1

Reviews in Mineralogy & Geochemistry

Vol. 61, pp. 1-5, 2006
Copyright Mineralogical Society of America

Sulfide Mineralogy and Geochemistry:

Introduction and Overview
David J. Vaughan
School of Earth, Atmospheric and Environmental Sciences
and Williamson Research Centre for Molecular Environmental Science
University of Manchester
Manchester, United Kingdom
e-mail: david.vaughan@manchester.ac.uk

BACKGROUND: WHY STUDY SULFIDES?

The metal sulfides are the raw materials for most of the world supplies of non-ferrous
metals and, therefore, can be considered the most important group of ore minerals. Although
there are several hundred known sulfide minerals, only a half dozen of them are sufficiently
abundant as to be regarded as rock-forming minerals (pyrite, pyrrhotite, galena, sphalerite,
chalcopyrite and chalcocite; see Bowles and Vaughan 2006). These mostly occur as accessory
minerals in certain major rock types, with pyrite being by far the most important volumetrically.
It is also important to note that the synthetic analogs of certain sulfide minerals are of interest
to physicists and materials scientists because of their properties (electrical, magnetic, optical)
and have found uses in various electronic or opto-electronic devices. Recently, this interest
has been directed towards the use in such devices of metal sulfide thin films and of sulfide
nanoparticles, topics touched upon in Chapter 3 but not discussed in detail in this volume (but
see, for example, Fuhs and Klenk 1998; Bernede et al. 1999; Trindade et al. 2001).
The importance of sulfide minerals in ores has long been, and continues to be, a major
reason for the interest of mineralogists and geochemists in these materials. Determining the
fundamental chemistry of sulfides is key to understanding their conditions of formation and,
hence, the geological processes by which certain ore deposits have formed. This, in turn, may
inform the strategies used in exploration for such deposits and their subsequent exploitation. In
this context, knowledge of structures, stabilities, phase relations and transformations, together
with the relevant thermodynamic and kinetic data, is critical. As with many geochemical
systems, much can also be learned from isotopic studies.
The practical contributions of mineralogists and geochemists to sulfide studies extend
beyond areas related to geological applications. The mining of sulfide ores, to satisfy ever
increasing world demand for metals, now involves extracting very large volumes of rock that
contains a few percent at most (and commonly less than one percent) of the metal being mined.
This is true of relatively low value metals such as copper; for the precious metals commonly
occurring as sulfides, or associated with them, the mineable concentrations (grades) are very
much lower. The as-mined ores therefore require extensive processing in order to produce
a concentrate with a much higher percentage content of the metal being extracted. Such
mineral processing (beneficiation) involves crushing and grinding of the ores to a very fine
grain size in order to liberate the valuable metal-bearing (sulfide) minerals which can then be
concentrated. In some cases, the metalliferous (sulfide) minerals may have specific electrical or
magnetic properties that can be exploited to enable separation and, hence, concentration. More
commonly, froth flotation is used, whereby the surfaces of particles of a particular mineral
phase are rendered water repellent by the addition of chemical reagents and hence are attracted
1529-6466/06/0061-0001$05.00

DOI: 10.2138/rmg.2006.61.1

Vaughan

to air bubbles pulsed through a mineral particle-water-reagent pulp. An understanding of the

surface chemistry and surface reactivity of sulfide minerals is central to this major industrial
process and, of course, knowledge of electrical and magnetic properties is very important in
cases where those particular properties can be utilized.
In the years since the publication of the first ever Reviews in Mineralogy volume (at
that time called MSA Short Course Notes) which was entitled Sulfide Mineralogy (Ribbe
1974), sulfides have become a focus of research interest for reasons centering on at least two
other areas in addition to their key role in ore deposit studies and mineral processing technology.
It is in these two new areas that much of the research on sulfides has been concentrated in recent
years. The first of these areas relates to the capacity of sulfides to react with natural waters and
acidify them; the resulting Acid Rock Drainage (ARD), or Acid Mine Drainage (AMD) where
the sulfides are the waste products of mining, has the capacity to damage or destroy vegetation,
fish and other aquatic life forms. These acid waters may also accelerate the dissolution of
associated minerals containing potentially toxic elements (e.g., As, Pb, Cd, Hg, etc.) and these
may, in turn, cause environmental damage. The much greater public awareness of the need to
prevent or control AMD and toxic metal pollution has led to regulation and legislation in many
parts of the world, and to the funding of research programs aimed at a greater understanding of
the factors controlling the breakdown of sulfide minerals. Amongst general references dealing
with these topics, which are all part of the emerging field of Environmental Mineralogy, are
the texts of Jambor and Blowes (1994), Vaughan and Wogelius (2000), Cotter-Howells et al.
(2000) and Jambor et al. (2003).
The second reason for even greater research interest in sulfide minerals arose initially
from the discoveries of active hydrothermal systems in the deep oceans. The presence of life
forms that have chemical rather than photosynthetic metabolisms, and that occur in association
with newly-forming sulfides, has encouraged research on the potential of sulfide surfaces
in catalyzing the reactions leading to assembling of the complex molecules needed for life
on Earth (see, for example, reviews by Vaughan and Lennie 1991; Russell and Hall 1997;
Hazen 2005). These developments have been associated with a great upsurge of interest in the
interactions between microbes and minerals, and in the role that minerals can play in biological
systems. In the rapidly growing field of geomicrobiology, metal sulfides are of major interest.
This interest is related to a variety of processes including, for example, those where bacteria
interact with sulfides as part of their metabolic activity and cause chemical changes such as
oxidation or reduction, or those in which biogenic sulfide minerals perform a specific function,
such as that of navigation in magnetotactic bacteria.
The development of research in areas such as geomicrobiology and environmental
mineralogy and geochemistry, is also leading to a greater appreciation of the role of sulfides
(particularly the iron sulfides) in the geochemical cycling of the elements at or near the surface
of the Earth. For example, the iron sulfides precipitated in the reducing environments beneath
the surface of modern sediments in many estuarine areas may play a key role in the trapping
of toxic metals and other pollutants. In our understanding of Earth Systems, geochemical
processes involving metal sulfides are an important part of the story.
Thus, interest in sulfide mineralogy and geochemistry has never been greater, given
the continuing importance of the long established applications in ore geology and mineral
technology, and the new fields of application related to geomicrobiology, the environment, and
Earth Systems.

PREVIOUS WORK: THE RELEVANT LITERATURE

The literature on sulfide mineralogy and geochemistry is spread across a very wide
range of journals and related publications. This includes not only journals of mineralogy

Introduction & Overview

and geochemistry but also of crystallography, spectroscopy, materials science, pure and
applied chemistry and physics, surface science, mineral technology and, more recently, of
biogeochemistry and the environmental sciences.
Textbooks devoted specifically to sulfide mineralogy are Ribbe (1974), Vaughan and Craig
(1978), and Kostov and Mincheeva-Stefanova (1981). All of these volumes are now out of
print, although sometimes still available through library copies. The text by Vaughan and Craig
(1978) has recently been made freely available on the internet (http://www.manchester.ac.uk/
digitallibrary/books/vaughan). As well as these books dealing with sulfide minerals in
general, Mills (1974) provides a wealth of thermodynamic data, and Shuey (1976) reviews
the electrical properties of many common sulfides. The books by Barnes (1979, 1997), Garrels
and Christ (1965) and Stanton (1972) also contain much of relevance to those interested in the
geochemical and petrological aspects of sulfide studies.
As all but a handful of the sulfide minerals are opaque to visible light, the standard
method used for initial identification (in a manner analogous to study of a petrographic
thin section) and for the characterization of textural and paragenetic relationships, is
examination in polished section using the reflected light microscope (commonly known as
ore microscopy). Here, the texts by Ramdohr (1969, 1980), Uytenbogaart and Burke (1971),
Craig and Vaughan (1994), Jambor and Vaughan (1990) and Cabri and Vaughan (1998) all
present much information on the ore microscopy and ore petrography of sulfides. Routine ore
microscopy involves qualitative observation of a range of properties, and this is often sufficient
for the trained observer to identify phases (with techniques such as X-ray powder diffraction
and electron probe microanalysis being used to provide confirmation and more detailed
characterization). Certain key properties observed qualitatively using the ore microscope can
also be measured using a suitably equipped microscope. Quantitative ore microscopy data
(reflectance, quantitative color values, indentation microhardness values) for sulfides are
provided by Criddle and Stanley (1993).

THE PRESENT TEXT: SCOPE AND CONTENT

The main objective of the present text is to provide an up-to-date review of sulfide
mineralogy and geochemistry, chiefly covering the areas previously dealt with in the books by
Ribbe (1974) and by Vaughan and Craig (1978). The emphasis is, therefore, on such topics as
crystal structure and classification, electrical and magnetic properties, spectroscopic studies,
chemical bonding, high and low temperature phase relations, thermochemistry, and stable
isotope systematics. In the context of this book, emphasis is on metal sulfides sensu stricto
where only the compounds of sulfur with one or more metals are considered. Where it is
appropriate for comparison, there is brief discussion of the selenide or telluride analogs of the
metal sulfides. When discussing crystal structures and structural relationships, the sulfosalt
minerals as well as the sulfides are considered in some detail (see Chapter 2; also for definition
of the term sulfosalt). However, in other chapters there is only limited discussion of
sulfosalts, in part because there is little information available beyond knowledge of chemical
composition and crystal structure.
Given the dramatic developments in areas of research that were virtually non-existent
at the time of the earlier reviews, major sections have been added here on sulfide mineral
surface chemistry and reactivity, formation and transformation of metal-sulfur clusters
and nanoparticles, modeling of hydrothermal precipitation, and on sulfides in biosystems.
However, it should be emphasized that the growth in the literature on certain aspects of sulfide
mineralogy over the past 20 years or so has been such that comprehensive coverage is not
possible in a single volume. Thus, the general area of sulfides in biosystems is probably
worthy of a volume in itself, and environmental sulfide geochemistry (including topics such

Vaughan

as oxidative breakdown of sulfides) is another area where far more could have been written. In
selecting areas for detailed coverage in this volume, we have been mindful of the existence of
other relatively recent review volumes, including those in the RiMG series. So, for example,
readers looking for more information on mineral-microbe interactions are referred to Banfield
and Nealson (1997), or on nanoparticles to Banfield and Navrotsky (2001). It has also been
our intention not to cover any aspects of the natural occurrence, textural or paragenetic
relationships involving sulfides, given the coverage already provided by Ramdohr (1969,
1980) and by Craig and Vaughan (1994), in particular. This is published information that,
although it may be supplemented by new observations, is likely to remain useful for a long
period and largely not be superceded by later work.
In the following chapters, the crystal structures, electrical and magnetic properties,
spectroscopic studies, chemical bonding, thermochemistry, phase relations, solution chemistry,
surface structure and chemistry, hydrothermal precipitation processes, sulfur isotope
geochemistry and geobiology of metal sulfides are reviewed. Makovicky (Chapter 2) discusses
the crystal structures and structural classification of sulfides and other chalcogenides (including
the sulfosalts) in terms of the relationships between structural units. This very comprehensive
survey, using a rather different and complementary approach to that used in previous review
volumes, shows the great diversity of sulfide structures and the wealth of materials that remain
to be characterized in detail. These materials include rare minerals, and synthetic sulfides that
may represent as yet undescribed minerals. Pearce, Pattrick and Vaughan (Chapter 3) review
the electrical and magnetic properties of sulfides, discussing the importance of this aspect
of the sulfides to any understanding of their electronic structures (chemical bonding) and to
applications ranging from geophysical prospecting and mineral extraction to geomagnetic and
palaeomagnetic studies. Rapidly developing new areas of interest discussed include studies of
the distinctive properties of sulfide nanoparticles. Wincott and Vaughan (Chapter 4) then outline
the spectroscopic methods employed to study the crystal chemistry and electronic structures of
sulfides. These range from UV-visible through infrared and Raman spectroscopies, to X-ray
emission, photoemission and absorption, and to nuclear spectroscopies. Chemical bonding
(electronic structure) in sulfides is the subject of the following chapter by Vaughan and
Rosso (Chapter 5), a topic which draws on knowledge of electrical and magnetic properties
and spectroscopic data as experimental input, as well as on a range of rapidly developing
computational methods. Attention then turns to the thermochemistry of sulfides in a chapter
by Sack and Ebel (Chapter 6) which is followed by discussion of phase equilibria at high
temperatures in the review by Fleet (Chapter 7). Sulfides in aqueous systems, with emphasis
on solution complexes and clusters, forms the subject matter of the chapter written by Rickard
and Luther (Chapter 8). Sulfide mineral surfaces are the focus of the next two chapters, both
by Rosso and Vaughan. The first of these chapters (Chapter 9) addresses characterization of the
pristine sulfide surface, its structure and chemistry; the second (Chapter 10) concerns surface
reactivity, including redox reactions, sorption phenomena, and the catalytic activity of sulfide
surfaces. Reed and Palandri (Chapter 11) show in the next chapter how much can now be
achieved in attempting to predict processes of sulfide precipitation in hydrothermal systems.
The final chapters deal with two distinctive areas of sulfide mineralogy and geochemistry. Seal
(Chapter 12) presents a comprehensive account of the theory and applications of sulfur isotope
geochemistry; sulfur isotope fractionation can provide the key to understanding the natural
processes of formation of sulfide deposits. In the final chapter, Posfai and Dunin-Borkowski
(Chapter 13) review the rapidly developing area of sulfides in biosystems, discussing aspects of
both sulfide mineral-microbe interactions and biomineralization processes involving sulfides.
It is inherent in multi-author compilations such as this volume that some relevant topics
have been given relatively little attention, or even omitted, and there is also occasional
duplication of material between chapters. In effect the reader should view each of the chapters
as a stand alone account, albeit complemented by the other chapters. It is hoped that readers

Introduction & Overview

will appreciate the perspectives offered by the authors in approaching their material from
very different standpoints. Having said this, every effort has been made to provide adequate
cross referencing between chapters. As noted above, no attempt has been made to review the
more petrological aspects of sulfide research (natural occurrence, textural and paragenetic
relationships of sulfides in rocks and ores). It had been hoped to include more discussion of
certain topics, such as the formation and transformation of metal sulfide precipitates, but in this
and a number of other areas, that will have to await a future volume. Our hope is that despite
its shortcomings, which are entirely the responsibility of the volume editor, this book will be a
fitting successor to the 1974 Sulfide Mineralogy volume, the book which launched the whole
Reviews in Mineralogy and Geochemistry series.

REFERENCES
Banfield JF, Navrotsky A (eds) (2001) Nanoparticles and the Environment. Rev Mineral Geochem, Vol. 44.
Mineralogical Society of America
Banfield JF, Nealson KH (eds) (1997) Geomicrobiology: Interactions between Microbes and Minerals. Rev
Mineral Geochem, Vol. 35. Mineralogical Society of America
Barnes HL (ed) (1979, 1997) Geochemistry of Hydrothermal Ore Deposits.(2nd and 3rd edition) WileyInterscience
Bernede JC, Pouzet J, Gourmelon E, Hadouda H (1999) Recent studies on photovoltaic thin films of binary
compounds. Synth Met 99:45-52
Bowles JFW, Vaughan DJ (2006) Oxides and Sulphides. Vol. 5A. Rock-Forming Minerals (Deer, Howie,
Zussman) Geol Soc London Publication (in press)
Cabri LJ, Vaughan DJ (1998) Modern Approaches to Ore and Environmental Mineralogy. Min Assoc Canada
Short Course, Vol. 27, 421 pp.
Cotter-Howells J, Campbell L, Batchelder M, Valsami-Jones E (eds) (2000) Environmental Mineralogy:
Microbial Interactions, Anthropogenic Influences, Contaminated Land and Waste Management. Mineral
Soc Monog 9
Craig JR, Vaughan DJ (1994) Ore Microscopy and Ore Petrography. (2nd edition) Wiley-Interscience
Criddle AJ, Stanley CJ (eds) 1993) Quantitative Data File for Ore Minerals. Chapman and Hall
Fuhs W, Klenk R (1998) Thin film solar cells. EUR 18656. World Conference on Photovoltaic Solar Energy
Conversion 1:381-386
Garrels RM, Christ CL (1965) Solutions, Minerals and Equilibria. Harper and Row
Hazen RM (ed) (2005) Genesis: Rocks, Minerals and the Geochemical Origin of Life. Elements 1:135-161
Jambor JL, Blowes DW (eds) (1994) The Environmental Geochemistry of Sulfide Minewastes. Mineral Assoc
Canada Short Course Handbook, Vol. 22
Jambor JL, Vaughan DJ (eds) (1990) Advanced Microscopic Studies of Ore Minerals. Mineral Assoc Canada
Short Course, Vol.17
Jambor JL, Blowes DW, Ritchie AIM (eds) (2003) Environmental Aspects of Minewastes. Mineral Assoc
Canada Short Course, Vol. 31
Kostov I, Mincheeva-Stefanova J (1981) Sulphide Minerals: Crystal Chemistry, Parageneses and Systematics.
Bulgarian Academy of Sciences
Mills KC (1974) Thermodynamic Data for Inorganic Sulphides, Selenides and Tellurides. Butterworth
Ramdohr P (1969, 1980) The Ore Minerals and their Intergrowths. (1st and 2nd English Editions) Pergamon
Ribbe PH (ed) (1974) Sulfide Mineralogy. Mineral Soc Am Short Course Notes. Vol. 1. Mineralogical Society
of America
Russell MJ, Hall A (1997). The emergence of life from iron monosulphide bubbles at a submarine hydrothermal
redox and pH front. J Geol Soc Lond 154:377-402
Shuey RT (1975) Semiconducting Ore Minerals. Devel in Econ Geol. No.4, Elsevier
Stanton RL (1972) Ore Petrology. McGraw Hill
Trindade T, OBrien P, Pickett NL (2001) Nanocrystalline semiconductors: synthesis properties, and
perspectives. Chem Mater 13:3843-3858
Uytenbogaart W, Burke EAJ (1971) Tables for Microscopic Identification of Ore Minerals. Elsevier
Vaughan DJ, Craig JR (1978) Mineral Chemistry of Metal Sulfides. Cambridge Univ Press, Cambridge [freely
available electronically at: http://www.manchester.ac.uk/digitallibrary/books/vaughan
Vaughan DJ, Lennie AR (1991) The iron sulphide minerals: their chemistry and role in nature. Science Progr
Edinburgh 75: 371-388
Vaughan DJ, Wogelius RA (2000) Environmental Mineralogy. Notes in Mineralogy Vol. 2. European Mineral
Union