Table Of ContentSecond Edition
The
Environmental
Chemistry of
Aluminum
Garrison Sposito, Ph.D.
Edited by
Department of Environmental Science,
Policy, and Management
University of California
Berkeley, California
| | | | LEWIS PUBLISHERS
BocaRaton London New York Washington, D.C.
LibraryofCongressCataloging-in-PublicationData
Theenvironmentalchemistryof aluminum / editedbyGarrisonSposito
—2 nd.ed.
p. cm.
Includesbibliographicalreferencesandindex.
ISBN1-56670-030-2(alk.paper)
1.Aluminum—E nvironmentalaspects. 2.Water—Pollution. 3.Soil—p ollution.
I.Sposito,Garrison, 1939-
TD427.A45E58 1995
628.5'2—dc20 95-20082
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FOR
GERALD LOCKLIN
AND
JOHN HEM
I sigh the lack ofmany a thing / sought,
And with old woes new wail my dear time’s waste:
But ifthe while I think on thee, dearfriend,
All losses are restored and sorrows end.
W.S.
PREFACE
The chemistry of aluminum in soils and natural waters has emerged as a scientific
problem of critical importance because of widespread public interest in the effects of
acidicdeposition anddeforestationpracticeson terrestrialecosystems. Acidic deposition
is perceived as responsible for major changes in forest productivity and surface water
quality over the last halfcentury in Europe, Russia, and North America. More recently,
deforestation of vast areas in Central and South America and in Southeast Asia has
exposedvery fragile soil ecosystems torapidincreases in toxicity biohazard.Environmen
tal chemists have responded to this public concern in a broad variety of laboratory and
field studies which have only substantiated the great complexity of aluminum bio
geochemistry.
The geochemistry of aluminum, like that of other common elements, is significant
environmentally because it has a direct bearing on the mobility, bioavailability, and
ecological impact of this metal. Evidence is growing that the specific toxicity effects
ofaluminum onterrestrialandaquaticorganisms arerelatedtothedetails ofitschemical
speciation. If this evidence proves to be of general validity, then the production of
innocuous chemical species will develop as amajorpathway of detoxification of alumi
num in both forested and agricultural ecosystems. An understanding of the factors that
controlthispathway willbeessential tothe managementofbiologicalresponse toacidic
deposition and deforestation practices.
This book is intended to provide a comprehensive, although fundamental, account
of the aqueous chemistry ofaluminum that is relevant to an environmental context. The
objective is to present the consensus ofexperts, noton unresolved issues at the frontier
ofresearch, buton the basic chemical phenomena involving aluminum in natural waters
and soils about which some degree of certainty can be expressed. Thus the level of
sophistication assumed is on aparwith thecontents ofastandard textbook, likeAquatic
Chemistry by W. Stumm and J. J. Morgan, but does not require expertise on particular
facetsofaluminum reactionsinaqueousmedia.Itis infactthesefacetsthat aredescribed
in the ten chapters of this book, with the hope that environmental chemists will find in
them reference material reflecting the recentchanges in arapidly developing discipline,
changes that have occasioned the need for a second edition of the book just six years
after the first.
The first three chapters discuss perhaps the most fundamental aspects of aluminum
chemistry:its quantitationinsoilsand natural waters,includingspeciationmeasurements,
and its stable chemical forms, both as a dissolved solute and as a solid phase. The
emphasisin these three chaptersis onproviding both criticalassessments ofanddefinitive
recommendationsfor laboratory methodologiesandmeasuredthermodynamicproperties
relating to aluminum species. The nextfourchapters build on this foundation to provide
details of what may be termed the polymeric chemistry of aluminum: its polynuclear
and colloidal hydrolytic species in aqueous solution, its complexes with natural organic
ligands including humic substances, and its surface reactions as both adsorptive and
adsorbent. These difficulttopics are treated firmly in thecontextofexperimentalresults,
as opposed to conceptual modeling, with transience and kinetics playing roles equal in
importance to stability and thermodynamics. Areas in which knowledge is not yet well
defined are identified throughout the discussion in these chapters as a guide to future
research. The final three chapters of the book describe the chemistry of aluminum in
natural environments: soils, surface waters, and watersheds. These chapters attempt to
integrate the results of controlled experimentation described in the first seven chapters
into pictures of aluminum solubility and speciation as they occurin nature. The problem
of spatial and temporal variability, metastability, and scale that emerge illustrate the
challengethat aqueousaluminumgeochemistrycontinuestopresent to environmentalsci
ence.
The ten chapters ofthis book can be read independently. Butkeep in mind that they
are like bands of color in the visible spectrum: each recognizably distinct while grading
into the others with overlapping subtopics and conclusions. A given chapter may be
taken,on itsprincipaltopics,tobethedefinitive statementofthis book,albeitnoattempt
has been made to suppress differing opinions that represent normal variability in the
inferences of experts concerning a difficult subject.
THE EDITOR
GarrisonSposito,Ph.D.received a B.S. degree in soils and agricultural chemistry
from the University of Arizona in 1961 and completed an M.S. degree there in soil
physics in 1963 under the direction of Duwayne M. Anderson. In September 1963 he
continued his graduate studies as a University Science Fellow on the Berkeley campus
of the University ofCalifornia. In July 1965, he received a Ph.D. degree in soil science
under the direction of Kenneth L. Babcock. He then joined Sonoma State University,
where he initiated and developed an undergraduate program in physics. He remained
in physics until 1974, when hejoined the soil science faculty of the Riverside campus
of the University of California. In 1988 he was appointed Professor of Soil Physical
Chemistry on the Berkeley campus, and in 1992 he was promoted to Professor Above-
Scale. In 1994 he accepted ajoint appointmentin Civil and Environmental Engineering
at Berkeley.
Dr. Sposito has made research contributions in the areas of: (1) water, solute, and
energy transport through porous media; ( ) adsorption, complexation, and precipitation
2
reactions in soils; (3) computermodeling of soil solution chemistry; and (4) soil organic
matter chemistry. He has published more than 220 technical journal articles, 50 book
chapters or conference papers, as well as book reviews and technical reports. He is
author of a textbook on quantum mechanics, 1970, a textbook on classical mechanics
(1976), a monograph on chemical thermodynamics applied to soil solutions (1981;
Russianedition, 1984), a monographonthe surfacechemistry ofsoils(1984), atextbook
on soil chemistry (1989; German edition, 1996); and an advanced textbook on chemical
kinetics in soils (1994).
Dr. Sposito was a NSF Summer Fellow in physics in 1971; a Senior Fulbright
Lecturer in theoretical solid-state physics in 1973; a NATO/Heinemann Senior Fellow
in soil physical chemistry in 1981; and a John Simon Guggenheim Fellow at the
University of Oxford in 1984. In 1982, Dr. Sposito was recipient of the Soil Science
Award, aresearch prize ofthe Soil Science Society ofAmerica, and in 1990hereceived
the Robert E. Horton Award from the Hydrology Section of the American Geophysical
Union for his research on mass transport through porous media. He is a Fellow of
the American Society of Agronomy, Soil Science Society of America, and American
Geophysical Union.
CONTRIBUTORS
Paul M. Bertsch Bruce S. Hemingway
Division of Biogeochemistry United States Geological Survey
University of Georgia National Center
Savannah River Ecology Laboratory Reston, VA 99092
Drawer E
Aiken, SC 29801 William H. Hendershot
Department of Natural Resource
Paul R. Bloom Sciences
Department of Soil Science Macdonald Campus
University of Minnesota McGill University
St. Paul, MN 55108 Ste-Anne-de-Bellenue
Quebec H9X 3V9
Francois Courchesne CANADA
Departement de Geographie
Universite de Montreal Philip M. Jardine
Montreal, Quebec H3C 3J7 Environmental Sciences Division
CANADA Oak Ridge National Laboratory
P.O. Box 2008
James A. Davis Oak Ridge, TN 37831-6038
United States Geological Survey
345 Middlefield Road Dean S. Jeffries
Menlo Park, CA 94025 National Water Research Institute
Burlington, Ontario L7R 4A6
Charles T. Driscoll CANADA
Department of Civil and
Environmental Engineering Willard L. Lindsay
Syracuse University Department of Soil and Crop Sciences
Syracuse, NY 13244-1190 Colorado State University
Fort Collins, CO 80523
M. Susan Erich
Department of Applied Ecology and Howard M. May
Environmental Science United States Geological Survey
University of Maine 3215 Marine Street
Orono, ME 04469 Boulder, CO 80303
Sabine Goldberg Darrell Kirk Nordstrom
United States Salinity Laboratory United States Geological Survey
450 W. Big Springs Road 3215 Marine Street
Riverside, CA 92507 Boulder, CO 80303
John Hem David R. Parker
(deceased) Department of Soil and Environmental
United States Geological Survey Sciences
345 Middlefield Road University of California
Menlo Park, CA 94025 Riverside, CA 92521
Kimberley M. Postek George F. Vance
Department of Civil and Department of Plant, Soil and Insect
Environmental Engineering Sciences
Syracuse University University of Wyoming
Syracuse, NY 13244-1190 Laramie, WY 82071-3354
Frank J. Sikora P. Mark Walthall
Environmental Research Center Department of Agronomy
Tennessee Valley Authority Louisiana State University
Muscle Shoals, AL 35660 Baton Rouge, LA 70803
Garrison Sposito Lucian W. Zelazny
Department of Environmental Science, Department of Crops and Soil
Policy, and Management Environmental Sciences
University of California Virginia Polytechnic Institute and State
Berkeley, CA 94720-3110 University
Blacksburg, VA 24061
Frank J. Stevenson
Department of Agronomy
University of Illinois
Urbana, IL 61801
