Biogeochemistry

Global Biogeochemical Cycles and the
Physical Climate System

by
Fred T. Mackenzie
Atmosphere
Ecosphere
Hydrosphere
Lithosphere
University Corporation for Atmospheric Research
National Center for Atmospheric Research UCAR Office of Programs
Understanding Global Change: Earth Science and Human Impacts
Global Biogeochemical Cycles and
the Physical Climate System
by
Fred T. Mackenzie
School of Ocean and Earth Science and Technology
University of Hawaii
National Oceanic and Atmospheric Administration
ii
Global Biogeochemical Cycles and the Physical Climate System
by Fred T. Mackenzie
An instructional module produced by the Global Change Instruction Program of the University
Corporation for Atmospheric Research with support from the National Science Foundation.
GCIP Staff Advisory Committee
Tom M.L. Wigley, Scientific Director Arthur Few
National Center for Atmospheric Research Rice University
Lucy Warner, Program Manager John Firor
University Corporation for Atmospheric Research National Center for Atmospheric Research
Carol Rasmussen, Editor William Moomaw
University Corporation for Atmospheric Research Tufts University
Linda Carbone, Secretary Ellen Mosley-Thompson
University Corporation for Atmospheric Research The Ohio State University
Jack Rhoton
East Tennessee State University
John Snow
University of Oklahoma
1999 by the University Corporation for Atmospheric Research. All rights reserved.
Any opinions, findings, conclusions, or recommentations expressed in this publication are those of the
authors and donot necessarily reflect the views of the National Science Foundation.
For more information on the Global Change Instruction Program, contact the UCAR Communications
office, P.O. Box 3000, Boulder, CO 80307-3000. Phone: 303-497-8600; fax: 303-497-8610;
lwarner@ucar.edu or carolr@ucar.edu
http://home.ucar.edu/ucargen/education/gcmod/contents.html
iii
A note on this series
This series has been designed by college professors to fill an urgent need for interdisciplinary materials
on global change. These materials are aimed at undergraduate students not majoring in science. The
modular materials can be integrated into a number of existing coursesin earth science, biology,
physics, astronomy, chemistry, meteorology, and the social sciences. They are written to capture the
interest of the student who has little grounding in math and technical aspects of science but whose intel-
lectual curiosity is piqued by concern for the environment. For a complete list of materials contact
UCAR Communications (see previous page).
Global Change
Instruction Program
v
Contents
Preface . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .vii
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .1
Chapter 1: Bigeochemical Processes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .3
Chapter 2: Biogeochemical Cycles and Climate . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .11
Chapter 3: The Modern Coupled C-N-P-S-O System . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .21
Chapter 4: Carbon Cycles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .23
Chapter 5: The Important Nutrient Nitrogen . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .29
Chapter 6: Phosphorus and Sulfur . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .36
Chapter 7: The Water Cycle . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .41
Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .44
Study Questions and Answers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .45
Glossary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .60
Supplementary Reading . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .68
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .69
Global Change
Instruction Program
vii
Preface
Global environmental change is a subject of
considerable public and scientific interest today.
Any discussion of change must involve the sub-
stances that are transported in cycles about the
earths surfacethrough its air, water, soil, rocks,
ice, and living and dead organic matter. Thinking
about these global biogeochemical cycles and
their role in environmental change requires us to
cross the usual boundaries between biology, ecol-
ogy, oceanography, meteorology, chemistry, and
geology. Because of the impact of human activi-
ties on the cycles, and consequently the climate,
the subject also involves the effects and conse-
quences of natural and human-induced change
for ecosystems, humans, and human infrastruc-
tures. This leads the discussion into the fields of
sociology, economics, and political science. Such
a broad and interdisciplinary topic is difficult to
capture completely in a module of this size. I
have made no attempt to do so but have concen-
trated on the biogeochemical cycles of five of the
major elements important to lifecarbon, nitro-
gen, phosphorus, sulfur, and oxygenand their
role in climatic change.
Biogeochemistry is the discipline that links
various aspects of biology, geology, and chem-
istry to investigate the surface environment of
the earth. This environment, the ecosphere (see
Figure 1), encompasses the biosphere (living and
dead organic matter) and parts of the other large
subdivisions (reservoirs) of the earths surface of
atmosphere (air), hydrosphere (water), shallow
crust (soils, sediments, and crustal rocks), and
cryosphere (ice). In this module, I focus on the
role biogeochemistry plays in regulating and
interacting with the climate system.
This module covers a great deal of material,
much of which is interdisciplinary. This presents
a problem for the writer of the material, the
teacher, and the student. Both teacher and stu-
dent generally will have more knowledge in one
discipline than in another. Also, each discipline
has a unique vocabulary. (Most of the interdisci-
plinary vocabulary in this module is defined
within the text or in the extensive glossary.)
Furthermore, the language of chemical equations
is used to describe processes operating within the
ecosphere. Therefore, it may take some additional
work and perhaps reference to basic texts in
chemistry, ecology, meteorology, etc., to digest
the material of this module.
The text begins by introducing some impor-
tant biogeochemical processes. This material is
not a laundry list of processes but a selection of
such processes as photosynthesis, weathering,
and deposition of sediments in the ocean as
examples of the nature and variety of biogeo-
chemical processes. The next subject is the histor-
ical (geological) nature of environmental change
on the earth. Emphasis is on the biogeochemical
cycles of atmospheric carbon dioxide and oxygen
through the past 600 million years of the history
of the earth. The major processes controlling
these cycles and their tie to climate are discussed.
We will see that for much of this time, the planet
has had a more equable climate than at present.
Finally, the text deals with parts of the mod-
ern biogeochemical cycles of five of the most
important elements essential for life: carbon,
nitrogen, phosphorus, sulfur, and oxygen. These
elements, along with hydrogen and a suite of
nutrient trace elements, interact through the
processes of photosynthesis and respiration
and/or decay. Processes and feedbacks within
the cycles are described in the context of the
potential for a global warming brought about by
human activities that have changed the composi-
tion of the atmosphere. Keep in mind that the
approach can be used to interpret the interaction
between biogeochemical cycles and climatic
change of any naturewarming or coolingand
at various space and time scales.
viii
An extensive glossary, study questions and
answers, and a supplementary reading section
conclude the module. The glossary is interdisci-
plinary and should help in understanding the
diverse material of the module. The study ques-
tions are designed to enable students to review
the text, to integrate the material, and to expand
their knowledge of the topics covered. Many of
the questions require calculations using standard
arithmetic. Mathematics is the foundation of sci-
ence, and it is necessary for students to get their
feet wet. The readings are broad in scope and of
a general nature.
I would like to thank John Firor, Dave
Schimel, and especially Tom Wigley for their
comments on the initial draft of this module.
Some of the material in this module comes from
research supported by the National Science
Foundation and the National Oceanographic and
Atmospheric Administration. The final version of
this module was written while I was a Fellow at
the Wissenschaftskolleg zu Berlin. I thank Prof.
Dr. Wolf Lepenies, rector of the institute, for pro-
viding space, facilities, and peace of mind to
accomplish the task. Many thanks to Michael
Shibao for drafting and in so doing substantially
improving the original illustrations for this mod-
ule. Finally, I am extremely indebted to Carol
Rasmussen of the University Corporation for
Atmospheric Research for her critical and labori-
ous editing. Without her, this module would not
have been completed.
Fred T. Mackenzie
School of Ocean and Earth
Science and Technology
University of Hawaii
June 1996
Global Change
Instruction Program
1
The global ecosphere is the thin film around
the earth where living things (the biosphere
1
)
interact with the atmosphere (air), hydrosphere
(water), cryosphere (ice), and lithosphere (soils and
shallowly buried rocks) in a complex system
involving biological, geological, and chemical
processes and cycles (Figure 1). This biogeochemi-
cal system of spheres and processes is powered
mainly by energy from the sun.
The ecosphere is made up of individual
ecosystems, such as tropical forests, grasslands,
tundra, coral reefs, and estuaries. Matter and
energy flow between and within these ecosys-
tems in interconnected biogeochemical cycles.
Gaseous chemical compounds are produced and
consumed in the ecosystems and exchanged
between them and the air. In the atmosphere,
they may react to form other compounds before
returning to the earths surface. Some of these
chemical species are greenhouse gases, like carbon
dioxide (CO
2
) and methane, which act in the
atmosphere to warm the planet. Others, like
dimethylsulfide gas, react with other atmospheric
chemicals to form minute airborne particles
(aerosols) that directly or indirectly help to cool the
climate.
The most common way of studying the glob-
al movements of these chemicals is by mathemat-
ical modeling of biogeochemical cycles at the
earths surface. Modeling also allows scientists to
estimate the effects of human activities on natural
biogeochemical cycles. Amodel is simply a set of
I ntroduction
Figure 1. The ecosphere, our life support system, showing its relationship to the other important spheres of the surface system of the earth
(after Christensen, 1991).
Atmosphere
Ecosphere
Hydrosphere Lithosphere
1
Terms in italics are defined in the glossary at the end of the text.
2
equations that describe some of the processes
found in the real world. Biogeochemical cycling
models generally include processes that move
materials and their rates of transfer among a lim-
ited number of well-studied spheres of the earth.
Biogeochemical cycles, however, have certain
properties that are inherently difficult to describe
and model. These include: (1) irreversibility, that
is, the system does not return to its exact previ-
ous state if it goes through a disturbance; (2) tran-
sitional phenomena, that is, the system tends to
switch from one state to another and another and
yet others, and perhaps back again, rather than
simply moving from before to after; (3) evolu-
tion, in which the system progressively changes
in a particular direction; and (4) processes that
either enhance the original perturbation to the
system (positive feedback) or relieve the perturba-
tion (negative feedback).
In Chapter 1 of this module, we shall first con-
sider some examples of biogeochemical processes.
In Chapters 2 and 3, we shall discuss how the bio-
geochemical cycles interact with climate, both in
previous eras and at present. In Chapters 46, we
shall discuss the present-day global biogeochemi-
cal cycles of several elements that are important
biologically and that interact with the climate sys-
tem. The cycles are looked at in the context of
global warming from an enhanced greenhouse
effect.
3
Innumerable biological, geological, and chemi-
cal processes cycle elements throughout the eco-
sphere. The few discussed in this section should
give the reader an idea of their variety and com-
plexity. As an example, consider a group of organ-
isms called the prokaryotes: the bacteria and blue-
green algae. The processes that these organisms are
involved with (summarized in Table 1) include:
the capture of carbon dioxide from the
atmosphere and its conversion to organic
matter (fixation of CO
2
)
the release of CO
2
back to the atmosphere
(through respiration and decay)
fermentation of sugar
methane production and oxidation
sulfur reduction and oxidation
nitrogen fixation, nitrification, and
denitrification.
This list is given only as an example; some of
these processes will not be discussed in the text.
These prokaryotic processes may take place
in a variety of ways, such as (1) autotrophy, in
which the organisms convert inorganic carbon in
the environment to organic matter; (2) heterotro-
phy, in which the products from the breakdown
of organic compounds are used to make new
organic materials; and (3) mixotrophy, in which
both inorganic and organic compounds are used
to make organic matter.
Biogeochemical Processes
Table 1. Biogeochemical reactions involving prokaryotes
Element Process Summary of partial Examples of organisms
chemical reactions involved in process
Carbon CO
2
fixation CO
2
+ H
2
(CH
2
O)n + Photoautotrophs:
A
2
(A= O, S) cyanobacteria, purple and green
sulfur bacteria
Chemoautotrophs:
sulfur and iron oxidizing bacteria
Methanogenesis COO
-
+ H
2
CH
4
Methanogenic bacteria
Methanotrophy CH
4
+ O
2
CO
2
Methanotrophic bacteria
Fermentation (CH
2
O)n + O
2
CO
2
Anaerobic heterotrophic bacteria
Respiration (CH
2
O)n + O
2
CO
2
Aerobic heterotrophic bacteria
Sulfur Sulfur reduction SO
4
+ H
2
H
2
S Sulfur-reducing bacteria
Sulfur oxidation H
2
S S
0
Purple and green sulfur phototrophs
S
0
+ O
2
SO
4
Sulfur oxidizing bacteria
Nitrogen N
2
fixation N
2
+ H
2
NH
4
Phototrophic bacteria, nitrogen-fixing
heterotrophic bacteria
Nitrification NH
4
+ O
2
NO
2
, NO
3
Nitrifying bacteria
Denitrification NO
2
, NO
3
N
2
O, N
2
Denitrifying bacteria
__________________________________________________________________
After Stolz et al., 1989
Global Change
Instruction Program
4
Principles of chemical reactions
Atoms and elements
Every object in the universe is composed of matter. Because matter can be converted to energy, it is essen-
tially a form of energy. Matter is composed of atoms, which are the smallest particles of an element that can
exist either alone or in combination. An atom is also the smallest particle that can enter into a chemical reac-
tion. Most atoms never change; they only combine with other atoms to make different substances. Radioactive
atoms, however, do change and eventually decay into stable, nonradioactive atoms.
Elements consist of atoms of the same kind and, when pure, cannot be decomposed by a chemical change.
There are 106 known elements; 103 are listed in the periodic table (Figure 2). The elements most used com-
mercially by people, in order of use, are carbon (C), in the form of coal, oil, and gas; sodium (Na), in table salt
and other products; iron (Fe), used in the steel industry; and nitrogen (N), sulfur (S), potassium (P), and calci-
um (Ca), all used in fertilizers or as soil conditioners for our food supply.
Compounds
When two or more atoms are bonded together in a definite proportion, a compound is formed. Examples of
compounds discussed in this text are water (H
2
O), carbon dioxide (CO
2
), salt (NaCl), and sugar (e.g., glucose,
C
6
H
12
O
6
). (All of the compounds named in the text are listed in Table 2.) The numbers in these chemical for-
mulas are the number of atoms of each substance in the compound. If only one atom of a substance is in the
compound, no number is given. The universe is composed of millions of these compounds, all created from the
elements given in the periodic table. The smallest particle of a compound that can exist and exhibit the prop-
erties of that compound is called a molecule.
A compound is a pure substance that can be decomposed by a chemical change. The atoms in the chemical
compound may rearrange themselves, or they may separate from the compound to form different compounds.
These changes and interactions among compounds are called chemical reactions.
Chemical equations
A chemical equation expresses a chemical reaction involving compounds or elements. The chemicals that
react together, called reactants, generally are shown on the left- hand side of the equation and the products on
the right- hand side. Consider the decay of plant material (represented by the chemical compound CH
2
O, a car-
bohydrate), which requires the oxygen gas (the chemical compound O
2
) in the earths atmosphere. The sim-
plest chemical equation representing this process is
CH
2
O + O
2
CO
2
+ H
2
O (1)
The arrow pointing right indicates that this process is irreversible; the plant material will be completely oxi-
dized to CO
2
and H
2
O in the presence of atmospheric oxygen. Other processes are highly reversible, and these
are usually represented by a double arrow. For example, the equilibrium between calcium carbonate and its
dissolved calcium and carbonate ions (atoms or molecules that have lost or gained electrons, with the number
lost or gained shown as a positive or negative superscript) is represented as
CaCO
3
Ca
2+
+ CO
3
2-
(2)
In chemical processes, matter cannot be created or destroyed. Thus, when a chemical equation is written,
the total number of atoms of any particular element on the left- hand side of a chemical equation must be
made to equal the total number of atoms of that element on the right- hand side of the equation. This is the
process of balancing a chemical equation. Balancing the equation expresses the fact that molecules usually
react in such a way as to bear simple, integral, numerical relationships to one another.
5
If these relationships are known, it is possible to calculate the masses of reactants and products by using
known atomic and molecular weights. In chemical terms, the amount of a substance is expressed in moles. One
mole of a substance is the amount that contains as many elementary entities as there are atoms in 12 grams of
carbon. This number is termed Avogadros constant, and its value is equal to 6.022 x 10
23
. In the chemical
equation given above for the equilibrium of CaCO
3
and its dissolved chemical species, one mole of CaCO
3
will
dissolve in water to make one mole of Ca
2+
and one mole of CO
3
2-
. In terms of mass, 100 grams of CaCO
3
will
react to give 40 grams of Ca
2+
and 60 grams of CO
3
2-
. If only 10 grams of CaCO
3
were to dissolve, then the
same proportions of Ca
2+
and CO
3
2-
would be present at the equilibrium: 4 and 6 grams, respectively.
Figure 2. Periodic table of the elements. Each box includes an elements atomic number,
chemical symbol, and atomic weight.
6
Table 2.
Chemical formulas and names used in this module
Al
2
Si
2
O
5
(OH)
4
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .kaolinite
Ca
2+
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .calcium ion
CaCO
3
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .calcium carbonate
CaSiO
3
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .calcium silicate
Ca
5
(PO
4
)
3
(OH,F) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .carbonate fluoroapatite
CH
2
O . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .carbohydrate
(CH
2
O)
106
(NH
3
)
16
H
3
PO
4
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .organic matter in marine phytoplankton
CH
4
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .methane
CO
2
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .carbon dioxide
CO
3
2-
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .carbonate ion
CS
2
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .carbon disulfide
C
6
H
12
O
6
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .sugar (glucose)
DIC . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .dissolved inorganic carbon
DMS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .dimethyl sulfide, (CH3)2S
HCO
3
-
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .bicarbonate ion
HNO
3
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .nitric acid
H
2
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .molecular hydrogen
H
2
O . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .water
H
2
S . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .hydrogen sulfide
H
2
SO
4
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .sulfuric acid
H
3
PO
4
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .phosphoric acid
H
4
SiO
4
0
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .monomeric silicic acid
KAlSi
3
O
8
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .orthoclase feldspar
MSA . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .methane-sulfonic acid
NaAlSi
3
O
8
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .albite
NaCl . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .sodium chloride, common table salt
NH
3
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .ammonia
NH
4
+
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .ammonium ion
NH
4
NO
3
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .ammonium nitrate
(NH
4
)
2
SO
4
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .ammonium sulfate
NMHC . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .nonmethane hydrocarbon
NO . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .nitric oxide
NO
3
-
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .nitrate ion
NO
x
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .oxides of nitrogen
N
2
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .diatomic nitrogen
N
2
O . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .nitrous oxide
OCS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .carbonyl sulfide
OH* . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .hydroxyl radical
OH
-
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .hydroxyl ion
O
2
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .diatomic oxygen (pure oxygen molecules)
O
3
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .ozone
PAN . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .peroxylacetyl nitrate
PH
3
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .phosphine or swamp gas
PO
4
3+
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .phosphate ion
SO
2
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .sulfur dioxide
SO
4
2-
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .sulfate ion
SO
x
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .oxides of sulfur
SiO
2
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .silica
7 DRAFT
Photosynthesis
We begin with perhaps the most important
biogeochemical process of all, photosynthesis. It is a
photoautotrophic process, that is, an autotrophic
reaction in the presence of light. Nutrients such as
phosphate (PO
4
3-
) and nitrate (NO
3
-
) are also nec-
essary for this reaction to occur.
In the early stages of our planets formation,
the atmosphere was very different from that of
today. There was no free molecular oxygen (O
2
),
which most of todays life forms require. In fact,
oxygen was a very powerful poison for the sim-
ple organisms that lived in this early, oxygen-
deficient (anaerobic) world. Both the organisms
and the earth had to evolve to a stage where the
organisms produced oxygen and emitted it to
their environment before more advanced life
forms could evolve. Photosynthesis, the process
of constructing complex organic molecules from
simple inorganic ones in the presence of light,
was a critical step in the evolution of life and
allowed the mass of living organisms to grow to
the level of today. In our world, the mass of living
organisms on earth is equivalent to about 600 bil-
lion tons of carbon. More than 99% of this carbon
is in land plants; the remainder is stored in
marine plants and in animals.
Photosynthesis is basically a chemical reaction
or process in which carbon-, hydrogen-, and oxy-
gen-bearing chemical compounds (carbohydrates)
are synthesized from atmospheric CO
2
and H
2
O or
another chemical compound that can act as a
hydrogen donor. The generalized reaction is
energy + nCO
2
+ 2nH
2
A(CH
2
O)n +
nH
2
O + 2nA (3)
where H
2
Ais a hydrogen donor molecule,
(CH
2
O) is a carbohydrate, and n stands for any
number. In higher plants, the donor molecule is
water, and n = 6. Thus for these plants the specific
reaction is
energy + 6CO
2
+ 12H
2
O C
6
H
12
O
6
+
6H
2
O +6O
2
(4)
For photosynthetic sulfur bacteria the donor mol-
ecule is hydrogen sulfide (H
2
S), and for nonsulfur
purple bacteria it is organic compounds.
Incidentally, the carbon dioxide and donor
molecule used for photosynthesis are not the
only requirements for plant growth. Plants also
need nitrogen, phosphorus, sulfur, potassium,
and a dozen or so trace elements, like zinc and
iron. As we shall see below, human activities are
changing the atmospheric concentrations of these
nutrients as well as that of carbon, with various
possible effects on plants.
The photosynthetic reactions that produce
organic matter on land differ from those in the
ocean because the proportions of carbon, nitro-
gen, sulfur, and phosphorus in land vegetation
differ from those in marine plankton. The ratio of
C:N:S:P in marine plankton is 106:16:1.7:1.
Known as the Redfield ratio, this proportion is
fairly constant for the surface-dwelling, micro-
scopic plants (phytoplankton) of the worlds
oceans. The C:N:S:P ratio for land plants is more
variable but averages 882:9:0.6:1. The amount of
carbon is so much greater in land vegetation
because it is stored as cellulose in the structural
tissues of trees and grasses.
From this summary, it can be seen that
photosynthesis (among other things) links the
biogeochemical processes and cycles of the indi-
vidual organic elements of carbon, nitrogen,
phosphorus, and sulfur. These elements, plus
hydrogen and oxygen, are the major constituents
of organic matter. Those six elements and about a
dozen or so minor elements are necessary for the
maintenance of organic structures and the physi-
ological functions of living organisms.
Respiration and Decay of
Organic Matter
In the life cycle, photosynthesis in plants is
balanced by the complementary processes of res-
piration and decay in plants and animals. In
plants, respiration is the breakdown of the com-
plex organic molecules that were formed during
photosynthesis. The chemical reactions for respi-
ration and decay are the reverse of those shown
above for the production of organic material. The
generalized reaction is
C
6
H
12
O
6
+ 6H
2
O + 6O
2
6CO
2
+
12H
2
O + energy (5)
8
Compare this with reaction 4. The amount of
energy released is about 686 kilocalories (kcal) for
each mole of C
6
H
12
O
6
(glucose, the most common
form of sugar in living things) that is broken down.
In animals, the respiratory oxidation of foods
that is, the loss of electrons from the carbon in
carbohydrates, occurring during digestion
provides energy for a variety of uses, including
maintenance of body temperature, muscular
movement, and synthesis of complex organic
compounds.
During the oxidation of organic matter, CO
2
,
nitrogen- and phosphorus-bearing nutrients, and
bioessential trace elements (e.g., iron) are returned
to the environment to be used again in the pro-
duction of more organic matter. When O
2
is avail-
able, it is the oxidizing agent (oxidant); however,
in oxygen-depleted (anoxic) waters, sediments,
and soils, other oxidants are used. These include
nitrate, sulfate, and iron and manganese oxides.
The chemical equations for respiration and
decay, either in an oxygenated or in an anoxic
environment, are more complex than the general-
ized reaction for photosynthesis given above. For
example, the chemical composition of average
marine phytoplanktona relatively simple form
of lifeis (CH
2
O)
106
(NH
3
)
16
H
3
PO
4
: 106 mole-
cules of carbohydrate, 16 of ammonia, and 1 of
phosphoric acid. When dead phytoplankton react
with O
2
in an oxygenated environment, the prod-
ucts are carbon dioxide, nitric acid, phosphoric
acid, and water:
(CH
2
O)
106
(NH
3
)
16
H
3
PO
4
+ 138O
2

106CO
2
+ 16HNO
3
+ H
3
PO
4
+ 122H
2
O (6)
For an example of respiration and decay in an
anoxic environment, let us consider the reduction
of sulfur in sulfate (SO
4
2-
) in the pore waters of
anoxic sediments. Bacteria use the oxygen origi-
nally bound in the sulfate to oxidize organic mat-
ter. Again using phytoplankton as the organic
matter, the equation for this chemical reaction is
(CH
2
O)
106
(NH
3
)
16
H
3
PO
4
+ 53SO
4
2-
106CO
2
+ 16NH
3
+ H
3
PO
4
+ 53S
2-
+ 106H
2
O (7)
This time, in addition to carbon dioxide, phos-
phoric acid, and water as in reaction 6, the prod-
ucts include ammonia (NH
3
) and sulfide (S
2-
).
Weathering of Rocks
Another very important set of biogeochemi-
cal processes is that involved with the break-
down of rocks exposed to rain, wind, and ice.
Weathering prepares rock for erosion and trans-
portation. Its products are dissolved chemical
species and solids derived from changes in the
primary minerals of the rock being weathered.
The solid products are predominantly clay min-
erals; there are also dissolved products, predomi-
nantly calcium, carbon, and silicon. Ultimately,
the products of weathering are either carried by
water, blown as dust, or carried by glaciers to the
ocean. Of the approximately 20 billion tons of
solids and dissolved materials reaching the ocean
annually from the land, more than 80% is deliv-
ered by rivers. However, high-temperature chem-
ical reactions in the presence of seawater along
the great submarine midocean ridges are signifi-
cant sources of dissolved calcium, silica, and iron
for the oceans.
An example of a chemical weathering reac-
tion is the weathering of the mineral albite (the
inorganic chemical compound NaAlSi
3
O
8
), found
in igneous rocks like basalt, to the clay mineral
kaolinite [Al
2
Si
2
O
5
(OH)
4
]. The reaction takes
place principally in the presence of soil water
and groundwater that contain significant amounts
of dissolved CO
2
. Although the ultimate source
of the CO
2
is the atmosphere, much of it does not
come directly from the air but is produced in
soils by the respiration of plants and the decay of
dead plants and animals. Because of these
processes, the concentration of CO
2
in soils may
be one or more orders of magnitude greater than
that of the atmosphere. The elevated CO
2
levels
give rise to acidic soil solutions, and these corro-
sive, low-pH soil solutions are responsible for the
weathering of rock minerals like albite:
2NaAlSi
3
O
8
+ 2CO
2
+ 11H
2
O
Al
2
Si
2
O
5
(OH)
4
+ 2Na
+
+ 2HCO
3
-
+ 4H4SiO
4
0
(8)
The products of this reaction, besides the
kaolinite, are sodium ion, bicarbonate ion, and
monomeric silicic acid.
In regions where human activities such as
coal burning release considerable amounts of sul-
fur and nitrogen oxide gases to the atmosphere,
9
such as the midwestern and eastern United States
and southern China, the pH of rainwater and
consequently soil water may be lower (more
acid) than natural values. This happens because
the gases oxidize and react with water in the
atmosphere and then rain out as sulfuric and
nitric acids, respectively. This phenomenon is the
environmental problem of acid deposition (often
called acid rain), which in extreme forms can be
responsible for increased fish mortalities in lakes
and decreased agricultural production.
Deposition in the Oceans
When the solid and dissolved products of
weathering reach the ocean, the solids settle out
because of their weight and are deposited on the
seafloor as gravel, sand, silt, and mud. How long
the dissolved products remain in the ocean
depends on how long it takes them to enter into a
chemical or biochemical reaction. As an example
of the periods involved, dissolved sodium in the
ocean has a long residence time, about 55 million
years. At the other end of the time scale, the resi-
dence time of dissolved silica is only 20,000 years.
Calcium and silica
Many of the processes by which dissolved
constituents are removed from the ocean involve
marine organisms. In todays oceans, dissolved
calcium and bicarbonate are precipitated as car-
bonate minerals in the skeletons of several kinds
of marine organisms: planktonic foraminifera (pro-
tozoans), pteropods (mollusks), and Cocco-
lithophoridae (algae), and bottom-dwelling (benthic)
corals, echinoids, mollusks, and coralline algae. Of
the total production of skeletal carbonate in the
oceans, equivalent to about 1 billion tons of carbon
per year, 80% is redissolved in the ocean as skele-
tal debris sinks to the seafloor. This efficient recy-
cling is due to the fact that although the surface
ocean is oversaturated with respect to calcium car-
bonate, the deeper sea is undersaturated with
respect to this mineral. The remaining 20% of the
oceans carbonate production accumulates in shal-
low-water and deep-sea sediments.
The amount of carbon in these sediments
only accounts for about one-half of the dissolved
inorganic carbon brought to the oceans annually
by rivers. The other half of the riverborne carbon
is released to the ocean and atmosphere when
skeletal carbonate minerals are formed.
Dissolved silica is also removed from the
oceans in the skeletons of marine organisms.
Certain of these organismsplanktonic diatoms
(algae), radiolarians (protozoans), dinoflaggelates
(protozoans), and benthic spongesuse dis-
solved silica to form their shells of opaline silica.
After these organisms die, most of the opal dis-
solves, because the oceans throughout their
extent are undersaturated with respect to this
chemical compound. Only about 40% of the total
annual production of skeletal silica sinks below
the parts of the ocean that daylight reaches (the
euphotic zone). Most of this siliceous material dis-
solves en route to the seafloor; only 5% of that
produced in the euphotic zone accumulates in
marine sediments. This amount is about equiva-
lent to the annual input of dissolved silica to the
oceans by rivers.
Sodium and magnesium
In contrast to carbon and silica, which are
removed from the ocean primarily by biological
processes, riverborne dissolved sodium and mag-
nesium are removed to a significant extent by
inorganic chemical reactions. Both of these ele-
ments are involved in hydrothermal reactions
between seawater circulating through midocean
ridges and the basalt rock making up the ridges.
In the hydrothermal reaction process, sodium
and magnesium are removed from the seawater.
Sodium is also removed from the ocean by the
precipitation of halite (common table salt, sodium
chloride) from seawater. This process is very
important as a removal mechanism for sodium
and chlorine, but only occurs when the right set
of climatic and tectonic conditions are achieved.
Only seawater in relatively isolated arms of the
sea can be sufficiently evaporated to reach halite
saturation. Thus, because such environments are
scarce today, it is likely that sodium and chlorine
brought to the oceans by rivers are currently
accumulating in seawater.
Some magnesium is also removed from sea-
water by chemical processes in the pore waters of
10
sediments. These processes taking place during
the burial of sediments are collectively referred to
as diagenesis. The relative importance of diagenet-
ic and hydrothermal reactions for the removal of
magnesium from seawater is a topic of current
scientific research and debate.
We can conclude from the above discussion
that the circulation of material through the eco-
sphere is complex and involves myriad chemical,
biological, and geological processes. The system
is truly biogeochemical in nature. On all time and
space scales, if the composition of the ecosphere
is regulated, the regulation is controlled by a
complex of interwoven inorganic and organic
processes. The maintenance of the equable envi-
ronment, including climate, that is required for
life to exist on earth is a product of this interact-
ing and interwoven web of biogeochemical
processes and cycles.
11
In this chapter, we will look at some repre-
sentative global biogeochemical cycles and their
role in climate. The elements whose cycles are
discussed are intimately connected through the
organic processes of photosynthesis and respira-
tion and/or decay. These elements are carbon
(C), nitrogen (N), sulfur (S), oxygen (O), andfor
completeness, because it is an important biologi-
cal nutrientphosphorus (P). We will begin with
a discussion of gases whose production or con-
sumption on the earths surface is accomplished
by biological reactions (biogenic gases) and the
possible effects of these gases on the earths cli-
mate. To set the stage, the greenhouse effect is
discussed briefly here.
Greenhouse gases, which are all naturally
biogenic in origin, allow incoming shortwave solar
radiation to pass through the atmosphere to the
earths surface, but when part of that radiation
(about 45%) is reradiated back toward space as
heat (infrared radiation), the gases absorb it and
thus retain it in the atmosphere. This is the green-
house effect. We can thank the natural green-
house effect for the earths equable climate.
Without it, the planet would be about 33C cooler
than its mean global temperature of 15C, that is,
18C. (See the Global Change Instruction
Module The Sun-Earth System, by John Streete.)
There can be, however, too much of a good
thing. In recent years, the concentrations of these
gases in the atmosphere have been rising because
of fossil fuel combustion, biomass burning, rice
paddy cultivation, and other human activities.
This buildup may absorb increased amounts of
outgoing infrared radiation, leading to an
enhanced greenhouse effect and global warming.
It is interesting and informative to put this
present-day worry in the context of public and
scientific concern about climate during the 1950s
and 1960s. Between about 1940 and 1970, global
mean temperatures remained nearly constant, or
even declined slightly. There was considerable
discussion and concern in the scientific literature
and in public forums about global cooling and
perhaps another ice age. Much of the discussion
below in the context of global warming is applic-
able to a scenario of global cooling as well. The
difference is that in a global cooling, many of the
feedbacks mentioned would act in the opposite
direction and would probably have different
magnitudes of change.
The Biogenic Gases and Climate
It is very likely that during the next century
the earths climate will change due to natural
causes. Changes in the amount of solar radiation
received by the planet, in the circulation of the
atmosphere and the oceans, and in volcanism can
affect climate on this time scale. On the longer
time scale, if left to its own recourse, the planet
will most likely enter another ice age about
10,00030,000 years from now.
On the other hand, human-induced climate
change during the next century is also very like-
ly. The flywheel of population growth and fossil
fuel burning is turning rapidly and will be diffi-
cult to slow in this time. The global population is
growing at a rate of 1.5% per year, a doubling
time of 45 years. This rate of growth implies a
population of about 10 billion by 2050. All these
people will require energy to sustain themselves
and to develop their industries, farms, and cities.
Most scenarios of future global energy use pro-
ject a continuous heavy reliance on fossil fuel
into the 21st century. Continued fossil fuel burn-
ing will result in continued emissions of CO
2
,
methane (CH
4
), and nitrous oxide (N
2
O) to the
atmosphere. These greenhouse gases will be
accompanied by emissions of trace metals, non-
methane hydrocarbons (NMHCs), oxides of sul-
fur (SO
x
), and the most reactive oxides of nitro-
gen (NO and NO
2
, collectively known as NO
x
).
Biogeochemical Cycles and Climate
Global Change
Instruction Program
12
The latter three groups of chemical compounds
react with other chemical components of the cli-
mate system, particularly the hydroxyl radical
(OH*). Also, SO
x
and NO
x
are the principal con-
stituents in acid deposition, and NO
x
and
NMHCs are involved in the formation of ozone
(O
3
), another greenhouse gas, in the troposphere.
The unchecked accumulation of these gases in
the atmosphere could lead to an uncomfortably
warm planet.
The burning of fossil fuels and the burning of
forests and other biomass are the principal
human-induced, or anthropogenic, emissions of
most biogenic gases to the earths atmosphere.
Also, fossil fuel burning and changes in land use
(such as deforestation) are responsible for many
of the global environmental problems the people
of the world face today. Fossil fuel burning alone
accounts for perhaps 80% of sulfur dioxide (SO
2
)
emissions from the land surface to the atmo-
sphere, 50% of carbon monoxide, 50% of NO
x
,
20% of methane, 20% of NMHCs, 5% of ammo-
nia, and 4% of nitrous oxide. It is also responsible
for 7090% of anthropogenic CO
2
emissions to
the atmosphere. This amount is equivalent to
about 10% of the natural CO
2
emissions from res-
piration and decay.
As mentioned previously, C, N, P, and S,
besides O and hydrogen (H), are the principal
elements that make up living matter. The biogeo-
chemical cycles of these elements are intimately
coupled through biological productivity and respira-
tion and/or decay. Ecosystems take energy from
their surrounding environment. The net result is
production of organic matter, more disorder on
the planet (increased entropy), and waste. The
waste may act as a pollutant. The biogenic gases
of carbon, nitrogen, and sulfur are a consequence
of this entropy production. Their fluxes maintain
the earths atmosphere in a state of disequilibrium.
The natural sources of these biogenic gases
are processes at the earths surface or chemical
reactions in the atmosphere. The processes by
which biogenic gases and other components
cycle through the coupled C-N-P-S-O system,
although in some environments operating close
to equilibrium, are principally controlled by the
rates at which the processes operate.
During the last half century, scientists have
tended to specialize. Consequently, most global
environmental systems have been little studied
or studied only in a piecemeal fashion. Only
recently has attention been paid to the coupled
earth-surface system of atmosphere, hydro-
sphere, biosphere, cryosphere, and shallow
lithosphere. Basic information on global reservoir
sizes and fluxes (e.g., biological productivity) is
lacking or is only partly known. An example of
this lack of data is the estimates of tropical forest
biomass, which vary by a factor of 2 or 3 for
Amazonia alone.
It is very unlikely that the anthropogenic
fluxes of gases to the atmosphere will substan-
tially decline as we enter the 21st century.
Population growth and our global reliance on
fossil fuels as an energy source make such a sce-
nario highly improbable. Thus, continued global
environmental change is a virtual inevitability. It
is likely that, by the middle of the next century,
the atmospheric concentration of CO
2
will be
double what it was before the Industrial
Revolution (to date, it has increased about 30%),
and concentrations of other greenhouse gases
will also increase. Such a change in the composi-
tion of the atmosphere portends a strong proba-
bility of climate change.
Historical Framework
It is worthwhile considering at this stage
how the earths biogeochemical cycles and cli-
mate system functioned prior to human interfer-
ence. It is impossible to consider the functioning
of all the biogeochemical cycles of concern
because of space limitations. Only the global bio-
geochemical cycles of carbon and oxygen are
used as examples in this section. We will end
with a brief summary of environmental condi-
tions just prior to major human interference in
the biogeochemical cycles and climate system.
Carbon
Carbon composes approximately 50% of all
living tissues. In the form of carbon dioxide, it is
necessary for plants to grow. Carbon dioxide also
helps to sustain an equable climate on earth. The
concentration of carbon dioxide in the
13
atmosphere has varied during the geologic past,
but has remained within limits that permit life to
exist on earth. Carbon dioxide is cycled through-
out the spheres of earth on different time scales.
We can refer to these scales as short-, medium-,
and long-term. Figures 3 and 4 illustrate the
processes involved in these time scales.
The short-term carbon cycle
Photosynthesis is part of the short-term car-
bon cycle (on the order of years). We can look at
the short-term cycling of carbon as carbon diox-
ide by beginning with the producers of organic
carbon, the plants. Carbon in the form of atmo-
spheric carbon dioxide is removed from the air
by plants. This removal occurs both on landfor
example, in forests and grasslandsand in
waterfor example, in lakes, rivers, and the
surface waters of the oceans. The primary pro-
ducers, the photosynthetic phytoplankton and
benthic plants in the oceans and plants on the
terrestrial surface, transform inorganic carbon as
carbon dioxide into organic carbon within their
tissues. Light and nutrients, like phosphate and
nitrate, are necessary for this reaction to occur.
Some of the energy from the light is used in the
growth of plants, and some remains stored in the
tissues of plants as carbohydrates.
Plants remove about 100 billion tons of car-
bon as carbon dioxide from the global atmo-
sphere each year, which is about 14% of the
atmospheres total carbon. Most, but not all, of
the carbon dioxide taken from the atmosphere
during photosynthesis is returned to the atmo-
sphere during respiration and decay. The annual
(b) Subduct i on
(a) Phot osynt hesi s- respi rat i on
Upt ake by
rocks i n
weat heri ng
(c) St ored oi l , gas, coal ,
and kerogen
Organi sms use
carbon f rom t he
ocean/ atmosphere
t o const ruct
organic matter and
shel l s of cal ci um
and carbonat e,
CaCO
3
CO
2
C
O
2
Decay
Figure 3. The biogeochemical cycle of carbon prior to human interference, showing (a) the short- term cycle, i.e., photosynthesis and
respiration; (b) the long- term cycle, involving accumulation of organic C and CaCO
3
in marine sediments, their subduction, their alteration,
and the return of CO
2
to the atmosphere via volcanism; and (c) the medium- term cycle, involving storage of C in organic materials in sedi-
mentary rocks. Ultimately this carbon is returned to the earths surface and undergoes weathering; in the process, O
2
is taken out of the
atmosphere and CO
2
is returned.
14
removal rate of atmospheric carbon dioxide in
photosynthesis is slightly larger on land than in
the ocean.
After photosynthesis, carbon may next be
transferred to a consumer organism if the plant is
eaten for food. The carbon stored in the tissue of
the plant enters an animals body and is used as
energy or stored for growth. Land animals, such
as cows and deer, are the primary consumer
organisms. Aquatic plants are eaten by zooplank-
ton (small sea animals) and larger animals. When
an animal breathes, some of this carbon that was
ATMOSPHERE
Carbon i n CO
2
gas
CO
2
f rom
def orest at i on
CO
2
f rom
decayi ng
organi c mat t er
and
respi rat i on
Oceans
absorb CO
2
BIOSPHERE
Organi c mat t er i n
pl ant s and ani mal s
Li vi ng pl ant s
ext ract CO
2
CO
2
f rom
cement
manuf act uri ng
CO
2
t o
weat heri ng
of l i mest one
and si l i cat e
CO
2
f rom
burni ng
of coal ,
oi l , and
gas
HYDROSPHERE
CO
2
di ssol ved i n ocean
Aquat i c pl ant s
put CO
2
i nt o wat er
Buri ed
organi c
mat t er
Preci pi t at i on
of CaCO
3
Kerogen
Coal , oi l , gas
LITHOSPHERE
Carbon in buried plants, animals, and sediments
CO
2
f rom
al t erat i on of
organi c
mat t er and
CaCO
3
Figure 4. The major reservoirs and fluxes in the biogeochemical cycle of carbon. The shapes surrounding the spheres are called boxes.
Arrows represent the processes and their directions that transfer carbon from one box to another. The carbon cycle can be conceived of as
a series of interlocking circuits in the reservoirs of atmosphere, biosphere, hydrosphere, and shallow lithosphere (crust). In our time, the
cycle would be in balance if it were not for human interference by burning of fossil fuels, cement manufacturing, and land- use activities
(e.g., deforestation) (after Skinner and Porter, 1987).
15
taken up from plants is released from the ani-
mals body as carbon dioxide gas.
Besides the carbon stored above ground in
living and dead vegetation, there is carbon below
ground in the root systems of terrestrial plants.
When the plants die, some of this carbon may be
released as carbon dioxide or methane gas to the
air trapped in the soil, or it may accumulate in
the soil itself as dead organic material. This dead
organic matter may be ingested by consumer
organisms, such as insects and worms living in
the soil.
Some of the organic carbon generated in land
environments is weathered and eroded, and the
organic debris is transported by streams to the
ocean. In the ocean, some of this debris, along
with the organic detritus of dead marine plants
and animals, settles to the ocean floor and accu-
mulates in the sediments. However, some of the
debris is respired in the ocean to carbon dioxide.
This carbon dioxide may leave the ocean and be
transported over the continents, where it is used
again in the production of land plants.
The long-term carbon cycle
The long-term carbon cycle (on the
order of tens to a hundred million
years) requires that we consider the
earths history over the last 600 million
years or sothe period covered by the
fossil record. Figure 5 defines the
terms and intervals of geologic time.
The long-term cycling of carbon
(Figures 3 and 4) involves intercon-
nections between the cycling of the
minerals calcium carbonate (CaCO
3
)
and calcium silicate (CaSiO
3
). This
series of processes dates back to the
beginning of plate tectonics. This
cycling includes not only the land and
ocean reservoirs but also that of lime-
stone rocks. Limestone rocks are main-
ly composed of calcium carbonate and
are the fossilized skeletal remains of
marine organisms or, less commonly,
inorganic chemical precipitates of cal-
cium carbonate. Limestones are great
storage containers for carbon. Most of
the carbon near the earths surface is
found in these rocks or in fossil organic matter in
sedimentary rocks. Weathering and erosion of the
earths surface result in the leaching of dissolved
calcium, carbon, and silica (SiO
2
) from limestones
and rocks containing calcium silicate.
The dissolved substances produced by
weathering are transported to the ocean by
rivers. As discussed in on p. 9, they are then used
to form the inorganic skeletons of benthic organ-
isms and plankton, which are composed of calci-
um carbonate and silica. During formation of the
calcium carbonate skeletons, the carbon dioxide
derived from the weathering of limestone is
returned to the atmosphere.
When marine animals and plants die, their
remains settle toward the seafloor, taking the car-
bon stored in their bodies with them. En route,
their organic matter is decomposed by bacteria,
just as on land. Some shells may dissolve. Thus,
animal and plant organic and skeletal matter is
turned back into dissolved carbon dioxide, nutri-
ents, calcium, and silica in the ocean. This carbon
dioxide is stored in the deeper waters of the
Figure 5. The geologic time scale the calendar of the earth. Geologic time is
divided into the intervals of eon, era, period, and epoch. The boundaries of these
intervals are based on absolute age dating using the radioactive decay of certain
elements (e.g., uranium, potassium, rubidium, and carbon) in rocks; the distribu-
tion of fossilized plants and animals found in the rocks; and certain worldwide
geologic events recorded in the rocks (after Skinner and Porter, 1987).
Eon Era Period Epoch Millions of years ago
Phanerozoic Cenozoic Quaternary Holocene
Pleistocene
Tertiary Pliocene
Miocene
Oligocene
Eocene
Paleocene
Mesozoic Cretaceous
Jurassic
Triassic
Paleozoic Permian
Carboniferous
Devonian
Silurian
Ordovician
Cambrian
Precambrian:
Proterozoic
Archean
Hadean
Today
0.01 (10,000 years ago)
1.6
5.3
23.7
36.6
57.8
65.0
144
208
245
286
360
408
438
505
545
2500
~ 3800
4600
16
oceans for hundreds to a thousand or so years
before being returned to the atmosphere when
the deep water moves upward (upwelling), usual-
ly because of divergent movements of surface
water.
Some of the animal and plant plankton sinks
to the bottom, where the carbon in the organic
matter and shells escapes degradation and
becomes part of the sediment. As the seafloor
spreads through plate tectonics, the sediments
containing the remains of marine plants and ani-
mals are carried along to subduction zones, where
they are transported down into the earths mantle.
At the severe pressures and high temperatures in
the subduction zones, organic matter is decom-
posed and calcium carbonate reacts with the sili-
ca found in the subducted rocks to form rocks
containing calcium silicate.
During this metamorphism, carbon dioxide is
released and makes its way into the atmosphere
in volcanic eruptions and via hot-spring dis-
charges. Once in the atmosphere, it can then
combine with rainwater. The rainwater falls on
the land surface and seeps down into the soils,
where it picks up more carbon dioxide from
decaying vegetation. This water, enriched in car-
bon dioxide, weathers and dissolves the com-
pounds of calcium and silica found in rocks of
the continents. The cycle begins again.
This series of processes has been active for at
least 600 million years, since the advent of the
first organisms that made shells (and were there-
fore the first to leave fossils). The processes were
important even earlier in earths history, when
calcium carbonate was deposited in the ocean by
inorganic processes.
Figure 6. Model calculation of atmospheric carbon dioxide during the last 600 million years. The horizontal axis shows time in millions of years
before the present (top) and geological time period (bottom). The left vertical axis shows the number of times todays C level that existed in the
atmosphere of the time; the right vertical axis shows the amount of CO
2
in the atmosphere. For example, 500 million years ago there was
about 14 times as much CO
2
in the atmosphere as there is today, with a total amount of about 37 x 10
18
grams (after Berner, 1991).
K Tr
1 8
1 6
1 4
1 2
1 0
8
6
4
2
0
2 0
3 0
4 0
5 0
1 0
0
6 0 0 5 0 0 4 0 0 3 0 0 2 0 0 1 0 0 0
T im e
M illio n s o f ye a rs b e fo re p re se n t B P )
C
O
2

i
n

t
h
e

a
t
m
o
s
p
h
e
r
e

r
e
l
a
t
i
v
e

t
o

p
r
e
s
e
n
t

d
a
y
A
t
m
o
s
p
h
e
r
i
c

C
O
2

1
0
1
8

g
r
a
m
s
)
P a le o zo ic M e so zo ic C e n o zo ic
C O S D C P J T
C - C a m b ria n
O - O rd o vic ia n
S - S ilu ria n
D - D e vo n ia n
C - C a rb o n ife ro u s
P - P e rm ia n
Tr - Tria ssic
J - J u ra ssic
K - C re ta c e o u s
T - Te rtia ry
P re se n t d a y
17
Atmospheric CO
2
levels of the past
One outcome of changes in the rates of
processes in the long-term biogeochemical
cycling of carbon is that atmospheric carbon
dioxide has varied in a quasicyclic fashion dur-
ing the last 600 million years of earths history.
Robert A. Berner of Yale University and col-
leagues have developed models of the carbon
cycle to calculate these variations. Figure 6 shows
the results of one such calculation.
Periods of high atmospheric carbon dioxide
levels are the result mainly of intense plate tec-
tonic activity, with increased metamorphism of
limestone and release of carbon dioxide to the
atmosphere from volcanoes. These high carbon
dioxide periods are often referred to as hothouses
or greenhouses. They are also periods of relative-
ly high sea level; for example, in the Cretaceous
and Cambrian periods, much of what would
become the present continent of North America
was covered by water. This flooding of the conti-
nental landscapes was due principally to the
large size and volume of the midocean ridges,
caused by intense plate tectonic activity. The
increase in ridge volume led to the displacement
of ocean water onto the continents of the time.
Periods with lower atmospheric carbon diox-
ide levels, such as the Carboniferous through
Triassic and much of the Cenozoic, are the out-
come of less intense plate tectonic activity and
increased removal of carbon dioxide from the
atmosphere by weathering. These intervals,
which include the present era, are extended cool
periods (ice houses) in the climatic history of the
earth. They are also times of relatively low sea
level due to a decrease in the volume of the
midocean ridges.
Biological and other factors also play a role
in regulating atmospheric carbon dioxide levels
over the long term. For example, the lowering of
atmospheric CO
2
from the high levels of the mid-
Paleozoic era, about 400 million years ago, was
not simply the result of the waning intensity of
plate tectonic processes. It followed the evolution
of land plants, which withdrew CO
2
from the
atmosphere by photosynthesis. Similarly, the
lowering after the Cretaceous period, about 100
million years ago, followed the appearance of
flowering plants, which resulted in an increase in
weathering rates and withdrawal of CO
2
from
the atmosphere.
The important point is that atmospheric CO
2
has varied by a factor of perhaps more than ten
during the last 600 million years of the earths
history. This variation certainly has had climatic
implications, because CO
2
is an important green-
house gas. In fact, for much of the last 600 mil-
lion years, the planet had a different atmospheric
composition and a more equable climate than
that of today.
The medium-term carbon cycle
Medium-term cycling of carbon dioxide (mil-
lions to tens of millions of years) involves organic
matter in sediments; coal, oil, and gas; and
atmospheric oxygen (Figures 3 and 4). It com-
mences, as does the short-term cycling, with the
removal of carbon dioxide from the atmosphere
by its incorporation into plants and the accumu-
lation of the dead plant and animal carbon in
sedimentary organic matter (the dead and fos-
silized remains of plants and animals). When
dispersed throughout a sedimentary rock, this
organic matter is termed kerogen. Shales are very
fine-grained sedimentary rocks that are often rich
in kerogen. Coal, oil, and gas deposits are also
the altered remains of the soft tissues of plants
and animals which have accumulated in a geo-
graphically restricted area.
Coal is derived mainly from terrestrial plant
material, which is often deposited in swampy
environments. The plant material is altered when
the swamp sediments are buried. If buried deep
enough, the dead plant material may be substan-
tially changed because of the increased tempera-
tures and pressures at depth. Different types of
coal are formed by varying conditions of temper-
ature and pressure. Anthracitea hard, dense,
black coalis formed by alteration of plant mate-
rial at a relatively high temperature and pressure.
Bituminous, brown coal is formed under less
intense conditions. Peat, used as a fuel in some
parts of the world, is little-altered plant material
that has not been buried deeply. It is high in car-
bon. Peat is an important component of tundra
areas in the Northern Hemisphere.
Oil and gas represent highly altered organic
matter, principally the altered remains of marine
18
phytoplankton that were deposited on the
seafloor. During burial, these organic materials
are broken down at elevated temperature and
pressure, forming oil and gas. The oil and gas
may migrate hundreds of miles in the subsurface
before coming to rest in large accumulations in
the voids of rocks. Often, oil and gas are formed
in shales; but as temperature and pressure
increase with depth, they move to more coarse-
grained rocks like sandstones and limestones. It
is in these latter rocks, dating from the Creta-
ceous and Cenozoic periods, that the great oil
and gas reserves of the world are found, like
those of the Persian Gulf.
These deposits of coal, oil, and gas come
from organic carbon that has escaped respiration
and decay. Thus, they represent carbon dioxide
that has been removed from the atmosphere. The
same is true of the kerogen dispersed as fine-
grained materials in the sedimentary rocks.
Because these materials were buried, the oxygen
that would have been used in their decay has
remained in the atmosphere. Eventually, howev-
er, the carbon in these deposits and in kerogen is
recycled into the atmosphere, returning carbon
dioxide to that reservoir and removing oxygen.
This happens when these fossil fuel deposits and
kerogen are uplifted by plate tectonic forces after
millions of years of burial and exposed to the
atmosphere. When this occurs, the oxygen that
previously accumulated in the atmosphere reacts
with the coal, oil, gas, and kerogen. The reaction
involves the decay of these organic materials in
the presence of oxygen (equation 5). This results
in the removal of oxygen from the atmosphere
and the return of carbon dioxide to the atmo-
sphere. The ongoing dynamic cycle is complete.
Fossil fuel is a nonrenewable energy source,
because coal, oil, and gas deposits take millions
of years and specific environmental conditions to
form. The mining of these deposits brings these
materials back to the surface much more rapidly
than natural processes do. The stored energy
from the long-dead organisms is released in the
form of heat when the coal, oil, and gas are
burned. This fossil fuel energy keeps us warm,
powers our cars, and moves the machinery of
industry. It is also a main cause of environmental
pollution, because a byproduct of fossil fuel
burning is the release of gases and particulate
materials into the environment. Climatic change
is an important potential global environmental
effect of the release of carbon dioxide and other
gases to the atmosphere by combustion.
In summary, carbon is found in all four major
surface spheres of the earth. In the ecosphere, it is
essential to every life form, occurring in all
organic matter. In the atmosphere, it is found as
the gases carbon dioxide, methane, and several
other compounds. It occurs as carbon dioxide
dissolved in lakes, rivers, and oceans in the
hydrosphere. In the earths crustpart of the
lithosphereit is found as calcium carbonate
originally deposited on the seafloor, as kerogen
dispersed in rocks, and as deposits of coal, oil,
and gas. It is because carbon is stored in the large
sedimentary reservoirs of limestone and fossil
organic carbon, and not in the atmosphere, that
life on earth is possible. If all this carbon were
stored in the atmosphere, there would be about
30 times the existing amount of CO
2
. The result
would be a substantial heating of the atmosphere
because of the increased absorption of the long-
wave infrared radiation emitted from the surface
of the earth. The greenhouse effect would be very
strong, and our planet would probably have a
temperature like that of Venus: 460C!
Oxygen
Oxygen composes 20.9% of the gases of the
atmosphere. The cycling of oxygen (Figure 7) is
strongly coupled to that of carbon (Figure 4).
Oxygen is produced by plants during photosyn-
thesis, when carbon dioxide is consumed. It is
removed by respiration and decay, when carbon
dioxide is produced. This is a short-term, nearly
balanced cycle on land, because the amount of
oxygen produced yearly by land plants is about
equivalent to the amount they use in the processes
of respiration and decay. On average, it takes
about a decade for oxygen and carbon dioxide to
cycle through living plants. However, a little ter-
restrial organic matter that has not undergone
respiration or decay, such as leaves and trunks of
trees and smaller-sized organic debris, leaks from
the land to the ocean via rivers. In the ocean,
some of this organic detritus escapes destruction
and is deposited in the sediments.
19
In the oceans, phytoplankton produce slight-
ly more oxygen than is consumed during the res-
piration and decay of marine life. As a result,
oxygen is released to the atmosphere. The organ-
ic carbon not decayed by this oxygen, along with
some of the terrestrial organic detritus mentioned
in the preceding paragraph, is deposited on the
seafloor and accumulates in the sediments of the
ocean. If this accumulation were not counteracted
by other processes, and no other factors were to
intervene, all the carbon dioxide in the atmo-
sphere would disappear in less than 10,000 years.
The oxygen content of the atmosphere would
double in less than several million years.
Fortunately, the overproduction of oxygen in the
oceans is balanced by the weathering of fossil
organic carbon and other materials in rocks on
land. During this process, carbon dioxide is
returned to the atmosphere.
If the burial of organic carbon in sediments
were enhanced, oxygen might accumulate in the
atmosphere. In fact, it seems to be the case that
times of high organic carbon burial in the past
gave rise to high atmospheric oxygen levels.
Figure 8 is a model calculation of atmospheric
oxygen concentration variations during the last
600 million years. Just before the Carboniferous,
vascular plants evolved and spread over the conti-
nents. Their remains were a new source of organ-
ic matter resistant to degradation by atmospheric
oxygen. During the Carboniferous and Permian,
large quantities of vascular plant organic matter
were buried in the vast coastal lowlands and
swamps of the time. This material became the
coal deposits mined from rocks of Carboniferous
and Permian age today. This large accumulation
of organic matter gave rise to the high atmospher-
ic oxygen levels of the late Paleozoic. Coal
deposits are also important in Cretaceous- and
early Cenozoicage rocks, another time of high
atmospheric oxygen concentrations.
Environmental Conditions Before
Human I nterference
From the above discussion, we can conclude
that the carbon and oxygen biogeochemical
cycles have changed throughout geologic time.
These changes have led to changes in atmospher-
ic composition and climate. Just prior to signifi-
cant human interference in the ecosphere, envi-
ronmental conditions were also changing natu-
rally because of a variety of factors. These factors
include external forcings, such as changes in the
orbit of the planet earth and in the flux of solar
radiation to the planetary surface, and internal
forcings, involving the behavior of the earths
ocean-atmosphere-land-biota-cryosphere system.
For about 1.6 million years, the earth has
experienced a series of cold and icy times known
as ice ages or glacial stages. These periods of
extensive glaciation of the continents alternated
with shorter and warmer periods, interglacial
stages like today. During the interglaciations, the
great glaciers that covered the continents of
Europe and North America to depths of two kilo-
meters or more melted. The glaciers retreated to
geographical positions similar to those of the pre-
sent continental ice sheets of Greenland and
Antarctica. As the glaciers waxed and waned
At mospheri c oxygen
At mospheri c
CO
2
Oxygen di ssol ved
i n t he ocean
Land bi ot a
Mari ne bi ot a
R
e
s
p
i r
a
t
i o
n
P
h
o
t
o
s
y
n
t
h
e
s
i
s
P
h
o
t
o
s
y
n
t
h
e
s
i
s
R
e
s
p
i
r
a
t
i
o
n
Mari ne sedi ment s
(organi c carbon)
Cont i nent al rocks
Figure 7. The biogeochemical cycle of oxygen. This cycle is strong-
ly coupled to that of carbon (Figure 4). The boxes represent the
major reservoirs of oxygen, and the arrows the fluxes of oxygen
from one box to another. The heavier the arrow, the larger the flux.
The broken lines show the flow of carbon in sedimentation on the
ocean floor, burial in sediments, and uplift by plate tectonic
processes. When uplifted, organic C is oxidized by oxygen in the
atmosphere, and CO
2
is released (after Andreae, 1987).
20
through the last 2 million years, global tempera-
tures went up and down, as did sea level. The
composition of the atmosphere and other envi-
ronmental conditions changed.
The earth, before extensive human interfer-
ence in its biogeochemical cycles, was recovering
from the climax of the last great glaciation 18,000
years ago. The recovery has not been smooth.
There have been times in the past 18,000 years
when the planet cooled quickly. Also, there have
been periods when the earth was warmer than
today. However, during the past several cen-
turies, the global environment has changed sub-
stantially and rapidly. Atmospheric trace gas con-
centrations, matter in runoff, temperature, and
other indicators have increased in magnitude. A
major reason for all the changes is the impact of
human activities on the environment.
1 0
0
2 0
3 0
3 5
1 0
0
6 0 0 5 0 0 4 0 0 3 0 0 2 0 0 1 0 0 0
T im e
M illio n s o f ye a rs b e fo re p re se n t B P )
O
x
y
g
e
n

1
0
2
0

g
r
a
m
s
)
O
2

a
s

p
e
r
c
e
n
t
a
g
e

o
f

a
t
m
o
s
p
h
e
r
i
c

g
a
s
e
s
P a le o zo ic M e so zo ic C e n o zo ic
C O S D C P Tr J K T
C - C a m b ria n
O - O rd o vic ia n
S - S ilu ria n
D - D e vo n ia n
C - C a rb o n ife ro u s
P - P e rm ia n
Tr - Tria ssic
J - J u ra ssic
K - C re ta c e o u s
T - Te rtia ry
P re se n t d a y
2 0
3 0
2 5
1 5
5
Figure 8. Model calculation of atmospheric oxygen during the past 600 million years. The dashed line across the figure shows todays
atmospheric concentration of O
2
. The left vertical axis shows the atmospheric O
2
level; the right vertical axis shows O
2
as a percentage of
the total atmospheric gases. The horizontal axis shows time in millions of years before the present and geological time period (after Berner
and Canfield, 1989).
21
The modern coupled C-N-P-S-O system is
multidimensional and complex, with numerous
processes, reservoirs, and fluxes. All these attrib-
utes are difficult to portray in detail. To see the
relationships between biogeochemical cycles and
climate, we will examine those biogeochemical
compounds that play a role in climatic change. In
particular, we will focus on the problem of an
enhanced greenhouse effect and global warming
brought about by human activities. Keep in mind
that the cycles also respond to a global cooling
and can feed back into any such cooling. The
processes discussed below would respond to
cooling in an opposite sense, to some extent, and
probably with different magnitudes of change.
Figures 920 show the biogeochemical cycles
of interest. The figures show that the burning of
forests and other biomass and fossil fuel
The Modern Coupled C-N-P-S-O System
METHANE
(fluxes = Mt C/ y)
F
o
s
s
i
l
f
u
e
l
b
u
r
n
i
n
g
3
4
7
6
B
i
o
m
a
s
s
b
u
r
n
i
n
g
1
6
3
1
L
a
n
d
f
i
l
l
s
1
6
5
3
R
i
c
e
p
a
d
d
i
e
s
1
9
1
2
7
C
H
4
h
y
d
r
a
t
e
0
7
6
S
o
i
l
u
p
t
a
k
e
1
1
3
4
P
r
o
d
u
c
t
i
o
n
f
r
o
m
l
i
v
e
s
t
o
c
k
5
6
1
5
0
F
r
e
s
h
w
a
t
e
r
1
1
9
N
a
t
u
r
a
l
w
e
t
l
a
n
d
s
7
6
1
5
0
O
c
e
a
n
4
1
6
M
a
i
n
l
y
O
H
*
d
e
p
l et i on
3
0
0
4
5
0
CO
CH
4
+ OH* H
2
O + CH
3
T
o

s
t
r
a
t
o
s
p
h
e
r
e
4
6 Cl i mat e sensi t i vi t y
0.3C/ CH
4
doubl i ng
17% greenhouse
CH
4
3750 Mt C
1.72 ppmv
Residence time = 10 y
Accumulation:
28 Mt C/ y
8 ppbv
Land Ocean
Figure 9. Part of the modern global biogeochemical cycle of methane, emphasizing exchanges of methane between the earths surface and
atmosphere and the fate of the gas in the atmosphere. The atmospheric reservoir is shown as a circle, including the amount of carbon in
teragrams (10
12
grams), equivalent to million metric tons (Mt). Flux ranges are also given in Mt C/ yr; arrows indicate the directions of the
fluxes. The proportion of C in the atmosphere is given in parts per million by volume (ppmv), the residence time in years, and the accumula-
tion rate per year in both Mt and parts per billion by volume (ppbv). The chemical reaction at the top of the figure shows the fate of methane
that escapes to the stratosphere (after Mackenzie, 1995; Houghton et al., 1996).
Global Change
Instruction Program
22
combustion are the major human sources of most
biogenic gases in the earths atmosphere. Many
of the natural exchanges of gases between the
earths surface and the atmosphere in these
cycles are driven by biological processes, which
involve bacteria. In the atmosphere, many of the
gases are oxidized, usually by hydroxyl radical
(OH*), a trace gas that is the atmospheres main
cleansing mechanism. The oxidized materials
then return to the earths surface, through biolog-
ical production of plants on land and in the
ocean and by wet and dry deposition.
Many of the natural processes shown in these
figures have feedbacks that affect the accumula-
tion of trace gases in the atmosphere and hence
affect the global climate. Because these feedbacks
are linked to biological processes, they are termed
biotic feedbacks. We shall explore the nature of
the feedbacks in the C-N-P-S-O system below.
CARBON MONOXIDE
(fluxes = Mt C/ y)
F
o
s
s
i
l
f
u
e
l
b
u
r
n
i
n
g
3
3
6
B
i
o
m
a
s
s
b
u
r
n
i
n
g
3
1
2
S
o
i
l
4
8
O
c
e
a
n
7
2
T
o

s
t
r
a
t
o
s
p
h
e
r
e
4
8
O
H
*
d
e
p
l
e
t
io
n
CO
2
1
2
1
2
O
H
*
d
epl et i on
NMHC
360
CO + OH* CO
2
+ H
O
H
*
d
e
p
l
e
t
i
o
n
CH
4
3
2
4
S
o
i
l

u
p
t
a
k
e
1
9
2
CO
228 Mt C
0.11 ppmv
Residence time = 0.2 y
Accumulation:
2 Mt C/ y
1 ppbv
Land Ocean
Figure 10. Part of the modern global biogeochemical cycle of carbon monoxide, emphasizing exchange of the gas between the earths
surface and its atmosphere and the fate of the gas in the atmosphere. See Figure 9 for an explanation of the units and abbreviations
used. Notice, as with methane, the role of OH* as an agent of oxidation of the reduced carbon gases (after Mackenzie, 1995; Houghton
et al., 1996).
23
The CH
4
-CO-CO
2
Connection
Figures 911 illustrate the biogeochemical
cycles of methane (CH
4
), carbon monoxide (CO),
and carbon dioxide between the earths surface
and atmosphere. We have a reasonably good
understanding of the major processes associated
with the exchange of these gases between the
surface and the atmosphere and of the gases
atmospheric reservoir sizes. However, the fluxes
associated with the various processes are less
well quantified.
All three of these gases have been accumulat-
ing in the atmosphere because of human activi-
ties. Since the late 18th century, global atmo-
spheric CO
2
concentrations have risen from
about 280 to about 360 parts per million by vol-
ume (ppmv), a change of approximately 30%.
This increase is principally the result of fossil fuel
burning and land-use activities such as deforesta-
tion, which add CO
2
to the atmosphere when the
burning carbon combines with atmospheric mol-
ecular oxygen. Because of this increase in CO
2
from human activities, the atmospheric reservoir
of oxygen gas has been reduced by less than 1%.
Thus, in the burning of fossils fuels, there is no
concern about depletion of atmospheric CO
2
.
The global concentration of CH
4
during this
period has more than doubled from about 800 to
1,720 parts per billion by volume (ppbv). As with
CO
2
, this increase is due to human activities, and
again as with CO
2
those activities include burn-
ing of biomass and fossil fuels. For methane,
though, rice paddies, farm and ranch animals
(which produce methane as they chew their cud),
and rotting landfills are also important. Landfills
emit CH
4
as methanogenic bacteria decompose the
wastes in an anaerobic environment.
Carbon monoxide has also been increasing in
concentration in the atmosphere, particularly in
the Northern Hemisphere where important
anthropogenic emission sources are located. The
rate of increase in the 1980s was approximately 1
ppbv per year, principally because of the same cul-
prits, fossil fuel and biomass burning (Figure 10).
The rates of increase of all three atmospheric
carbon gases slowed during the late 1980s and
early 1990s because of a variety of natural and
human-induced causes.
Major processes in the CH
4
and CO cycles
CH
4
and CO are reduced gases, that is, they
may react with other chemical compounds by the
loss of electrons from the carbon in the com-
pounds. The carbon in CH
4
has a valence of 4;
the carbon in CO has a valence of +2. The biogeo-
chemical cycles of these two gases and CO
2
are
connected because OH* oxidizes CH
4
and CO to
CO
2
, which has a valence of +4. This CO
2
can
then be used by plants and other organic matter.
The decay of this organic matter, in turn, leads to
the release of CH
4
and CO from the earth and
oceans.
The major natural processes involving
exchange of CH
4
between the earths surface and
the atmosphere (shown on the right-hand side of
Figure 9) are
evasion (release) to the atmosphere from the
ocean and natural wetland and freshwater
ecosystems,
leakage from underground natural gas
deposits into the atmosphere (in Figure 9,
this is included in the fossil fuel burning
flux), and
uptake of CH
4
in soils due to the activity of
methanotrophic bacteria.
The major sink of CH
4
is the atmosphere,
where it is oxidized principally by reaction with
OH* (top right-hand side of Figure 9).
Approximately 300450 million tons of carbon
Carbon Cycles
Global Change
Instruction Program
24
annually are oxidized this way. During the past
hundred years, the change in the concentration of
methane in the atmosphere could be responsible
for about 20% of the warming due to an
enhanced greenhouse effect. If CH
4
concentration
were to double in the atmosphere, one would
expect, based on the ability of the gas to warm
the atmosphere, a rise of approximately 0.3C in
global mean temperature.
Soils are both a natural source of CO to the
atmosphere and a natural sink of the gas from
the atmosphere (Figure 10). The source is the bac-
terial decomposition of organic matter in soils,
and bacteria and algae in the ocean. The sink is
also the result of bacterial processes.
The atmosphere is also both a source and
sink of CO. It is the most important sink of CO,
as with CH
4
, through the oxidation of CO to CO
2
via OH*. This process transfers approximately
1,200 million tons of carbon to the atmospheric
CO
2
reservoir annually (Figure 10). The atmo-
sphere is a source of CO because nonmethane
hydrocarbons (NMHCs) are oxidized to that
compound by OH*.
CH
4
and CO feedbacks to global climate change
Respiration and the bacterial decomposition
of organic matter emit CH
4
and CO from soils to
the atmosphere. Because the rates of these
processes increase with increasing temperature,
the emissions might increase in a world that was
warming. This would be a positive feedback on
any initial warming of the earth. However,
because soils are also sinks for atmospheric CH
4
and CO, and emissions of these gases are sensi-
tive to the amount of moisture in the soil, the sit-
uation is more complex.
In general, it is likely that warmer tempera-
tures in the high northern latitudes will lead to
an increase in CH
4
fluxes from CH
4
trapped in
permafrost, decomposable organic matter frozen
in permafrost, and decomposing CH
4
gas
hydratessubstances in which CH
4
is locked in a
structure of water ice. These hydrates are stable
only at low temperatures or under pressures
exceeding ten atmospheres. They are stored in
sediments under shallow seas, particularly in the
Arctic region, and also in permafrost. The flux of
methane escaping to the atmosphere from this
source is poorly known today (Figure 9).
Because CH
4
and CO react easily with OH*
in the atmosphere, increases in their atmospheric
concentrations (and in those of the reduced N
and S gases) would affect the concentration of
OH*, thus having an impact on the atmospheres
ability to cleanse itself. It is possible that an
increase in the flux of CO to the atmosphere,
because of the gas short residence time there,
could deplete OH* and consequently cause less
CH
4
to be removed from the atmosphere. If so,
CH
4
would accumulate faster in the atmosphere,
leading to an increased rate of global warming.
However, the overall effect is likely to be small.
Furthermore, increased atmospheric CH
4
would
probably lead to increased production of water
vapor in the stratosphere (Figure 9), where
methane and OH* react to form water vapor and
CH
3
. Water vapor is a greenhouse gas, and its
increased production in the stratosphere is a pos-
itive, but minor, feedback in a scenario of a
warming earth.
In summary, although the various effects are
difficult to quantify, it is likely that an initial
warming of the climate would lead to a net
increase in fluxes of CH
4
and CO to the atmo-
sphere and accumulation there. This situation
constitutes a positive feedback on the concentra-
tion of these gases in the atmosphere and hence
on global warming. Any global cooling would
probably result in an opposite effect.
The CO
2
Cycle
The most important trace gas contributing to
the potential of an enhanced greenhouse effect is
CO
2
. From 1765 to 1995, CO
2
accounted for about
60% of the human-induced warming due to the
accumulation of greenhouse gases in the atmo-
sphere. Adoubling of the concentration of CO
2
in
the atmosphere could eventually lead to an
increase in global mean temperature of about
1.54.5C.
Figure 11 shows the major processes, both
natural and human, affecting the exchange of
CO
2
between the atmosphere and earths surface.
Estimates of the fluxes associated with the
processes are also shown. Let us begin our
25
exploration of Figure 11 by considering the ocean
fluxes. The total exchange of CO
2
between the
ocean and atmosphere amounts to about 90 bil-
lion tons of carbon per year. Much of this carbon
exchange involves
evasion of CO
2
from the warm surface
waters of the tropics and from upwelling
regions, and
invasion (uptake) of CO
2
into higher-latitude,
colder, surface waters (see equation 9, p. 27).
Almost half of this exchangeclose to 45 bil-
lion tons of carbon annuallyis involved in net
primary production due to CO
2
fixation by
photoautotrophic marine plankton. Aslightly
larger amount of CO
2
is returned to the atmos-
phere by respiration and decay in the ocean. The
difference between the two amounts implies that
the ocean, prior to human interference in the
global biogeochemical cycle of carbon, was a net
heterotrophic system and supplied CO
2
to the
atmosphere. The CO
2
released from the ocean was
subsequently used in organic production on land.
In contrast, the terrestrial biota were a net
autotrophic system before humans interfered with
the carbon cycle. In other words, the land biota
produced more organic carbon than was con-
sumed. (Compare the rates for net primary
CARBON DIOXIDE
(fluxes = Mt C/ y)
L
a
n
d
u
s
e
1
6
0
0
F
o
s
s
i
l
f
u
e
l
b
u
r
n
i
n
g
6
1
0
0
R
e
s
p
i
r
a
t
i
o
n
-
d
e
c
a
y
6
1
4
4
0
N
e
t
p
r
i
m
a
r
y
p
r
o
d
u
c
t
i
o
n
6
3
0
0
0
W
e
a
t
h
e
r
i
n
g
2
1
6
V
o
l
c
a
n
i
c
6
0
C
a
C
O
3
p
r
e
c
i
p
i
t
a
t
i
o
n
1
6
8
R
e
s
p
i
r
a
t
i
o
n
-
d
e
c
a
y
4
5
2
5
2
N
e
t
p
r
i
m
a
r
y
p
r
o
d
u
c
t
i
o
n
4
5
0
0
0
O
H
*
d
e
p
l e
t
i
o
n
CO
Cl i mat e sensi t i vi t y
2.5C/ CO
2
doubl i ng
60% greenhouse
O
x
i
d
a
t
i
o
n
o
f
f
o
s
s
i
l
C
H
2
O
3
6
1
2
1
2
Excess
4412
To ocean
2000
To t errest ri al real m
2412
Lat e di agenesi s- m
et am
o
rp
h
i s
m 60
CO
2
752000 Mt C
360 ppmv
Residence time = 6.5 y
Accumulation:
3100 Mt C/ y
1.5 ppmv
Land Ocean
Figure 11. Part of the modern global biogeochemical cycle of carbon dioxide, emphasizing its exchanges between the earths surface and its
atmosphere. See Figure 9 for an explanation of the units and abbreviations used. If there were a doubling of the CO
2
concentration in the
atmosphere, one would expect a rise in temperature of 23C at the earths surface and in the lower atmosphere. CO
2
accounts for about
60% of the enhanced greenhouse effect. Note that fossil fuel burning and land- use practices released to the atmosphere about 7,700 Mt of
carbon in 1995. The atmosphere was a major sink for this anthropogenic carbon, but the ocean and the terrestrial biosphere took up about
50% of it. Compare this figure with Figure 4 (after Mackenzie, 1995; Houghton et al., 1996).
26
production and respiration-decay in Figure 11.)
This excess organic carbon, approximately 400
million tons annually, eventually made its way
into river waters in particulate and dissolved
forms. It was then transported to the oceans,
where some portion of it decayed. The CO
2
gen-
erated by this decay led to the pristine het-
erotrophic state of the ocean. In addition, the pre-
cipitation of calcium carbonate in the ocean also
led to the evasion of CO
2
to the atmosphere
(Figure 11).
During the past several centuries, as fossil
fuel burning and land-use changes added CO
2
to
the atmosphere, the ocean went from a net source
to a net sink of CO
2
from the atmosphere. The
concentration of CO
2
in the atmosphere rose, and
the gradient of CO
2
concentration between the
atmosphere and ocean changed. This change
favored the net uptake of CO
2
in the ocean by
solution of the gas in surface seawater (see
Equation 9, p. 27). This oceanic sink of anthro-
pogenic CO
2
was on the order of 2,000 million
tons of carbon per year during the 1980s,
although it varies annually.
Continuing with the exploration of Figure 11,
we see that volcanic emissions of CO
2
from land
and under the sea amount to about 60 million
tons of carbon annually. This flux varies each
year with the intensity of volcanic activity. The
processes of diagenesis and metamorphism cre-
ate a flux of about the same size as that of vol-
canism. These processes occur as buried sedi-
mentary materials change; calcium carbonate and
silica are converted to calcium silicate and CO
2
.
The CO
2
is consequently released to the atmo-
sphere via volcanism, hot springs, and seepage
from deep within sedimentary basins.
Weathering of minerals on land removes CO
2
from the atmosphere, and weathering of sedi-
mentary organic matter (kerogen and fossil fuel)
at the land surface by oxygen adds CO
2
to the
atmosphere (Figure 11). As mentioned in Chapter
2, the balance between the weathering fluxes and
those of volcanism, diagenesis, and metamor-
phism has changed throughout geologic time.
These changes are in part responsible for the
long-term variation in atmospheric CO
2
during
geologic time (Figure 6).
Keep in mind, as mentioned in the previous
section, that CO
2
is coupled to the reduced car-
bon gases through the oxidation of CH
4
and CO
by OH* in the atmosphere. Therefore, any initial
warming of the planet and consequent enhanced
emissions of CH
4
and CO from the earths sur-
face because of human activities could potential-
ly lead to an increase in the accumulation of CO
2
in the atmosphere, a positive feedback.
The imbalance in the cycle and feedbacks
The notorious problem with atmospheric
CO
2
today is the difficulty in balancing the
known sinks with the source from fossil fuel
combustion and land-use activities such as bio-
mass burning. The problem is illustrated in
Figure 11.
We know that carbon is accumulating in the
atmosphere at the rate of 3,300 million tons annu-
ally. We also know that the amount of carbon put
into the atmosphere from land-use activities is
1,600 million tons of carbon per year (with an
uncertainty of 1,000 million tons, plus or minus),
and the flux from fossil fuel burning plus cement
manufacturing is 6,100 million tons per yeara
total of around 7,700 million tons. Subtracting the
known atmospheric accumulation of carbon from
the known source, we see that the fate of roughly
3,000 to 4,000 million tons of human-produced
carbon per year is not known. The lower number
is within the rather large error margins of recent
estimates of how much anthropogenic CO
2
the
ocean takes up annually, but the upper amount is
out of the range of these estimates.
These numbers suggest that there may be
another important sink (sometimes called the
missing sink) of anthropogenic CO
2
besides the
atmosphere and ocean. This sink has been
hypothesized to be the Northern Hemispheres
midlatitude forests and soils. If that is the case, a
rather strange situation has developed with
respect to the modern carbon cycle. While tropi-
cal rain forest ecosystems are sources of carbon to
the atmosphere because of deforestation at rates
of about 1% of the worlds forested area per year,
higher-latitude terrestrial ecosystems may be
sinks of carbon.
27
Such a net sink implies that some processes
of carbon storage on land have changed. Some or
all of the following changes may have occurred.
Increased atmospheric levels of CO
2
act as a
fertilizer and stimulate productivity in
plants. This leads to storage of carbon in bio-
mass or in soil organic carbon.
Plant productivity is stimulated by increased
NO
3
-
and NH
4
+
from fertilizers used in farm-
ing and from deposition of anthropogenic N
from the atmosphere. Carbon once more is
stored in biomass or in soil.
Vegetation regrows in previously disturbed
ecosystems, or grows in undisturbed ones.
The first process on this list, carbon dioxide
fertilization, is a potentially strong negative feed-
back on the accumulation of anthropogenic CO
2
in the atmosphere and hence on global warming.
We know from experiments on plants and small
ecosystems that almost all agricultural crops and
a few perennial plants, when subjected to
increased CO
2
levels, will increase their rates of
photosynthesis and growth. If this enhancement
should also occur in large ecosystems, like
forests, CO
2
would be withdrawn from the
atmosphere and stored in plant organic matter.
Humans have put excess phosphorus, nitrate,
and ammonia nutrients into the environment by
applying fertilizers to the land surface, burning
fossil fuels and biomass, and discharging sewage
containing nitrogen and phosphorus. These
nutrients can stimulate increased plant growth in
the soil and aquatic environments. This eutrophi-
cation of both land and marine environments is a
negative feedback on accumulation of carbon in
the atmosphere from anthropogenic sources and
hence is a negative feedback on warming of the
earth. Total land and ocean eutrophication may
amount to a billion tons of carbon per year.
Other processes and feedbacks involving CO
2
What about other processes and feedbacks in
the biogeochemical cycle of CO
2
that might
change with a global warming? Perhaps one of
the strongest potential positive biotic feedbacks
in the terrestrial environment is the effect of
increasing temperature on photosynthesis and
respiration. The rates of both processes in vegeta-
tion and microbial life increase with increasing
temperature. However, respiration rates are more
sensitive to temperature change. In a warming
world, increased respiration could temporarily
increase the flux of CO
2
to the atmosphere by as
much as 13 billion tons of carbon per year. This
increased flux is a potentially strong positive
feedback on CO
2
accumulation in the atmosphere
and hence on global warming.
Achange in the ocean temperature would
affect the amount of dissolved inorganic carbon
in seawater. The equation relevant to this effect
is
CO
2
(g) + H
2
O + CO
3
2-
= 2HCO
3
-
(9)
The (g) is gas, and the equal sign implies the
reaction is an equilibrium representation of the
process.
For a warmer ocean surface, this reaction
moves from right to leftthe bicarbonate ions
break down into carbon dioxide, water, and car-
bonate. Thus the concentration of CO
2
in the
water will increase, and CO
2
will evade from the
seawater to the atmosphere. For a temperature
increase of 1C, the change in CO
2
concentration
is on the order of 10 x 10
-6
atmospheres (10 atm).
This is a positive feedback that could amplify
a future atmospheric CO
2
increase by about
5%.
At a constant temperature, as you add CO
2
to the ocean, equation 9 goes from left to right,
consuming carbonate ion and producing bicar-
bonate ion. This process too has the effect of
reducing the oceans ability to take up CO
2
.
Feedbacks involving ocean circulation are
strongly linked to the biogeochemical cycling of
carbon and nutrients in the ocean. If the ocean
began to warm, the waters at the surface would
warm more than those at depth. This change
would decrease the amount of nutrients rising
from the deep ocean into the euphotic zone. With
fewer nutrients, there could be a consequent
decrease in biological productivity, followed by
less organic carbon escaping the euphotic zone
and settling into the deep sea in a set of processes
known as the biological pump. It is also conceiv-
able that changes in wind patterns and wind
intensities along the western coastal margins of
28
continents could lead to changes in the upwelling
of CO
2
and nutrients to the surface ocean.
There are several other potential feedbacks
involving CO
2
, the ocean, and climatic change,
but it is difficult to determine their importance:
Increased ultraviolet radiation because of
stratospheric ozone depletion may affect the
capacity of certain marine ecosystems, e.g.,
around the Antarctic, to remove carbon from
the atmosphere.
With warming, the composition and distribu-
tion of algae, jellyfish, and other marine
species could change.
The rates of delivery to the ocean of iron,
molybdenum, and other trace metals essen-
tial to marine life may change.
An increase in the rate of decomposition of
dissolved organic carbon in the ocean could
occur. There are about 1,000 billion tons of
dissolved organic carbon in the ocean.
The biological processes associated with
these possibilities could change the concen-
tration of CO
2
in surface waters and hence
the amount of anthropogenic CO
2
the ocean
can take up.
Finally, with a rise in atmospheric CO
2
to
about 1,000 ppmv, the pH of the ocean could
fall sufficiently to make it difficult for the
organisms that build skeletons of calcite
enriched by magnesium (e.g., coralline algae
and sea urchins) and aragonite (e.g., corals)
to produce shells.
29
Nitrogen forms part of the molecules that
make up living things, such as amino acids (the
building blocks of proteins) and DNA. The nitro-
gen in proteins bonds together various amino
acids to form the protein structure. The amount
of nitrogen in the atmosphere is very large com-
pared to that in the oceans or rocks. Of the ele-
ments C, N, P, S, and O, only nitrogen is found in
more abundance in the atmosphere than in rocks.
The complete biogeochemical cycle of nitro-
gen is very complex. Figures 1217 show only
portions of it. There are six major forms of atmo-
spheric nitrogen: the gaseous forms of diatomic
nitrogen (N
2
), ammonia (NH
3
), nitrous oxide
(N
2
O), and NO
x
(NO and NO
2
), and the aerosols
of ammonium (NH
4
+
) and nitrate (NO
3
-
). In this
chapter, we will focus on the cycles of the first
four of these forms, and also discuss nonmethane
hydrocarbons, the cycles of which are closely
related to those of NO
x
.
The I mportant Nutrient Nitrogen
Figure 12. Part of the modern global biogeochemical cycle of nitrogen, emphasizing interactions among the land, atmosphere, and ocean.
Fluxes between the ocean, land, and groundwater are shown as arrows, with quantities given in Mt N/yr. Fluxes within reservoirs are shown
as circling arrows. Ind. fix is industrially fixed N (for the manufacture of fertilizers), Bio. fix is biologically fixed N, DN is dissolved N, PON is
particulate organic nitrogen, and pollutant is the excess nitrogen that has resulted from human activities (modified from Mackenzie, 1995).
NITROGEN
(fluxes = Mt N/ y)
N
2
O
N
2
O
At mospheri c
CO
2
560
8000
Ocean
Land
Groundwater
42 Rice cultivation
20 Combust i on
78 Ind. f i x.
126 Bi o. f i x.
Accumulation
Organi c N
28
Agri cul t ure
9
Human waste
20
Aerosol
14
Ri ver
35 DN
27 PON
> 21 pol l ut ant
Enhanced organi c
product i on- buri al
216 Mt C/ y
Deni t ri f i cat i on
1.4 2.6
N
2

f
i
x
a
t
i
o
n
Evasi on
Global Change
Instruction Program
30
N
2
The overwhelming majority of nitrogen in
the atmosphere is in the form of N
2
. The other
forms exist only in small quantities. Biological
fixation and denitrification are the major process-
es leading to exchange of nitrogen between the
earths surface and the atmosphere (Figure 12).
Biological fixation is the process whereby N
2
is
withdrawn from the atmosphere and converted
to N compounds that plants can use (e.g., NH
3
and subsequently NO
3
-
). Denitrification is the
process by which nitrogen as N
2
or as N
2
O is
returned to the atmosphere. Both processes are
mediated by a variety of bacteria living in soils
and water.
The exchange fluxes between the earths sur-
face and the atmosphere are small compared to
the internal recycling of nitrogen within the land
and ocean realms (Figures 12 and 13). Combustion
practices, the production of commercial fertilizers,
and rice paddy cultivation add fixed nitrogen to
the earths surface. Because of these human activi-
ties, the amount of nitrogen on land is increasing
(Figure 12). About 30 million tons of nitrogen are
leached from agricutural fertilizers and human
waste each year and added to groundwater sys-
tems and runoff. Some of this nitrogen makes its
way to rivers and then to lakes and the coastal
oceans. On a global scale, rivers may already
carry more nitrogen from human activities than
was transported in the natural state (Figure 12).
This increased nitrogen flux to lakes, rivers, and
coastal marine environments is one cause of
increased regional and global eutrophication of
these systems. Note, however, that rivers supply
only a small percentage of nitrogen to the coastal
zone (Figure 13). Most of the nitrogen there, other
than that recycled in the zone, upwelled from the
deep ocean to the surface.
Scientists have calculated how much this
human-caused increase in nitrogen is likely to be
ORGANIC NITROGEN
(fluxes = Mt N/ y)
Surface
open ocean
Deep ocean
Coastal
zone
Vert i cal
mi xi ng
670
Organi c
mat t er
sedi ment at i on
900
Export
200
U
p
w
e
l
l
i
n
g 2
0
6
Ri vers
Di ssol ved N 35
Part i cul at e N 27
Figure 13. River input of N to the ocean compared to the fluxes involved with the internal recycling of N in the ocean due to biological pro-
ductivity and decay. Besides the ocean fluxes shown, about 90% of the nitrogen involved in biological production is simply recycled in the
shallow surface waters of the coastal and open oceans. Some nitrogen escapes from the surface ocean in organic matter that settles to the
deep ocean, where the organic matter is decayed and the nitrogen released. It then returns to the surface via upwelling in the coastal zone
and vertical mixing in the open ocean. Some nitrogen, about 30 Mt per year, is buried in marine sediments in organic matter (see Figure
12). Some N is transported to the open ocean from the coastal environment (after Mackenzie, 1995; Houghton et al., 1996).
NITROUS OXIDE
(fluxes = Mt N/ y)
S
o
i
l
s
~
7
C
o
m
b
u
s
t
i
o
n
0
.
1
0
.
3
B
i
o
m
a
s
s
b
u
r
n
i
n
g
0
.
0
2
0
.
3
F
e
r
t
i
l
i
z
e
r
0
.
0
1
2
.
2
O
c
e
a
n
1
.
5
3
T
o

s
t
r
a
t
o
s
p
h
e
r
e
5

9
0.4C/ N
2
O doubl i ng
5% greenhouse
N
2
O
1510 Mt N
312 ppbv
Residence time = 130 y
Accumulation:
3.6 Mt C/ y
0.8 ppbv
Land Ocean
~ 85%
+ h
N
2
NO
x
< 15%
+ O
3
Figure 14. Part of the modern global biogeochemical cycle of nitrous oxide. Symbols and units are as in Figure 9. This gas is responsible for
5% of the enhanced greenhouse effect. A doubling of its atmospheric concentration could lead to about a 0.4C increase in global tempera-
ture. Notice the reaction of this long- lifetime gas in the stratosphere, leading to the destruction of stratospheric ozone. The fluxes in this
cycle are not well known (modified from Mackenzie, 1995).
31
changing ocean productivity and the flux of
organic carbon from the oceans euphotic zone.
The calculations show that in the 1980s there may
have been an increased organic carbon flux from
the atmosphere to the oceanic environment of
about 200 million tons of carbon per year (Figure
12), which is buried in marine sediments. This
flux takes from the atmosphere about 3% of the
increase occurring today as a result of fossil fuel
burning. While relatively small, this is a possible
negative biotic feedback on atmospheric CO
2
and
hence global climate change.
N
2
O
N
2
O is a natural product of biological deni-
trification in soils and in the ocean (Figure 14).
The N
2
O produced by denitrification is only
about 15% of all N returned to the atmosphere;
the rest is in the form of N
2
.
N
2
O is an important greenhouse gas, account-
ing for about 9% of the enhanced greenhouse
effect since the 18th century. It has a present
atmospheric concentration of 312 ppmv and a resi-
dence time of about 130 years. This concentration
is about 8% greater than in preindustrial time and
32
is increasing at a rate of 0.20.3% per year because
of human activities, including the combustion of
fossil fuels, burning of biomass, and emissions
from urea and ammonium nitrate applied to crop-
lands. These emissions amount to 0.13 to 2.8 mil-
lion tons of nitrogen annually (Figure 14).
N
2
O is chemically inert in the troposphere. In
the stratosphere, it can be converted photochemi-
cally to nitric oxide (NO), which acts as a catalyst
in the destruction of stratospheric ozone (see
sidebar). The series of reactions by which this is
accomplished has been one of the regulators of
stratospheric ozone concentration through geo-
logic time.
The flux of N
2
O from the earth to the atmo-
sphere has been increasing because of the rapidly
increasing use of industrially fixed nitrogen (up
to the late 1980s), increases in fossil fuel burning
and biomass burning, and increases in organic
carbon in coastal waters. This last process is an
important link between the carbon and nitrogen
cycles. The rate of denitrification and conse-
quently of N
2
O emissions from coastal waters
may have increased because rivers are bringing
more organic carbon to these systems or because
these systems are undergoing eutrophication as
they receive increased inputs of nutrients from
fertilizer, sewage, and the atmosphere.
With warming, the most important biotic
feedbacks involving N
2
O are changes in the
denitrification (and nitrification) rates in soils,
sediments, and ocean water. Also, N
2
O fluxes
from nitrogen-bearing fertilizers applied to the
land surface and sewage discharges into aquatic
systems will be affected by warming. Because the
reactions involving N
2
O are bacterially mediated,
it is likely that an increase in temperature will
lead to enhanced evasion rates of N
2
O from the
earths surface. This is a positive biotic feedback
on accumulation of N
2
O in the atmosphere and,
hence, on global warming. It could also lead to a
small enhanced destruction of stratospheric
ozone (Figure 14).
NH
3
The biogeochemical cycle of ammonia (NH
3
)
is shown in Figure 15. Ammonia is released to the
atmosphere by organic decomposition and
volatilization. There, it reacts with water droplets to
form ammonium ion (NH
4
+
) and hydroxyl ion
(OH
-
). NH
4
+
appears to be removed from the
atmosphere mainly by being deposited back on
the earth in the aerosols of ammonium sulfate
[(NH
4
)
2
SO
4
] and ammonium nitrate (NH
4
NO
3
).
Incidentally, (NH
4
)
2
SO
4
links the nitrogen and sul-
fur biogeochemical cycles, since its deposition on
the earth is also one of the ways oxidized sulfur is
removed from the atmosphere; the other is by
deposition of sulfuric acid (H
2
SO
4
).
Two interactions in the NH
3
cycle are impor-
tant in considerations of global warming. The
first is its interaction with OH* to produce NO
x
.
In a warmer world, the decomposition that
releases NH
3
would probably be enhanced,
which would slightly increase the stress on the
OH* concentration of the atmosphere and
enhance production of NO
x
(Figure 16). The
effects of increased NO
x
concentrations are dis-
cussed in the following section. The second impor-
tant interaction is NH
3
s reaction with NO
3
and
SO
4
to produce aerosols containing ammonium
(Figure 15). Aerosols are known to cool the planet,
although the amount of the effect is unclear. An
increase in atmospheric NH
3
could lead to a small
negative feedback on potential warming.
The ammonia cycle also gives us information
on nitrogen fertilization of the terrestrial bio-
sphere. About four-fifths of the N released to the
atmosphere each year in NH
3
comes from human
N
2
O reactions leading to the destruction
of stratospheric ozone
NO formation in the middle stratosphere (2030 km):
N
2
O + ultraviolet light NO + N (10)
N
2
O + O 2NO (11)
Ozone destruction:
NO + O
3
NO
2
+ O
2
O
3
+ ultraviolet light O
2
+ O
NO
2
+ O NO + O
2
_____________________________________
2O
3
+ ultraviolet light 3O
2
(net reaction) (12)
33
activities50 out of 62 million tons. Only about
12 million tons of ammonia nitrogen per year
comes from natural bacterial decomposition in
soils. About 25% of the human-produced flux is
transported away from the continents to the
oceanic atmosphere. The rest, about 37 million
tons of nitrogen per year, falls back on the land
surface and may be available for terrestrial
organic productivity.
Now its time for a back-of-the-envelope cal-
culation. If this 37 million tons of nitrogen were
to fertilize land plant production with a ratio of C
to N of 100 to 1, the plants would require more
than 3 billion tons of carbon per year. The phos-
phorus accumulating on land each year from
agricultural fertilizers and sewage amounts to
about 8.5 million tons (see Figure 18, p. 36)just
about the amount of phosphorus needed to
sustain this magnitude of land plant production.
This calculation gives some idea of the potential
of fertilization of the land as a sink for the excess
CO
2
that we are emitting to the atmosphere by
fossil fuel burning and land-use practices.
NO
x
and NMHCs
This brings us to the cycles of NO
x
and the
NMHCs (Figures 16 and 17). We will begin with
NO
x
. It has several natural sources: on the earth,
bacterial decomposition of organic matter in
soils; in the atmosphere, lightning, mixing from
the stratosphere, and oxidation of ammonia. NO
x
also has anthropogenic sources: fossil fuel and
biomass burning. The main sink of NO
x
is
deposition on earth of chemical products that were
produced in the atmosphere by photochemical
AMMONIA
(fluxes = Mt N/ y)
NO
x
Ocean Land Ocean Land
O
H
*
d
epl et i on
6
+
NH
4
2 Mt N
Variable conc.
Residence time =
0.01 y
O
r
g
a
n
i
c
d
e
c
o
m
p
o
s
i
t
i
o
n
v
o
l
a
t
i
z
a
t
i
o
n
C
o
m
b
u
s
t
i
o
n
O
r
g
a
n
i
c
d
e
c
o
m
p
o
s
i
t
i
o
n
+ H
2
O
7
v
o
l
a
t
i
l
i
z
a
t
i
o
n
3
3
5
5
W
e
t
-
d
r
y
d
e
p
o
s
i
t
i
o
n
8
9
N
O3
S
O4
89
NH
3
2 Mt N
Variable conc.
Residence time =
0.01 y
Figure 15. Part of the modern global biogeochemical cycle of ammonia, including that of the ammonium ion (NH
4
+
). See Figure 9 for an
explanation of the units and symbols used. Most of the ammonia emissions from the land surface are due to human activities. Ammonia is
removed from the atmosphere mainly in rain and as small, solid aerosol particles after reaction with water and with nitrate and sulfate.
Through reaction with OH*, a small amount of NH
3
is converted to nitrogen oxides, e.g., NO and NO
2
(modified from Mackenzie, 1995).
34
reactions with NO
x
, such as HNO
3
and organic
nitrates.
NMHCs (also called volatile organic com-
pounds, or VOCs) are natural byproducts of
plant productivity in terrestrial and marine envi-
ronments. Thus, their fluxes to the atmosphere
change greatly with the seasons. They also have
anthropogenic sourcesonce again, fossil fuel
and biomass burning. Their main sink is in the
atmosphere, through oxidation with OH*.
Effects of NO
x
on ozone
Increasing temperature alone would proba-
bly increase the flux of NO
x
from soils to the
atmosphere, potentially depleting OH* and form-
ing more methane and ozone in the troposphere
(Figure 16). For tropospheric ozone, however, the
effect of increasing temperature is not at all
straightforward. The concentration of ozone in
the troposphere depends in a complex way on
the atmospheric concentrations of several other
biogenic trace gases, including CH
4
, CO, and the
NMHCs.
In general, when there is little NO
x
in the tro-
posphere (530 pptv), increases in the concentra-
tions of CH
4
, CO, and NMHCs lead to a decrease
in the concentration of O
3
. At high NO
x
concen-
trations (generally greater than about 90 pptv),
increases in these three gases lead to an increase
in ozone. The combination of high NO
x
and
NMHCs in the troposphere disrupts the natural
cycle of production and destruction of ozone,
and ozone accumulates. In urban areas, this con-
tributes to air pollution.
NITROGEN OXIDES
(fluxes = Mt N/ y)
NH
3
Land Ocean Land
C
o
m
b
u
s
t
i
o
n
2
1
Tropospheri c
O
3
Greenhouse gas
O
H
*
d
e
p
l
e
t
i
o
n
6
F
r
o
m
s
t
r
a
t
o
s
p
h
e
r
e
1
L
i
g
h
t
n
i
n
g
5
Phot ol ysi s
T
h
e
rm
al decomposi t i o
n
S
o
i
l
s
2
0
B
i
o
m
a
s
s
b
u
r
n
i
n
g
Phot ochemi cal
3
W
e
t
-
d
r
y
d
e
p
o
s
i
t
i
o
n
5
6
56
NO
x
HNO
3
PAN
Organic nitrates
Figure 16. Part of the modern biogeochemical cycle of the nitrogen oxides. About one- half of the emissions of these gases to the atmo-
sphere comes from the combustion of fossil fuels. In the atmosphere, the gases are converted to several other chemical species, mainly
HNO
3
, and removed from the atmosphere both in rain and in dust. Notice the tie to tropospheric O
3
(see text), a greenhouse gas and a
component of smog (modified from Mackenzie, 1995).
35
Effects of NO
x
on OH*
The concentration of OH*, which is mainly
responsible for cleansing the atmosphere,
depends on the concentrations of trace gases, tro-
pospheric ozone, and water vapor. Elevated con-
centrations of O
3
, NO
x
, and H
2
O will increase
OH* levels. (Generally, changes in NO
x
concen-
trations affect OH* in the same way they affect
ozone, described above, except to a lesser degree.)
On the other hand, increases in CH
4
, CO, and
NMHCs will lead to lower levels of OH*.
One critical positive feedback is that increas-
es in CO concentrations in the atmosphere could
lead to a reduction in OH*, because NO
x
has too
short a lifetime to counteract that effect on a global
scale. Decreased concentrations of OH* could lead
to an increase in the lifetime of CH
4
, a positive,
but small, feedback on the accumulation of CH
4
in
the atmosphere and hence global warming.
Figure 17. Part of the modern global biogeochemical cycle of the nonmethane hydrocarbons. Land vegetation and phytoplankton naturally
produce these compounds. Their human sources include industrial practices, transportation, and fossil fuel combustion. These compounds
react in the atmosphere with OH* and are important in controlling that compounds concentration in the troposphere. They are also respon-
sible for disrupting the natural production and destruction of the ozone cycle in the troposphere. In conjunction with NO
x
, they can lead to
increased concentrations of O
3
in the troposphere (modified from Mackenzie, 1995; Guenther et al., 1995).
NONMETHANE
HYDROCARBONS
(fluxes = Mt C/ y)
Tropospheri c
O
3
Greenhouse gas
T
e
r
r
e
s
t
r
i
a
l
v
e
g
e
t
a
t
i
o
n
t
e
r
p
e
n
e
,
i
s
o
p
r
e
n
e
B
i
o
m
a
s
s
b
u
r
n
i
n
g
1
5
0
O
c
e
a
n
O
H
*
d
e
p
l
e
t
i o
n
1
3
0
0
+ NO
x
1
1
4
5
c
o
m
b
u
s
t
i
o
n
,
s
o
l
v
e
n
t
s
e
t
h
e
n
e
,
p
r
o
p
e
n
e
5
NMHCs
Land Ocean
36 DRAFT
The I mportant Nutrient Phosphorus
Phosphorus is a key nutrient, fueling organic
productivity on land and in water. Aportion of its
cycle is shown in Figure 18. The P cycle is consid-
ered here both because it is closely coupled with
those of carbon and nitrogen and for completeness.
Controversy still exists, particularly between
marine biologists and geochemists, as to whether
phosphorus or nitrogen is the limiting nutrient in
the marine environment. Globally and on a long
time scale, phosphorus is probably the limiting
nutrient, if for no other reason than that the
atmosphere contains essentially an unlimited sup-
ply of nitrogen for fixation in aquatic systems.
The major difference between the phosphorus
cycle and the carbon, nitrogen, and sulfur cycles
is that no biological process generates an impor-
tant gas flux of phosphorus from the earths sur-
face to the atmosphere (Figure 18). Aphosphorus
gas known as phosphine or swamp gas (PH
3gas
)
causes a small flux, but the amount is insignifi-
cant compared to other fluxes of phosphorus. As
with nitrogen, fluxes of phosphorus between the
Phosphorus and Sulfur
Global Change
Instruction Program
PHOSPHORUS
(fluxes = Mt P/ y)
1085
Accumulation
Ocean
186
Land
8.5 Acc.
Atmosphere
0.03 Mt P
Resi dence t i me =
2.4 days
Sea sal t
0.31
Sea sal t
0.03
Dust
3.1
Dust
3.72
Dust
1.09
Human
act i vi t i es
0.47
Wet - dr y
f al l out
0.28
Mi ni ng
12.1
Ri vers
Fi sheri es
0.31
2.9 DP (1.5 pol l ut ant )
Enhanced organi c
product i on- buri al
140 Mt C/ y
Organi c P
1.6
At mospheri c
CO
2
Figure 18. Part of the modern global biogeochemical cycle of phosphorus, emphasizing the exchange of P among the land, atmosphere, and
ocean. Units and symbols are as in Figure 9. Notice, as with nitrogen (Figure 12), that the internal recycling fluxes in the ocean and land reser-
voirs by organic production and decay are much larger than the exchanges. Also as with nitrogen, the land is gaining P because of its mining,
its use in the manufacture of fertilizers and detergents, and sewage inputs. Wet- dry fallout is the precipitation of phosphorus on the ocean as
particles and in rain. DP is dissolved phosphorus, and pollutant is excess phosphorus from human activities (modified from Mackenzie, 1995).
37
land, ocean, and atmosphere are small compared
to the amounts that cycle within the land and
ocean systems.
Sinks and sources
Unlike nitrogen, phosphorus accumulates in
both organic and inorganic sediments. Because of
the direct tie between N and P in organic matter,
the only organic sink shown in Figure 16 is the
important phosphorus flux to sediments as P
incorporated in dead organic matter (bottom
right-hand corner of the figure). The inorganic
sinks, which are not shown in the figure, involve
the precipitation of the mineral carbonate fluoro-
apatite [Ca
5
(PO
4
)
3
(OH,F)], scavenging by iron
oxy-hydroxides, and incorporation in oxidized
iron coatings on the surfaces of calcium carbonate.
Phosphorus mining is the largest source of P
to the land surface. Much of the mined phospho-
rite rock is used to make commercial fertilizers.
The major impact of humankind on the phospho-
rus cycle results from the application of both com-
mercial and organic fertilizers to croplands and
the disposal of sewage. Phosphorus from these
sources is introduced to streams via direct sewage
discharge or by leaching. The increased amount of
phosphorus in rivers, lakes, and coastal marine
waters results in increased rates of eutrophication
of these systems in cases where phosphorus is the
limiting nutrient.
Feedbacks
Two major biological feedbacks in the phos-
phorus cycle may be of importance in global cli-
mate change. One involves the enhanced eutrophi-
cation of aquatic systems as a result of human
activities, as just mentioned. The global dissolved
phosphorus flux, carried by rivers to the coasts,
has doubled since preindustrial times because of
these activities (Figure 18). The resulting eutrophi-
cation of the coastal regions has led to a potential
accumulation of organic carbon in these systems of
about 140 million tons of carbon per year (Figure
18, top right). This enhanced flux is a negative
feedback on the accumulation of anthropogenic
CO
2
in the atmosphere today and, as with nitro-
gen, could become more important in the future.
The second biological feedback has to do with
the land reservoir of phosphorus. Notice in Figure
18 that phosphorus is accumulating on land
because of mining, fertilizer use, and sewage dis-
charges. Because most chemical weathering and
biological decomposition rates increase with
increasing temperature, a climate warming would
mean that phosphorus in this reservoir may be
more easily leached into aquatic systems. This
additional phosphorus could increase eutrophica-
tion in these systems and lead to increased accu-
mulation of organic matter. This flux is a negative
feedback on CO
2
accumulation in the atmosphere
and hence on global warming. However, the effect
is quite small. If all the phosphorus now stored on
land were leached and transported by rivers to
coastal systems, and all the other nutrients in
coastal marine systems could be used for plant
growth (which may not be the case), the increase
in organic carbon storage would be 800 million
tons. This is equivalent to only 13% of one years
flux of carbon to the atmosphere because of the
burning of fossil fuels.
Reduced and Oxidized Sulfur Gases
The reduced and oxidized sulfur cycles
(Figures 19 and 20) are closely tied, because the
reduced sulfur gases that dominate the earths
biological sulfur emissions are oxidized in the
atmosphere. These reduced gases are dimethyl-
sulfide or DMS [(CH
3
)
2
S] and carbonyl sulfide
(OCS), which are emitted by the ocean surface,
and hydrogen sulfide (H
2
S), emitted by decaying
terrestrial vegetation. Oxidation converts these
gases to sulfur dioxide (SO
2
) gas and sulfate
aerosol, that is, microscopic sulfur-containing
particles. Sulfur enters the atmosphere as the
earth emits the reduced sulfur gases and leaves
the atmosphere as sulfate aerosol floats or is
washed to the earth.
The chemistry of DMS and OCS has two
major connections with climate, by way of cloud
condensation nuclei and stratospheric sulfate.
Cloud condensation nuclei
DMS is produced by bacteria in phytoplank-
ton. Its concentration in the oceans is very low, but
it is found nearly everywhere at the sea surface,
38
where it may escape into the troposphere. Once
airborne, it is oxidized by OH* to sulfate within a
few days. Along with other chemical species in the
atmosphere, it condenses into small (micron-sized)
aerosol particles. These atmospheric sulfate
aerosols act as cloud condensation nuclei (CCN)
the centers on which water droplets may form,
facilitating cloud formation. In the remote marine
atmosphere, DMS emissions are likely the main
source of the aerosols that act as CCN.
One hypothesis argues that a warming of
earths climate could lead to enhanced phyto-
plankton growth and thus greater emission of
DMS from the sea surface. The increased DMS
flux could result in increased production of sulfate
aerosols and CCN in the remote marine atmo-
sphere, creating more and denser clouds. Besides
leading to more rain, clouds also reflect incoming
solar radiation and have a cooling effect on the
lower atmosphere and surface of the earth. Thus
an increase in cloud cover would give rise to a
cooling of the troposphere, a negative biotic feed-
back on global warming. To counteract a warming
owing to a doubling of atmospheric CO
2
would
require a 25% increase in the number of cloud con-
densation nuclei.
The validity of this hypothesis is not yet con-
firmed by real-world evidence. For example, in ice
cores collected by drilling at Vostok Station in
Antarctica, a record of methane-sulfonic acid
(MSA) has been obtained from the ice. MSAis a
product of DMS oxidation. If this theory were cor-
rect, one would expect to find more MSAin ice
that dates from warmer periods, since increased
REDUCED SULFUR
(fluxes = Mt S/ y)
Climate sensitivity
DMSSO
4
CCNcool i ng
OH* depl et i on
67
Sul f at e vei l
B
i
o
l
o
g
i
c
a
l
d
e
c
a
y
D
e
c
a
y
-
e
x
c
r
e
t
i
o
n
SO
4
2
5
D
M
S
,
H
2
S
4
2
D
M
S
,
O
C
S
T
o

s
t
r
a
t
o
s
p
h
e
r
e
0
.
0
6

O
C
S
SO
2
Reduced S
0.5 Mt S
0.1 ppbv
Residence time =
2.8 days
Land Ocean
Figure 19. Part of the global biogeochemical cycle of reduced sulfur. See Figure 9 for an explanation of the units and symbols used. Reduced
sulfur gases are naturally produced both on land and in the ocean by biological processes. They are eventually removed from the atmo-
sphere by reaction with OH* and conversion to SO
2
and thence to sulfate aerosol (see Figure 20). Sulfate aerosol is produced by the oxida-
tion of OCS in the stratosphere to form the sulfate veil during times of low volcanic activity. Sulfate aerosol is responsible for the scattering
and reflection of solar energy and thus cools the planet (modified from Mackenzie, 1995).
39
levels of the compound would wash out of the
atmosphere. However, the record shows just the
opposite: higher levels of MSAin the ice from the
last ice age, which culminated 18,000 years ago,
than in this and past interglacial stages.
Stratospheric sulfate
OCS is produced mainly by the photolysis of
organic sulfur in the surface waters of the ocean
and by photochemical oxidation of the biogenic
gas carbon disulfide (CS
2
) in the atmosphere. It is
the most abundant reduced sulfur species in the
remote marine atmosphere. Because it is chemi-
cally inert, it has a long residence time in the tro-
posphere and can enter the stratosphere. Once in
the stratosphere, OCS is destroyed by reacting
with ultraviolet light and atomic oxygen. It is con-
verted to SO
2
and then on to sulfate aerosol. This
reduced sulfur gas supplies about half of the
mass of sulfate aerosol found in the lower strato-
sphere (the so-called Junge layer).
If global warming causes any change in the
flux of OCS to the stratosphere, it will have an
effect on climate through change in the Junge
layer. An increased stratospheric sulfate burden
would give rise to cooling of the atmosphere; a
decreased burden would lead to warming. The
likely feedback effect on an initial warming is dif-
ficult to predict.
Figure 20. Part of the global biogeochemical cycle of oxidized sulfur. See Figure 9 for an explanation of the units and symbols used. Notice
that the flux of oxidized sulfur from land as SO
2
is dominated by the combustion of fossil fuels and biomass burning. This sulfur reacts with
OH* to produce sulfate aerosols of ammonium and hydrogen. About 40% of the sulfur falling back on the earths surface is derived from
these sources. Volcanism can add sulfate aerosols to the stratosphere and produce a temporary cooling of the planet, as after the eruption
of Mt. Pinatubo in 1991. Sulfate aerosols derived from combustion of fossil fuels and biomass burning exert a strong cooling effect, but only
in the regions where they are produced (modified from Mackenzie, 1995).
OXIDIZED SULFUR
(fluxes = Mt S/ y)
Reduced S
Ocean
B
i
o
m
a
s
s
b
u
r
n
i
n
g
7 Rai n and dr y
deposi t i on
O
H
*
d
e
p
l
e
t
i
o
n
6
7
Cool i ng
V
o
l
c
a
n
i
s
m
T
o

s
t
r
a
t
o
s
p
h
e
r
e
Sul f at e vei l
To t roposphere
OH* depl et i on
4
9
S
e
a
a
e
r
o
s
o
l
115
C
o
m
b
u
s
t
i
o
n
8
0
V
o
l
c
a
n
i
s
m
1
0
1
6
0
4
5
SO
4
SO
2
0.5 Mt S
0.1 ppbv
Residence time =
1.2 days
Land Earth surface
SO
4
aerosol
2 Mt S
0.35 ppbv
Residence time =
4.6 days
40
Oxidized sulfur
To complete the picture of the global cycle of
sulfur gas species, the earth surfaceatmosphere
oxidized sulfur cycle is shown in Figure 20.
Natural sources of oxidized sulfur in the atmo-
sphere include oxidation of reduced sulfur gases
as mentioned above, volcanism, and aerosols from
the sea. The oxidized sulfur is removed from the
atmosphere by deposition of aerosols.
One of the most dramatic demonstrations of
the connection between volcanism, sulfate
aerosols, and climate was the eruption of Mt.
Pinatubo in the Philippines in 1991. The eruption
plume rose high into the stratosphere, where sul-
fate aerosol was generated and distributed over
much of the globe. The aerosol scattered and
reflected solar energy back to space. This event led
to a cooling of the planet of about 0.5C during
199193. At its maximum in 1993, the cooling
reached 34 watts per square meter. This is con-
siderably more than the enhanced greenhouse
forcing of +2.5 watts per square meter.
Human activities have strongly interfered
with the global biogeochemical cycle of oxidized
sulfur. This disturbance in the cycle has led to the
acidification of land and freshwater systemsthe
problem of acid precipitation. Of the total global
deposition of oxidized sulfur today, approximately
40% is derived from the human activities of com-
bustion of fossil fuels, biomass burning, and
smelting of sulfide ores. The deposits from these
activities vary enormously spatially.
Recently a new hypothesis has emerged link-
ing our sulfur emissions with climate. In the
Northern Hemisphere, emissions of SO
2
have led
to an increased mass of sulfate aerosol. Because of
the aerosols short lifetime in the atmosphere, it
remains concentrated over the eastern half of the
continent and the western Atlantic Ocean. This
regional enhancement could be cooling the atmo-
sphere enough to explain the discrepancy between
the observed temperature record of the past 100
years and the higher temperatures predicted by
climate models that include only the effects of
increased greenhouse gases and not increased
aerosols. On the other hand, when climate model-
ers attempt to introduce the cooling effect of
sulfate aerosols into their models, the modeled
temperatures are generally lower than those
observed in the recent past. This difficulty implies
that sulfate aerosols are an important component
of the temperature record, but that the amount by
which they cool the planet is not yet known.
41
The water cycle (Figure 21) is important in the
context of biogeochemical cycling in the C, N, P, S,
and O system, as well as being important in its
own right. Water circulating through the ecosphere
is part of a continuous hydrologic cycle that makes
life on earth possible. The water cycle is the driver
cycle for transport of many elements at the earths
surface. In the atmosphere, water vapor is the most
important greenhouse gas, and its behavior during
a global warming is of concern.
The water cycle is a balanced system, with
water stored in many places at any one time
(Table 3). The cycle involves the transfer of water
in its various forms of liquid, vapor, ice, and
snow through the land, air, and water environ-
ments. Both matter and energy are involved in
the transfer. The transfer begins when heat from
the sun warms the ocean and land surfaces and
causes water to evaporate. The water vapor enters
the atmosphere and generally moves with the
The Water Cycle
At mospheri c wat er vapor t ransport
(40)
S
o
l
a
r

r
a
d
i
a
t
i
o
n
Cl oud
Evaporat i on
Transpi rat i on
(71)
Lake
Surf ace wat er
Soi l s
Evaporat i on
(425)
Preci pi t at i on
(385)
Ocean
Groundwat er f l ow
Land
Preci pi t at i on of
Snow, i ce, rai n
(111)
S
u
r
f
a
c
e

r
u
n
o
f
f
Percol at i on
G
l
a
c
i
e
r
Ri ver
Ret urn f l ow (40)
Figure 21. The global biogeochemical cycle of water (the hydrologic cycle), showing the major processes of water movement.
Numbers in parentheses show the water budget in thousands of cubic kilometers per year (after Maurits la Rivire, 1990.)
Global Change
Instruction Program
42
circulation of the air. On a global
scale, warm air rises in the atmos-
phere and cooler air descends. The
water vapor rises with the warm
air. The farther from the warm plan-
etary surface the air travels, the
cooler it becomes. Cooling causes
water vapor to condense on small
particles (cloud condensation
nuclei) in the atmosphere and to
precipitate as rain, snow, or ice and
fall back to the earths surface.
When the precipitation reaches the
land surface, it is evaporated direct-
ly back into the atmosphere, runs
off or is absorbed into the ground,
or is frozen in snow or ice. Also,
plants require water and absorb it,
retaining some of the water in their
tissue. The rest is returned to the atmosphere
through transpiration. Precipitation on land is
equal to evapotranspiration plus runoff to the
ocean. That is, over the land, there is more pre-
cipitation than evapotranspiration.
For the ocean, the situation is reversed. Much
of the water evaporated from the ocean returns
there directly; however, a small amount (about
8% of that evaporated) is carried by atmospheric
winds over the continents, where it precipitates.
Once on the ground, the water finds its way to
streams, lakes, or rivers in runoff or by percola-
tion into and through groundwater. In due time,
the water will return to the ocean, mainly in
stream and river flows and less importantly in
groundwater. This return flow balances the net
loss from the ocean surface by evaporation.
Snow and ice may remain on the land for a
long time before the water in these forms of pre-
cipitation evaporates to the atmosphere or
returns via rivers or as direct glacial meltwater to
the oceans. The snow and ice that feed glaciers
may remain locked up in the cryosphere for
thousands of years, but finally the ice will melt,
and the water will travel to another part of the
hydrologic cycle.
Water vapor in the atmosphere is the princi-
pal greenhouse gas. Because the amount of water
vapor in the atmosphere is dependent on the
temperature of the planet, any initial warming of
the planet will probably lead to more water
vapor in the atmosphere. The increased water
vapor has the potential to absorb more infrared
radiation reradiated from the planetary surface
and thus lead to further warming. This is another
example of a positive feedback.
Water droplets form in the troposphere by
condensation of water on cloud condensation
nuclei. These particles may absorb or reflect ener-
gy. The amount of water vapor in part deter-
mines the types and distribution of clouds that
form in the atmosphere. In terms of predicting
the effects of increasing concentrations of green-
house gases in the atmosphere on temperature
and other climatic variables, general circulation
models (GCMs) and other types of models have
been used. The GCMs are very complex comput-
er representations of the atmosphere or atmo-
sphere-ocean system that are used in the model-
ing of global climate change. In these models, the
effects of clouds on the radiant energy budget of
the planet are a major source of uncertainty in
attempting to predict future climate change.
Clouds regulate the radiative heating of the
planet. They reflect a significant part of the
incoming solar radiation. Clouds also absorb
longwave, infrared radiation emitted by the earth.
At the cold tops of clouds, energy is emitted to
space. In 1984 the Earth Radiation Budget
Experiment (ERBE) was launched. This
Table 3. Distribution of water in the ecosphere
Reservoir Volume (10
6
km
3
) Percent of total
________________________________________________________________
Ocean 1370 97.25
Cryosphere
(ice caps and glaciers) 29 2.05
Groundwater 9.5 0.68
Lakes 0.125 0.01
Soils 0.065 0.005
Atmosphere 0.013 0.001
Rivers 0.0017 0.0001
Biosphere 0.0006 0.00004
___________________________________________________________
Total 1408.7 100
After Berner and Berner, 1996.
43
experiment involves a system of three satellites
that provide data on incoming and outgoing radi-
ation. One result of this experiment so far is the
demonstration that clouds have a net cooling
effect on the earth. On a global scale, clouds
reduce the amount of radiative heating of the
planet by 13 watts per square meter. This is a
large number when compared to the +2.5 watts
per square meter attributed to the increase in
atmospheric greenhouse gases during the last
century. It is also large compared to the radiative
heating that could arise from a doubling of
atmospheric carbon dioxide concentrations in the
next centuryabout +4 watts per square meter.
Thus, a small change in the types and distribution
of clouds may have a large effect on the radiation
budget compared to the effect of changing green-
house gas composition owing to human activities.
In a world already warmed by greenhouse
gases released from human activities, it is difficult
to predict what will happen to the types and dis-
tribution of clouds. Too little is known about the
complex processes of cloud formation and, in par-
ticular, the response of clouds to a warming earth.
Also, these complex processes are difficult to sim-
ulate in the general circulation models. One diffi-
culty lies with the problem of reproducing cloud
physics in the models. Asecond difficulty is that
GCMs only perform calculations at widely
separated points over the globe and relatively
infrequently. Cloud formation involves very
dynamic processes at short time and spatial
scales.
Clouds may act as a positive or negative feed-
back in a future earth warmed by the enhanced
greenhouse effect. This ambiguity accounts in
part for the range of estimates of the average
temperature increase predicted by the GCMs for
a doubling of the atmospheric carbon dioxide
concentration.
Afinal comment on the water cycle is that it
is being significantly affected by water usage and
contamination of water stocks. Currently, humans
use an amount of water equivalent to about 25%
of total terrestrial evapotranspiration and 55%, or
6,800 cubic kilometers per year, of the runoff of
water from the continents that is accessible. Only
about 20% of the worlds drainage basins have
pristine water quality. There is little doubt that
the worlds water resources will be significantly
strained in the 21st century.
44
Conclusion
Global Change
Instruction Program
An analogy is commonly made between the
earths surface system and a giant chemical engi-
neering factory. In the natural system, material
circulation is driven by energy from the sun and,
to a much lesser extent, from radioactive decay of
elements in the earths interior and motions of its
tides. This is a mechanical and inorganic view of
the earth. In another and more realistic sense,
the earth has a natural metabolism; materials
have circulated about its surface for millions of
years in a complex, interconnected web of bio-
geochemical cycles. An array of physical, chemi-
cal, and biological processes weather and erode
rocks and transfer materials in and out of the
atmosphere, from the atmosphere to the biota
and back again, to the oceans via rivers, and to
the continents by uplift. Each element has a nat-
ural biogeochemical cycle. It is these cycles and
their relationship to the physical climate system
that have led to the development of a relatively
stable and resilient surface system during
geologic time. Life has evolved in this system
and plays a strong role in the development and
maintenance of the system through processes,
fluxes, and feedbacks.
Human activities have contributed materials
to the biogeochemical cycles. Some of these mate-
rials enter element cycles already naturally in
operation; they are the same chemical species that
have circulated for millions of years. Other mate-
rials are synthetic compounds and are foreign to
the natural environment. These anthropogenic
fluxes are leading to a number and variety of
environmental issues, including the possibility of
global climate change. There is no doubt that
human activities have interfered in biogeochemi-
cal cycles and have modified the composition of
the atmosphere. Understanding the consequences
of this interference requires better quantitative
descriptions of these cycles, their interconnec-
tions, and, in particular, their coupled response to
perturbations, such as a change in climate.
45
Questions
Chemistry
1. The most simple chemical expression for the production of organic matter in plants is
CO
2
+ H
2
O = CH
2
O + O
2
The chemical compound CH
2
O is organic matter; CO
2
is carbon dioxide gas; O
2
is diatomic
oxygen; and H
2
O is water. The atomic weights of the elements C, H, and O are, respectively, 12, 1,
and 16.
A. What are the gram molecular weights of the compounds of CH
2
O, CO
2
, O
2
, and H
2
O?
B. What is the weight of one mole of each of these compounds?
C. If 10 moles of plant matter have been produced, how many moles of CO
2
did it take to produce
the plant matter? How many grams of CO
2
?
D. If the C:N ratio of the plant material in moles is 106:16 (that of marine phytoplankton), how many
moles of nitrogen were needed to produce the plant matter?
E. If the source of the nitrogen were nitrate (NO
3
-
) in the euphotic zone of the ocean, how many
grams of nitrate were consumed in the process?
2. Write a balanced chemical reaction for the weathering of the mineral orthoclase feldspar (KAlSi
3
O
8
)
by water containing dissolved CO
2
. The products that are formed in this weathering reaction are:
kaolinite [(Al
2
Si
2
O
10
(OH)
4
], bicarbonate (HCO
3
-
), monomeric silicic acid (H
4
SiO
4
o
), and dissolved
potassium ion (K
+
). (Hint: to begin, balance the reaction on aluminum.)
3. The concentration of dissolved potassium (K
+
) in the ocean is 390 mg/kg. The atomic weight of
potassium is 39. The average density of seawater is 1.027 g/cm
3
.
A. What is the concentration of K
+
in seawater in moles/kg?
B. What is its concentration in parts per million by volume of seawater?
4. The average molecular weight of the gases in the atmosphere is 29 and the mass of the atmosphere
is 52 x 10
20
grams.
A. What is the total number of moles of gases in the atmosphere?
B. Carbon dioxide gas makes up 0.036 % of the atmosphere in moles. How many moles of CO
2
are there in the atmosphere? How many grams?
Study Questions and Answers
Global Change
Instruction Program
46
5. Water vapor in the atmosphere averages about 0.2% of the atmosphere in weight.
A. What is the total mass of water vapor in the atmosphere?
B. How many moles of H
2
O vapor are there in the atmosphere?
The Oceans, Atmosphere, Sediments, and Rocks
1. The average depth of the ocean is 3.8 kilometers and the average upwelling rate of deep water into the
surface open ocean and into coastal environments is 4 m/yr. The area of the ocean is 3.6 x 10
18
cm
2
.
A. About how long would it take to upwell the entire volume of the ocean?
B. The average nitrogen content of deep water is about 40 x 10
-6
moles per liter (L). What is the
annual rate of addition of nitrogen to the surface water due to upwelling?
C. At a molar ratio of C:N of 106:16, what is the productivity in the global surface ocean in grams (g)
C/m
2
/yr sustained by the upwelling of nitrogen?
2. One source of the deep water of the worlds oceans is in the Norwegian Sea. Here water is sufficient-
ly dense to sink to the bottom. This water mainly forms from the cooling by evaporation of water
carried northward by the Gulf Stream. The Gulf Stream carries heat to the high latitudes of the
North Atlantic Ocean which helps to moderate the climate of Europe. There is considerable interest
in the rate of formation of North Atlantic deep water (NADW) because of the role it plays in climate.
Possible changes in the rate of its formation have been cited as the cause of rapid climate change in
the past. Any global warming could modify the rate of deep water formation.
A. How would you expect the residence time of the deep water to change from the Atlantic Ocean to
the Pacific Ocean?
B. How does the deep water return to the surface?
C. If the continental glaciers were to begin melting because of a global warming, what would you
expect might happen to the rate of deep water formation and the climate of Europe?
3. The winds of the earth tend to blow along latitudinal lines around the planet. The major wind belts are
the Polar Easterlies, Westerlies, Trade Winds, and Equatorial Easterlies in both the Northern and
Southern Hemispheres. The winds drive the surface currents of the ocean. Cool air that has descended
at midlatitudes moves toward the equator as the Northeast and Southeast Trade Winds in the Northern
and Southern Hemispheres, respectively. These winds exert a force on the sea surface, and currents are
generated that flow toward the equator. Both the winds of the atmosphere and the surface currents of
the ocean converge near the equator. The warm equatorial air rises and moves north and south toward
the poles. The converging ocean currents generate westward-flowing equatorial currents.
A. Based on the above, would you expect a pollutant gas like carbon monoxide with major anthro-
pogenic sources in the Northern Hemisphere and a short atmospheric residence time to be evenly
distributed in the troposphere?
B. Is there an equatorial barrier to the dispersal of floating tar balls produced when petroleum
tankers spill oil in the shipping lanes of the North Atlantic?
C. Does such a barrier exist for the deep waters of the ocean?
47
4. The very finest particles of airborne dust carried by winds off the Sahara Desert travel in the tropo-
sphere for long distances westward across the Atlantic Ocean. These particles are deposited on the
ocean surface and settle out at a rate of 500 cm/yr. How long would it take such particles to reach
the bottom of the Atlantic Ocean at 4 km?
5. The global atmosphere in 1996 contained about 360 ppmv of CO
2
. This concentration is equivalent to
a partial pressure of CO
2
(PCO
2
) of 10
-3.45
atmosphere (atm).
A. What is the concentration of dissolved CO
2
in the surface ocean in equilibrium with atmospheric
CO
2
at a temperature of 25C?
B. In the year 1700, when atmospheric CO
2
was at a concentration level of 280 ppmv (PCO
2
= 10
-3.55
atm), what was the concentration of CO
2
in the surface ocean?
C. What was the percentage change in atmospheric CO
2
concentration between 1700 and 1996?
6. The primary energy sources for the earth are:
solar radiation, 0.5 cal/cm
2
/min (about 343 W/m
2
)
heat flow from the interior of the earth, 0.9 x 10
-4
cal/cm
2
/min
tidal energy, 0.9 x 10
-5
cal/cm
2
/min.
About 49% of the solar radiation is absorbed by earths surface and reradiated to space as longwave,
infrared radiation.
A. What percentage of the total comes from the combination of heat from the interior of the earth
and tidal energy?
B. In units of W/m
2
, how much solar radiation reaches the earths surface and is absorbed there?
What does this energy do?
C. Of the 388 W/m
2
of longwave radiation emitted to space by the earths surface, 326 W/m
2
are
absorbed by water vapor, CO
2
, and other greenhouse gases in the atmosphere and reradiated
back to the earth. What happens to this energy, and what effect does it have on the earth?
7. The area of land today is 150 x 10
12
m
2
, and the mean elevation of the continents is 0.84 km. The con-
tinents are being eroded at a rate of 200 x 10
14
g/yr. The average density of rock is 2.7 g/cm
3
.
A. At the current rate of erosion, how long would it take to wear the continents down to sea level?
B. Your answer to question 7Awas a period of time much less than the age of the earth of 4.6 billion
years. In that case, why are there any continents?
8. The total mass of sedimentary rock younger than 600 x 10
6
years is 1.8 x 10
18
metric tons. Its mean
residence time is 400 x 10
6
years.
A. In an unchanging system, what is the flux of sediment in and out of the sedimentary rock reservoir?
B. How does sediment get into the sedimentary rock reservoir and how does it get out?
48
9. What chemical species of nitrogen, sulfur, and carbon might you expect to find in a water-logged
(anoxic) soil? In a well-aerated soil?
10. What does the weathering of silicate minerals subtract from or add to the atmosphere?
Ecology
1. Tropical rain forests have a total area of 17 x 10
12
m
2
, and estuaries have an area of 1.4 x 10
12
m
2
.
Their mean net primary production is 2,000 g dry plant matter/m
2
/yr and 1,800 g dry plant
matter/m
2
/yr, respectively. Their mean plant biomasses in kg C/m
2
are 20 and 0.45, respectively.
Forty-five percent of dry plant matter is carbon.
A. What is the total net primary production of tropical rain forests and estuaries in metric tons of dry
plant matter and carbon per year?
B. What is the total plant mass of these ecosystems in metric tons of dry plant matter and carbon?
C. The tropical rain forests of the world lost 9% of their area due to cutting in the 1980s. How much
dry plant matter does this cutting represent? How much carbon?
D. If all of the carbon in the cut trees of question 1C were emitted to the atmosphere by burning and
slow oxidation, how many grams of CO
2
would this represent? What fraction of the atmospheric
CO
2
reservoir is this (see Figure 11)?
E. Estuaries receive 1.5 x 10
12
g of pollutant dissolved phosphorus annually (see Figure 18). This
amount of P could support how much additional plant productivity as dry matter and as C/m
2
per year?
F. If all the additional plant matter in 1Awere buried in the sediments of the estuaries, would this
flux qualify as a biological feedback to the accumulation of CO
2
in the atmosphere? Explain. What
percentage of the atmospheric flux of 6 x 10
15
g C from fossil fuel burning in 1995 does the addi-
tional total plant production in estuaries represent?
2. The net primary production of the earths surface is 0.37 kg dry matter/m
2
/yr.
A. With a total area of 510 x 10
12
m
2
, what is the total production of dry matter?
B. How much carbon does the production in 2Arepresent?
C. Total production on land exceeds that in the ocean by perhaps as much as two times. What is the
annual total production on land and in the ocean?
3. What is the difference between autotrophy and heterotrophy?
4. What are three biogeochemical processes performed by the prokaryotes?
5. What is cultural eutrophication? Why may this phenomenon qualify as a negative feedback to the
accumulation of CO
2
in the atmosphere?
49
Biogeochemical Cycles
1. Construct a diagram showing the reservoirs and fluxes in the global biogeochemical cycle of water.
Use the information in Figure 21 and Table 3, and the reservoirs of atmosphere, land, and ocean.
A. What is the residence time of water in the ocean with respect to the flux of water via the rivers to
the ocean?
B. If the concentration of dissolved calcium is 400 ppm in the ocean and 15 ppm in average river
water, what is the residence time of calcium in the ocean?
2. Anearly rectangular-shaped lake is 5 km long, 2 km wide, and 100 m deep and contains 0.001 mg/L
of dissolved mercury. Ariver discharges 2 x 10
12
L/yr of water with a concentration of mercury of
0.0005 mg/L into the lake.
A. What is the water volume in the lake (in liters)?
B. What is the total mass of mercury in the lake?
C. What is the residence time of mercury in the lake?
D. An industrial plant near the mouth of the river accidentally discharges mercury into the lake. How
long will it take for most (95%) of the mercury contamination to work its way out of the lake?
3. The terrestrial living biomass contains 600 x 10
9
tons of carbon. It is argued that during the decade of
the 1980s, about 135 x 10
12
moles of anthropogenic CO
2
were taken up annually by the terrestrial
biomass.
A. What would be the average annual percentage increase in the mass of carbon in the terrestrial
biosphere?
B. Do you believe such an increase would be detectable by doing field studies to determine the
increase in biomass?
4. The mixed layer of the ocean is the vertical layer that is well stirred by winds blowing across the sur-
face of the sea. Chemical and physical characteristics of the water column are rather uniform over
the depth of the mixed layer. The average thickness of the mixed layer throughout the worlds
oceans is about 100 meters but varies from 50 to 300 meters. The average total dissolved inorganic
carbon (DIC, HCO
3
-
+ CO
3
2-
+ CO
2
) content of the mixed layer is 2.2 micromoles (mmol) per kg.
A. What is the total mass (reservoir) of DIC in the mixed layer of the ocean in moles of carbon? (The
area of the ocean is 360 x 10
12
m
2
.)
B. The ocean takes up about 2 billion tons of carbon annually from the human activities of fossil fuel
combustion, cement manufacturing, and deforestation. What is the annual increase in dissolved
carbon in the mixed layer of the ocean in mmol/kg due to this absorption of anthropogenic CO
2
?
C. Use the annual increase you derived from 4B and assume the DIC content of the mixed layer was
2.2 mmol/kg in 1975. What would be the percentage increase in the DIC content of the mixed
layer from 1975 to 1996?
50
5. Total evaporation is 496 x 10
3
km
3
H
2
O/yr over the earths surface.
A. What is the residence time of water in the atmosphere?
B. If a pollutant is susceptible to being rained out (washed out) of the atmosphere, would you expect
it to mix evenly throughout the troposphere?
6. What are the three major processes controlling atmospheric CO
2
concentration levels on a long time
scale? Write a balanced set of chemical equations demonstrating these processes.
7. What is the connection between organic matter and atmospheric O
2
?
8. What is the major difference between the biogeochemical cycle of phosphorus and those of carbon,
nitrogen, and sulfur?
9. What is the major difference in the reactivity of DMS and OCS in the atmosphere?
10. The mean atmospheric lifetime (residence time) of NH
3
is 14 days; that of CO is 60 days. How do the
rates of destruction of these gases in the atmosphere by OH* compare qualitatively?
11. Referring to Figures 911, what is the major reaction in the atmosphere that couples the biogeochemical
cycles of CH
4
, CO, and CO
2
? What percentage of the enhanced greenhouse forcing on climate is due to
CO
2
? To CH
4
? What are the sources of emissions of CH
4
to the atmosphere from human activities? Of
CO
2
and CO? If the concentration of CO
2
in the atmosphere were doubled, what would be the poten-
tial increase in temperature? How much more effective is CH
4
than CO
2
as a greenhouse gas?
12. Referring to Figure 12, what is the ratio of anthropogenic N fluxes on land involving fixation of
atmospheric N to natural biological fixation? What is the minimum percentage of the N fixed by
human activities that is discharged to the ocean by rivers? What is the important environmental
problem related to this additional N flux to the ocean?
13. Referring to Figure 13, what is the ratio of these two fluxes: the upwelling flux of N to the coastal zone and
the dissolved N flux to the ocean via rivers? Which flux would you expect to change during the next
century?
14. Referring to Figure 14, based on the summation of the high and low estimates of fluxes of N
2
O from
earths surface to the atmosphere, what is the range in residence time estimates for N
2
O in the
atmosphere? What percentage of the enhanced greenhouse forcing of climate is due to N
2
O?
15. Referring to Figure 16, of the total flux of NO
x
to the atmosphere, what percentage is from human
activities? What is the principal type of reaction that destroys NO
x
in the atmosphere? Write the
reaction for the destruction of NO
2
and its subsequent removal as HNO
3
.
16. Referring to Figure 18, the total mass of P in land plants is 1,800 million tons and that in marine
plankton is 73 million tons. What is the ratio of the internal recycling flux in the ocean to that on land?
What is the residence time of P in the land biota relative to the recycling flux? In the marine plankton?
51
Answers
Chemistry
1. This question is designed to enable the student to review basic knowledge of the meaning of a chem-
ical equation. Many biogeochemical processes are simply described by chemical reactions. In this
reaction, there are four pure substances that can be decomposed by a chemical change, that is, four
chemical compounds: CO
2(gas)
, H
2
O
(liquid)
, CH
2
O
(solid)
, and O
2(gas)
. The atoms in these compounds
may separate from one another and rearrange themselves during a chemical reaction. In this case, in
the presence of light and available nutrients, plant material has formed from CO
2
and H
2
O, and the
carbon atom in CO
2
has been rearranged into the carbon atom of CH
2
O. This reaction further shows
that all chemical equations must balance. The total number of atoms of an element on the left-hand
side of an equation must equal the total number of atoms of that element on the right-hand side of
the equation.
A. The atomic weights of the elements in these compounds are C = 12, H = 1, O = 16. Thus, the sum-
mation of these weights, or the gram molecular weight, for CH
2
O is 12 + (2 x 1) + 16 = 30 g; for
O
2
, 2 x 16 = 32 g; for CO
2
, 12 + (2 x 16) = 44 g; and for H
2
O, (2 x 1) + 16 = 18 g.
B. The weight of one mole of these compounds is CH
2
O = 30 g; O
2
= 32 g; CO
2
= 44 g; and H
2
O = 18 g.
C. The relationships between the compounds as shown in the equation must always be preserved;
thus one unitthat is, one mole of the reactant compound CO
2
must react with an equivalent
number of moles of the reactant compound H
2
O to give you a ratio of product compounds of
CH
2
O:O
2
= 1:1. Thus, the formation of 10 moles of plant material requires 10 moles, or 10 moles x
44 g/mole = 440 g of CO
2
.
D. At a molar ratio (that is, a ratio of moles) of C:N = 106:16, the moles of nitrogen are 16/106 x 10
moles = 1.51 moles.
E. The atomic weight of N is 14. The reaction required 1.51 moles of N or 1.51 moles of NO
3
-
. (There
is 1 mole of N in 1 mole of NO
3
-
.) The molecular weight of NO
3
-
is 14 + (3 x 16) = 62 g. Thus, the
grams of nitrate consumed were 1.51 moles NO
3
-
x 62 g NO
3
-
/mole = 93.6 g NO
3
-
.
2. This question again deals with chemical reactions. The equation to be balanced represents the weath-
ering of a common mineral found at the surface of the earth. The student not only learns to balance a
reaction on the basis of atoms but also on the basis of charge. The reason for starting the balance on
aluminum is that solids containing aluminum are very insoluble at the temperature and pressure of
weathering. Thus, it is assumed that all the aluminum from the weathering of orthoclase feldspar is
simply transferred to the solid weathering product kaolinite. Of course, this is not true, but it is a
reasonable approximation.
2KAlSi
3
O
8
+ 2CO
2
+ 11H
2
O = Al
2
Si
2
O
5
(OH)
4
+ 2 K
+
+ 2HCO
3
-
+ 4H
4
SiO
4
0
3. Dissolved potassium is the sixth most important dissolved constituent in seawater. Its concentration is
important to biological processes, although it is a minor essential element for phytoplankton productivity.
A. The concentration of K
+
in the ocean in moles/kg = 390 x 10
-3
g/kg seawater 39 g/mole = 10 x
10
-3
moles/kg seawater or 10 millimoles.
52
B. The average density of seawater is 1.027 g/cm
3
. Thus, 1 kg of seawater is equivalent to 1,000 g of
seawater 1.027 g/cm
3
= 973.7 cm
3
of seawater. The concentration in parts per million by volume
of seawater is 390 x 10
-3
g/kg seawater x 1.027 x 10
-3
kg/cm
3
x 1,000 cm
3
/L seawater = 400.5 x
10
-3
g/L = 400.5 mg/L = 400.5 ppmv of seawater.
4. The atmosphere is an important reservoir that exchanges materials with the earths surface. Its composi-
tion has changed on a geological time scale and on the human scale of generations because of the activi-
ties of human society. This problem illustrates the fact that although atmospheric CO
2
accounts for 60% of
the enhanced greenhouse effect, it represents a relatively small part of the total atmospheric mass.
A. The mass of the atmosphere can be obtained from the weight of air above 1 cm
2
of the earths sur-
face and the total area of the earth: 1,031 g/cm
2
x 5.1 x 10
18
cm
2
= 52 x 10
20
g. The total number of
moles of gases in the atmosphere is 52 x 10
20
g 29 g/mole = 1.8 x 10
20
moles.
B. The number of moles of CO
2
is 0.00036 x 1.8 x 10
20
moles = 64.8 x 10
15
moles. The mass of CO
2
in
grams is 64.8 x 10
15
moles x 44 g/mole = 2,850 x 10
15
g = 2,850 x 10
9
metric tons = 2,850 gigatons
x (12 44) = 777 gigatons of C 12 g/mole = 64.8 x 10
15
moles C.
5. Water vapor is the most important greenhouse gas, yet as the following calculation shows, it is a
small portion of the mass of the atmosphere.
A. The total mass of water vapor in the atmosphere is 0.002 x 52 x 10
20
g = 10.4 x 10
18
g.
B. There are 10.4 x 10
18
g 18 g/mole = 57.8 x 10
16
moles of water vapor.
The Oceans, Atmosphere, Sediments, and Rocks
1. Upwelling is an important process in the ocean. It involves the upward movement of water and dis-
solved constituents from depth in the ocean to the surface. Upwelling occurs in the coastal regions of
offshore Peru, California, Namibia, Mauritania, and Somalia, and in open ocean equatorial regions
and the high latitudes of the Southern Hemisphere.
A. To upwell the volume of the ocean with an average depth of 3,800 m at the mean upwelling rate
of 4 m/yr would take 3,800 m 4 m/yr = 950 years.
B. 400 cm of water rises 1 cm
2
/yr. With an ocean area of 3.6 x 10
18
cm
2
, this is equivalent to a vol-
ume of water of 1,440 x 10
18
cm
3
/yr or 1,440 x 10
15
L/yr x 40 x 10
-6
moles N/L = 57.6 x 10
12
moles N/yr x 14 g/mole = 806 x 10
12
g N/yr.
C. 806 x 10
12
g N/yr 14 g/mole = 57.6 x 10
12
moles of N/yr. At a C:N ratio of 106:16 = 382 x 10
12
moles C/yr x 12 g/mole = 4.6 x 10
15
g C/yr 360 x 10
12
m
2
= 13 g C/m
2
/yr. This productivity is
only about 10% of global marine net primary productivity (Figure 11). This calculation illustrates
the fact that much of the nitrogen used in biological productivity in the euphotic zone of the
ocean comes from recycling of the N within this zone.
2. The formation of the deep water of the ocean is part of the conveyor belt circulation pattern of the
world oceans. This pattern is not well known from observations; our understanding of it is based
mainly on theoretical models. The North Atlantic deep water (NADW) flows southward at depth
from its source in the high latitudes of the North Atlantic Ocean and meets a northward-flowing cur-
rent (the Antarctic Bottom Water, ABW) whose water originated by sinking in the Weddell Sea near
Antarctica. The currents merge and part of the water flows into the deep Indian Ocean and Pacific
53
Ocean. Water upwells to the surface in all basins of the ocean. In addition, warm water returns from
the Pacific and Indian Oceans into the Atlantic Ocean at about the depth of the thermocline. We
believe these return flows to the Atlantic Ocean occur through the Drake Passage between Antarctica
and South America and through the Bering Sea into the Arctic Ocean and thence to the Atlantic
Ocean. The return flows in the high latitudes of the North Atlantic sink as the NADW.
A. Because of this pattern of circulation, the deep water of the worlds oceans generally gets older
from the Atlantic Ocean to the Indian Ocean to the Pacific Ocean. The time the water stays out of
contact with the atmosphere, that is, its residence time, increases toward the Pacific Ocean. The
residence time of the bottom waters of the Atlantic Ocean is 200500 years; that of the Pacific
Ocean is 1,0002,000 years.
B. By upwelling as described above.
C. This is a difficult question and one that is asked by a number of scientists today. The answer is of
concern to the worlds people because of the link to climate. It is likely that any substantial melt-
ing of sea ice and the continental glacier of Greenland would add fresh water to the surface of the
ocean in the high latitudes of the North Atlantic for some period of time. This would affect the
rate of deep water formation because of the change in the salt content of surface ocean water. In
turn, the pattern of the conveyor belt circulation of the ocean could be altered. One suggestion is
that there would be a less intense flow of warm water northward by the Gulf Stream, and the cli-
mate of Europe would cool.
3. A. Because of the short residence time of CO in the atmosphere (about 70 days) and the fact that
the upwelling of air near the equator effectively separates air exchange in the troposphere
between the two hemispheres, the gas would not be evenly distributed. Higher concentrations
would be found in the Northern Hemisphere troposphere than in the Southern Hemisphere. In
fact, observations show a strong gradient in the concentration of CO between the two hemi-
spheres, with higher concentrations in the North.
B. The barrier is the convergence of the North Equatorial Current and the South Equatorial Current
near the equator and their westward flows. This converging pattern inhibits exchange of surface
waters between the Northern Hemisphere and the Southern Hemisphere. Floating tar balls in the
North Atlantic would be caught in the North Equatorial Current and transported westward to the
northward-moving Gulf Stream.
C. No, the NADW moves southward at depth in the North Atlantic Ocean into the South Atlantic
Ocean. The ABW moves north at depth. Neither current is involved with surface ocean currents.
4. The fine dust particles would take 4 km x 10
5
cm/km = 4 x 10
5
cm 500 cm/yr = 800 years. In actu-
al fact, they settle much faster because they are encapsulated in the fecal pellets of animal plankton
(zooplankton) in the ocean. During feeding the zooplankton inadvertently pass them through their
guts and excrete them contained in bigger mucilaginous fecal particles that sink at rates of 350 m/day.
5. To answer this question requires an understanding of some basic chemistry. The equilibrium
between a gas and a solution is normally given by Henrys Law, which states that the concentration
of the gas in the solution equals a constant (known as the Henrys Law constant) times the partial
pressure of the gas. For CO
2
, the expression is
[CO
2
] = K
H
PCO
2
54
The brackets around CO
2
denote its concentration in moles/L. The partial pressure of CO
2
(PCO
2
) is
in atmospheres. The value of K
H
varies with the composition of the solution and the temperature.
For seawater at 25C, K
H
equals 10
-1.54
.
A. Carbon dioxide dissolves in seawater to an extent determined by the CO
2
concentration in the
atmosphere and the reactions that occur in the seawater. At 25C and with an atmospheric CO
2
concentration of PCO
2
= 10
-3.45
atm, the relationship is
[CO
2
] = 10
-1.54
x 10
-3.45
= 10
-4.99
mole/L
B. In 1700 for a PCO
2
= 10
-3.55
atm, we have
[CO
2
] = 10
-1.54
x 10
-3.55
= 10
-5.09
mole/L
C. The percentage change is [(10
-4.99
mole/L 10
-5.09
mole/L) 10
-5.09
mole/L] x 100 = 26%. Thus,
the dissolved CO
2
concentration in the surface ocean has changed by this percentage over the
past 300 years because of fossil fuel combustion and biomass burning.
6. A. The percentage is [(0.9 x 10
-4
cal/cm
2
/min + 0.9 x 10
-5
cal/cm
2
/min) 0.5 cal/cm
2
/min + 0.9 x
10
-4
cal/cm
2
/min + 0.9 x 10
-5
cal/cm
2
/min] x 100 = 0.02%.
B. The amount of energy reaching the earths surface and absorbed is 343 W/m
2
x 0.49 = 168 W/m
2
.
This energy is used to heat the atmosphere and surface of the earth; to evaporate water; to gener-
ate rising air masses (thermals); to drive wind, waves, and currents; and for photosynthesis.
C. The energy is reabsorbed, keeping the earth warm.
7. A. Provided there were no processes restoring the continents, they would be reduced to sea level by
erosion in 150 x 10
12
m
2
x 840 m = 126 x 10
15
m
3
x 10
6
cm
3
/m
3
= 126 x 10
21
cm
3
x 2.7 g/cm
3
=
340 x 10
21
g 200 x 10
14
g/yr = 17 x 10
6
years.
B. This is a question that has plagued geologists for two centuries. There must be processes that add
mass to the continents to keep them above sea level. Certainly lavas originating in the interior of
the earth add material to the continents. In subduction zones, not all the rock of the oceanic crust
is transported down toward the interior of the earth. Some of it is added to the continents and
increases their area and thickness. Finally, continents often collide during their movement about
the earths surface. In the collisions, the continents act as a great vise, squeezing sediments origi-
nally derived from their erosion and other sources into high mountain ranges. This action adds
volume back to the continents. The collision of India with Asia followed by the formation of the
Himalayan Mountains is an example of such an event. Thus, there is a great rock cycle at work in
which the continents are eroded and their materials deposited in the ocean. The sediments of the
oceans are buried to great depths or transported to subduction zones. In either case, the sedimen-
tary material is eventually returned to the continents to be uplifted to their surfaces and eroded,
completing the cycle.
8. A. This question simply uses the concept of residence time, where = mass flux; therefore, flux =
mass = 1.8 x 10
18
metric tons 600 x 10
6
yr = 3 x 10
9
metric tons/yr = 30 x 10
14
g/yr.
Interestingly, this flux is much less than that of erosion and thus deposition in the oceans today. This
implies that today is somewhat unusual in terms of geologic history. We know that to be the case from
other geological information.
55
B. Sediment (clay, mud, silt, sand, gravel, and skeletal and organic materials) enters the sedimentary
rock reservoir by erosion of rocks, transportation of the eroded debris, and subsequent deposition
on the seafloor, followed by burial in some cases to depths of 12 km. The sediment gets out by
uplift due to plate tectonic movements and re-erosion of the sedimentary mass.
9. The chemical species in anoxic soils are chiefly reduced forms of the compounds CH
4
, CO, NH
3
, and H
2
S
(see Figures 9, 10, 15, and 19). CO
2
occurs as well, although it is a relatively oxidized form of carbon. In a
well-aerated soil, we might expect O
2
, CO
2
, N
2
, and SO
2
.
10. Your answer to Question 2 in the Chemistry section shows that the weathering of silicate minerals
subtracts CO
2
from the atmosphere. This subtraction must be balanced by an addition of CO
2
from
other processes or the atmosphere would run out of CO
2
in about 6,000 years. Those processes
involve hydrothermal reactions at midocean ridges and the subduction and/or burial of carbonate
minerals to realms of higher pressure and temperature, where carbonates are converted to silicates,
and CO
2
is released back to the atmosphere by volcanism and other processes.
Ecology
1. This question is designed to give the student a feeling for some of the characteristics of two impor-
tant ecosystems that are being severely impacted by human activities. These activities are the defor-
estation of tropical rain forests and their conversion to pasture and urban areas and the eutrophica-
tion of coastal marine environments.
A. The total net primary production of tropical rain forests and estuaries is:
Rain forests: 17 x 10
12
m
2
x 2,000 g dry matter/m
2
/yr = 34 x 10
15
g dry matter x 0.45 = 15.3 x 10
15
g C.
Dividing by 10
6
g/metric ton, we get 34 x 10
9
metric tons dry matter and 15.3 x 10
9
metric tons C.
Estuaries: 1.4 x 10
12
m
2
x 1,800 g dry matter/m
2
/yr = 2.52 x 10
15
g dry matter x 0.45 = 1.13 x 10
15
g C.
Dividing by 10
6
g/metric ton, we get 2.52 x 10
9
metric tons dry matter and 1.13 x 10
9
metric tons C.
Notice that although the NPP of tropical rain forests and estuaries is similar, the smaller area of estu-
aries leads to more than an order of magnitude difference between the total net primary production
of the two ecosystems.
B. The total plant mass (biomass) of these ecosystems is:
Rain forests: 17 x 10
12
m
2
x 20 kg C/m
2
= 340 x 10
12
kg C 10
3
kg/metric ton = 340 x 10
9
metric
tons C 0.45 = 755 x 10
9
metric tons dry matter.
Estuaries: 1.4 x 10
12
m
2
x 0.45 kg C/m
2
= 630 x 10
9
kg C 10
3
kg/metric ton = 6.3 x 10
8
metric
tons C 0.45 = 1.4 x 10
9
metric tons dry matter. Notice the orders-of-magnitude difference
between the biomass of tropical rain forests and estuaries.
C. In ten years, 9% of the area of rain forests was lost; this represents 755 x 10
9
metric tons dry
matter x 0.09 = 68 x 10
9
metric tons dry matter x 0.45 = 30.6 x 10
9
metric tons C.
D. The grams of CO
2
emitted to the atmosphere in this ten-year period would be 30.6 x 10
9
metric
tons C x 10
6
g/metric ton = 30.6 x 10
15
g C x (44 12) = 112 x 10
15
g CO
2
. This flux represents
(Figure 11) the size of the atmospheric CO
2
reservoir of 744 x 10
15
g C x (44 12) = 2,730 x 10
15
g
CO
2
. 112 x 10
15
g CO
2
2,730 x 10
15
g CO
2
= 0.041, or 4% of the atmospheric reservoir.
56
The flux would represent about 3 x 10
15
g C/yr for the decade of the 1980s. The magnitude of the
flux is too high, meaning that all the woody plant material was not burned to CO
2
. Some remains
on the ground as waste from the cutting, and some has gone into lumber. The flux of CO
2
to the
atmosphere from all land-use activities in tropical rain forests for the 1980s was on the order of
11.6 x 10
15
g C/yr.
E. At a C:P ratio of 106:1, the additional plant productivity supported by the pollutant P would be
1.5 x 10
12
g P/yr 31 g/mole = 48.4 x 10
9
moles P/yr x (106 1) = 5.13 x 10
12
moles C/yr.
Divided by the estuary area of 1.4 x 10
12
m
2
= 3.7 moles C/m
2
/yr = 44 g C/m
2
/yr 0.45 = 98 g
dry matter/m
2
/yr, or about a 5% increase in the productivity of the worlds estuaries.
F. In fact, because the pollutant P will be used more than once in plant productivity in estuaries, the
total organic carbon that could be buried in the sediments of estuaries amounts to 140 x 10
12
g
C/yr (Figure 18). This flux does qualify as a negative biological feedback because the additional P
has been added to the earths surface by the human activities of fertilizer application to croplands
and sewage discharge. Some of this P makes its way to lakes and coastal marine environments
and increases the productivity of such aquatic systems. The flux represents (140 x 10
12
g C/yr 6
x 10
15
g C/yr) x 100 = 2% of the fossil fuel flux in 1995. Not much!
2. A. The total production of dry matter is 510 x 10
12
m
2
x 0.37 kg dry matter/m
2
/yr = 188.7 x 10
12
kg
dry matter/yr.
B. 188.7 x 10
12
kg dry matter/yr x 0.45 = 84.9 x 10
12
kg C/yr.
C. Let total production in the ocean = X; then production on land = 2X. Thus X + 2X = 188.7 x 10
12
kg dry matter/yr, i.e., 3X = 188.7 x 10
12
kg dry matter/yr; X = ocean production = 62.9 x 10
12
kg
dry matter/yr and 2X = land production = 125.8 x 10
12
kg dry matter/yr.
3. Autotrophy is the biochemical pathway by which an organism uses CO
2
as a source of carbon and
simple inorganic nutrient compounds of N and P for synthesis of organic matter. In heterotrophy,
more complex organic materials are used as the source of carbon for metabolic processes.
4. Prokaryotesthe Kingdom Monera, including the bacteria and cyanobacteriatake part in a variety
of biogeochemical processes (see Table 1). We often forget the fact that the bacteria are responsible
for the decay of organic matter both on land and in the ocean. In other words, it is their metabolic
activity that returns CO
2
and other gases and nutrients back to the environment. The cyanobacteria
are photoautotrophic and produce oxygen as a metabolic byproduct. These organisms were responsi-
ble for the initial growth of oxygen in the earths atmosphere. The processes include CO
2
fixation,
nitrogen fixation, and oxidation of sulfur as examples.
5. Eutrophication is the set of processes leading to the overnourishment of a lake, river, or marine envi-
ronment; consequent rapid plant growth and death; and oxygen deficiency of the system. This is a
natural set of processes in certain environments. When it occurs because the excess nutrients come
from fertilizers, sewage, detergents, etc., it is called cultural eutrophication. This term distinguishes
the natural situation from that produced by the activities of people.
57
Biogeochemical Cycles
1. See Figure 22.
A. The residence time = = mass of
water in the ocean divided by the
flux of water to the ocean by rivers:
1,370 x 10
6
km
3
40 x 10
3
km
3
/yr =
34,250 years.
B. of Ca in the ocean is (1,370 x 10
6
km
3
x 10
12
L/km
3
x 400 mg/L) (40
x 10
3
km
3
/yr x 10
12
L/km
3
x 15
mg/L) = 913,000 years.
2. Here we apply the concept of residence time in the context of how long it takes for a lake to recover
from a single input of a chemical into it. This is an environmental problem often encountered in
developing, as well as developed, countries.
A. The volume of the lake is 5 km x 2 km x 0.1 km = 1 km
3
x 10
12
L/km
3
= 1 x 10
12
L.
B. The mass of mercury (Hg) is 1 x 10
12
L x 1 x 10
-6
g Hg/L = 1 x 10
6
g Hg.
C. The flux of mercury by the river to the lake is 2 x 10
12
L/yr x 5 x 10
-7
g Hg/L = 1 x 10
6
g Hg/yr;
thus the residence time of Hg (
Hg
) in the lake is 1 x 10
6
g Hg 1 x 10
6
g Hg/yr = 1 year.
D. The time to reach a new equilibriumthat is, for the Hg input to work its way through the lake
is 3 x
Hg
= 3 x 1 yr = 3 yr. In this period of time, 95% of the Hg input would be gone.
3. This question provides the student with a feeling for the problem of looking for a needle in a
haystack that scientists have when observing the change in the size of the terrestrial living biomass
due to uptake and storage of anthropogenic CO
2
.
A. 600 x 10
9
tons C x 10
6
g/ton = 600 x 10
15
g C. 135 x 10
12
moles C/yr x 12 g/mole = 16.2 x 10
14
g
C/yr. The annual % change would be (16.2 x 10
14
g C/yr 600 x 10
15
g C) x 100 = 0.27% per year.
B. Most unlikely. For the decade of the 1980s, this would be only a 2.7% change in the mass of living
biomass globally. This amount of change would be difficult to measure by field studies, even if
they were aimed at seeing a change in the amount of organic carbon stored in terrestrial vegeta-
tion. However, if the storage continues, such measurements could provide information in a few
years.
4. A. The total DIC in the mixed layer is 360 x 10
12
m
2
x 10
2
m = 360 x 10
14
m
3
x 10
6
cm
3
/m
3
= 360 x
10
20
cm
3
x 1.027 g/cm
3
= 37 x 10
21
g 10
3
g/kg = 37 x 10
18
kg seawater x 2.2 x 10
-3
moles C/kg
seawater = 81.4 x 10
15
moles C.
B. 2 x 10
9
tons C/yr = 2 x 10
15
g/yr 12 g/mole = 166.7 x 10
12
moles C/yr 37 x 10
18
kg seawater = 4.5 x
10
-6
moles C/kg seawater/yr = 4.5 micromoles C/kg seawater/yr. Actual measurements of the change
in the DIC content of seawater over time show an increase of about 1 micromole per year. The differ-
ence is due to the fact that the anthropogenic carbon taken up by the ocean mixes deeper in the ocean
than the average depth of the mixed layer used in the problem, on average about 300400 meters.
Plants Animals
Soil
LAND ATMOSPHERE
Water Biota
Sediment
OCEAN
Figure 22.
58
C. Using 1 micromole per year as the average carbon uptake since 1975, we get 1 x 10
-6
mole C/kg/yr
x 21 yr = 21 x 10
-6
moles C/kg 2.2 x 10
-3
moles C/kg x 100 = 0.95%. It was not until the late 1980s
that scientists were able to measure these small changes in seawater DIC accurately and precisely.
5. Referring to Table 3, the total amount of water in the atmosphere as water vapor is 0.013 x 10
6
km
3
; thus
the residence time of water vapor in the atmosphere calculated with respect to total evaporation (must
equal precipitation) is 0.013 x 10
6
km
3
H
2
O 496 x 10
3
km
3
H
2
O/yr = 0.026 yr x 365 days/yr = 9.6 days.
B. No, the pollutant would not mix evenly throughout the troposphere because of waters very short
residence time in the atmosphere. In general, the dust and aerosol content of the troposphere
exhibits a regional pattern and is most concentrated near sources, downwind from sources, and in
regions of relatively dry climate. However, the dust plume in the troposphere derived from the
Sahara and Sahel areas of Africa can be seen in satellite images extending all the way across the
Atlantic Ocean.
6. The three major processes are (1) inputs of volcanic CO
2
derived from the metamorphism of CaCO
3
to
CaSiO
3
, (2) weathering of silicate minerals like CaSiO
3
and then deposition of calcium carbonate and
silica in the ocean, and (3) the evolution of plants and their effect on weathering. The reactions are
1. CaCO
3
+ SiO
2
CaSiO
3
+ CO
2
2. CaSiO
3
+ 2CO
2
+ 3H
2
O Ca
2+
+ 2HCO
3
-
+ H
4
SiO
4
0
, and then
Ca
2+
+ 2HCO
3
-
+ H
4
SiO
4
0
CaCO
3
+ SiO
2
+ 3H
2
O + CO
2
3. CO
2
+ H
2
O CH
2
O + O
2
7. The connection is simply the fact that when organic matter is buried in sediments of the ocean, oxy-
gen not used to oxidize the organic matter is left in the atmosphere. With the continuous burial of
organic matter on the seafloor, the oxygen content would increase in a few millions of years to levels
that would lead to burning of forests and grasslands. This does not happen because the buried organ-
ic matter is returned to the earths surface through uplift by plate tectonic processes. On exposure to
the atmosphere, the organic matter is oxidized, and the oxygen is removed from the atmosphere.
8. The major difference is that there is not a major gas of phosphorus that resides in the atmosphere or
is transported through it (see Figure 18). This statement is not true of carbon, nitrogen, and sulfur.
All of these elements have important gaseous compounds in the atmosphere that exchange with the
earths surface. (See the text sections on the cycles of C, N, and S.)
9. DMS in the troposphere reacts fairly rapidly with hydroxyl radical in the presence of light, water,
and oxygen to make sulfate aerosol. On the contrary, OCS is inert in the troposphere but is converted
in the stratosphere to sulfate aerosol (see Figure 19).
10. The difference in residence time implies that ammonia reacts more rapidly than carbon monoxide in
the atmosphere (see Figures 10 and 16). This is simply a consequence of the fact that the shorter the
residence time (lifetime) of a chemical compound in a reservoir, the more reactive the substance.
59
11. This question and the following five questions relate to relationships depicted in the figures of the
biogenic trace gases. They are designed to help the student to study the figures and interpret them.
The major reaction in the atmosphere coupling the biogeochemical cycles of CH
4
, CO, and CO
2
is the
oxidation of the reduced carbon gas CH
4
to CO and then on to CO
2
by OH*. About 60% of the
enhanced greenhouse forcing is due to CO
2
, and about 20% is due to CH
4
. The major anthropogenic
sources of emissions of CH
4
to the atmosphere are fossil fuel burning and leakage from gas transmis-
sion pipelines, biomass burning, landfills, rice paddies, and enteric fermentation in domesticated
animals. CO emissions come from fossil fuel and biomass burning. Land-use activities and fossil fuel
burning are the major anthropogenic sources of CO
2
to the atmosphere. Adoubling of atmospheric
CO
2
concentration could lead to a 2.5C increase in mean global temperature. Molecule for molecule,
CH
4
is about 20 times more effective as a greenhouse gas than CO
2
. (Compare the amount of tem-
perature change per ppbv for the two gases.)
12. The ratio is (42 + 20 + 78) x 10
6
metric tons N/yr 126 x 10
6
metric tons N/yr = 1.1:1. The anthro-
pogenic nitrogen fluxes on land slightly exceed the natural biological fixation flux! The minimum
percentage is (21 x 10
6
6
metric tons N/yr) x 100 = 15%. The additional
nitrogen flux to the ocean is a cause of eutrophication of coastal marine environments.
13. The ratio is 206 x 10
6
6
metric tons N/yr = 3.3:1. This is a difficult question
to answer. On the time scale of a century, it is very likely that the flux of N to the ocean from rivers
and groundwaters will increase because of continuous use of industrial fertilizers, atmospheric
deposition of anthropogenic nitrogen, and disposal of sewage. If there is climatic change on this time
scale, it is uncertain whether the upwelling rate of the worlds oceans will change. However, a
warming of the global surface layer of the ocean would most likely lead to a slowing of upwelling
and thus delivery of nutrients to the surface ocean.
14. The range is 143 to 339 years. 73 x 10
6
tons N (2.9 + 0.1 + 0.02 + 0.01 + 1.4) x 10
6
tons N/yr = 339
years. 1,500 x 10
6
tons N (5.2 + 0.3 + 0.2 + 2.2 + 2.6) = 143 years. N
2
O accounts for about 9% of the
enhanced greenhouse effect.
15. The percentage from human activities is [(21 + 3) x 10
6
tons N/yr (21 + 3 + 20) x 10
6
tons N/yr] x
100 = 54.5%. Human activities substantially interfere with the fluxes of NO
x
. Environmental prob-
lems associated with the anthropogenic fluxes are acid deposition, photochemical smog, and
increased tropospheric ozone, a greenhouse gas. The principal reaction leading to destruction of NO
x
in the atmosphere is photochemical. The products of the reaction are nitric acid, peroxylacetyl
nitrate, and organic nitrates. The reaction is NO
2
+ OH*+ light HNO
3
.
16. The ratio is 1,085 x 10
6
tons P/yr 186 x 10
6
tons P/yr = 5.8:1.
The residence time of P in the marine biota relative to the recycling flux is 73 x 10
6
tons P 1,085 x10
6
tons P/yr = 0.07 years. That for P in the land biota is 1,800 x 10
6
tons P 186 x 10
6
tons P/yr = 9.6 years.
The phytoplanktyon of the ocean turn over much more rapidly than do terrestrial plants. There are
more generations of death and birth for marine plankton than for most plants growing on land.
60
Acid depositionthe fallout of acidic substances, primarily of nitrogen and sulfur, from the atmosphere
on to the earths surface in rain, snow, or other forms. Acid rain has a pH generally less than 5 (aver-
aged over a year).
Aerosolthe suspension of very fine, generally micrometer-sized, solid and liquid particles in the atmo-
sphere.
Albedothe amount of incident radiation that is reflected by a surface and thus does not contribute to
the heating of the surface. The albedo of the whole earth is approximately 30%. The albedo of clean
snow is about 90% and that of water is about 10%.
Anaerobican organism that does not need oxygen to carry on its metabolism or an environment with-
out oxygen.
Anoxicwithout oxygen.
Anthropogenicof, relating to, or influenced by the impact of humans on nature.
Atomthe smallest component of an element having the chemical properties of the element. An atom
consists of a nucleus of neutrons and protons and one or more electrons bound to the nucleus by electri-
cal attraction.
Autotrophythe biochemical pathway by which an organism uses carbon dioxide as a source of carbon
and simple nutrient compounds for synthesis of organic matter.
Autotrophic systeman environment in which the difference between gross photosynthesis and gross
respiration is positive. In such a terrestrial or aquatic environment, the net transfer of carbon dioxide is
into the system.
Bacteriaone-celled organisms having a spherical, spiral, or rod shape belonging to the Kingdom Monera.
Benthicof, relating to, or occurring at the bottom of a body of water.
Bioessentialrequired by virtually all living organisms. The major bioessential elements are oxygen,
carbon, nitrogen, phosphorus, sulfur, potassium, magnesium, and calcium. Minor or trace quantities of
iron, manganese, copper, zinc, boron, silicon, molybdenum, chlorine, vanadium, cobalt, and sodium are
also required by organisms.
Biogenic gasa gas whose production or consumption on earth is accomplished by biological reactions.
Biogeochemical cyclerepresentation of biological, geological, and chemical processes that involve the
movement of an element or compound about the surface of the earth.
Biogeochemical systemthe interactive system of biogeochemical processes and cycles of elements and
compounds.
Biogeochemistrythe discipline that links various aspects of biology, geology, and chemistry to investi-
gate the surface environment of the earth.
Global Change
Instruction Program
Glossary
61
Biological productivitythe rate of production per unit area of organic matter by producer organisms.
For example, the rate may be given as grams of carbon per square meter per year for a marine grass
community. There are several kinds of productivity. Gross primary production (GPP) refers to the total
amount of plant material produced by photosynthesis in a defined area in an interval of time. Net pri-
mary production (NPP) is the net amount of plant material produced per unit area per unit time and is
the difference between GPP and cell respiration. Net ecosystem production (NEP) is the difference
between GPP and cell respiration plus heterotrophic processes of decay.
Biological pumpthe set of processes by which organic carbon is exported from the surface ocean to
the deep sea.
Biomassthe amount of living matter in a unit area or volume of habitat. For example, the total bio-
mass of the worlds tropical rain forests is 42 kilograms of dry matter per square meter of forest, or a
total of 420 billion tons of dry matter (equivalent to approximately 170 billion tons of carbon).
Biospherethe living and dead organic components of the earth. Sometimes this term is used in the
same way as the term ecosphere in this module, and sometimes for only the living animals and plants.
Climatethe characteristic long-term environmental conditions of temperature, precipitation, winds,
etc., in a region or for the globe at present or in the past (paleoclimate).
Cloud condensation nucleiairborne particles of very small size, generally less than one micrometer in
diameter, that serve as sites on which liquid cloud droplets condense when an air mass is supersaturat-
ed with water vapor. The particles are commonly composed of water-soluble material.
Coccolithophoridaea family of planktonic algae that build skeletons of micrometer-sized disc-shaped
plates of calcite, called coccoliths.
Concentrationthe fraction of the total of a substance made up of one component. For example, seawa-
ter contains 400 parts per million by weight of calcium. Concentration is also expressed in moles per
liter or kilogram or in percent (that is, parts per hundred), parts per thousand (/
), per million (ppm),

per billion (ppb), and so forth, either by weight or by volume.
Coupledthe condition in which information from one part of the system is provided to, and influences
the behavior of, other parts. The biogeochemical cycles of the elements necessary for life are coupled
through processes that are essential for life, e.g., photosynthesis and respiration.
Crustthe outer layer of the earth, enriched in silicon, sodium, and potassium and having a thickness
of 35 kilometers beneath the continents and 10 kilometers beneath the oceans.
Cryospherethe icy part of the earth; its continental and mountain glaciers, ice sheets, and ice shelves;
a reservoir in the earths surface system.
Decaythe oxidative process of conversion of organic tissue to simpler organic and inorganic com-
pounds. The oxidizing agent may be diatomic oxygen (O
2
), nitrate (NO
3
-
), or other chemical compounds.
Denitrificationthe conversion, principally by bacteria, of compounds of nitrogen in soils and aquatic
systems to nitrogen gas (N
2
) and nitrous oxide gas (N
2
O) and the eventual release of these gases to
the atmosphere.
Diagenesisthe collection of physical, chemical, and biological processes that operate on a sediment
after deposition.
Diatomplanktonic and benthic freshwater and marine algae that commonly use silicon to build a
skeleton of opal.
62
Dry depositionthe deposition of materials from the atmosphere on to the earths surface in the form
of solid particles. Such particles also may be washed out of the atmosphere by rain.
Ecospherethe system that includes the biosphere and its interactions with the air, water, and soils and
sediments of the earth.
Ecosystemcomplex of a community or group of communities and the environment that functions as
an ecological unit in nature.
Electromagnetic spectrumthe entire range of radiation. The wavelengths (distances between adjacent
peaks) of the electromagnetic waves within the spectrum range from kilometers for radio waves to bil-
lionths of a meter (nanometers) for X rays.
Entropya scientific measure of the degree of disorder in a system. The greater the disorder the greater is
the entropy of the system. The Second Law of Thermodynamics states that entropy is always increasing.
Equilibriumstable, balanced state in which all influences on a system are countered by others.
Erosionthe set of processes by which the surface of the earth is worn away by the action of water,
wind, glacial ice, etc.
Euphotic zonethe upper, lighted zone of the ocean or a lake in which most of the productivity of
plants occurs. In the ocean, the euphotic zone extends from the surface to a depth where the light inten-
sity is reduced to about 0.11.0% of that available at the surface. The depth of the euphotic zone
depends on season and latitude.
Eutrophicationthe set of processes leading to overnourishment of an aquatic system in nutrients,
rapid plant growth and death, and oxygen consumption and deficiency in the system. These processes
occur naturally in some aquatic systems but may be speeded up by additions of nutrients from human
activities (e.g., fertilizer application) to the systems. Human-induced eutrophication is often called cul-
tural eutrophication.
Evaporationthe physical process by which water is converted from liquid to vapor and is transported
into the atmosphere.
Evapotranspirationthe combined processes of evaporation and transpiration.
Evasionthe escape or release of a gas from the surface of the ocean or land to the atmosphere.
Evolutionthe pattern of development and change in a variable from one state to another. Biological
evolution describes the pattern of emergence, development, and extinction of organic species through
geologic time.
Feedbacka process or mechanism in which some fraction of the output is returned or fed back to
the input. Feedback loops may either stabilize (negative feedback) or destabilize (positive feedback) a
system undergoing a perturbation. These feedback loops exist in both the biogeochemical cycles and the
climate system.
Fermentationthe bacterial process of conversion of sugars to carbon dioxide.
Fixationsee Nitrogen fixation.
Fluxthe movement of a variable or a substance into or out of a reservoir.
Foraminiferaanimal plankton (zooplankton) in the ocean belonging to the Phylum Protozoa that com-
monly have a shell of calcium carbonate.
63
Forcingthe ability of a variable, like the concentration of a greenhouse gas in the atmosphere, to
induce a change in a system. Aforcing function controls the behavior of a system and often makes it
regular and predictable.
General circulation model (GCM)a simulation, usually performed on a large computer, of the large-
scale, or general, wind and ocean systems on earth to calculate climate and its changes.
Geologic time scalea calendar of earth history. The time scale is divided into variable time units of
eon, era, period, and epoch (see Figure 5).
Glacial stagean extended cold interval of time within the Pleistocene Epoch in which continental glac-
iers covered much of the Northern Hemisphere continents, atmospheric CO
2
concentrations were low,
and sea level was low.
Greenhouse effectthe warming of the earths atmosphere and surface by the atmospheric greenhouse
gases. These gases absorb and reradiate longwave radiation from the earth, keeping it in the atmosphere
and thus warming the global temperature. Without the natural greenhouse effect, the planet would be
about 33C cooler than its global mean annual temperature of 15C, that is, 18C. Because of inputs
from human activities, these gases are increasing in concentration in the atmosphere. This may lead to
an enhanced greenhouse effect and warming of the planet.
Greenhouse gasan atmospheric gas that absorbs and radiates energy in the infrared part of the elec-
tromagnetic spectrum. Such gases include water vapor, carbon dioxide, methane, nitrous oxide, tropo-
spheric ozone, and the synthetic chlorofluorocarbon gases. These gases warm the atmosphere and the
earths surface below.
Groundwaterthe water beneath the ground, largely formed by the seepage of surface water downward.
Heterotrophic systeman environment in which the difference between gross photosynthesis and gross
respiration is negative. In such a terrestrial or aquatic environment, the net transfer of carbon dioxide is
out of the system.
Heterotrophya biochemical pathway in which organic substrates are used by organisms to make
organic matter.
Hothousean extended period of geologic time during which the earth was warm.
Hydrospherethe watery envelope surrounding the earth; a reservoir in the earths surface system.
Hydrothermal reactiona chemical reaction involving hot water and minerals in a rock.
Hydroxyl radical (OH*)the excited chemical compound of hydrogen and oxygen in the atmosphere
with an imbalance of electric charge. The hydroxyl radical is responsible for the oxidation of many
chemically reduced gases emitted from the surface of the earth.
Ice agea glacial stage, especially within the Pleistocene Epoch, beginning about 1.8 million years ago.
Ice housean extended period of geologic time in which the earth was cool.
Infrared radiationthe region of the electromagnetic spectrum with wavelengths longer than visible
light (about 1 micrometer) but shorter than microwaves (about 1 millimeter). Commonly known as heat.
Radiation emitted from the earth back to space is predominantly infrared radiation.
Interglacial stagean extended warm interval of time within the Pleistocene Epoch in which the conti-
nental glaciers retreated and atmospheric CO
2
concentrations and sea level were low.
Ionan electrically charged atom or group of atoms formed by the loss or gain of one or more electrons.
Apositive ion, the cation, is created by an electron loss, and a negative ion, the anion, is created by an
electron gain.
64
Irreversible processa process in which the entropy change is greater than zero. After the process is
complete, the system is more disordered than and different from its initial state.
Kerogenfossil organic matter dispersed throughout a rock.
Leachingthe selective removal of substances from a substrate, usually with water. For example, rainwa-
ter percolating through a soil can dissolve nitrogen and transport it to the groundwater. This is leaching.
Lifetimea measure of the reactivity of an atmospheric chemical compound. The more reactive the
compound, the shorter its atmospheric lifetime. Analogous to residence time.
Limestonea sedimentary rock consisting predominantly of calcium carbonate minerals.
Limiting nutrientthe chemical compound, generally inorganic, that limits productivity in a terrestrial
or aquatic environment. Examples are nitrate, phosphate, and iron.
Lithospherethe dynamic subdivision of earth on the order of 100 kilometers in thickness forming the
outer, rigid part of the planet. Also, the solid portion of the earth, composed of minerals, rocks, and
soils; a reservoir in the earths surface system.
Mantlethe portion of earth between its crust and its innermost zone (the core). The mantle is enriched
in magnesium and iron and has a thickness of about 2,900 kilometers.
Metamorphismthe set of processes that lead to a change in the structure or composition of a rock due
to pressure and temperature. Ametamorphic rock is formed from a preexisting rock by an increase in
pressure and temperature.
Methanogenesisthe conversion of organic material to methane, principally by bacteria.
Methanotrophythe conversion of methane to carbon dioxide, principally by bacteria.
Midocean ridgeany of several seismically active, submarine mountain ranges that are found in the
Atlantic, Indian, and Pacific Oceans. These ridges are regions where the seafloor originates and are the
source of the lithospheric plates.
Mixotrophythe use of both organic and inorganic materials to make organic matter.
Moleone gram atomic weight of an element or one gram molecular weight of a compound. One gram
atomic weight of an element is its atomic weight expressed in grams (i.e., the atomic weight of oxygen
is 16; its gram atomic weight is 16 grams). One gram molecular weight of a compound is its molecular
weight expressed in grams (i.e., the molecular weight of carbon dioxide is 44; its gram molecular weight
is 44 grams).
Moleculethe smallest physical unit of an atom or compound, consisting of one or more similar atoms
in an element and two or more different atoms in a compound.
Negative feedbacka process or mechanism that relieves or subtracts from an initial perturbation to a system.
Net primary productionsee Biological productivity.
Nitrificationthe conversion of ammonium to nitrite and nitrate by nitrifying bacteria.
Nitrogen fixationthe conversion of diatomic nitrogen gas (N
2
) to ammonium by bacteria. Also, the indus-
trial conversion of free nitrogen into combined forms used as starting materials for fertilizers and explosives.
Nutrienta substance that supplies nutrition to a living organism, like phosphorus and nitrogen.
Organicpertaining to a class of chemical compounds that include carbon as a component; characteris-
tic of or derived from living organisms.
65
Oxidationthe removal of electrons from an atom or molecule. Oxidizing capacity is the intrinsic abili-
ty of a system to oxidize reduced substances.
pHthe negative logarithm of the effective hydrogen ion concentration, used in expressing both acidity
and alkalinity on a scale whose values run from 0 to 14, with 7 representing neutrality. Numbers less
than 7 denote increasing acidity, and numbers greater than 7 increasing alkaline (basic) conditions.
Photoautotrophythe conversion of inorganic carbon into organic matter in the presence of light.
Photochemicalpertaining to chemical reactions involving chemical compounds in the presence of
light. Urban smog is the result of a complex series of photochemical reactions involving ozone, nitrogen
and sulfur oxides, and hydrocarbons.
Photolysis (photodissociation)pertaining to chemical reactions triggered by light that convert a com-
plex compound to more simple products. The photolysis of ammonia is an example: 2NH
3
N
2
+ 3H
2
.
Photosynthesisthe synthesis of complex organic materials (e.g., carbohydrates) from carbon dioxide, water,
and nutrients, using sunlight as a source of energy with the aid of chlorophyll and associated pigments.
Phytoplanktonminute plant life that passively floats in a body of water. The phytoplankton are at the
base of the food chain in the ocean.
Planktonminute plant and animal life of the ocean ranging in size from 5 micrometers to 3 centime-
ters. The plant plankton are the phytoplankton; the animal plankton are the zooplankton.
Plate tectonicsthe theory of global tectonics in which the lithosphere is divided into a number of
crustal plates that move on the underlying plastic asthenosphere. These plates may collide with adjacent
plates, slide under or over them, or move past them in a nearly horizontal direction. The sources of the
plates are the great midocean ridges of the worlds oceans, where hot molten material upwells from
within the earth. The plates are destroyed at subduction zones, like that along the western margin of the
Pacific Ocean, where they sink down into the underlying asthenosphere.
Positive feedbacka process or mechanism that reinforces or adds to an initial perturbation of a system.
Precipitationthe removal of water from the atmosphere and its deposition on the earths surface in the
form of rain, ice, or snow.
Prokaryoteany cellular organism that has no membrane about its nucleus and no organelles in the
cytoplasm except ribosomes. Prokaryotic genetic material is in the form of single, continuous strands
forming coils or loops, characteristic of all organisms of the Kingdom Monera, such as bacteria or
cyanobacteria.
Protozoaneukaryotic organism of the Kingdom Protoctista, Phylum Protozoa, with a membrane-
bound nucleus and organelles within a mass of protoplasm. Planktonic foraminifera and radiolarians
which secrete shells of calcium carbonate and opal, respectively, are members of the group.
Radicalan electronically excited compound with an imbalance of electric charge, which enables it to
react rapidly with another molecule.
Redfield ratiothe relatively constant ratio of 106:16:1 of the bioessential elements carbon, nitrogen,
and phosphorus in marine plankton. The concept of the Redfield ratio has been applied to the terrestrial
realm as well as to organic matter in soils and sediments.
Reductionthe chemical process by which an atom or a molecule gains electrons.
66
Reservoir or stocka part of a system that can store or accumulate and be a source of one of the sub-
stances that compose the system. For example, the atmosphere is a reservoir of the surface system of the
earth (the ecosphere). It can store water vapor released to it from the land by evapotranspiration and
from the ocean by evaporation, and return the water to the earths surface as precipitation.
Residence timethe total mass of a substance in a reservoir divided by its rate of inflow or outflow.
The residence time is a measure of the reactivity of the substance in the reservoir. For example, the resi-
dence time of sodium in the ocean is very long (55 million years). Therefore, sodium does not enter into
chemical or biochemical reactions that remove it very rapidly from the ocean. In contrast, the residence
time of dissolved silica in the ocean is about 20,000 years. This compound is readily taken up by certain
types of plankton to build their skeletons.
Respirationthe physical and chemical processes by which an organism supplies its cells and tissues with
the oxygen needed for metabolism and releases carbon dioxide formed in the energy-producing reactions.
Reversible processa process in which the change in entropy is zero. In general, after the process is
complete, the state of the system is as it was initially.
Saturationthe degree to which a solution or a gas is at equilibrium with one of its components. It is
measured in several different ways. For example, a humidity of 125% would be a supersaturation of 25%
with respect to water vapor in the air. Saturation of seawater with respect to the mineral calcite (CaCO
3
)
of 50% would mean that the seawater was 50% undersaturated with respect to calcite. If a lake water
contained exactly enough dissolved CO
2
to be in equilibrium with the atmosphere, it would have a satu-
ration of 100% with respect to CO
2
.
Sedimentary rocka rock formed from the erosion of preexisting rocks and the deposition of the erod-
ed materials as sediment. Sedimentary rocks are also formed by inorganic or biological precipitation of
minerals from natural waters.
Shortwave radiationgenerally, the region of the electromagnetic spectrumwith wavelengths shorter than
0.5 micrometers. Solar radiation has an important component of shortwave radiation of varying intensity.
Solar radiationthe electromagnetic radiation emitted by the sun. It includes energy wavelengths from
the very short ultraviolet (<0.2 micrometers) to about 3 micrometers.
Stratospherethe region of the upper atmosphere extending upward from the troposphere to about 30
kilometers above the earths surface. This region is characterized by an increase in temperature as alti-
tude increases.
Subduction zonethe juncture of two lithospheric plates where the collision of the plates results in one
plates being drawn down or overridden by another plate. This region is the sink of the crustal plates of
the earth.
Systema selected set of interactive components. An example of a simple system is an air conditioning
unit. Abiogeochemical system consists of reservoirs, processes and mechanisms, and associated fluxes
involving material transport. The global climate system is very complex and involves all the physical,
chemical, and biological interactions that control the long-term environmental conditions of the world.
Thermoclinethe depth range in the ocean where the temperature decreases rapidly with increasing
depth. The thermocline is about one kilometer thick and extends from the base of the surface layer of the
ocean at a depth of 50300 meters to a depth of about 8001,000 meters.
Trace gasa gas present in the atmosphere in a very low concentration (less than 1% of the composition of
the atmosphere). For example, methane, nitrous oxide, and carbon monoxide are considered trace gases.
66
67
Transitional phenomenona feature of a system that changes from one state to another. Such a change
may be relatively slow or more generally abrupt. In the boiling of water, the change from the state of
little water motion to that of turbulence is a transitional phenomenon.
Transpirationthe process by which water in plants is excreted through a plant membrane as water vapor.
Tropospherethe lowest level of the atmosphere, up to 813 kilometers high, within which there is a
steady drop in temperature with increasing altitude. It is the region where most cloud formations occur
and weather conditions manifest themselves.
Ultraviolet radiationthe region of the electromagnetic spectrum with wavelengths longer than 0.5
nanometers but shorter than 0.5 micrometers. Solar radiation has an important component of ultraviolet
radiation of varying intensity.
Uptakegenerally, the incorporation of a substance into a solid or liquid. For example, the invasion of
CO
2
into the ocean represents the uptake of CO
2
from the atmosphere.
Upwellingthe upward movement of water from depths of typically 50150 meters at speeds of
approximately 13 meters per day. The upwelling of water generally results from the lateral movement
of surface water. Upwelling zones in the ocean are found along the western margins of the continents, in
equatorial regions, and at high latitudes of the Southern Hemisphere.
Vascular planteither a plant with seeds that are not enclosed in a fruit or seed case, such as pine, fir,
spruce, and other cone-bearing trees or shrubs (gymnosperm), or a flowering plant that produces
encased seeds, such as oak, maple, and eucalyptus trees (angiosperm).
Volatilizationthe conversion of a substance into the gas or vapor state and its emission into the environment.
Washoutthe scavenging of particles from the atmosphere by rainfall and their subsequent deposition
on the surface of the earth.
Weatheringthe set of chemical, physical, and biological processes that lead to the disintegration of
minerals, kerogen, and rocks.
Wet depositionthe deposition on the earths surface of solid particles and dissolved chemical com-
pounds in rain.
Zooplanktonminute animal life in a body of water that generally drift passively or swim very weakly.
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