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Nickel sulfide formation at low temperature: Initial precipitates, solubility

and transformation products

Article  in  Environmental Chemistry · January 2010

DOI: 10.1071/EN10076

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R. T. Wilkin and D. A. Rogers, Environ. Chem. 2010, 7, 514–523. doi:10.1071/EN10076 www.publish.csiro.au/journals/env

Nickel sulfide formation at low temperature: initial

precipitates, solubility and transformation products

Richard T. WilkinA,B and David A. RogersA

A
US Environmental Protection Agency, National Risk Management Research Laboratory,
Ground Water and Ecosystems Restoration Division, 919 Kerr Research Drive,
Ada, OK 74820, USA.
B
Corresponding author. Email: [email protected]

Environmental context. Remediation technologies often rely on manipulation of redox conditions or natural
redox processes to favour microbial sulfate-reduction and mineral sulfide formation for treatment of inorganic
contaminants in groundwater, including nickel. However, few data are available on the structural properties,
solubility and mineral transformation processes involving nickel sulfides. These data are needed in order to
constrain the long term performance of groundwater remediation efforts.

Abstract. The formation of nickel sulfides has been examined experimentally over the temperature range from 25 to
608C. At all conditions studied, hexagonal (a-NiS) was the initial precipitate from solution containing Ni2þ and dissolved
sulfide. Freshly precipitated nickel sulfide possesses significant residual Ni–O coordination as revealed by X-ray
absorption spectroscopy. With progressive aging, residual Ni–O coordination is replaced by Ni–S coordination. The
formation of millerite (b-NiS, rhombohedral) was not detected in any of the synthesis experiments. In the presence
of elemental sulfur, hexagonal NiS converted to polydymite (Ni3S4) and vaesite (NiS2). Thus, conversion of nickel
monosulfide to thiospinel and disulfide structures appears to be redox dependent, analogous to aging and transformation
processes of iron sulfides. In the absence of elemental sulfur or with only hydrogen sulfide or bisulfide present,
transformation of hexagonal NiS was not observed after 1680 h at 608C. Low-pH solubility experiments yielded a
solubility product for hexagonal NiS of log Ks0 ¼ 2.69  0.26. Solubility data at pH 4 3 suggest that Ni–bisulfide
complexation is important in controlling the solubility of Ni in sulfidic solutions.

Additional keywords: groundwater, remediation, X-ray absorption spectroscopy.

Introduction
temperature from aqueous solutions typical of groundwater.
Sources of nickel contamination to groundwater and surface water Furthermore, thermodynamic data for nickel minerals, and
are primarily from mining sites, metal smelting and refining nickel sulfides in particular, that can be used to construct
operations, and metal plating facilities.[1] Thoenen[2] also discusses geochemical models of environmental transport and fate
the behaviour of nickel in groundwater impacted by radioactive are somewhat sparse and perhaps unreliable.[2,8,9] In order of
waste repositories. Nickel mobility in aquatic environments is decreasing Ni/S, minerals in the Ni–S system include heazle-
generally thought to be controlled by mineral solubility, and by the woodite (Ni3S2), godlevskite (Ni7S6), a-NiS (hexagonal), b-NiS
competition between sorption at mineral and organic surfaces (millerite, rhombohedral), polydymite (Ni3S4) and vaesite (NiS2).
and ligand formation to form non-sorptive complexes. Redox The Fe–Ni–S system also includes pentlandite ((Ni,Fe)9S8),
conditions, pH and concentrations of soluble organic compounds violarite (FeNi2S4) and bravoite ((Fe,Ni)S2).
appear to be the primary geochemical factors important to devel- The focus of this study was to assess the nature of low-
oping transport and fate models of nickel in aquatic environments. temperature (o608C) nickel sulfide precipitates formed in the
In situ technologies for treating groundwater contaminated system Ni–S–H2O. The experiments conducted were abiotic and
with metals often rely on redox manipulation to support serve as a point of reference for studies of metal sulfide
sulfate-reducing bacteria and subsequent precipitation of precipitation in the presence of sulfate-reducing bacteria.[10]
insoluble metal sulfides. For example, the permeable reactive The solubility of the initial precipitate is reported and properties
barrier (PRB) technology with organic-carbon-based reactive of initial and aged precipitates are characterised using X-ray
media has been applied to remediate nickel-contaminated diffraction (XRD) and X-ray absorption spectroscopy (XAS).
groundwater.[3–5] Understanding the physicochemical proper-
ties of the desired precipitates is essential for developing
Experimental methods
predictive models of cleanup efforts and ultimately for evaluat-
ing the long-term performance of groundwater remedies. Synthesis experiments
The mineralogy of nickel sulfides is largely known from Nickel sulfides were prepared by mixing NiII and SII solutions at
experimental investigations and studies of hydrothermal molar [Ni/S] ratios of 0.5, 1 and 2. Stock NiII solutions were
and magmatic systems.[6,7] Few investigations, however, are prepared from NiSO46H2O (Baker), and stock NaHS solutions
available on the nature of nickel sulfides that precipitate at low were prepared by purging NaOH solutions with 10% H2S gas

Ó CSIRO 2010 514 1448-2517/10/060514

Nickel sulfide formation

(Air Liquide, balance N2). All solutions were made up from Laboratory). The Ni K-edge (8333 eV) spectra were collected
deoxygenated and deionised water by purging with ultra high- using a silicon (111) double-crystal monochromator at room
purity N2 gas in a gas washing bottle. Solutions were mixed into temperature and ambient pressure in transmission mode with
125 mL glass, screw-top bottles. Room-temperature aging gas-filled ion chambers. Samples and reference compounds
experiments were conducted inside of an anaerobic glovebox were prepared as thin films sealed with Kapton tape. Energy
(Coy Laboratories). Glass bottles were placed in N2-purged con- calibration was accomplished during each scan by setting the
tainers and into an oven for experiments at 608C. In some first inflection of a nickel foil spectrum to 8333 eV. Multiple
experiments, elemental sulfur (Aldrich) was added to the bottles at scans of each sample were collected and each scan was aligned
a molar [Ni/S] ratio of 0.25. At the end of the experiments, the using the nickel foil reference. The scans started at 8100 eV
precipitates were filtered through 47-mm diameter 1.0 mm mem- using a step size of 5 eV. Across the absorption edge, the step
brane filters (Nucleopore) and rinsed with deoxygenated water. size was reduced to 0.25 eV. The EXAFS data were collected
Elemental sulfur was removed by rinsing with CS2 and methanol. with a step size of 0.05 Å1 in k-space.
The precipitates were dried in an evacuated desiccator and stored Raw data from multiple scans were merged and processed
until analysis with the solid phase techniques described below. using the Athena software package.[11] The merged and averaged
spectra were background corrected and step height normalised.
Solubility experiments Extended X-ray absorption fine structure (EXAFS) spectra were fit
Nickel sulfide precipitates for solubility experiments were pre- with theoretical phase-shift and amplitude functions calculated
pared by mixing equal volumes of 0.10 M NiII and 0.10 M NaHS using the ab initio FEFF6 program.[12,13] Radial distribution
solutions. The supernatant was replaced with deoxygenated and functions around the Ni absorber were determined by Fourier
distilled water until the specific conductance of the solution was transformation of the k3-weighted EXAFS functions using a
o50 mS cm1 as measured with a Eutech ECTestr. A 15-mL truncated k-range of 2.5–10 Å1 and the fitting range was 1–3 Å
volume of the NiS-suspension was transferred to a 45-mL glass (R-space). The EXAFS data were fit with interatomic distance (R),
VOA vial, which was immediately filled with a freshly prepared Debye–Waller (s2) and the energy offset (DE0) parameters.
NaHS solution (104 to 101 M), and the pH was adjusted with Whenever possible, the coordination number was fixed using
Ultra H2SO4. The VOA vials were placed in an anaerobic glo- crystallographic data. Crystal structures for nickel hydroxide,[14]
vebox and aged for up to ,300 h. At the end of the experiments, hexagonal nickel sulfide,[15] polydymite,[16] and vaesite[17] were
solutions were collected, filtered through 0.2 or 0.02 mm syringe used to develop atomic scattering models and to fit the experi-
filters, and stored for Ni analysis by inductively coupled plasma– mental EXAFS data collected from the synthetic samples. The
optical emission spectrometry (ICP-OES, Perkin-Elmer Optima passive amplitude reduction factor, S20, was fixed at 0.80 for all
3300DV) or inductively coupled plasma–mass spectrometry samples. The EXAFS fitting model was then parameterised by a
(ICP-MS, PQExcell, Thermo Elemental). For all solution mea- change in the Ni–S, Ni–O and Ni–Ni bond distances, a s2 value for
surements of Ni, quality assurance tests involved duplicate the Ni–S, Ni–O and Ni–Ni signals, and one energy shift value, DE0.
samples, blanks, sample matrix spikes, calibration check stan- Linear combination fits (LCF) were performed using
dards and second-source quality control samples. The detection XANES and EXAFS spectra with the Athena software package.
limit for Ni was 0.032 ppb using ICP-MS. The Ni concentration The E0 was set to 8340 eV for all spectra. XANES fitting was
in blank samples was below this detection limit. Measurements carried out from 20 eV to þ50 eV around E0. EXAFS spectra
of specific conductivity and pH were made with electrodes. The were analysed over a k-range of 2–10 Å1.
pH electrode (ThermoOrion semi-micro 911600) was calibrated
with NIST-traceable buffers (2.00, 4.01 and 7.00). Dissolved Results and discussion
sulfide measurements were made using the methylene blue X-ray diffraction
method with a HACH DR2700 spectrometer. Based on duplicate Precipitates formed after mixing NiII and NaHS solutions were
or triplicate analyses of selected solutions, the estimated uncer- consistently shown to be hexagonal NiS (a-NiS) by X-ray
tainty in measurements of nickel and dissolved sulfide is 3 and
5% respectively. In some cases, the final solids were separated Table 1. Ni sulfide synthesis results at 258 and 608C
as described above and analysed using X-ray diffraction. Products abbreviations are: pd, polydymite; v, vaesite; parentheses indicate
trace amount detected. pH values measured at the end of the synthesis
X-ray diffraction experiments. Product distribution determined by X-ray diffraction
Powder X-ray diffraction analyses were conducted to determine
the mineralogy of precipitates formed in the synthesis and solu- Sample Time (h) pH NiII (M) SII (M) S0 (g) T (8C) Products
bility experiments. Solids (,50 mg) were mounted on a zero-
NiS01 20 2.7 0.1 0.1 – 25 a-NiS
background quartz plate and scanned with Fe (X-ray) radiation NiS02 20 2.3 0.1 0.1 – 60 a-NiS
over a range of 10 to 908 2-theta (0.18 min1 and 0.018 step NiS05 312 2.5 0.1 0.1 1.3 60 pd, v
intervals; 13.3 h scans) using a Rigaku Miniflex II Diffractometer. NiS06 168 1.8 0.1 0.1 1.3 25 pd, (v)
All sample manipulations, including the X-ray scans, were carried NiS07 1152 1.7 0.1 0.1 1.3 25 pd, v
out within a Coy anaerobic glove box. Data collected from the NiS18 120 2.9 0.1 0.2 – 60 a-NiS
scans were imported into the computer program Jade (Materials NiS19 1680 2.4 0.1 0.2 1.3 60 v, pd
Data, Inc.) for analysis and matched to the Powder Diffraction NiS17 120 3.1 0.1 0.2 1.3 60 pd, (v)
File Data Base (PDF, International Centre for Diffraction Data). NiS20 1680 2.8 0.1 0.2 – 60 a-NiS
NiHY02 1680 5.3 0.1 0.1 1.3 60 v
X-ray absorption spectroscopy NiHY03 2160 4.8 0.1 0.2 1.3 60 v
aNiS2 1 2.2 0.2 0.2 – 25 a-NiS
X-ray absorption spectroscopy (XAS) measurements were NiS50 24 7.7 0.1 0.05 – 25 a-NiS
made at the high-photon-flux insertion device beamline (10-ID), NiS51 24 5.6 0.1 0.05 – 25 a-NiS
MR-CAT, at the Advanced Photon Source (Argonne National

515
 R. T. Wilkin and D. A. Rogers

diffraction. In fact, hexagonal NiS was the only crystalline coordination of Ni in a-NiS to 5-fold coordination in millerite.
product observed from solutions with Ni/S ranging from 0.5 to 2 There was no indication of phase inversion from the a-b form
in the absence of elemental sulfur (Table 1). Interestingly, even after 1680 h of aging in aqueous solution at 608C (Table 1).
millerite (rhombohedral NiS) was not detected in any of the Past experimental studies have extensively relied on silica–glass
synthesis experiments (Fig. 1, Table 1). Stoichiometric NiS tube experiments for synthesis and phase transition investiga-
crystallises in two structures: the low-temperature rhombohe- tions involving nickel sulfides.[6,18] However, Štrbac et al.[20]
dral phase (millerite) and the high-temperature phase (a-NiS), also used an aqueous synthesis pathway to prepare a-NiS at
which has the NiAs-type hexagonal structure and is known to room temperature.
persist metastably at ambient conditions, but has not been found The analysis of XRD data presented in Fig. 1 showed that
in nature.[18] The kinetics of the a-b transition in synthetic with increasing aging of hexagonal NiS, the amplitude of the
monosulfide depends on pressure, temperature, and composi- diffraction peaks increased and the full width at half maximum
tion of the a-NiS, which can be nickel deficient.[18,19] The (FWHM) of the most prominent reflection (102; d ¼ 1.97 Å)
transition involves structural reordering from octahedral decreased slightly from 0.75 to 0.73. This result implies that

No S0

(c)
Intensity

(b)

(a)

With S0

(f)
Intensity

(e)

(d)

10 20 30 40 50 60 70 80 90
100
-NiS
I(f)

50
0
100
-NiS
I(f)

50
0
100
Vaesite
I(f)

50
0
100
Polydymite
I(f)

50
0
10 20 30 40 50 60 70 80 90
Degrees 2-theta, FeK

Fig. 1. X-ray diffraction patterns of synthetic nickel sulfides: (a) hexagonal nickel sulfide (258C, 20 h aging);
(b) hexagonal nickel sulfide (608C, 20 h aging); (c) hexagonal nickel sulfide (608C, 120 h aging); (d) polydymite
(258C, 120 h aging, with S0); (e) vaesite/polydymite (608C, 312 h, with S0); and (f) vaesite (608C, 1680 h aging,
with S0). Powder Diffraction data files shown for a-NiS (02–1280), b-NiS (01–086–2281), vaesite (00–011–0099)
and polydymite (01–076–1813).

516
Nickel sulfide formation

the average particle size of hexagonal NiS increases slightly progressively transforms to the thiospinel (polydymite) and
with aging. The XRD data also suggest that only a minor finally to the disulfide (vaesite), which likely represents the
amount of crystalline hexagonal NiS had formed after 20 h at thermodynamically stable nickel sulfide at low temperature.
258C, and that most of the Ni-precipitate was not yet sufficiently Gramp et al.[10] reported the formation of heazlewoodite
long-range-ordered to produce pronounced XRD peaks. Note (Ni3S2) and vaesite in biotic experiments with sulfate-reducing
that the XRD technique is sensitive only to well ordered material bacteria at temperatures up to 608C and aging times of 336 h.
in the solid phase. In the forthcoming section on XAS analysis, The nickel monosulfides, hexagonal NiS and millerite, were not
both the crystalline and disordered components of the solids are observed reaction products in these biotic systems; however,
probed. mineral aging time was not systematically examined, so it is
The addition of elemental sulfur to the synthesis experiments unclear whether the nickel monosulfides were precursors to
resulted in the formation of nickel sulfides with increased S/Ni heazlewoodite and vaesite in the experiments conducted by
relative to hexagonal NiS (Table 1). Both polydymite and Gramp et al.[10]
vaesite were observed in systems where initial hexagonal NiS
precipitates were aged in the presence of S(0). Polydymite X-ray absorption spectroscopy
appeared to be a transient phase formed during aging of
The XANES spectra of precipitated hexagonal NiS show
hexagonal NiS with S(0). Complete transformation of hexa-
structural changes with increasing aging time (Fig. 2). With
gonal NiS to vaesite was observed at 608C after 1860 and 2160 h
progressive aging, the Ni absorption edge position decreases to
(Fig. 1; Table 1). These trends are similar to experimental
lower energies. Freshly precipitated (1 h) hexagonal NiS shows
observations in the Fe–S–H2O system. For example, greigite
two absorption maxima at 8342.4 and 8346.0 eV respectively.
(Fe3S4) and pyrite (FeS2) are commonly observed mineral
These absorption maxima are also diagnostic of Ni(OH)2. With
products when mackinawite (FeS) is aged in the presence of
progressive aging and improved crystallinity, as indicated by
S0.[21,22] By analogy, it is reasonable to hypothesise that hexa-
the sharpness and intensity of XRD peaks, these absorption
gonal NiS represents the initial metastable sulfide–mineral
edge energies are replaced by a dominant feature at 8339.7 eV
product as NiII reacts with dissolved sulfide at low temperature.
(Fig. 2). The aging–time trend evident in the XANES spectra
With increased aging and in the presence of S0, hexagonal NiS
suggests a transition from dominantly Ni–O coordination in
freshly precipitated material to Ni–S coordination. LCF ana-
lysis is presented below to provide a quantitative description of
this transition using both XANES and EXAFS regions of the
(e) spectra. Spectroscopic results suggest that aging time is a cri-
tical parameter in controlling XANES structure of nickel
(d ) monosulfide. This may be a complicating factor for inter-
Absorption

preting Ni K-edge XANES data for samples collected from the

(c) field in cases where the structural nature of nickel precipitates
is unknown.
(b) Linear combination fitting was carried out to estimate the
proportion of Ni–O and Ni–S coordination in precipitated
(a) hexagonal NiS after 1 h, after 20 h at 258C and after 20 h at
608C. End-members used in the fitting routine were precipitated
Ni(OH)2 and crystalline hexagonal NiS (aged for 120 h at 608C).
The LCF results are summarised in Table 2 and plotted in Fig. 3.
8330 8340 8350 8360 8370 8380 XANES fit results show a significant component (81%) of Ni–O
coordination in precipitated hexagonal NiS after 1 h of aging.
After 20 h of aging at 258C, the percentage of Ni–O coordination
decreases to 39%; and after 20 h at 608, the Ni–O component
is o5%. The Ni–S coordination progressively dominates
8339.7
First derivative

Table 2. Results of linear combination fits of XANES and k2-weighted

Ni K-edge EXAFS spectra of precipitated hexagonal NiS using Ni(OH)2
and crystalline hexagonal NiS (120 h, 608C) as fit components
P
ðdatai fiti Þ2
R-factor reflects the goodness of fit: R-factor ¼ Pðdatai Þ2
8346.0

Sample Component (%) R-factor

8342.2

Ni(OH)2 a-NiS

8330 8340 8350 8360 8370 8380 XANES

1 h, 258C 81 19 0.0007
Energy (eV)
20 h, 258C 39 61 0.0004
20 h, 608C 4 96 0.0001
Fig. 2. Ni K-edge XANES spectra and first-derivative for (a) precipitated
EXAFS
Ni(OH)2; (b) hexagonal nickel sulfide (258C, 1 h aging); (c) hexagonal nickel
1 h, 258C 71 29 0.03
sulfide (258C, 20 h aging); (d) hexagonal nickel sulfide (608C, 20 h aging);
20 h, 258C 51 49 0.04
and (e) hexagonal nickel sulfide (608C, 120 h aging). XANES trends suggest
20 h, 608C 9 91 0.01
progressive loss of Ni–O coordination with aging.

517
 R. T. Wilkin and D. A. Rogers

Table 3. EXAFS fit parameter results for synthetic Ni hydroxide and

Ni sulfides
20 h, CN, coordination number; R, interatomic distance; s2, Debye–Waller
60C parameter; DE0, is the energy offset parameter; R-factor is a measure of the
goodness of fit

Sample Bond pair R (Å) CN s2 (Å1) DE0 R-factor

Ni hydroxide Ni–O 2.05 6.0A 0.001 4.1 0.024

Ni–Ni 3.1 6.0A 0.006
a-NiS (1 h) Ni–S 2.38 6.0A 0.005 2.5 0.017
Normalised absorption

20 h, Ni–Ni 3.08 6.0A 0.009

Ni–O 2.05 1.5 0.009
x(k)k 2 (Å2)

25C
a-NiS (20 h) Ni–S 2.38 6.0A 0.009 5.5 0.018
Ni–Ni 3.05 6.0A 0.008
Ni–O 2.06 0.5 0.009
a-NiS (120 h, 608C) Ni–S 2.4 6.0A 0.01 6.5 0.015
Ni–Ni 2.65 6.0A 0.005
Ni–O – –
Polydymite Ni–S 2.22 4.0A 0.009 3.2 0.052
1 h, Ni–Ni 4.38 12A 0.007
25C Vaesite Ni–S 2.41 6.0A 0.002 3.5 0.023
Ni–Ni 4.04 12A 0.004

A
Fixed value.

scattering path. The first coordination shell surrounding nickel

involves sulfur atoms which are at a distance of 2.40 Å. As noted
8325 8340 8355 8370 8385 2 4 6 8 10
above this change in atomic structure is also indicated in the
near-edge XANES spectra. The use of X-ray absorption spectro-
Energy (eV) k (Å1)
scopy clearly reveals progressive sulfur for oxygen substitution
Fig. 3. Linear combination of fits (LCF) of Ni K-edge XANES and EXAFS in the nickel sulfide precipitates. Analysis of the polydymite
spectra of hexagonal NIS with variable aging parameters. Filled circles sample showed a Ni–S shell described by 4 S atoms at an
represent experimental data and solid lines show the fits. XANES LCF: average distance of 2.23 Å. The reduced fit of this sample likely
orange lines represent the NiS component, blue lines represent the Ni(OH)2 reflects that the sample contained a minor amount of vaesite as
component, and red lines show the combined fit. EXAFS LCF: the red lines indicated by the XRD data. Synthetic vaesite shows a first
represent the combined fit. A summary of LCF results is given in Table 2. coordination shell feature at 2.41 Å corresponding to the Ni–S
bond distance, and a second shell expression at 4.03 Å corre-
with increasing aging time. LCF fitting of k2-weighted spectra sponding to Ni–Ni bonding. Overall the experimental EXAFS
shows similar trends, confirming mixed Ni–O and Ni–S spectra show a good match with scattering paths derived from
coordination in the series of aged hexagonal NiS samples the crystal structures, indicating that EXAFS data could be a
(Table 2). Taken together, the XRD and XAS studies indicate useful tool for probing the nickel bonding environment in
that initial nickel sulfide precipitates display short-range samples collected from natural systems.
order with significant residual Ni–O coordination. This situation
is perhaps expected because Ni2þ, with the d8 electronic Solubility
configuration, is comparatively slow to exchange water and The low pH solubility controlling reaction for hexagonal NiS
undergo ligand substitution compared to other first row divalent can be expressed as:
transition metal ions.[23,24] These spectroscopic data provide
some confirmation of the trends predicted in Morse and NiS þ 2Hþ ¼ Ni2þ þ H2 S0 ðaqÞ ð1Þ
Luther[23] and Rickard and Luther[24] and suggest that time where
resolved EXAFS methods could realistically be used to collect
experimental rate data on SH for OH exchange involving log Ks0 ¼ logfNi2þ g þ logfH2 S0 ðaqÞg þ 2pH ð2Þ
metals such as Ni, Co and V.
The results of EXAFS data fitting for synthetic nickel and curly brackets indicate activity. The results of hexagonal NiS
hydroxide, hexagonal nickel sulfide, polydymite and vaesite solubility measurements at low pH are listed in Table 4. Tests
are given in Table 3. Experimental k3-weighted EXAFS spectra comparing nickel concentrations in solutions after passing
and their Fourier transforms are shown in Fig. 4 along with the through 0.02- and 0.2-mm filters showed no statistical differ-
theoretical fits derived from crystal structure data. The spectra ences, indicating that particulates or large clusters were not
are uncorrected for phase shift. For the synthetic nickel hydro- present in the solubility experiments. Solution data were spe-
xide, we observe a Ni–O bond distance of ,2.05 Å which is ciated with the Geochemist’s Workbench 8.0[26] software pack-
consistent with results from previous EXAFS analysis of nickel age using the ‘thermo.com.v8.r6þ’ thermodynamic database
oxides.[25] For hexagonal nickel sulfide aged for 1 h, the EXAFS and the B-dot version of the Debye–Hückel equation to calculate
signal is dominated by the Ni–O scattering path. However, after activity coefficients for Ni2þ. Nickel complexes considered in
120 h at 608 the EXAFS signal is dominated by the Ni–S the model included Ni2þ, Ni(OH)02, Ni(OH) 0
3 and NiSO4; the

518
Nickel sulfide formation

(g)

Fourier transformation magnitude

(f)

(e)
x(k)k 3 (Å3)

(d)

(c)

(b)

(a)

2 4 6 8 10 0 1 2 3 4 5 6
k (Å1) R  R (Å)

Fig. 4. k3-weighted EXAFS and Fourier transforms uncorrected for backscatterer phase shift for
(a) nickel hydroxide; (b) hexagonal nickel sulfide (258C, 1 h aging); (c) hexagonal nickel sulfide (258C,
20 h aging); (d) hexagonal nickel sulfide (608C, 20 h aging); (e) hexagonal nickel sulfide (608C, 120 h
aging); (f) polydymite (258C, 120 h, S0); and (g) vaesite (608C, 1680 h, S0). Filled circles represent
experimental EXAFS data and dotted lines represent the least-squares best fit.

Table 4. Solubility data for hexagonal NiS (258C)

Final pH values are listed. Curly brackets indicate activity values. I is the ionic strength

Sample Time (h) pH Ni (ppm) H2S(aq) (ppm) log{Ni} log{H2S} I log IAP

DR-NiS21 84 1.22 182 374 3.30 1.93 0.219 2.79

DR-NiS19 84 1.41 243 217 3.20 2.17 0.215 2.55
DR-NiS17 84 1.57 149 43 3.07 2.88 0.191 2.80
DR-NiS15 84 1.58 165 27 3.03 3.07 0.196 2.94
DR-NiS20 240 1.34 301 186 3.00 2.24 0.154 2.56
DR-NiS18 240 1.39 219 43 2.88 2.88 0.156 2.97
DR-NiS16 240 1.45 215 43 2.88 2.88 0.156 2.86
DR-NiS14 240 1.65 429 26 2.53 3.09 0.098 2.32
NiS7–02 48 2.03 1.50 1040 4.85 1.49 0.016 2.28
NiS5–08 48 2.58 1.10 36 4.88 2.95 0.007 2.67
DR-NiS25 120 2.17 12.3 19 4.00 3.22 0.050 2.88
DR-NiS23 120 2.29 44.4 7.9 3.39 3.66 0.032 2.47
DR-NiS49 168 2.71 10.0 6.9 4.00 3.67 0.056 2.25
DR-NiS37 192 2.34 0.95 142 5.22 2.36 0.133 2.89
DR-NiS26 288 2.03 23.4 15 3.73 3.33 0.060 3.00
DR-NiS50 288 2.10 6.74 217 4.33 2.17 0.094 2.29
DR-NiS38 288 2.19 1.13 973 5.80 1.52 0.134 2.94
DR-NiS24 288 2.20 34.9 4.7 3.52 3.84 0.039 2.95
DR-NiS48 288 2.31 5.75 33 4.29 2.99 0.035 2.65
NiS25A 24 6.14 0.95 29.8 4.91 3.03 0.014 –
NiS25D 24 5.33 0.06 27.9 6.07 3.06 0.001 –
NiS5–02 48 6.85 0.54 26.3 5.14 3.09 0.003 –
NiS5–07 48 6.61 0.34 24.9 5.34 3.11 0.003 –
NiS5–06 48 6.40 0.12 23.6 5.79 3.13 0.003 –
NiS26C 24 4.00 0.21 21.8 5.50 3.17 0.001 –
NiS26C 24 4.00 0.15 21.8 5.70 3.17 0.001 –
NiS24C 24 5.66 0.43 19.7 5.16 3.21 0.000 –
NiS5–05 48 6.83 0.42 19.6 5.25 3.22 0.003 –
NiS11A 48 3.35 0.81 11.0 5.20 3.48 0.051 –
NiS11B 48 3.35 1.22 11.0 5.00 3.48 0.051 –
DR-NiS46 288 2.92 5.21 9.6 4.23 3.52 0.011 –

519
 R. T. Wilkin and D. A. Rogers

(a) 2
thermodynamic database includes no entries for nickel bisulfide
complexes. Values entered into the ‘React’ user window were 1
pH 1.5
total concentrations of Ni, H2S, Na, SO4 and pH. In most cases
the calculated concentration of Ni complexes was less than 5% of 0
the total Ni concentration. Rearranging Eqn 2 gives: 1

Log m(H2S)
pH 2.5

logfH2 S g ¼  logfNi g þ ðlog Ks0  2pHÞ

0 2þ
ð3Þ 2

3
A plot of log m(Ni) v. log m(H2S0) reveals the expected slope
of 1 for solubility experiments at pH 1.5 to 2.5 and low 4
ionic strength (Fig. 5a). Furthermore, there is no systematic
change in the log IAP (ion activity product) for reaction 1 5
below pH 3 (Fig. 5b); log IAP ¼ 2.69  0.26 (average value 
6
1 s.d.). This value is taken to be representative of log Ks0 for 8 7 6 5 4 3 2 1 0
reaction 1. Log m(Ni)
Reversibility of the solubility experiments was constrained (b) 2
by conducting a set of experiments from both undersaturated
1 ‘-NiS’
and oversaturated conditions (Fig. 5c). Oversaturated conditions
were achieved by simply mixing NiII and NaHS solutions and
0
sampling after 24 h. Undersaturated conditions were achieved
by first precipitating NiS, followed by dialysis and addition of 1
Log IAP

fresh NaHS solutions. Results show a reasonable bracketing of

the average log Ks0 value from undersaturated and oversaturated 2 Hexagonal NiS
conditions. It appears that equilibrium conditions were reached 3
ino100 h in the batch experiments. X-ray diffraction analyses of
NiS precipitates after completion of the solubility experiments 4
‘-NiS’
did not show any significant changes relative to the initial
5
product, although in some cases traces of polydymite were ‘-NiS’
detected in longer-term solubility runs. 6
At this point it is interesting to compare the log Ks0 value 1.0 1.5 2.0 2.5 3.0
for hexagonal NiS, the precipitate that consistently forms at pH
low temperature when Ni2þ is added to sulfide solutions, with (c) 0
solubility products for nickel monosulfide found in various
thermodynamic databases (Fig. 5b). The solubility product
1
for hexagonal NiS reported here is intermediate to the so-called
‘a-NiS’ and ‘b-NiS’ precipitates entered in the MINTEQ Oversaturation
A2 database (from Thiel and Gessner[27]; see discussion in 2
Log IAP

Thoenen[2] and Carlsson and Vuorinen[8]). It is unknown,

however, what structural or compositional forms the ‘a-NiS’,
‘b-NiS’ and ‘g-NiS’ phases actually represent, but it is impor- 3 Undersaturation

tant not to confuse these designations with structural or

mineralogical designations, i.e. hexagonal NiS (a-NiS) and 4
rhombohedral NiS (b-NiS). The a, b and g designations were
based upon chemical extractions in the original work of
Thiel and Gessner,[27] with the a-form being the most labile 6
and g-form being the most refractory. 0 50 100 150 200 250
Thermodynamic data for millerite are reported in Wagman Time (h)
et al.,[28] Vaughan and Craig,[29] and Robie and Hemingway[30]
(see Table 5). Solubility products derived from the Gibbs free Fig. 5. Hexagonal NiS solubility data. (a) Logarithm of Ni concentration v.
logarithm of H2S(aq) concentration (squares ¼ pH 2.2–2.5; circles ¼
energy values provided in these references range from 1.1 to
pH 1.2–1.4). (b) log IAP (ion activity product) v. pH. (c) log IAP v. time.
3.2 (Table 5). Assuming that hexagonal NiS is metastable to
millerite at ambient conditions, then only the values provided
by Vaughan and Craig[29] and Robie and Hemingway[30] are
consistent with our new solubility-derived Gibbs free energy
value for hexagonal NiS, 88.8 kJ mol1. The observed At pH 43 it is clear that the solubility controlling reaction
precipitation of hexagonal NiS over millerite is possibly related (Eqn 1) does not hold. At constant total dissolved sulfide
to kinetic factors and preference for solution precipitation to (,0.001m), Ni concentrations are much greater over the pH
develop 6-fold coordination over 5-fold coordination. In any range from 3 to 47 compared to concentrations predicted by
case, we believe the data presented here represent the first NiS Eqn 1 (see Fig. 6). This implies that other species control NiS
solubility data that can be clearly linked to a specific structural solubility, and reasonably these species are Ni–bisulfide com-
form. There remains an important need to conduct solubility plexes. Although our dataset on NiS solubility over a range of
studies on synthetic or natural specimens of millerite for pH and total dissolved sulfide values is limited, a speciation
comparison purposes. model is shown by the bold curve on Fig. 6 using the solubility

520
Nickel sulfide formation

Table 5. Selected thermodynamic data for nickel minerals

Free energy value for a-NiS calculated with experimental log Ks0 value and DG8f for Ni2þ (45.6 kJ mol1, Robie and Hemingway[30]), H2S(aq)
(27.87 kJ mol1, Wagman et al.[28]) and S0 (0 kJ mol1, Wagman et al.[28]). Values for log Ks0 of millerite are based on the DG8f values given in the cited
reference and the DG8f values for Ni2þ, H2S(aq) and S0 given above. The thermo.com.v8.r6þ (Lawrence Livermore National Laboratory database) free energy
values were calculated using the database entries along with the DG8f values for Ni2þ, H2S(aq) and S0

Mineral Stoichiometry DG8f (kJ mol1) log Ks0 Reference

a-NiS NiS 88.8 A

2.69 (0.26) This study
Millerite NiS 79.5 1.06 Wagman et al.[28]
NiS 91.6A 3.18 Vaughan and Craig[29]
NiS 88.3 2.60 Robie and Hemingway[30]
Polydymite Ni3S4 312.5 – Vaughan and Craig[29]
Ni3S4 311.7A – thermo.com.v8.r6þ
Heazlewoodite Ni3S2 210.0 – Vaughan and Craig[29]
Ni3S2 210.2 – Robie and Hemingway[30]
Ni3S2 196.8A – thermo.com.v8.r6þ
Vaesite NiS2 126.4 – Vaughan and Craig[29]
NiS2 126.3A – thermo.com.v8.r6þ
Ni(OH)2 Ni(OH)2 447.2A – thermo.com.v8.r6þ

A
Value used to construct the Eh–pH diagrams in Fig. 7.

0 should be noted that data for various nickel bisulfide complexes

(e.g. NiHSþ, Ni(HS)02, Ni2(HS)3þ, Ni3(HS)5þ) are available in
2
the literature.[24,31–33] Inclusion of these species, in general,
does not improve the solubility model shown in Fig. 6. Further
experimental work is needed in order to better constrain a
4 Sum solubility model for NiS using a range of possible Ni–bisulfide
log Ni (molal)

complexes, including those proposed in the literature.

6
Stability relations
8 Thermodynamic data related to the formation of nickel-bearing
minerals were retrieved from the ‘thermo.com.v8.r6þ’ database
10 Ni(HS) NiHS and other selected sources, including solubility data from this
3
study (Table 5). These data are used to construct Eh–pH dia-
Ni2 grams in the system Ni–S–H2O to illustrate the thermodynamic
12 limits on low-temperature nickel sulfide formation. Calcula-
2 4 6 8 tions show that vaesite is the stable nickel sulfide in anoxic low-
pH
temperature environments over much of Eh–pH space (Fig. 7a).
Polydymite, millerite and heazlewoodite show limited stable
Fig. 6. Logarithm of Ni concentration in equilibrium with a-NiS as a
function of pH (total dissolved sulfide ¼ 0.001 m). Filled circles are mea-
regions at higher pH and generally at redox conditions inter-
sured Ni concentrations and lines are calculated using equilibrium constants mediate between vaesite and Ni(OH)2. The stability region for
(see text). nickel monosulfide is largely restricted to pH 47 and low Eh
conditions. Nickel oxide (bunsenite) has not been reported from
low-temperature environments and has been excluded from
these calculations, replaced by Ni(OH)2. Suppression of vaesite,
expression in Eqn 1 along with the addition of possible polydymite, heazlewoodite and millerite (which was not
Ni–bisulfide complexes, NiHSþ and Ni(HS)
3 . The following observed in our experiments) produces an Eh–pH diagram that
formation reactions were used: shows the metastability field for a-NiS. Exclusion of these
nickel sulfides from the calculations does not change the overall
Ni2 þ þ HS ¼ NiHSþ log b1 ¼ 5:49 ð4Þ topology of the Eh–pH diagram in that a-NiS occupies a
metastable region over a broad pH range at low Eh. On the
basis of these thermodynamic relationships, vaesite would be
and expected to form in typical low-temperature groundwater
systems that attain equilibrium, with the possibility of nickel
Ni2 þ þ 3HS ¼ NiðHSÞ
3 log b3 ¼ 18:7 ð5Þ monosulfide and polydymite in more restricted Eh–pH regions.
Results of the experimental studies suggest that kinetic factors
The value for log b1 is taken from the MINTEQ A2 database may prevent the equilibrium condition from developing, so that
and the log b3 value is estimated based on nickel solubility nickel sulfide precipitates may include a-NiS and aging pro-
data collected at a total sulfide concentration of ,1 mM. It ducts, e.g. polydymite.

521
 R. T. Wilkin and D. A. Rogers

(a) O2 2. Freshly precipitated nickel sulfide possesses significant

H2O residual Ni–O coordination as revealed by X-ray absorption
1
spectroscopy. With progressive aging, residual Ni–O coor-
SO2
HSO
4

dination is replaced by Ni–S coordination, consistent with

recent observations reported in Huang et al.[34]
3. Transformation of a-NiS to polydymite and vaesite was
0.5
observed only in the presence of elemental sulfur. Thermo-
dynamic calculations suggest that vaesite is stable over a
S0 Ni2 broad pH range at low Eh.
Eh (V)

4. The solubility product of a-NiS was determined to be

log Ks0 ¼ 2.69  0.26. The Gibbs free energy of formation
0
H2O Ni(OH)2 of a-NiS consistent with this solubility product is
H2 Vaesite 88.8 kJ mol1.

Ni(OH)
3
Solubility data for a-NiS suggest that Ni–bisulfide com-
H2S

HS

Polydymite plexes are likely to be important at environmentally relevant pH

0.5
and concentrations of dissolved sulfide. Current thermodynamic
Millerite databases used for modelling transport and fate may not be
25C Heazlewoodite adequate to accurately model Ni solubility in sulfidic
0 2 4 6 8 10 12 14 groundwater.
pH
Acknowledgements
(b)
The USA Environmental Protection Agency through its Office of Research
and Development funded the research described here. It has not been
1
HSO42

subjected to agency review and therefore does not necessarily reflect the
SO42

views of the agency, and no official endorsement should be inferred. Use

of the Advanced Photon Source was supported by the USA Department of
Energy, Office of Science, Office of Basic Energy Sciences, under Con-
tract No. DE-AC02–06CH11357. MRCAT operations are supported by the
0.5 Department of Energy and the MRCAT member institutions. Additionally
the authors would like to thank Tomohiro Shibata for his assistance with
Ni2
Eh (V)

the XAS data collection. Mention of trade names or commercial products

does not constitute endorsement or recommendation for use. We greatly
S0 appreciate the constructive comments provided by two anonymous
0 Ni(OH)2 reviewers.

α-NiS
Ni(OH)

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