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Chapter 1
Environmental Chemistry and the Five Spheres
of the Environment

Environmental Chemistry, 10th Edition

Stanley E. Manahan
Taylor and Francis/CRC Press
2017

For questions, contact:

Stanley E. Manahan
manahans@missouri.edu
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1.1 Earth and the Earth System

Earth’s environment consists of five closely related and
interacting spheres
(1) The hydrosphere: Water
(2) The atmosphere: Air
(3) The geosphere: Rock, mineral matter, soil
(4) The anthrosphere: Things humans make and do
(5) Biosphere: Living organisms.
These five spheres compose the Earth System

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Figure 1.1 The five interrelated and interacting spheres
of the environment that compose the Earth System

Matter
Energy
erehpsordyH

A n th r o sp h er e
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Earth’s two great fluids that circulate and

exchange matter and energy
(1) Surface water, especially in the oceans and rivers
(2) Air in the atmosphere
The two great fluids are important driving forces behind
biogeochemical cycles (next slide)
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1.2 Biogeochemical Cycles in the Earth System

Biogeochemical cycles involve circulation and
placement of matter in the Earth System
• Often based upon specific elements such as those
that are nutrients for organisms
• Most have an atmospheric component; phosphorus
cycle is one that does not
• Many are involved with the anthrosphere, for example,
nitrogen from the atmosphere bound as nitrogen
compounds by industrial chemical synthesis and
released to the nitrogen cycle
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Atmospheric carbon dioxide
Figure 1.2 The

Photosynthesis
Carbon dioxidedissolving from
the atmosphereinto water carbon cycle

Respiration
Combustion
Carbon in the Biospheric
anthrosphere carbon, CH2O

Humic carbon in soil

Dissolved carbon dioxide

and carbonates in the Carbon in the
hydrosphere Inorganic carbon in geosphere
limestoneand other rocks
CO2 CH4

Inorganic and organic carbon in sediments, Fossil carbon in fuels

anoxic decay of organic carbon CO2, CH4 such as coal
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Some Important Biogeochemical Cycles
• Oxygen cycle: Vast reservoir in atmosphere, present in water and
rocks, O2 released by photosynthesis, taken up by respiration
• Nitrogen cycle: Vast amount of N2 gas in the atmosphere, bound in N
compounds by microorganisms and industrial processes, essential
plant nutrient, released back to the atmosphere by denitrification
• Sulfur cycle: In atmosphere as SO2 and sulfate aerosols, in many
minerals, sulfur compounds acted upon by bacteria, in proteins in the
biosphere
• Phosphorous cycle: Endogenous without an atmospheric
component, essential in biomolecules such as nucleic acids, plant
nutrient crucial for food crops, excess in water can cause
eutrophication, a pollution condition in water
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1.3 Natural Capital of the Earth System
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Earth’s natural capital is its capacity to provide

materials, protection, and conditions conducive
to life
• Natural resources, such as minerals, soil, water
• Ecosystem services, which include
• Hospitable climate
• Waste assimilation
• Protection from ultraviolet radiation
 Figure 1.3 Stages of economic development 10

with respect to utilization of Earth’s natural

capital
Burden on Earth’s Natural Capital

Regulation Pollution prevention,

recycling
Recognition of
problems

Future
Industrial revolution,
unrestricted Sustainable
development development,
green technology
Pre-
industrial

Timeof Economic Development

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Economic systems must evolve that provide

good living standards while they
• Increase well-being
• Increase wealth and capital
• Increase efficiency of production
• Conserve resources while reducing wastes

Economic systems must emphasize provision

of services rather than material goods that
deplete resources
• Emulate nature’s systems
• Apply principles of green chemistry and industrial
ecology
 1.4 Environmental chemistry describes the origin, 12

transport, reactions, effects, and fates of chemical

species in the five spheres of the Earth System as shown
in Figure 1.4 Atmosphere

SO2 +1/2O2 +H2O ® H2SO4

H2SO4

S(coal) +O2 ® SO2

Anthrosphere Biosphere
H2SO4, sulfates

Geosphere Hydrosphere
 1.5 Environmental Chemistry of Water and The 13
Hydrosphere Circulation of water in the
hydrologic cycle

Water vapor
in theatmosphere

Liquid water in theatmosphere

in clouds, fog, rainfall

Water in theanthrosphere, Ice,

municipal and industrial use snow
Water in the
biosphere

Ocean Water wells

water

Fresh surface
water
Water circulates through the Water in thegeosphere
Goundwater in aquifers
environment in the hydrologic cycle
 Many important chemical and biochemical 14

processes occur in water

Gas exchange • Pollution of water is a concern, for example by
with atmosphere biodegradable oxygen-depleting contaminants
O2

CO2
-
NO3 2HCO3 + hn Photosynthesis
{CH2O} + O2(g) + CO2-
R ed u c tio n O x id a tio n

a ti
C h el o n 3
CO2- Acid-base HCO- + OH-
3 + H2O 3
Cd2+ 2+ 2- Precipitation
Ca + CO3 CaCO3(s)
2- Microbial
2{CH2O} + SO4 + 2H+ action
H2S(g) + 2H2O + 2CO2(g)
+
NH4
Leaching Uptake

Sediment
Ground-
water
• Water treatment processes are especially important
with growing practice of water recycling
 Stratosphere
1.6 The Atmosphere 15

High atmosphere
Ozone in the stratosphere, protection
against UV radiation
Much less dense air
(Stabilization of temperature (green-
house effect) of the atmosphere

Troposphere
Thinning air
N2, O2, argon, raw
material gases from Chemical and photo-
the atmosphere chemical processes
CO2¯
O2 , H2O Water vapor from
the hydrosphere
Gases and Gases and particles
particles from the from the anthrosphere
geosphere Water (rain) to the
geosphere and
hydrosphere
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Air and the Atmosphere

• Source of essential gases
• Oxygen for animals and other organisms
• Carbon dioxide for plant photosynthesis
• Nitrogen converted to chemically combined form as a
plant nutrient
• Oxygen, nitrogen and argon for industrial uses
• Protective functions
• Filters out damaging ultraviolet radiation
• Regulates Earth’s surface temperature within a range
compatible with life
Aspects of Atmospheric Science
• Movement of air masses
• Heat balance
• Chemical properties and reactions
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Atmospheric Chemistry and Pollution
SO2,O2
Photochemical
reactions: Reactions occur
O2 + hn ® O +O insidewater droplets
O +O2 ® O3 And on particle
H2SO4 surfaces

Air pollutants of various kinds are found

in the atmosphere
· Particles including those that contain toxic lead
· Sulfur oxides, SO2, and nitrogen oxides, NO, NO2
· Acidic species that produce acid rain, H2SO4
· Ozone, O3
· Photochemical smog — oxidants, aldehydes
· Greenhouse gases, excess CO2, CH4
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Earth: The Geosphere
Solid iron-rich inner core/molten outer core/mantle/crust
Crust is Earth’s thin outer skin (5-40 km thick)
• Interacts with other spheres
• Provides life support, food, minerals, fuels
Geology is the science of the geosphere
• Considers mineral solids
• Interaction with water
• Interaction with atmosphere
• Effects upon and by living organisms
• Engineering geology considers human interactions
with and modifications of the geosphere
Geochemistry describes chemical phenomena in the
geosphere
Geosphere as a source of Earth’s natural capital
• Soil and plant nutrients • Minerals • Fuels
 The Rock Cycle in the 19
Geosphere
Weathering, erosion
Transport, sedimentation
Soil

Igneous Heat, pressure

rock Sedimentary
rock

Metamorphic
rock
Upwelling, solidifying magma

Hot, molten magma

1.8 Environmental Chemistry of the Anthrosphere 20

Communications
Renewableenergy
Utilities

Buildings

Food production Water

systems

Machines
Dwellings

Extractive
industries Transportation
The anthrosphere is a potential source of 21

pollutants that contaminate the Earth System

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Industrial Ecology in the Anthrosphere
• Industrial ecology views an industrial system like an
industrial ecosystem
• Practice of efficient industrial metabolism
• Enterprises interact to make use of what would be
wastes from other enterprises
• Optimizes utilization of resources, energy, and capital

Green Chemistry in the Anthrosphere

• Practice of chemical science and manufacturing
within a framework of indutrial ecology
• Sustainable, safe, and non-polluting
• Consumes minimum amounts of materials and energy
• Produces little or no waste material
 The Biosphere: Living Organisms 23

Photosynthesis, production
of biomass, {CH2O}

Algaethat form the O2 CO2

baseof aquatic
ecosystems food chains N2
Carnivores Biomass
production
Biodegradation of dead Herbivores
biomass, animal wastes
Aquatic plants Cyclization of biomass and
Water-dwelling Aquatic plants nutrients in ecosystems
animals
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The sustainability of a thriving biosphere is the top

priority in maintaining a healthy Earth
• Production of biomass that is the base of the food chain
of organisms and is a source of renewable materials and
fuels
• Fixing of carbon and solar energy by photosynthesis,
removal of CO2 from the atmosphere
• Biodegradation and detoxication of wastes and pollutants
• Weathering of rocks in the geosphere
• Mediation of crucial biogeochemical cycles
• Production of some pollutants and toxicants, such as
acid mine water by action of bacteria on pyrite or
methymercury compounds by anoxic bacteria
metabolizing inorganic mercury
• Nitrification and denitrification processes
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Toxicological Chemistry and Biochemistry
Effect of toxic substances on organisms is a significant concern
regarding the biosphere and its relationship to environmental chemistry
Toxicology is the science of poisons or toxicants, substances that
damage or destroy living tissue or that cause biochemical processes to
malfunction
Toxicological chemistry and biochemistry relate the chemical nature of
substances to their toxic effects on organisms

Toxicant . . . +. . . Organism Toxic

Effect

Toxicological
Toxicology
Chemistry
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1.10 As We Enter the Anthropocene
Humans existing in the relatively hospitable Holocene
epoch for about 10,000 years
Now entering the Anthropocene epoch
• Conditions determined by human activities
• Humans have the capacity to change global conditions
• Importance of the anthrosphere in determining the
status of the Anthropocene
Much of what happens in Anthropocene is detrimental to
the Earth System
• Global climate change
• Population pressures
• Depletion of Earth’s natural capital
If Earth is to remain hospitable for humans the
Anthropocene must be of brief duration
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The Sustainocene
The Sustainocene would be a new epoch designed and
managed by humans for preserving, sustaining, and
enhancement of the Earth System
Must recognize human impact on Earth is due largely to
• Population • Affluence • Consumptive technology
Recognize technology can be developed that is positive
for the Earth System
Sustainocene will require, as examples
• Understanding of the Earth System
• Understanding of environmental chemistry
• Best practices of industrial ecology
• Application of green chemistry
• Emphasis upon renewable resources and energy