Narrative for a Lecture on Environmental Chemistry
Slide 1: Environmental chemistry is that branch of chemical science that deals with the production, transport,
reactions, effects, and fates of chemical species in the water, air, terrestrial, and biological environment and
the effects of human activities thereon.
ENVIRONMENTAL CHEMISTRY
Environmental chemistry is that branch of chemical
science that deals with the production, transport,
reactions, effects, and fates of chemical species in
the water, air, terrestrial, and biological environments
and the effects of human activities thereon.
Reference: Stanley E. Manahan, Fundamentals of Environmental
Chemistry, 3rd ed., Taylor & Francis/CRC Press, 2009
(manahans@missouri.edu)
For additional information about environmental chemistry and to
download this and other presentations see:
http://sites.google.com/site/manahan1937/Home
http://manahans1.googlepages.com/
Slide 2: The definition of environmental chemistry is illustrated with a typical pollutant species. In this case sulfur
in coal is oxidized to sulfur dioxide gas that is emitted to the atmosphere. The sulfur dioxide gas can be oxidized
to sulfuric acid by atmospheric chemical processes, fall back to Earth as acid rain, affect a receptor such as plants,
and end up in a "sink" such as a body of water or soil.
ILLUSTRATION OF THE DEFINITION
OF ENVIRONMENTAL CHEMISTRY
SO2 + 1/2O2 + H2O
H2SO4
SO2
H2SO4
S(coal) + O2
SO2
H2SO4, sulfates
Slide 3: In the past many environmental problems were caused by practices that now
seem to be totally unacceptable as expressed from the quote in this slide from what was
regarded as a reputable book on the American chemical industry in 1954. The result was
polluted air, polluted water, dangerous hazardous waste sites, and harm to living
organisms.
The Old Attitude: “By sensible definition any by-product of
a chemical operation for which there is no profitable use is a
waste. The most convenient, least expensive way of disposing
of said waste—up the chimney or down the river—is best.”
(From American Chemical Industry
—a History, W. Haynes,
Van Nostrand Publishers, 1954)
Up the stack
Into the
river
Out the door
Slide 4: Dating from around 1970, laws and regulations were implemented to control air
and water pollution and to clean up hazardous waste sites. These measures have relied
largely upon “end of pipe” controls in which pollutants were generated but were removed
before release to the environment. Although costly and requiring constant vigilance to
make sure that standards have been met, these measures have been successful in reducing
pollution and preventing increases in pollutant releases.
Currently: A “command-and-control” approach using “endof-pipe” treatment measures and remediation of waste sites
has reduced major environmental problems
Stack controls
Wastewater
treatment
Remediation
Slide 5: As an alternative to the regulatory approach, the tendency now is toward
sustainability with systems that emphasize recycling of materials, exchange of materials
between concerns, and zero discharge of wastes. Properly designed, such systems are
inherently friendly to the environment and reduce the need for measures that emphasize
purely pollution control.
Now the goal must be to close the loop, recycle as
much as possible, avoid discharge of pollutants or
wastes, and apply the principles of industrial ecology,
green chemistry, and green engineering
Zero discharge
Recycle
Material exchange
Slide 6: Traditionally, environmental science has considered four environmental
spheres: water, air, living organisms, and earth. But it is important to consider a fifth
environmental sphere, the anthrosphere, which consists of the things that humans make
and do. The remainder of this lecture considers environmental chemistry within a
framework of these five environmental spheres.
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Atmosphere
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Slide 7: A variety of chemical and biochemical phenomena occur in the hydrosphere.
Some of these are shown in this slide for a body of water stratified with a warmer
oxygenated upper layer floating on top of a cooler oxygen-deficient lower layer, a
common phenomenon during summer months. Gases are exchanged with the atmosphere
at the surface and solutes are exchanged between water and sediment. Photosynthesis
produces biomass, represented here as [CH2O]. In the oxygen-deficient lower layer
biomass undergoes biodegradation by the action of anoxic bacteria using oxidizing agents
other than O2. When sulfate functions as the oxidizing agent odorous hydrogen sulfide
gas may be evolved.
CHEMICAL AND BIOCHEMICAL PHENOMENA
IN A STRATIFIED BODY OF WATER
Gas exchange with the atmosphere
O2
CO2
Reduction Oxidation
NO3
NH4+
ati
Chel on
Cd2+
2HCO3 + h! Photosynthesis
{CH2O} + O2(g) + CO23CO23 - + H2O Acid-base HCO3 + OH
2+
2 - Precipitation
CaCO3(s)
Microbial
22{CH2O} + SO4 + 2H+ action
H2S(g) + 2H2O + 2CO2(g)
Ca
+ CO3
Leaching Uptake
Sediment
Groundwater
Slide 8: An important aspect of water chemistry is water treatment. This slide shows the
activated sludge process used to treat municipal wastewater. A suspension of
microorganisms in an aerated tank biodegrades organic wastes represented as [CH2O].
This removes oxygen demand from the water so that it will not deplete oxygen when
discharged to a stream or body of water. The microorganisms settle in a settling basin and
are pumped back to the aeration tank, greatly speeding the biodegradation process.
Excess microorganisms, sewage sludge or biosolids also represented as {CH2O}, are
taken to an anaerobic digester where they produce combustible methane, CH4, and carbon
dioxide. The methane may provide fuel sufficient to run the engines that produce all the
power needed by the plant.
ACTIVATED SLUDGE WASTEWATER TREATMENT
Wastewater containing
BOD, {CH2O}
Aeration tank
{CH2O} + O2 ! CO2 + H2O + Biomass
Organic N ! NH4+, NO3Organic P ! H2PO4-, HPO422Organic S ! SO4
Sludge
settling
Purified water
with reduced
BOD
Air
Settled sludge with viable microorganisms
Byproduct methane
fuel gas
Anaerobic digester
2{CH2O} ! CH4 + CO2
Excess sludge to
anaerobic digester
Slide 9: As water supplies become more limited around the world, renovation and re-use
of wastewater become more important. This slide shows a system for purifying
wastewater treated by the activated sludge process so that it can be used for applications
such as groundwater recharge and irrigation. Advanced treatment processes can even
bring the wastewater up to drinking water standards. A feature of the system shown is a
wetlands area where algae and plants growing profusely in the fertile wastewater remove
excess nutrients and produce biomass that can be converted to biofuels. The largest
purification and water reuse project of its kind worldwide, the Orange County California
Groundwater Replenishment System, utilizes a three-step process of microfiltration,
reverse osmosis and ultraviolet light to purify highly-treated sewer water to state and
federal drinking water standards (http://www.gwrsystem.com/).
Secondary wastewater
treatment effluent
Plants and algae harvested
for energy production
Wetlands
Water purified
in wetlands
Groundwater recharge
Non-potable use, irrigation
Activated carbon filtration
for organics removal
Membrane filtration, may
include reverse osmosis
Potable water to
municipal water system
Retentate with impurities
not passed through membrane
to disposal, treatment
Slide 10: The atmosphere is essential for life on Earth as a source of oxygen for organisms, carbon dioxide
for plants, stabilization of surface temperatures (the good greenhouse effect), and protection from damaging
ultraviolet radiation from ozone (O3) in the stratosphere. Although the atmosphere extends far above Earthís
surface, over 99% of it is within a few kilometers of the surface. In fact, if Earth were a classroom globe,
virtually all of the atmosphereís air would be in a layer the thickness of the varnish on the globe! A distinctive
feature of atmospheric chemistry is the ability of energetic photons of ultraviolet radiation (hînuî) to put large
amounts of energy into a single molecule as shown here for the photodissociation of stratospheric O2 leading
to ozone formation.
Thinning air
High-altitude ozone, O3, protection from ultraviolet radiation
Temperature stabilization
(greenhouse effect)
N2, O2, argon, raw material gases
to the anthrosphere
Chemical and photochemical
processes
Water vapor from
the hydrosphere
Gases and particles
from the anthrosphere
Water (rainfall) to
the hydrosphere
and geosphere
Temperature
inversions
Exchange of O2 and CO2
with the biosphere, release
of H2O from plants
Gases and particles
from the geosphere
Slide 11: Atmospheric chemistry is complex involving literally hundreds of reactions.
Photochemical reactions occur when photons of ultraviolet radiation split molecules apart
producing reactive fragments with unpaired electrons (represented as dots in the slide)
known as free radicals. These species undergo chain reactions such as those responsible
for the ozone, organic oxidants, aldehydes, and solids characteristic of the unpleasant
ingredients of photochemical smog that afflicts Los Angeles, Mexico City, and other
urban areas around the world. Reactions such as the formation of sulfuric acid from
sulfur dioxide may occur inside water droplets and on the surfaces of particles suspended
in the atmosphere.
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Slide 12: There are many different kinds of air pollutants. Particles obscure visibility and
can be detrimental to respiration. Primary particles are those that enter the atmosphere as
particles whereas secondary particles are produced by reactions of gases in the
atmosphere. Several inorganic gases, mostly oxides of nitrogen, sulfur, and carbon are air
pollutants. Photochemical smog results when nitrogen oxides and hydrocarbons in
stagnant air masses subjected to solar radiation undergo photochemical reactions to form
ozone, organic oxidants such as peroxyacetyl nitrate (PAN), ozone, aldehydes, and other
species that tend to be detrimental to visibility, respiratory systems, and eyes.
AIR POLLUTANTS
Primary Particles
• Pollen • Dust • Fly ash • Polycyclic aromatic hydrocarbons
Secondary Particles (formed from gas reactions)
• Smog particles • Sulfuric acid droplets • Salts such as (NH4)2SO4
Inorganic Gases
• O3 • SO2 • NO • NO2 • CO • H2S • HCl • NH3
Organics
• Hydrocarbons including those that form photochemical smog
• Odorous organic sulfur compounds • Organohalides
• Amines and other organonitrogen compounds
• Organo-oxygen compounds including aldehydes and ketones
Photochemical Smog
• Smog particles • Ozone • Organic oxidants (PAN)
• Aldehydes
Slide 13: Although it is a normal constituent of the atmosphere essential to supply the carbon required for plant
photosynthesis, carbon dioxide may turn out to be a harmful air pollutant at higher levels. This is because of its role
in re-absorbing the infrared radiation by which Earth radiates back into space the solar energy received from the sun.
This greenhouse effect is essential to life on Earth because it keeps the surface warm enough for living organisms to
thrive. However, if too much carbon dioxide is present in the atmosphere, Earthís surface will become too warmóthe
bad greenhouse effectóleading to melting of polar ice caps and glaciers, elevated sea levels, severe droughts, and other
detrimental effects. As shown in the plot, on this slide, atmospheric carbon dioxide levels from the burning of fossil
fuels and other sources have been increasing by about 1 part per million per year, now closer to 2 parts per million
per year. The resulting doubling of atmospheric carbon dioxide levels within the next century could have substantial,
perhaps catastrophic, effects upon the global climate.
LEVELS OF ATMOSPHERIC
CARBON DIOXIDE
385
380
390
380
2010
2005
370
CO2 level, ppm by volume
360
350
345
340
335
330
325
320
315
1960
1970
1980
Year
1990
2000
2010
Slide 14: The geosphere has a very close relationship with the hydrosphere, the
atmosphere, and the biosphere and is strongly affected by human activities in the
anthrosphere. On Earth’s surface, the geosphere is composed of rocks in turn made of
various minerals and usually a thin layer of soil. Igneous rocks thrust upward by tectonic
forces are broken down (weathered) by physical, chemical, and biological processes and
material from them is deposited as sedimentary rock. Heat and pressure convert
sedimentary rock to metamorphic rock.
Weathering, erosion
Transport, sedimentation
Igneous
rock
Sedimentary
rock
Heat, pressure
Metamorphic
rock
Upwelling, solidifying magma
Hot, molten magma
Slide 15: Geochemistry is the chemistry of rocks and minerals in the geosphere as it
relates to the hydrosphere, atmosphere, biosphere, and, very recently in the geological
timetable, the anthrosphere. The geochemical reaction shown in the slide is important in
putting dissolved calcium and bicarbonate ion (water alkalinity) into water. The
dissolution of calcium carbonate (limestone) by this process causes the formation of
caves and cavities in limestone rock formations. Environmental geochemistry is the
environmental branch of geochemistry and is important in considering the effects and
fates of pollutants in the geosphere.
GEOCHEMISTRY
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For example, carbon dioxide from the atmosphere dissolves in water
in the hydrosphere, then reacts with limestone in the geosphere:
• CaCO3(s) + H2O + CO2(aq) ! Ca2+(aq) + 2HCO3-(aq)
ENVIRONMENTAL GEOCHEMISTRY
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Slide 16: The geosphere is a crucial source of natural capital including essential metals,
fuels, and plant nutrients. The geosphere is an important repository of wastes. One such
waste for which the geosphere is likely to become a very important repository in the
future is carbon dioxide from fossil fuel combustion that is currently released to the
atmosphere where it causes global warming.
THE GEOSPHERE AS A SOURCE OF NATURAL CAPITAL
Natural capital is a term that describes the resources or value of the
environment such as in providing essential materials or absorbing
wastes
The geosphere is a crucial source of natural capital
• Fuels, such as natural gas
• Metals, such as iron or copper
• Nonmetals, such as clay, sand, gravel
• Plant nutrients, such as phosphorus
• Absorption of wastes, such as carbon dioxide from fuel combustion
pumped underground (carbon sequestration)
The most important aspect of natural capital in the geosphere is the
ability of soil to support plant growth for food production (next slide)
Slide 17: Soil is a crucial component of natural capital because all terrestrial organisms
including humans depend upon it for their existence. The layer of productive soil on
Earth’s surface is extremely thin and subject to damage and erosion. Much productive
soil has been lost or ruined and soil conservation is a top priority for sustainability.
SOIL: THE MOST IMPORTANT GEOSPHERIC RESOURCE
Soil is obviously of crucial importance as a support for plant growth
Soil is composed of finely divided, highly weathered mineral matter
and organic matter from the partial biodegradation of plant material
Earth’s soil is a very thin layer; if Earth were a classroom globe, the
average thickness of the total soil resource would be about the same
as the diameter of a human cell!
Soil is divided into layers called soil horizons (next slide)
Slide 18: Soil is typically divided into layers called horizons. Many important chemical
and biochemical reactions occur in soil. Soil is subject to water and wind erosion, and
one of the earliest environmental movements, dating back to around 1900 in the U.S., has
been soil conservation. Large areas of formerly productive agricultural land have been
turned to desert by poor agricultural and animal grazing practices, a large problem for
sustainability.
SOIL HORIZONS
Regolith: unconsolidated
rock debris, organic matter
Vegetation
O horizon from
decayed and decaying
plant biomass
A horizon, topsoil, layer of root
growth, biodegradation, high
organic content
E horizon, layer that is
weathered and leached,
often by organic acids
from the A horizon
B horizon, or subsoil, reposiitory of organic matter, salts,
and clay particles
C horizon, weathered
parent rock
Bedrock
Slide 19: Living organisms constitute the biosphere. Through photosynthesis of plants
and algae it is the basis of the food chain. In addition to food, the biosphere is a crucial
source of biomass for raw material and, in the future, for synthetic fuel. This slide shows
a heavy growth of switchgrass, a plant that is remarkably productive of biomass on poor
soil and that has significant potential as a renewable fuel resource.
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Slide 20: A major consideration with respect to the biosphere is the effect of toxic substances on
organisms. Toxicological chemistry addresses the relationship between the chemical nature of substances
and their toxic effects.
A MAJOR CONCERN REGARDING THE
BIOSPHERE IS THE EFFECT OF TOXIC
SUBSTANCES ON ORGANISMS:
TOXICOLOGICAL CHEMISTRY
Toxicant
..... + .....
Toxic
effect
Organism
Toxicological chemistry
Toxicology
Slide 21: An interesting aspect of toxicological chemistry is the wide range of toxicities
of various substances. The LD50 values shown in this slide are the doses in mg toxic
substance to kg body mass estimated to kill 50% of test subjects. Diethylhexylphthalate
(DEHP) is a low toxicity plasticizer added to plastics such as polyvinylchloride to make
them more flexible. Malathion, an organophosphate insecticide, is relatively safe because
mammals, but not insects, can hydrolyze the molecule to safe materials. Though an
effective, highly biodegradable organophosphate insecticide, parathion is now banned
because of its toxic effects. Tetrodotoxin is the toxin of the puffer fish. The Australian
inland taipan snake is known at a “two-step” snake; if it strikes you, you take two steps
then fall down dead. TCDD is the infamous dioxin, which causes an unsightly chloracne
skin condition in humans but is deadly to some other species such as guinea pigs.
Botulinus toxin produced by botulinus bacteria is one of the most toxic substances
known, but in dilute form has many medical uses and is the basis of Botox used to
remove skin wrinkles.
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Slide 22: Illustrating the great differences in toxicities of substances, if the big red circle represents a fatal dose
of parathion organophosphate insecticide, now banned because of its toxicity if not handled properly, the little
black dot represents a fatal dose of organophosphate Sarin nerve gasóquite a difference!
RELATIVE TOXICITIES OF TWO
ORGANOPHOSPHATE
COMMPOUNDS. PARATHION IS
A PESTICIDE NOW BANNED
BECAUSE OF ITS TOXICITY AND
SARIN IS A MILITARY POISON
NERVE GAS.
If this area represents a
fatal dose of parathion,
the area of the circle below
represents a fatal dose of Sarin
Slide 23: The body metabolizes toxic substances to detoxify them. Benzene, once widely
used as a solvent and reagent in organic chemistry laboratories, but now discontinued
because of its potential to cause blood abnormalities and possibly leukemia, is
metabolized by cytochrome P-450 enzymes to products such as phenol and trans,transmuconic acid that are eliminated through urine. Benzene oxepin and benzene oxide are
reactive intermediates that react with biomolecules in the body to produce the toxic
effects of benzene.
EXAMPLE OF BENZENE
METABOLISM THAT CAUSES
BLOOD ABNORMALITIES
H
+ {O} Enzymatic
O
O
epoxidation
H
Benzene epoxide
H
Benzene oxepin
OH
Nonenzymatic
O rearrangement
H
Phenol
Other metabolic products including the following:
OH
OH
Catechol
O
O
p-benzoquinone
O
H
H
HO C C C C C C OH
O
H
H
trans,trans-muconic acid
Slide 24: Benzene has been replaced in the laboratory with toluene, which has solvent
and chemical properties that are largely similar to those of benzene. However, the –CH3
side group on toluene is readily oxidized by body enzymes to benzoic acid, a harmless,
common food metabolite. Benzoic acid is conjugated with one of the body’s natural
amino acids, glycine, to produce hippuric acid, which is eliminated through urine. Some
older organic chemistry laboratory manuals recommend collecting urine from horses
from which hippuric acid can be extracted. The collection procedure is at best messy and
can be hazardous because horses are notorious for objecting to donation of their body
fluids or parts to science.
BENZENE IS LARGELY REPLACED BY
TOLUENE, WHICH IS METABOLIZED TO
HARMLESS PRODUCTS
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Slide 25: The anthrosphere is the fifth environmental sphere to be considered. It consists
of the many things that humans make or do, only a few of which are shown here. The
anthrosphere is so important in determining conditions on Earth that in 2000 the Nobel
Prize winning atmospheric scientist Paul Crutzen made a convincing argument that we
are now leaving the Holocene Epoch, which began with the latest interglacial period
about 12,000 years ago and have entered the Anthropocene Epoch in which human
activities, such as emissions of massive amounts of global-warming carbon dioxide to the
atmosphere, predominate in determining Earth’s environment.
THE ANTHROSPHERE
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in us k chin
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fa au ind es
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er m tom s, i of v
y, m o nc ar
pl and ach bil lud an a in es es ir - ,
-
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Structures used for
manufacturing,
commerce,
and other
activities
TransUtilities,
portation sysincluding
water,
tems, including railfuel,
and
electricity
Anthro- distribution systems,
roads, airports, and
waterways consphere and waste collection
structed or modsystems, (sewers)
ified for water
Mines,
transport
Structures
oil wells, and
and devices used
other structures
Food
for communications,
used by extractive
production industries
such as telephone
systems,
lines and radio
including cultitransmitter
vated fields,
towers
irrigation systems,
and animal feedlots
Slide 26: Shown here is a general outline of a manufacturing process in the anthrosphere
such as might be used in the chemical industry. One aspect of manufacturing that has
caused many problems is the production and improper disposal of hazardous waste
substances including toxic heavy metals and organochlorine compounds that have a
tendency to undergo bioaccumulation. One of the most notorious hazardous waste
disposal sites in the U.S. is the Love Canal site near Niagara Falls, New York, where
21,000 tons of chemical wastes containing more than 80 different compounds were
disposed.
Processing
raw material
to finished
material
Recycled
material
Raw material
from extractive
sources
Fabrication and assembly
of product
Recycled
parts
Raw material
from renewable
sources
Finished
material
Energy
Transportation
Communication
Recycling and disposal
Product distribution
Consumer
Spent product
Waste
Slide 27: Dating from the 1990s, green chemistry has become an important discipline in
the practice of sustainable, environmentally safe chemical science and technology.
Green chemistry is the practice of chemical science and
manufacturing within a framework of industrial ecology in a
manner that is sustainable, safe, and non-polluting and that
consumes minimum amounts of materials and energy while
producing little or no waste material.
Reaction
conditions,
catalysts
Recycle
Product
Control
Renewable
feedstocks
No waste
Degradability
Slide 28: Industrial ecology dating from around 1990 is very much related to green
chemistry. It calls for various enterprises to practice industrial metabolism co-existing to
mutual advantage in industrial ecosystems.
INDUSTRIAL ECOLOGY
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Slide 29: A number of industrial ecosystems have developed around the world, the most
commonly cited example of which is the one in Kalundborg, Denmark. Here is shown a
hypothetical industrial ecosystem in which methane (natural gas) is produced
thermochemically from carbon fixed as organic matter, represented as {CH2O} using as a
reagent elemental hydrogen produced from the electrolysis of water by windpower.
N2
Water electrolysis
Electricity by wind-generated
Ammonia
H2 synthesis
electricity
Carbon Fixation by
H2 Brackish water
NH3
NH3
photosynthesis
wastewater
CO2 + H2O + h!!"
Water
{CH2O} Hydrogenation
Pyrolysis
purification
{CH2O} + O2
CO2
Combustion
CO2
Fixed
carbon H2
Biorefinery
Pure water
Organics
Lignite Electricity Gasification
Municipal
Byproduct heat
Electricity
methane
commercial
synthesis
District
Solid wastes, wastewater
heating
CH4, main Solids, CO
2
cooling
product
Biological treatment
including anoxic
Water to purification, recycle,
digestion
irrigation, algae ponds
Slide 30: Sustainability must be the goal, leaving Earth in a condition to support future
generations with a good quality of life.
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Slide 31: When it comes to sustainability, energy is the key component. For a
sustainable world future energy supplies must be sustainable, abundant, safe,
environmentally benign, and affordable. Meeting these criteria is a huge challenge.
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Slide 32: Abundant, sustainable energy can enable accomplishment of all of the goals
listed in this slide plus many more.
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Slide 33: There are many energy alternatives, a number of which are from renewable
sources.
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Slide 34: Arguably the most promising renewable energy alternative is windpower. One
problem with it is its intermittent nature, although some places such as parts of the Texas
panhandle have essentially constant wind. Windpower can be used to generate elemental
hydrogen used as a fuel and chemical reagent for synthetic fuels production which
overcomes any problems from its intermittent nature.
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Slide 35: Earth is the only home we have and ever can have. Environmental chemistry
and the practice of green chemistry and related areas such as industrial ecology are
essential to sustaining our home.
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