Phosphate Minerals

450 Pages·1984·16.476 MB·English

by  Jerome O. Nriagu (auth.), Dr. Jerome O. Nriagu, Professor Dr. Paul B. Moore (eds.)

Phosphate Minerals
Edited by
1. O. N riagu and P. B. Moore
With Contributions by
F. Betts, N. C. Blumenthal, D. R Bouldin, V. F. Buchwald
p. 1. Cook, R Flicoteaux, J. P. Le Geros, R Z. LeGeros
J. Lucas, P. B. Moore, G. H. Nancollas, WP. Nash, Y Nathan
J. O. Nriagu, RT. Oglesby, A. S. Posner, Y Tardy
M. B. Tomson, P. Vieillard, L. Vignona
With 83 Figures
Springer -Verlag
Berlin Heidelberg New York Tokyo 1984
Dr. JEROME O. NRIAGU
National Water Research Institute;
Burlington, Ontario L 7R 4A6, Canada
Professor Dr. PAUL B. MOORE
Department of Geophysical Sciences, University of Chicago,
Chicago, Illinois 60637, USA
ISBN-13:978-3-642-64738-6 e-ISBN-13:978-3-642-61736-2
DOl: 10.1007/978-3-642-61736-2
Library of Congress Cataloging in Publication Data. Main entry under title: Phosphate
minerals. Bibliography: p. Includes index. 1. Phosphates. I. Nriagu, Jerome O.
II. Moore, Paul B. (paul Brian), 1940- . III. Betts, F. QE389.64.P46 1983 549'.72
83-17160
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Preface
The literature on the geology, chemistry, and biochemistry of
phosphorus generally takes its mineralogy for granted. The in
cidental information on phosphate minerals given in these texts is
often obsolescent and inaccurate. The few mineralogical texts that
have dealt comprehensively with the phosphate minerals have now
become outdated, and typically present the essential information in
a manner unsuitable for nongeological readers. This volume is
intended as a ready reference for workers who require good basic
information on phosphate minerals or their synthetic equivalents.
The topics covered should appeal to geologists and geochemists,
lithologists, environmental scientists and engineers, chemists and
biochemists who have any interest in the intricate world of
phosphorus.
The hard tissues of many vertebrates and the many pathological
calcifications consist mostly of phosphate minerals. The precipita
tion of these compounds also plays a major role in the ecological
cycling of phosphorus, and occasionally even dominates the
behavior of many trace metals in many geochemical and biolog
ical systems. Indeed, many pegmatitic phosphate minerals have
acquired some notoriety because of the rarer trace metals which
they tend to accumulate. With the commercialization of phosphate
fertilizers since the early part of the 19th century, phosphate
minerals have assumed an important role in industrial chemistry
and agriculture. Clearly, the study of phosphate minerals is
important from the economic, agricultural, environmental and
(human and animal) health viewpoint.
Phosphate minerals are among the most complex and varie
gated in the entire mineral kingdom. This volume summarizes the
determinative properties of the 300 or so known minerals which
have been relatively well characterized. It reviews the current
knowledge on the nucleation and growth of phosphate minerals
and summarizes the available thermochemical data for these
compounds. The volume deals comprehensively with the physical
and chemical controls on the formation and weathering of
VI Preface
phosphate minerals in various milieu, from the igneous and meta
morphic rocks to biological systems. The recent influence of pollu
tion on the precipitation of phosphate minerals in soils and
sediments has also been highlighted.
Any success of this volume depends very much on the efforts of
our distinguished group of contributors. We are also indebted to
Springer-Verlag for invaluable editorial assistance.
Burlington, Ontario, Canada JEROME O. NRIAGU
Chicago, Illinois, U.S.A. PAUL B. MOORE
Contents
Chapter 1 Phosphate Minerals: Their Properties and General
Modes of Occurrence. J. O. NRIAGU ....... .
Chapter 2 The Nucleation and Growth of Phosphate Minerals.
G. H. NANCOLLAS. (With 9 Figures) . . . . . . . . 137
Chapter 3 Crystallochemical Aspects of the Phosphate Minerals.
P. B. MOORE. (With 6 Figures). . . . . . . . . .. 155
Chapter 4 Thermochemical Properties of Phosphates. P. VIEILLARD
and Y. TARDY. (With 1 Figure) .......... 171
Chapter 5 Phosphate Minerals in Meteorites and Lunar Rocks.
V. F. BUCHWALD ................ 199
Chapter 6 Phosphate Minerals in Terrestrial Igneous and Meta
morphic Rocks. W. P. NASH. (With 5 Figures) . . . . 215
Chapter 7 Spatial and Temporal Controls on the Formation of
Phosphate Deposits - A Review. P. J. COOK. (With
11 Figures) . . . . . . . . . . . . . . . . . . . 242
Chapter 8 The Mineralogy and Geochemistry of Phosphorites.
Y. NATHAN. . . . . . . . . . . . . . . . . . . 275
Chapter 9 Weathering of Phosphate Minerals. R. FLICOTEAUX and
J. LUCAS. (With 10 Figures). . . . . . . . . . . . 292
Chapter 10 Formation and Stability of Base Metal Phosphates in
Soils and Sediments. J. o. NRIAGU. (With 6 Figures) 318
Chapter 11 Chemistry and Structure of Precipitated Hydroxy
apatites. A. S. POSNER, N. C. BLUMENTHAL and F. BETTS.
(With 7 Figures). . . . . . . . . . . . . . . . . 330
Chapter 12 Phosphate Minerals in Human Tissues. R. Z. LEGEROS
and J. P. LEGEROS. (With 21 Figures). . . . . . . . 351
Chapter 13 Precipitation of Phosphate Minerals in Waste Water
Treatment Systems. M. B. TOMSON and L. VIGNONA.
(With 3 Figures). . . . . . . . . . . . . . . . . 386
Chapter 14 Phosphorus in the Environment. R. T. OGLESBY and
D. R. BOULDIN. (With 4 Figures) . . 400
Subject Index . 425
Author Index . 435
List of Contributors
You will find the addresses at the beginning ofthe respective contributions
Betts, F. 330 Nancollas, G. H. 137
Blumenthal, N. C. 330 Nash, W. P. 215
Bouldin, D. R. 400 Nathan, Y. 275
Buchwald, V. F. 199 Nriagu, J. O. 1, 318
Cook, P. J. 242 Oglesby, R. T. 400
Flicoteaux, R. 292 Posner, A. S. 330
LeGeros, J. P. 351 Tardy, Y. 171
LeGeros, R. Z. 351 Tomson, M. B. 386
Lucas, J. 292 Vieillard, P. 171
Moore, P. B. 155 Vignona, L. 386
Chapter 1 Phosphate Minerals:
Their Properties and General Modes of Occurrence
JEROME O. NRIAGU
Introduction
This chapter presents a review of the physical, chemical and crystallographic prop
erties of phosphate minerals, and discusses their general modes of occurrence. It
provides the necessary backdrop to the subsequent chapters which deal intensively
with the various aspects of the important group of compounds.
I have relied heavily on the Encyclopedia of Minerals (by Roberts et al., 1974)
for information on phosphate minerals published before 1973. Their mineral data
have been checked and where necessary modified in the light of more recent find
ings. For the new minerals described since 1973, I have used the New Minerals sec
tion of the American Mineralogist, Lists of New Mineral Names of Mineralogical
Magazine and the recent compilation, A Manual ofM ineral Names, by Embrey and
Fuller (1980). Other compendia consulted during the preparation of the report are
listed below.
An attempt has been made to present what is considered to be the best infor
mation available on each mineral species. I have not endeavored to reconcile the
conflicting data and opinions which certainly abound in the scientific literature. Al
so, no attempt has been made to present an exhaustive reference for each mineral;
to do so could easily have doubled the size of the chapter. For easy reference, the
minerals have been described alphabetically. Such a presentation strategy obvi
ously obscures any important crystallo-chemica1 relationships which are described
by Moore (Chap. 3 this Vol.).
Historical
Phosphate minerals have been known and prized since remote antiquity. Turquois
has been found among the remains of many ancient civilizations, including Egypt,
Mesopotamia, India and China. As early as 3,400 B.C., it was obtained from the
Sinai peninsula, Egypt, in what was probably one of the earliest hard-rock mining
operations in the world. A necklase with a turquois pendant rudely fashioned into
the form of an ibex has been found which dates to the Old Empire, about 3,500
B.C. (Kunz, 1971). Its name means Turkish and was presumably acquired because
the first supply of the mineral to Europe came from Persia by way of Turkey. The
National Water Research Institute, Box 5050, Burlington, Ontario L 7R 4A6, Canada
2 Phosphate Minerals: Their Properties and General Modes of Occurrence
most famous ancient workings of turquois were located on the south slopes of the
Ali-Mirsa-Kuh mountains near Nishapur, Iran and in the Kara Tube mountains
near Samarkand (Eichholz 1962, p 253). Ancient turquois mines are also known
in Siberia, Turkestan, Asia Minor, the Sinai Peninsula, Silesia, and Saxony in Ger
many. Numerous deposits in Arizona, California, Colorado, Nevada, New
Mexico, and Utah were opened centuries ago by the American Indians and some
are still being worked. Best known are the mines in the Cerrilos Hills, near Santa
Fe, New Mexico (Encyclopedia Britannica 968, p 415).
Turquois was especially prized in Tibet, where it was used as one of the com
monest decorative stones on all the ancient Tibetan works of art, taking a place
almost equivalent to jade in China (Laufer 19l3). The Tibetan word for it, gyu, is
indigenous, suggesting that the mineral has been known since remote times. The
se-se,
Chinese term believed by some scholars to mean turquois, has been identified
with the gem minerals of Badakshan (Laufer 19l3). Turquois was mentioned fre
quently in the official histories of the Thang, and has been mined in China since
the Yuan time (Needham 1959, p 672).
Theophrastus (ca. 4th century B.C.) referred to the blue turquois used by the
Persians in inlay work (Eichholz 1962, p 215). Bolos of Mendes (ca. 200 B.c.), who
wrote about mirabilia and on the counterfeiting of precious metals and gems, also
spoke of the famous Therminaean and Persian green turquois (Eichholz 1962, p
219). Pliny (37:18) described various kinds of turquois under the heading of
smaragdis. He described the various sources of green turquois (cal/aina) in ancient
times, and then gives the following rather convoluted account of the prospecting
and mining of this mineral (Pliny, 38:33): "It [cal/aina, green turquois] occurs in
the hinterland beyond India among the inhabitants of the Caucasus, the Hyrcani,
Sacae and Dahae. It is of exceptional size, but is porous and full of flaws. A far
purer and finer stone is found in Carmania. In both localities, however, 'callaina'
occurs amidst inaccessible icy crags, where it is seen as an eye shaped swelling
loosely adhering to the rocks, as though it had been attached to them, rather than
formed upon them. Thus tribes accustomed to riding on horseback and too lazy
to use their feet find it irksome to climb in search of the stones; and they are also
deterred by the risks. They, therefore, shoot at them from a distance with their
slings and dislodge them, moss and all. This is the article that pays their taxes, this
they acknowledge to be the most beautiful thing that can be worn on neck or fin
gers, from this they derive their wealth, this is their pride and joy as they boast of
the number that they have shot down since their childhood, an operation in which
success varies, seeing that some win fine stones with their first shot, while many
reach old age without obtaining one. Such, then, is the way in which they hunt the
'callaina'. Subsequently, the stone is shaped by the drill, being in other respects an
easy stone to deal with. The best stones have the colour of 'smaragdus', so that it
is obvious, after all, that their attractiveness is not their own. They are enhanced
by being set in gold, and no gem sets off gold so well. The finer specimens lose their
colour if they are touched by oil, unguents or even undiluted wine, whereas the less
valuable ones preserve it more steadfastly. No gemstone is more easily counter
feited by means of imitations in glass. Some authorities say that 'callainae' are
found in Arabia inside the nests of the birds known as 'melanchoryphi' or 'black
caps'."
Historical 3
The accounts left by the Medieval writers indicate that turquois has continued
to be highly sought-after as a gem and ornamental Stone in every age and culture
for nearly 80 centuries (see Kunz, 1971 for detailed discussion).
Apatite has also been used since ancient times. Bone mineral was used in the
cupellation oflead to recover the silver long before Roman times. The use of bone
ash is suggested in the following passage from Amos (2: 1), "I will not turn away
the punishment thereof, because he burned the bones of the king of Edom into
lime". The white pigment of many ancient painters consisted of ground bone ash.
The alchemists used bones and other phosphatic material, such as urine, in many
of their operations and undoubtedly synthesized a number of metal orthophosph
ates of varying degrees of purity. With the commercialization of phosphate fertil
izers during the early part of the 19th century, phosphate minerals assumed a major
role in industrial chemistry, agriculture and global economics.
Beside turquois and apatite, only six other still valid phosphate minerals were
characterized before 1800. These include lazulite, pyromorphite (in essence, lead
apatite), torbernite and vivianite. Mandarino (1977) estimates that less than 100
valid mineral species were known prior to 1800, although many more names were
used as synonyms. This implies that around 1800, the phosphate minerals consti
tuted about 6% of all the known minerals, or roughly the same fraction as today.
The historical pattern in the subsequent introduction of new phosphate minerals
(still valid) into the scientific literature is as follows:
Period New minerals reported
Pre -1800 7
1801-1820 7
1821-1840 16
1841-1860 11
1861-1880 32
1881-1900 16
1901-1910 11
1911-1920 16
1921-1930 21
1931-1940 13
1941-1950 16
1951-1960 41
1961-1970 35
1971-1980 65
1981 14
The figures show that between 1800 and 1900, the number of new phosphate
minerals reported every 20 years averaged about 20. The unusually high number
between 1861 and 1880 probably reflects the fact that determinative mineralogy at
tained the status of a scientific discipline during this period. Since 1900, the number
of new phosphate minerals reported has increased quite dramatically. Twenty
seven new minerals were reported between 1901 and 1920, 34 between 1921 and