simazine, and
cyanazine used for weed control on corn and soybeans
Although widely used to control weeds on crops
genetically engineered to resist it, glyphosate has a very
strong affinity for soil and rarely gets into water

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Figure 7.11 The two major bipyridilium herbicides

Paraquat, used since 1965, has caused many deaths
because of its high toxicity

Figure 7.12 Triazine herbicides of which atrazine is

especially common in water in corn-growing areas

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Figure 7.13 Chlorophenoxy herbicides

2,4,5-T (Agent Orange) no longer used

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Figure 7.14 Miscellaneous herbicides (others shown in text)

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Pollutants from Pesticide Manufacture

2,3,7,8-Tetrachlorodibenzo-p-dioxin (TCDD or dioxin)
Badly contaminated some areas in 1970s
Highly toxic to some animals
Figure 7.15 Structural formula of TCDD

Kepone, manufacture of which badly

contaminated the James River of
Virginia in the 1970s

7.12 Polychlorinated Biphenyls (PCBs)

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Figure 7.16 Structural formula of PCBs (209 congeners)

Very high chemical, thermal, and biological stability

Had many uses, especially in electrical equipment
Highly persistent and found in water, sediments, bird and
fish tissues
Contamination of Hudson River sediments from electrical
equipment manufacture
Now banned

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7.13 Emerging Water Pollutants, Pharmaceuticals,

Household Wastes

Emerging water pollutants are relatively new substance

coming into use that may get into water and that may have
undiscovered pollution effects
Nanomaterials composed of very small particles with
many developing uses including pharmaceuticals
Siloxanes (silicones) used in cosmetic products, waterrepellant windshield coatings, detergents
Disinfection byproducts (trihalomethanes)
Household wastes including surfactants, flame
retardants, and plasticizers (bisphenol-A)

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Pharmaceuticals and Partial Degradation Products

Figure 7.17 Some pharmaceuticals and pharmaceutical
metabolites found in water

Feminization of male fish exposed to sewage

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Bactericides in water
Used in soaps, shampoo, deoderants, lotions, other
Triclosan and its methyl derivative found in Swiss waters

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Estrogenic Substances in Wastewater

Disrupt endocrine gland activities regulating metabolism
and reproductive functions of organisms
Aquatic organisms (fish, frogs, alligators) exhibit
Reproductive dysfunction Altered sex characteristic
Abnormal serum steroid levels
Substances include
Oral contraceptives Hormonal treatments
Cancer treatments
Nonionic surfactant polyethoxylates are estrogenic
substances
Much less potent than hormonal substances
But released in enormous quantities

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Biorefractory Organic Pollutants

Poorly biodegradable organics
Also called persistent organic pollutants, POP
Include prominently chlorinated hydrocarbons
Examples are benzene, chloroform, tetrachloroethylene
Biorefractory compounds are not well removed by
biological treatment and may require physical means such
as carbon adsorption

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Perfluorinated Compounds as POPs

Brominated Compounds as POPs

Benzotriazole, tolyltriazoles and naphthenic acids are POPs

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7.14 Radionuclides in the Aquatic Environment

Figure 7.18 Production of fission products from uranium
fission

Radionuclides produce ionizing radiation as alpha particles,

beta particles, gamma rays

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See Table 7.5, Radionuclides that may be in water

Carbon-14 from cosmic processes
Radium-226 from uranium
Especially significant water pollutant in some areas
Fission products important in health
Strontium-90 that substitutes for calcium in bone
Iodine-131 that affects thyroid
Cesium-137 that substitutes for sodium
Radionuclides are characterized by half-lives in which half
of the radioisotopes decay
Radiation from radionuclides damages living organisms by
breaking bonds in biological macromolecules
Bone marrow may be damaged in acute cases
Genetic effects (damage to DNA) is of particular concern

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