ISSN 0016-7029, Geochemistry International, 2008, Vol. 46, No. 6, pp. 565–577. © Pleiades Publishing, Ltd., 2008.

Original Russian Text © V.L. Tauson, D.N. Babkin, E.E. Lustenberg, S.V. Lipko, I.Yu. Parkhomenko, 2008, published in Geokhimiya, 2008, No. 6, pp. 615–628.

Surface Typochemistry of Hydrothermal Pyrite:

Electron Spectroscopic and Scanning Probe Microscopic Data.
I. Synthetic Pyrite
V. L. Tauson, D. N. Babkin, E. E. Lustenberg, S. V. Lipko, and I. Yu. Parkhomenko
Vinogradov Institute of Geochemistry, Siberian Branch, Russian Academy of Sciences,
ul. Favorskogo 1a, Irkutsk, 664033 Russia
e-mail: vltauson@igc.irk.ru
Received February 19, 2007

Abstract—Techniques of X-ray photoelectron and Auger electron spectroscopy, scanning probe microscopy
were used to demonstrate that the natural surface of hydrothermally synthesized pyrite, as well as vacuum frac-
tures, contain a number of sulfide-sulfur species: disulfide, monosulfide, and, more rarely, polysulfide. The nat-
ural surface of hydrothermal pyrite is chemically modified compared to the inner volume into a nonautonomous
phase film up to ~500 nm thick, which has a variable composition resembling that of pyrrhotite but with broader
variations toward FeS2. Its principal distinctive feature is the presence of a peak at ~710 eV in the XPS Fe 2p3/2
spectrum, which is often higher than the main peak of bivalent low-spin Fe(II) in the pyrite structure (707 eV).
The “basic” structure of the nonautonomous phase is a layer of variable composition Fe2+[S, S2, Sn]2–, whose
S/S2 ratio varies from ~0.5 to ~2.0, averaging at ~1.1. This layer may include admixtures of minor elements, as
follows from the appearance of a nonautonomous phase in the presence of As, which does not, however, form
an individual phase. The polymerization of S at the surface is thereby more significant. The major oxisulfide
components of this phase may be the sulfite and thiosulfate ions at a subordinate concentration of sulfate
because of the instability of coexisting sulfate and disulfide ions, which results, in the presence of oxygen, in
sulfite (thiosulfate) and sulfide ions in the nonautonomous phase. In line with XPS, scanning probe microscopic
(SPM) data show that, at a high S activity in the “pure” system, the surface of the crystals contains practically
no nanometer-sized phases and is characterized by low roughness (14–17 nm). At a low S fugacity in equilib-
rium with pyrrhotite and sphalerite, the average roughness of the surface increases to 25–65 nm, with the max-
imum height of the surface features of ~100–500 nm. This is consistent with Auger spectroscopic data, obtained
after the etching (ion milling) of the surface with Ar+, on the thickness of the nonstoichiometric surface layer.
Comparison with analogous data on other sulfides shows that crystals growing in hydrothermal environments
have surface layers up to ~500 nm thick, which are different from the main volume of the crystal in chemistry,
stoichiometry, and, possibly, also structure. This is scale of the surface heterogeneity at which the typochemis-
try of mineral surfaces may be manifested. The typochemistry of pyrite stems from the ability of the nonauto-
nomous phase to “record” the growth conditions of crystals in terms of two major factors: the purity of the sys-
tem (the occurrence of other phases, including virtual ones, i.e., potentially possible phases of admixture ele-
ments) and S fugacity (which influences the S/S2 ratio at the surface). The geochemical role of the surface
nonautonomous phase in pyrite may be very significant, particularly when minor elements are captured that are
incompatible with the pyrite structure but can be easily accommodated in the less rigid structure of the nonau-
tonomous phase.
DOI: 10.1134/S0016702908060037

INTRODUCTION ical equipment of X-ray photoelectron spectroscopy

The most dynamically developing avenues in the
chemistry of mineral surfaces are the investigation of
pristine fracture surfaces, which are obtained in an inert
gas atmosphere or under vacuum in the intermediate
(transfer) chamber of a spectrometer, and the examina-
tion of the mechanisms of oxidation, leaching, and
other analogous processes proceeding at the surfaces of
minerals during the processing and concentration of
ores. The progress achieved in these fields (particularly
in the former) over the past years was related mostly to
the transition from the application of traditional analyt-
(XPS) to the use of synchrotron radiation (XPS-SR),
which provides a higher surface sensitivity and spectral
resolution. This approach made it possible to examine
in much detail atomic transformations in the surface
layer (for example, with reference to pyrite, discussed
here) and to identify such phenomena as autofredox
reactions and polymerization of the ligand [1, 2]. At the
same time, the geochemical and genetic aspects of the
problem remained largely uncertain, because these
results did not immediately pertain to real (but not syn-
thetic, obtained under high vacuum, which is atypical

565
566 TAUSON et al.
of natural terrestrial processes) mineral surfaces.
Another methodology of the research was proposed in
[3, 4] and involved the distinguishing of the primary
(juvenile) surface and factors affecting it depending on
the conditions under which the minerals were pro-
duced, as well as studying the chemistry of the surfaces
and its variations with depth in the crystal for minerals
from ore deposits of various genetic types. Our research
was centered on a detailed justification of this
approach. In its first part (presented in this publication),
we analyze data on pyrite crystals synthesized under
hydrothermal conditions. The second part of this
research (an oncoming paper) will be devoted to natural
pyrite crystals from gold deposits of various genetic
types. We will thereby pay attention to advances along
the aforementioned “classic” lines of research concern-
ing the mechanisms of the reconstruction and stabiliza-
tion of mineral surfaces, although, as could be a priori
thought, the applicability of this information to real sit-
uations is limited. We focused our study on pyrite
because the geochemistry, morphology, and structure
of this mineral widely spread at ore deposits, as well as
its typochemistry and typomorphism, continuously
attract keen interest of many researchers in hope of
developing criteria for searches for and identification of
ore deposits and evaluating the physicochemical condi-
tions under which ore mineralization was produced at
them [5, 6]. At the same time, many aspects of the sur-
face properties of this mineral remain largely obscure.
EXPERIMENTAL AND ANALYTICAL
TECHNIQUES
Pyrite crystals were synthesized (1) in sealed optical
quality quartz glass ampoules at T = 400°C and P =
0.5 kbar [7] and (2) by the conventional technique of
hydrothermal thermal-gradient synthesis in Ti inserts at
T = 400 and 500°C and P = 0.5 and 1 kbar [8]. The
inserts or quartz glass ampoules were placed in stain-
less steel autoclaves and held for 3 days at 400 or 450°ë
to homogenize the material and then for 9 days at a tem-
perature gradient (15°ë along the outer wall of the
autoclave). The mineralizers were either pure NH4Cl
solutions or those with added HCl or Na2S and (more
rarely) 20% solution of CaCl2. The experiments ended
with the quenching of the autoclaves in running cold
water. Pyrite was synthesized in both “pure” systems,
whose starting materials contained only Fe and S, and
multicomponent systems, which contained, along with
these elements, also ZnS or As. Pyrite crystallized
together with sphalerite or sphalerite + pyrrhotite in the
former case, and no additional phases were formed in
the latter one, but the crystals contained As (a few hun-
dredths of a weight percent in the bulk of the crystal and
up to ~1 wt % in the surface layer; according to Auger
electron spectroscopy, of As L3M45M45). The single
pyrite crystals obtained in quartz ampoules were no
larger than 1 mm, and we could examine them only by
Auger spectroscopy. The crystals grown in Ti inserts
GEOCHEMISTRY INTERNATIONAL
were as large as 5 mm (along edges) and had cubic (in
the pure system) and cuboctahedral and more compli-
cated (in the systems with As) morphologies [9]. Some
of the experiments were carried out with the use of Ti
“traps” to gather the fluid for analysis and pH determi-
nation.
The surface of the synthesized crystals was analyzed
by X-ray photoelectron spectroscopy (XPS) and Auger
electron spectroscopy (AES) on LAS-3000 (Riber).
The instrument was equipped with an OPX-150 hemi-
spherical electron analyzer with a retarding potential
and Auger electron spectrometer with a cylindrical mir-
ror analyzer and energy resolution of no worse than
0.3%. Atoms at the sample surface were excited by the
radiation from an Al anode (AlKα = 1486.6 eV) at an
emission current of 20 mA and a tube voltage of 10 kV.
Vacuum in the chamber was 5 × 10–10 torr. The spectra
were calibrated on the C1s line of carbon with a binding
energy of 285 eV. The spectra were standardized using
the line Au 4f7/2at 84.0 eV. The spectra were processed
by a specialized program with regard for the nonlinear
background and the mixed Lorentz-Gaussian shapes of
the peaks. This made it possible to subtract overlapping
peaks and to obtain exact energy values (within ±0.1 eV),
FWHM parameter (bull peak width at its half-maxi-
mum height), and areas beneath the peaks, which were
used to calculate the atomic concentrations of elements
and their speciation (in the presence of chemical shifts)
accurate to ±10%. The surface of the samples was ion
milled with a beam of Ar+ ions with an energy of 2 keV
and an emission current of 20 mA. For this purpose, Ar
was pumped into the analytical chamber to a pressure
of 2 × 10–5 torr.
The Auger spectra were registered in the differential
form dN(E)/dE at a primary beam energy of 2.5 keV
and a modulation voltage of 2.3 V. To run the analytical
profiles, i.e., to analyze the crystal composition for a
certain depth from its surface, we etched the crystal at
a rate of approximately 0.1 nm/s by a beam of Ar ions.
The Auger spectra were successively registered at spec-
ified time intervals of etching (5–10 min). We applied
conventional techniques for the processing of spectra
in order to obtain qualitative and quantitative informa-
tion on the composition of the surface [10]; the atomic
concentrations of elements were calculated from the
intensities of Auger peaks with the use of element sen-
sitivity coefficients. The peaks were localized accurate
to ±0.1 eV, and elemental compositions were analyzed
accurate to ±10% rel.
The surface topography of the crystals was exam-
ined on an SMM-2000 (Russia) scanning probe in the
modes of scanning tunneling microscopy (STM) and
atomic force microscopy (AFM) in contact mode. In
the absence of vacuum at solid conducting samples, the
resolution of STM amounted to a few tenths of a
nanometer. The software of the microscope makes it
possible to analyze the roughness and other character-
Vol. 46 No. 6 2008
 SURFACE TYPOCHEMISTRY OF HYDROTHERMAL PYRITE 567

istics of surfaces and determine the height and shapes Table 1. Energy of the S 2p3/2 binding of S particles in the
of nanometer-sized features on them. structures of pyrite and some other compounds
Crystal matrix
S species Binding energy, eV
IDENTIFICATION OF S AND Fe SPECIATION or compound
ON THE SURFACE OF PYRITE CRYSTALS S2– FeS2 161.4–161.8
We used a traditional radiation source to excite XPS S2– (sur.)* FeS2 161.2
spectra and thus failed to identify fine features of the 2–
surface S and Fe speciation (compare with [1, 11]). S 2 (sur.)* FeS2 162.0
However, high-resolution data led us to propose a 2–
model for the convolution of the spectra in situations S 2 (bulk)* FeS2 162.7
allowed by the resolution of the peaks. For example, if 2–
S2 FeS2 162.3–162.5
the difference between the “bulk” and “surface” sulfide
and disulfide ions (of the order of a few tens of an eV) 2–
S n (n > 2) FeS2 163.2–163.7
is comparable with the resolution of the peaks of the
spin-orbital S 2p doublet, then the sulfide and disulfide S0 (S8) α-S 164.0–164.2
ions can be distinguished even if traditional methods 2– Na and K sulfites
are applied, because the chemical shift then amounts to SO 3 165.6–167.5
and hydrosulfites
1 eV, and modern software taking into account the 2– Na thiosulfate and thio- 161.7–162.9 (SII)**
actual shapes of the peaks and overlaps makes it possi- S2 O3
sulfate pentahydrite 167.6–168.6 (SVI)
ble to resolve them. Table 1 presents binding energy val-
ues for the component 3/2 of the S2p3/2–1/2 doublet 2–
S2 O y Na and K sulfoxides 163.8–169.0
(mostly based on data on pyrite; in the absence of infor- (y = 5÷8)
mation on this mineral, we utilized data on correspond-
2–
ing chemical compounds). Analogous data on Fe 2p3/2 SO 4 Fe2+ and Fe3+ sulfates 168.7–169.1
are reported in Table 2. In the analysis, we used materi-
als from [1, 2, 11–20] and sources referred to therein. If * (sur.) and (bulk) mean purely surface (atoms in the first layer) and
“bulk” (deeper layers) states, respectively (XPS-SR data);
the volume of the data was sufficient (n ≥ ~10), we ** S in two oxidation states (formally, S2– and S6+)
selected average values, otherwise intervals and expert
estimates were utilized. The data listed in Tables 1 and 2
provide a rough idea on the distribution of Fe and S on Table 2. Position of the Fe 2p3/2 peak for various Fe2+ and
the surface of pyrite, and this distribution may be char- Fe3+ compounds
acterized as follows:
Range of values, Most probable value,
(1) bivalent “pyrite” Fe (bulk, as it is referred to in Compound
eV eV
2–
[1]), i.e., that is bound to the S 2 anion in the same FeS2 706.5–707.6 707.0
manner as in the pyrite structure, makes the predomi- FeS 706.8–713.6 710.0
nant (in terms of intensity) contribution to the XPS
peak of Fe 2p3/2 and has a bond energy of
707 eV; this FeO 709.1–710.7 709.8
peak may be correlated with the S 2p doublet, which FeCO3 710.2–710.5 710.5
2– FeSO4 710.8–713.6 711.0
corresponds to the S 2 , dianion with a binding energy
Fe3O4 707.9–711.4 709.8
of the most intense peak 2p3/2
162.5 eV;
Fe2O3 710.4–711.8 711.0
(2) bivalent “nonpyrite” Fe, which can be related to
FeOOH 710.2–711.8 711.1
the presence of Fe2+ sulfide, oxide, or carbonate in the
absence of the sulfate ion on the surface; the position of Fe2(SO4)3 713.1–713.3 713.2
the Fe 2p3/2 peak is in this case at
710 eV, and its inten-
sity should correlate with either the line of oxygen (if
this is oxide or carbonate) or the sulfide sulfur peak (5) an intermediate S oxidation state, which is char-
(S 2p3/2
161.5 eV, if this is monosulfide); acterized by peaks S 2p3/2 within the range of 166
(sulfite) to 169 eV (salts of higher sulfoxide anions).
(3) trivalent Fe, which is characterized by the posi-
tion of the peak Fe 2p3/2 at
711 eV, if it is not sulfate
but oxide or oxi-hydroxide; the peak of the Fe–O com- RESULTS
ponents on the pyrite surface in contact with air has the
same position [20]; Auger Spectroscopy
(4) sulfate of trivalent Fe, which is characterized by Based on the analysis of differential Auger spectra
the greatest chemical shift for both Fe and S, the peak of pyrite crystals obtained at 450°ë, 1 kbar in NH4Cl
Fe 2p3/2 is displaced to 713 eV and the peak S 2p3/2 solutions, we have arrived at the conclusion [4] that the
shifts toward 169 eV. surface of hydrothermal and metasomatic pyrite is oxi-

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568 TAUSON et al.

Table 3. Data obtained on hydrothermally synthesized pyrite crystals with the use of Auger electron spectroscopy with the
ion milling of the surface with Ar+
Conditions of synthesis Depth of the Composition of surface
Exp. no.
T, °C P, kbar Solution composition layer, nm* (S/Fe)at O, at %
1 450 1 20% CaCl2 120 1.0–1.1 6–10
2** 450 1 20% NH4Cl 30–240 1.3–1.9 2–8
3 400 0.5 10% NH4Cl 90–240 1.0–1.5 0–6
4 400 0.5 same 60–240 1.0–1.7 5–7
5 400 0.5 " 60–360 1.1–1.9 0–8
6** 400 1 9% NH4Cl + 1% HCl 30–360 1.0–2.0 0–5
7*** 400 1 10% NH4Cl 120 0.5–0.6 7–15
Note: experiments 3–5 were conducted in quartz ampoules, and the others were carried out in Ti inserts;
* approximate value calculated from the average etching rate [3];
** in association with S0;
*** in association with pyrrhotite and sphalerite.

dized to a depth of approximately 0.1–0.5 µm. The
original (juvenile) surface of a crystal growing under
these conditions without adsorbed gases may contain
about 10–20 at % oxygen in the oxide–sulfide layer.
These measurements were conducted on samples that
were held in air for a fairly long time after the experi-
ments, and this could modify the composition of their
surface layers [19, 20]. Because of this, we undertook
an analogous study of fresh samples, which were ana-
lyzed within as brief as possible time span after their
synthesis and which were stored in an Ar atmosphere in
sealed glass ampoules during this time. The results are
presented in Table 3 and reveal a degree of oxidation of
the fresh surface of hydrothermal pyrite (synthesized at
400–450°ë in chloride solutions in quartz or Ti contain-
ers) even lower than the degrees of oxidation reported
in [4]. The oxygen concentrations in the surface layers
of the crystals are at a minimum (0–8 at %) in the pres-
ence of free sulfur (S0) and are slightly higher (up to
15 at %) in association with pyrrhotite, i.e., at the low-
est possible sulfur activity for pyrite at a given temper-
ature. In general, we detected a decrease in the oxygen
concentration with depth in the crystals (in the course
of its etching). This decrease is not always monotonous,
most probably because of the heterogeneity of the sur-
face itself and because it is hard to successively etch and
conduct analysis at exactly the same points [21]. The
thickness of the oxygen-bearing layer of the crystal is
~200–400 nm, according to the earlier data [4]. It is par-
ticularly interesting to examine the stoichiometry of the
surface layer [22, 23]. Table 3 shows the S/Fe atomic
proportions, which do not reach the pyrite stoichiome-
try even with regard for (O, Cl) anionic admixtures in
the surface layer but assume intermediate values
between 1 and 2 (i.e., FeS and FeS2). Values close to 2
are characteristic of crystals obtained in the presence of
excess S, when S0 occurred as an individual phase. The
general tendency is an increase in the S/Fe ratio with
depth in the crystal, and the non-stoichiometry occurs
within a layer ~300 nm thick. Our data indicate that the
juvenile surface of hydrothermal pyrite can contain sul-
fide sulfur in two modes: as S2– and S– (the formal S
valence in the disulfide ion). This observation is impor-
tant for the further analysis of the X-ray photoelectron
spectra.
XPS
Table 4 reports the conditions under which the crys-
tals were synthesized and the results obtained by ana-
lyzing their spectra. For brevity’s sake, the table does
not show some less important details, for example, the
characteristics of the less intense component 2p1/2 of the
S 2P doublet and the proportions of the Lorentz and
Gauss functions in the deconvolution of the peaks. Note
that the shapes of the peaks were approximated by a
mixed Lorentzian–Gaussian function in variable pro-
portions. The results reported in Table 4 will be dis-
cussed below, and here we will consider only the most
topical problems related to the peaks. In order to eluci-
date the situation, we will compare all obtained data
and the results of crystal etching. It should be, however,
borne in mind that etching notably differs in XPS and
Auger spectroscopy. In the former case, Ar+ ions bom-
bard the whole surface of the sample, which is fairly
uneven and rough, because it consists of surfaces of dis-
crete, randomly oriented crystals. Because of this, the
etching rate in this situation is practically unknown:
randomly oriented crystals are ion-milled at different
rates, and it is hard to expect any clear-cut correlations.
In our experiments, etching was carried out for 0.5 and
1 h, and its effect was pronounced the most conspicu-
ously in a decrease of the concentrations in the surface
of oxide sulfur species: they decreased to value compa-

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 SURFACE TYPOCHEMISTRY OF HYDROTHERMAL PYRITE 569

Table 4. XPS data on synthetic pyrite

Conditions of synthesis XPS data***
Exp.
P, Solution com- Fe 2p3/2 S 2p3/2
no. T, °C Phases**
kbar position* E, eV F, eV Rel. peak at % E, eV F, eV Rel. peak at %
7 400 1 10% NH4Cl Py, Po, Sp 707.2 2.1 FeII–S2 3 161.0 6.9 S 51
(20.6; –8.0) 711.0 4.0 FeII–S (np) 68 163.0 4.8 S2 39
713.0 4.0 FeIII–SO4 29 168.0 5.0 SO4 10
8 400 1 same Py, Sp 708.0 2.5 FeII–S2 30 161.0 3.0 S 28
(1.9; –6.9) 710.0 3.0 FeII-S (np) 42 163.0 4.8 S2 51
712.5 2.5 FeIII–SO4 28 168.0 5.0 SO4 21
9 400 0.5 " Py, S0 706.0 4.0 FeII–S2 76 162.0 1.6 S (in S2O3) 34
(–2.4) 709.1 3.3 FeII–S (np) 18 163.5 3.1 S2 + S0(Sn?) 34
712.2 2.5 FeIII–S2O3 6 167.0 5.0 S2O3 32
etching for 1 h
706.0 4.0 FeII–S2 91 161.5 3.0 S 42
710.0 2.5 FeII–S (np) 9 163.0 4.0 S2 50
167.1 4.9 S2O3 8
10 400 0.5 " Py 706.0 4.0 FeII–S2 80 161.0 3.0 S 49
709.7 3.1 FeII–S (np) 16 162.5 2.7 S2 48
713.0 2.5 FeIII–SO4 4 167.5 2.0 SO4 3
etching for 1 h
706.0 5.5 FeII–S2 95 161.0 3.0 S 38
711.0 2.6 FeII–S (np) 5 163.0 4.0 S2 60
167.5 2.0 SO4 2
11 450 1 " (0.9) Py 706.8 4.0 FeII–S2 100 161.6 3.5 S 56
163.0 4.1 S2 35
166.0 3.0 SO3 9
etching for 0.5 h
706.0 4.0 FeII–S2 71 161.6 3.0 S 45
712.0 7.0 FeIII–SO3 29 163.4 3.1 Sn 37
166.0 4.0 SO3 18
12 450 1 9% NH4Cl Py (As) 706.7 5.2 FeII–S2 65 160.8 5.0 S 67
+ 1% Na2S 710.1 4.6 FeII–S (np) 35 162.3 3.3 S2 33
(8.2)
etching for 0.5 h
706.8 3.9 FeII–S2 56 162.0 3.1 S 55
710.4 6.0 FeII–S (np) 44 163.4 2.9 Sn 29
166.0 3.0 SO3 16
13 450 1 9% NH4Cl Py, S0 706.8 4.5 FeII–S2 100 162.5 2.5 S2 61
+ 1% Na2S 164.3 2.5 S0 26
(7.2) 166.0 3.0 SO3 9
168.0 2.0 SO4 4
etching for 0.5 h
706.0 4.0 FeII–S2 90 160.8 2.5 S 47
710.1 3.0 FeII–S (np) 10 162.3 3.2 S2 51
166.0 2.1 SO3 2
14 450 1 10% NH4Cl Py (As) 706.1 4.0 FeII–S2 28 161.5 2.8 S 40
(1.0) 709.3 5.0 FeII–S (np) 49 163.5 2.6 Sn 52
711.0 4.0 FeII–S2O3 23 167.0 2.0 S2O3 8
etching for 0.5 h
707.0 5.0 FeII–S2 48 161.0 2.1 S 38
710.0 5.0 FeII–S (np) 30 163.3 2.4 Sn 49
712.0 7.0 FeIII–S2O3 22 167.0 2.0 S2O3 13

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570 TAUSON et al.

Table 4. (Contd.)
Conditions of synthesis XPS data***
Exp.
P, Solution com- Fe 2p3/2 S 2p3/2
no. T, °C Phases**
kbar position* E, eV F, eV Rel. peak at % E, eV F, eV Rel. peak at %
15 450 1 10% NH4Cl Py (As) 706.1 3.5 FeII–S2 32 161.3 2.3 S 22
(1.2) 709.0 3.5 FeII–S (np) 31 163.0 2.2 S2 32
712.0 7.0 FeIII–S2O3 37 167.5 5.0 S2O3 37
170.0 2.0 SO4 9
etching for 0.5 h
706.6 3.9 FeII–S2 44 161.0 2.5 S 49
710.5 4.0 FeII–S (np) 56 163.0 2.7 S2 41
167.0 2.0 S2O3 10
16 450 1 20% CaCl2 Py (As) Poor resolution of the spectrum 161.0 2.6 S 50
(0.9) 163.3 3.0 Sn 44
167.0 2.0 S2O3 6
etching for 0.5 h
706.5 3.8 FeII–S2 48 160.5 3.0 S 55
711.0 7.0 FeII–S (np) 52 162.5 3.0 S2 37
166.0 2.0 SO3 8
* numerals in parentheses show the pH of the trapped solution;
** synthesized phases: Py—pyrite; Py(As)—As-bearing pyrite (<~0.1 wt % As); Po—pyrrhotite; S0—elementary sulfur;
Sp—sphalerite (numerals in parentheses show mol % FeS in sphalerite and the corresponding ( log f S ), bar, value);
2

*** E—binding energy, F—bull width at half maximum of peak height, see text to the normalization of the peaks. In calculating at %, the
total of all species of the element was assumed to be equal to 100%.

rable with the AES data during 1-h etching for a layer
at a depth of ~100–200 nm (Table 4, experiments 9, 10).
Etching for 0.5 h is less efficient and does not always
reveal a decrease in the concentrations of oxide sulfur
species. Note that, according to the AES data, we
describe the spectrum of reduced sulfur with two 2p3/2–1/2
doublets, which are provisionally ascribed to mono-
and disulfide sulfur (polysulfide in some cases). This
approach seems to be somewhat artificial but is war-
ranted by the fact that the spectra (if described by a sin-
gle doublet with a 2p3/2 leading line in the vicinity of
162 eV) occur to be shifted toward either S2– (~161) or
2–
S 2 (~163 eV). Because of this, the only way out was
to assume that the surface always contained two sulfur
species in variable proportions, which was also con-
firmed by AES data (Table 3). However, their quantita-
tive proportions should be evaluated very cautiously,
although such data are presented in the last column of
Table 4. In principle, etching should decrease the S/S2
ratio (as in Table 4, we do not specify here the charges
of the species). This is actually the case (experiments
10, 11, and 12), although the opposite examples were
also encountered (experiments 15, 16). In some situa-
tions, particularly in the presence of As, a peak appears
whose binding energy is close to that of polysulfides
(Table 1). If S0 is present at the surface, this can be
explained by the closeness of the corresponding peak to
164 eV (experiments 9, 13). However, in its absence,
these could actually be polysulfide ions. In this context
it is pertinent to mention experiment 14, in which a high
concentration of the polysulfide ion Sn (n > 2) also
remained after etching. It could have been explained by
the effect of As on the bond energy of S in the surface,
but, according to [2], the 2p3/2 peak in arsenopyrite is
shifted for approximately 0.2 eV toward lower (but not
higher) energy values compared to the analogous S peak
in the disulfide ion of pyrite, a phenomenon reportedly
explained by the slightly lower electron density at the
S atom (because of the differences in the bond lengths).
Concerning the proportion of oxidized sulfur species, it
is pertinent to mention that it is fairly difficult to distin-
guish between the sulfite and thiosulfate and between
the sulfate and thiosulfate ions based on the binding
2–
energy in the presence of S 2 and S2–, and this can be
done only with regard for data on the state of Fe. We
usually admitted the presence of sulfate when a Fe 2p3/2
peak appeared near 713 eV (it corresponded to trivalent
Fe) (Table 2): this provides evidence for the maximum
degree of oxidation, which logically should correspond
to the maximum oxidation of the S species, i.e., the
occurrence of sulfate. It usually corresponds to the peak
S 2p3/2 at 168 eV, which is slightly lower than in Table 1.
It should be borne in mind that these data pertain to the
“bulk” material, and binding energy values are lower in
the surface (for example, by 0.5−0.7 eV for the disul-
fide ion of pyrite; Table 1). We believe that the peak at

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 SURFACE TYPOCHEMISTRY OF HYDROTHERMAL PYRITE 571

Table 5. Fe fraction and the total fraction of oxidized S species on the surface of pyrite crystals synthesized in various systems
Py in multiphase Py in the system Py in the “pure” “Pure” Py in association
Element
systems with As system with S0
Fraction of Fe(np) 0.42–0.68 0.3–0.49 0–0.16 0–0.18
Fraction of oxidized 0.1–0.21 0.06–0.46 0.03–0.18 0.13–0.32
S species

166 eV is related to the sulfite ion and explain the inter-
mediate cases by the presence of thiosulfate. Recall that
S is contained in the thiosulfate ion in two chemical
states: with formal valences of +6 and –2. Because of
this, if the presence of thiosulfate is admitted, its contri-
bution to the intensity of the peak of S2– should be taken
into account proceeding from the approximately equal
intensities of peaks for both valence modes of S in thio-
sulfate [24] (see also Table 6, experiment 9).
The interpretation of Fe peaks is a fairly compli-
cated task, and here we adhere in this context to the ide-
ology described in [20], whose authors approximated
the Fe 2p3/2 spectrum by a small number of explicit
peaks. Another approach was employed in [1], in which
the high-energy “tail” of the 2p3/2 peak was described
by a series of virtual, i.e., not resolved, multiplet peaks
related to various spin states of the Fe2+ and Fe3+ ions.
The major peak at 707 eV (~70% of the whole signal)
was attributed to Fe2+ of “bulk” (i.e., completely coor-
dinated, as in the crystal volume) sites of Fe atoms in a
low-spin state in pyrite. Our data indicate that the inter-
pretation [1] should be invalidated for naturally occur-
ring surfaces of pyrite crystals (but not vacuum frac-
tures), because all data indicate that the multiplets have
low intensities, whereas the additional peaks appearing
in our samples (particularly at ~710 eV) have intensi-
ties either comparable with or (often) even strongly
exceeding that of the peak at 707 eV. Note that an anal-
ogous peak at 709.6 eV was described in [20] as peak 2
for the fresh surface of pyrite and was interpreted fairly
uncertainly: as corresponding to some surface defects
of unknown structure. However, its intensity accounted
for as little as 19% of the major peak at 707 eV, whereas
this peak often prevails in our spectra (experiments 7, 8,
14). Moreover, it often appears in the absence of any
traces of oxide species and oxygen on the surface (par-
ticularly during ion milling), i.e., obviously is not
related to FeO (Table 2). Because the fraction of Fe cor-
responding to this peak is at a minimum in pyrite in the
“pure” system and at a maximum in the multiphase sys-
tem (Table 5), it is reasonable to think that the peak at
~710 eV belongs to Fe2+ of a nonautonomous surface
phase. The possibility of the origin of nonautonomous
phases and their composition were discussed in [3] with
reference to natural pyrite. In fact, the occurrence of a
nonstoichiometric layer on the surface of pyrite crystals
with two modes of S occurrence (mono- and disulfide)
definitely points to the existence of a certain nonauton-
omous phase of variable composition, which is similar
to pyrrhotite but with broader compositional variations
toward FeS2. According to the data of Table 5, the frac-
tion of Fe in the nonautonomous phase in the Fe–Zn–S
system is 42–68%, i.e., is almost as high as in the sys-
tems with As (30–49%), although no individual As
phases appear in them; finally, this fraction in the
“pure” systems is insignificant (0–18%). It shows no
pervasive correlation with the fraction of oxidized S
species in the surface layer (Table 5) and with possible
crystallization in acidic (pH 0.9–1.2) or weakly alka-
line (pH 7.2–8.2) solutions. Neither shows it an unam-
biguous relation to the S/S2 ratio, although (at equal
other experimental conditions) both of these values
markedly decrease with increasing S activity in the sys-
tem, as can be clearly seen in Fig. 1 and Table 6. Com-
paring Figs. 1a with 1c and 1b with 1d, one can see how
much are the differences between the S 2p doublets and
the corresponding Fe 2p3/2 spectra in our experiments
with different S activity. The differences in fs2 are about
one order of magnitude at the complete variation for the
pyrite stability field at this temperature encompassing
almost six orders of magnitude. However, the contribu-
tions of monosulfide S and Fe of the nonautonomous
phase (which is denoted FeII-S(np) in Table 4 to
emphasize its relation to the “pyrrhotite” mode of Fe
occurrence) to the corresponding spectra are much
higher at a low S fugacity, when pyrrhotite appears in
the system. This is fully consistent with our idea that
the nonautonomous phase on the pyrite surface resem-
bles pyrrhotite. Conceivably, the composition of the
nonautonomous phase at a high S activity enriches in
sulfoxide anions (sulfite and thiosulfate ions) and,
sometimes, in polysulfide ions (Tables 4 and 6). Etch-
ing materials indicate that the S/S2 ratios may thereby
remain high enough (experiments 9, 13). Recall how-
Table 6. Fraction of nonautonomous Fe phase and the mono-
sulfide/disulfide ion ratio on the surface depending on S fugac-
ity in the experiments at 400°C in 10% NH4Cl solution
Exp. no. Fe(np)/ ∑ Fe S/S2 – log f S2 , bar
7 0.68 1.31 8.0
8 0.42 0.55 6.9
9 0.18 0.02* 2.4
* the monosulfide concentration was determined with the deduc-
tion of S2– from the composition of the thiosulfate ion.

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572 TAUSON et al.

Intensity (normalized)
1.1
1.0 experiment (b)
0.9 sum of components (‡)
0.8 deconvolution
0.7
0.6
0.5
0.4
0.3
0.2
0.1
0
1.1
1.0 (c) (d)
0.9
0.8
0.7
0.6
0.5
0.4
0.3
0.2
0.1
0
175 170 165 160 155 720 715 710 705 700
Binding energy, eV

Fig. 1. XPS S 2p and Fe 2p3/2 spectra for pyrite crystals in experiments (a, b) 8 and (c, d) 7 (Table 4). As the sulfur fugacity decreases
and pyrrhotite appears, the S/S2 ratio increases and the FeII-S(np) peak at ~710 eV becomes predominant in the Fe 2p3/2 spectrum.

ever that the procedure used to obtain these values was
not faultless, and this part of the problem calls for fur-
ther investigation on high-resolution XPS-SR equip-
ment. Another possible reason for the absence of a
clearly pronounced dependence between the Fe con-
centration of the nonautonomous phase and the S/S2
ratio is the higher surface sensitivity of the Fe 2p spec-
trum compared to that of S 2p [2]. In the former case,
photoelectrons come from an almost two times lower
number of surface layers. The appearance of a rela-
tively low concentration of a nonautonomous Fe phase
in experiment 13 as a result of etching was associated
with the nearly complete removal of oxidized S species
(SO3 and SO4) from the surface. In another “pure” sys-
tem without excess S (experiment 11), etching resulted
in the appearance of Fe3+, which was likely accompa-
nied with the polymerization of S and an increase in the
sulfite ion concentration (Fig. 2). Finally, the results of
experiment 12 demonstrate that the concentration of
FeII–S(np) in the presence of As can be high even in the
absolute absence of sulfoxide anions, and etching did
not decrease the concentration of this mode of Fe
occurrence and resulted (as in the previous case) only
in S polymerization and the appearance of the sulfite
ion (Table 4, Fig. 3). Hence, etching of the pure surface
can bring about the formation of trivalent Fe, which
does not change its valence in the presence of As and is
accommodated in the nonautonomous phase.
SPM
Scanning probe microscopy was applied to visualize
the nonautonomous phases and examine their morphol-
ogy and size characteristics. The surface of the exam-
ined crystals was almost not treated: we only carefully
purified it on a paper filter soaked in ethanol. We exam-
ined three types of samples: “pure” pyrite (Table 4,
experiment 11), pyrite from the multiphase system
whose surface was almost completely covered with a
nonautonomous phase (Figs. 1c, 1d, experiment 7), and
pyrite synthesized in the system with a single solid
phase but in the presence of As (experiment 14). We
obtained five scans for each of these samples various
magnifications. Figure 4 shows three-dimensional
AFM images in the contact mode, which display amaz-
ingly significant differences between the morphologies of
the surfaces. While the surface of “pure” pyrite contains
only single submicrometer-sized inclusions (Fig. 4a), a
well-developed nanometer-sized structure of the non-
autonomous phase was observed in the Fe–Zn–S sys-
tem (Fig. 4b), and an analogous structure, but at a
smaller scale, is also pronounced in the system with As
(Fig. 4c; note that the scale of the scan is 2.5 times
lower than that in Fig. 4b). Moreover, in the system
with As, the surface included areas not occupied by the
nonautonomous phase. The boundary of one of these
domains is shown in Fig. 5 in tunnel mode. The images
were analyzed for a number of parameters, and the
most indicative of these were the maximum height of
the “topographic” features and the roughness of the sur-

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 SURFACE TYPOCHEMISTRY OF HYDROTHERMAL PYRITE 573

Intensity (normalized)
1.1 (b)
1.0 experiment
(‡)
0.9 sum of components
0.8 deconvolution
0.7
0.6
0.5
0.4
0.3
0.2
0.1
0
1.1
1.0 (c) (d)
0.9
0.8
0.7
0.6
0.5
0.4
0.3
0.2
0.1
0
175 170 165 160 155 720 715 710 705 700
Binding energy, eV

Fig. 2. XPS S 2p and Fe 2p3/2 spectra for pyrite crystals in experiment 11: (a, b) original crystals, (c, d) after ion milling with Ar+
for 0.5 h. It is worth noting the absence of the FeII-S(np) peak at ~710 eV for this “pure” system. Ion milling resulted in the appear-
2– 2–
ance of a wide FeIII peak, an increase in SO 3 , and the appearance of S n .

Intensity (normalized)
1.1 (b)
1.0 experiment (‡)
0.9 sum of components
0.8 deconvolution
0.7
0.6
0.5
0.4
0.3
0.2
0.1
0
1.1
1.0 (c) (d)
0.9
0.8
0.7
0.6
0.5
0.4
0.3
0.2
0.1
0
175 170 165 160 155 720 715 710 705 700
Binding energy, eV

Fig. 3. XPS S 2p and Fe 2p3/2 spectra for pyrite crystals in experiment 12. The peak FeII-S(np) at ~710 eV appears in the presence
of As in the system and the absence of sulfoxide anions. The ion milling of the surface induced the appearance of the sulfite ion and
polymerization of sulfur.

GEOCHEMISTRY INTERNATIONAL Vol. 46 No. 6 2008

574 TAUSON et al.

(a) (‡)

Z, µm
1.031
0
3.838
0

Y, µ µm
m X,
3.838 0

(b)
Z, nm
456.4 (b) Z, nm
0 95.52
5.098 0
0 0

Y, µ µm
m X,

m
X, µ
5.098 0

(c)
Z, nm
195.4
0
1.912
0
Y, µm
µm X,
1.912 0
Fig. 4. Three-dimensional atomic force microscopic images
of the surface of pyrite crystals: (a) experiment 11 (Table 4),
“pure” pyrite; (b) experiment 7, pyrite from the multiphase
system; (c) experiment 14, pyrite with an As admixture. The
scans in Figs. 4b and 4c show the nanometer-sized granular
structure of the nonautonomous phase with various grain
sizes.
face, which was applied in the format of the Mean Area
Roughness over the scan field. The latter was 14–17 nm
for pure pyrite and ranged from 14 to 50 nm for the sys-
tem with As and from 25 to 65 nm for pyrite in the mul-
tiphase system. The maximum height of the features on
the surface with nonautonomous phases ranged from
~100 to ~500 nm, which is consistent with the afore-
mentioned AES data on the thickness of the nonstoichi-
ometric layer that consisted of the nonautonomous
phase.
0
Y, µm 2.559
2.559
Fig. 5. (a) Two- and (b) three-dimensional scanning tunnel-
ing microscopic images of an area of the nonautonomous
phase on the surface of a crystal from experiment 14.
DISCUSSION
The two major mechanisms commonly discussed in
various variants for the relaxation and reconstruction of
the surface of pyrite in application to the ultrapure sur-
face of a vacuum fracture are as follows: an auto-redox
reaction and the polymerization of the ligand. Both of
these variants have to explain the experimentally estab-
lished fact of the presence of three modes of S occur-
2–
rence on the pyrite surface: the S 2 , disulfide ion, the
2–
S2– monosulfides ion, and the S n (n > 2) polysulfide
ion. Their proportions in the vacuum fracture of a pyrite
crystal are 85 : 15 : 5 [25]. It is thought that the latter
two are produced due to the instability of the disulfide
ion because of a mechanical effect (fracturing and
crushing [26], etc.), which resulted in the breaking of
the S–S bond and the origin of the S– ion-radical. The
further scenarios may be different. One of the transfor-
mation means does not affect Fe and implies the com-
bination of two radicals S– + S– = S2– + S0 [1, 27] or their
2– 2–
interaction with the disulfide ion 2S– + S 2 = S2– + S 3
[2]. The formation of elementary S should likely be
viewed as the limiting case of polymerization. Another
scenario assumes the oxidation of bivalent Fe: S– + Fe2+ =

GEOCHEMISTRY INTERNATIONAL Vol. 46 No. 6 2008

 SURFACE TYPOCHEMISTRY OF HYDROTHERMAL PYRITE
S2– + Fe3+ [2]. The second mechanism implies the insta-
bility of the disulfide ion itself, which is “dispropor-
2– 2–
tionated” according to the reaction 2S 2 = S 3 + S2–
[25]. It was demonstrated in [2] that the surface of
pyrite crystals is stabilized by redox reactions, and
polymerization on this surface is at a minimum or is
absent, whereas the surfaces of other Fe dichalco-
genides (marcasite, arsenopyrite, and loellingite) of the
orthorhombic crystal system is stabilized according to
both mechanisms. Polymerization is at a maximum for
loellingite, whose surface does not contain either
monomers or dimmers. The proportions of these mech-
anisms are controlled by the “bulk” crystal structure,
the distributions of atom spacings, and the electronega-
tivities of the atoms [2]. Various mechanisms were pro-
posed to account for the oxidation of the surface of
pyrite [19, 20, 25, 28]. Here we discuss them only cur-
sorily, to the extent necessary for understanding the
chemical features of crystal surfaces.
The data of our research do not contradict currently
adopted concepts that the natural surface of pyrite, as
well as its vacuum fractures, contain more than one
mode of sulfide S occurrence: disulfide, monosulfides,
and, more rarely, polysulfide (Table 4). This is, how-
ever, the only analogy between them. It could be
expected that the bombardment of the surface with Ar+
should have produced Fe3+ and S polymers according to
the mechanisms discussed above, with the participation
of S–. This was the case with experiments 11 and 12
(Table 4), but generally no unambiguous relations can
be traced. According to our data, the natural surface of
hydrothermal pyrite is chemically modified, compared
to the volume of the crystal, into a surface (up to
~300 nm thick) pyrrhotite-like nonautonomous phase.
Its principally important distinctive feature is the occur-
rence of a peak at ~710 eV in the Fe 2p3/2 spectrum,
with this peak often having a height greater than that of
the peak of bivalent low-spin Fe(II) in the pyrite struc-
ture (707 eV). As was shown by the spectroscopic
results and those of scanning probe microscopy, the
nonautonomous phase is highly sensitive to the purity
of the system. Since this phase is transitional (in the
chemical sense) between pyrite and pyrrhotite, it is sen-
sitive to the S activity: the closer to the pyrrhotite field,
the greater its contribution to the surface modes of Fe
and S. This means that, according to the classification
[29], this phase can be attributed to a nonautonomous
“prephase,” i.e., a surface phase object formed during
the crystallization under conditions close to the stabil-
ity field of the neighboring “bulk” phase. In this situa-
tion, even a small excess of the chemical potential of
the component (because of, for example, a temperature
gradient) can significantly affect the composition of the
surface layer. The “basic” structure of the nonautono-
mous phase may contain no oxidized modes of S spe-
cies and be a layer of variable composition Fe2+[S, S2,
Sn]2– with the S/S2 ratio varying from ~0.5 to ~2.0,
averaging at ~1.1 (Table 4). This layer may include
GEOCHEMISTRY INTERNATIONAL Vol. 46 No. 6
575
minor elements, which, in turn, affect its structure. This
follows from the appearance of a nonautonomous phase
in the presence of As, although this element does not
produce any individual phases. The polymerization of S
is pronounced more clearly at the surface, according to
the aforementioned data [2]. These data confirm that
there may be another mechanism forming a nonauton-
omous phase: a polymorphic transition in the surface
layer [30]. During its crystallization, pyrite may con-
tain a thin surface film of a nonautonomous phase (mar-
casite) that is unstable in volume, and this leads to the
enrichment of the crystal surface in As and, for exam-
ple, Au because of the structural similarity between
marcasite and arsenopyrite.
2–
An increase in the SO 3 concentration during etch-
ing (Table 4, experiments 11, 12) demonstrates that the
layer underlying the nonautonomous phase may con-
tain oxidized S species. The main oxisulfide compo-
nents of this phase are the sulfite and thiosulfite ions at
a subordinate amount of sulfate. The latter may, how-
ever, “overlap” the nonautonomous phase as a result of
later oxidation processes. Thus, the fine structure of the
surface layer can be more complicated. We believe that
the reason for this is the instability of coexisting sulfate
and disulfide ions, which results (in the presence of
oxygen) in the appearance of the sulfite (thiosulfate)
and sulfide ions in the nonautonomous phase according
to the formal reaction
FeSO4 + FeS2 + 1/2O2 = [FeSO3 + FeS](np) + SO2.
The formation of sulfide was documented during Cd
2–
adsorption on pyrite as a result of S 2 disproportion-
ation [31]. Sulfite– and thiosulfate–sulfide complexes
with “thiosulfate” bonds like O3S–S may be regarded as
thermodynamic compromises needed for the coexist-
ence of oxidized and reduced S species. It is interesting
that such instability of coexisting polysulfide and sul-
fate ions is also manifested in lazurite, an S-bearing
aluminosilicate mineral, during its heating in air, which
results in the origin of the sulfite ion [32]. Comparison
with data on pyrrhotite and galena [7, 21, 30] shows
that sulfide crystals growing in hydrothermal environ-
ments have surface layers up to ~500 nm thick, whose
chemical composition, stoichiometry, and possibly,
also structure differ from those in the crystal volume.
This is the scale of the surface heterogeneity at which
the typochemistry of mineral surfaces can manifest
itself. This range of sizes is inaccessible for electron-
microprobe or ion-microprobe analytical techniques
and can be efficiently examined by methods of surface
spectroscopy, scanning probe microscopy [30], and
high-resolution scanning electron microscopy.
CONCLUSIONS
Models for the reconstruction of fresh pyrite surface
produced by vacuum fracture are only partly applicable
to the situation of the real surface of hydrothermally
2008
576 TAUSON et al.
2–
synthesized pyrite. Although the same species S 2 , S2−,
and
2–
Sn (n > 2) were detected under different condi-
tions and in proportions determined by these condi-
tions, the appearance of these species is controlled not
2–
by auto-redox reactions or S 2 , disproportionation but
by the development of a pyrrhotite-like nonautonomous
phase in the surface layer of the crystal (~300 nm
thick). This phase contains variable proportions of FeII,
2–
S2–, S 2 , and (more rarely) the polysulfide ion. The oxi-
dized S species of the phase are dominated by the
sulfite and thiosulfate ions. The chemistry of the nonau-
tonomous phase is likely determined by the instability
of association of the sulfate and polysulfide (disulfide)
ions, for which a more suitable “thermodynamic com-
promise” is a sulfide–sulfite (thiosulfate) ion associa-
tion. The typochemistry of the pyrite surface is based
on the ability of the nonautonomous phase to “record”
the growth conditions of the crystals in terms of two
major factors: the purity of the system (the occurrence
of additional phases, including virtual ones, i.e., poten-
tially possible phase of minor elements) and S fugacity.
SPM data indicate that the surface of the crystals at a
high S fugacity contains almost no nonautonomous
phases and is characterized by low roughness (14–17 nm).
At a low S fugacity in equilibrium with pyrrhotite and
Fe-rich sphalerite, the average roughness of the surface
increases to 25–65 nm, and the maximum height of the
“topographic” features reaches ~100–500 nm. This is
consistent with the data of Auger spectroscopy with the
ion milling of the surface by Ar+ ions on the average
thickness of the surface layer of approximately 300 nm.
The most typical feature of the nonautonomous phase
on pyrite is its XPS peak of FeII 2p2/3 at ~710 eV, with
the intensity of this peak often exceeding that of the
peak of low-spin FeII in the pyrite structure (707 eV).
The nonautonomous phase on the pyrite crystal surface
can be regarded as a precursor phase according to the
classification [29]; this phase can be formed in the pres-
ence of As by a process similar to a polymorphic tran-
sition (pyrite–marcasite). In this case it shows charac-
teristics typical of the surface of orthorhombic Fe
dichalcogenides: the formation of the polysulfite ion by
the reaction of S polymerization [2]. The geochemical
role of the surface nonautonomous phase on pyrite may
also be significant, particularly during the uptake of
minor elements that are incompatible with the pyrite
structure but can be readily accommodated in the less
rigid structure of the nonautonomous phase. Because of
the abundance of S species and the absence of hard con-
straints in terms of space and bond length (because of
the variations in the sulfide/disulfide ratio), many of
them can be incorporated into the surface layer even
being absolutely incompatible with the crystal matrix.
This important geochemical conclusion drawn from
our results will be considered in detail in our oncoming
paper and illustrated by the example of pyrite from var-
ious gold deposits.
GEOCHEMISTRY INTERNATIONAL
ACKNOWLEDGMENTS
The authors thank Yu.V. Shchegol’kov for assis-
tance in the spectroscopic research.
This study was supported by the Russian Founda-
tion for Basic Research (project no. 06-05-64171) and
the Siberian Branch of the Russian Academy of Sciences
(integration project 96). The equipment for the AFM and
STM measurements was provided for us by Rosnauka
in 2004 within the scope of a program for the support
of equipment availability for research organizations.
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