First-principles study of sulfur isotope fractionation in pyrite-type disulfides

Liu, Shanqi; Li, Yongbing; Liu, Jianming; Shi, Yaolin

doi:10.2138/am-2015-5003

Cited by 18 publications

(20 citation statements)

References 55 publications

Supporting

Mentioning

Contrasting

Unclassified

Order By: Relevance

“…6а, результаты на-стоящей работы хорошо согласуются с расчетами из первых принципов на основе функционала плотности (Liu et al, 2015;, с другой стороны, наблюдается существенное расхождение с более ранними результатами (Blanchard et al, 2009), также выполненными в рамках подхода, основанного на использовании функционала электронной плотности. В более поздних работах (Liu et al, 2015; использовалось приближение, не требующее введения масштабирующего множителя (scaling factor) для согласия расчетных и наблюдаемых фундаментальных частот тепловых колебаний. Первые оценки 34 S/ 32 S β-фактора пирита на основе мессбауэровской спектроскопии и теплоёмкости также оказались неточными, т.к.…”

Section: S/ 32 S β-факторы для пиритаunclassified

“…По данным мессбауэровской спектроскопии и теплоёмкости определены β-факторы серы для пирита. Полученные 34 S/ 32 S β-факторы хорошо согласуются с расчетами из первых принципов (Liu et al, 2015;. В то же время аналогичные расчеты (Blanchard et al, 2009) приводят к более высоким значениям 34 S/ 32 S β-факторов для пирита.…”

Section: выводыunclassified

“…Равновесные изотопные коэффициенты фракционирования серы между пиритом и другими серосодержащими соединениями исследовались еще с 60-х годов прошлого столетия (Kajiwara et al, 1969;Kajiwara, Krouse, 1971;Smith et al, 1977;Ohmoto, Rye 1979;Seal II, 2006). Исследования в этой области не потеряли актуальность и сейчас, причем последние теоретические оценки β-факторов серы для пирита, выполненные из первых принципов (Blanchard et al, 2009;Liu et al, 2015;, показали определенное отклонение от результатов, полученных ранее. Попытки оценки β-факторов железа для пирита имеют значительно более короткую историю.…”

unclassified

See 2 more Smart Citations

Iron and sulfur isotope factors for pyrite from experimental gamma-resonant studies and heat capacity

Polyakov

Поляков²,

Осадчий

et al. 2019

Геохимия

View full text Add to dashboard Cite

Pyrite Moessbauer spectra (FeS2) is measured in the temperature range from 90 to 295 K. The temperature dependence of the isomer shift is described by the Debye model with Moessbauer temperature θM=551.4 K. Using these results, we calculated the kinetic energy of thermal vibrations of the iron sublattice of pyrite and the iron β-factor for pyrite: 103lnβ57Fe/54Fe=(1.2665±0.0391)x–(0.4584±0.0283) × 10-2x2+(0.2581±0.0239) × 10-4x3; x=106/T 2 (K-2) The Moessbauer-derived iron β-factor for pyrite agrees well with results of ab initio calculations, 57Fe nuclear inelastic γ-resonant scattering synchrotron experiments and direct isotope exchange experiments between pyrite and Fe2+ dissolved in water. Heat capacity of pyrite is measured at temperatures from 79 to 300 K. Its temperature dependence are described using the Thirring expansion. Based on this expansion, the kinetic energy of thermal vibrations of total crystalline lattice of pyrite is calculated. The kinetic energy of the thermal vibrations of the sulfur sublattice in pyrite is found by subtracting the iron sublattice kinetic energy from the total kinetic energy of pyrite crystalline lattice. Temperature dependence of 34S/32S β-factor for pyrite calculated from the kinetic energy of the sulfur sublattice is following: 103lnβ34Fe/32Fe=(1.7532±0.0623) x–(1.0470±0.0752) × 10-2 x2+(1.0424±0.1126) × 10-4 x3; x=106/T 2 (K-2) This 34S/32S β-factor values exhibit a good agreement with of ab initio calculations and isotope-exchange experimental results in the pyrite-sphalerite-galenite system.

show abstract

Section: S/ 32 S β-факторы для пиритаunclassified

Section: выводыunclassified

unclassified

See 1 more Smart Citation

Iron and sulfur isotope factors for pyrite from experimental gamma-resonant studies and heat capacity

Polyakov

Поляков²,

Осадчий

et al. 2019

Геохимия

View full text Add to dashboard Cite

show abstract

“…Several researchers have carried out experimental measurements of fractionation between pyrite and other sulphides，such as: ZnS-PbS-FeS2-S (Grootenboer andSchwarcz, 1969), FeS2-ZnS-PbS (Kajiwara et al, 1969;Smith et al, 1977), FeS2-CuFeS2-PbS-ZnS (Kajiwara andKrouse, 1971), FeS2-PbS-S (Salomons, 1971), and some sulphide minerals-H2S system (Ohmoto and Rye, 1979;Ohmoto and Goldhaber, 1997). In contrast, theoretical calculations have not been reported except for in the studies of Polyakov et al (2007), Blanchard et al (2009), Polyakov and Soultanov (2011), and Liu et al (2015). Furthermore, there are scarcely any studies on S isotope fractionation in transition metal sulpharsenides and sulphantimonides.…”

Section: Introductionmentioning

confidence: 99%

“…Recent studies have demonstrated that the first-principles calculation based on density functional theory is a powerful tool for calculating the isotope fractionation factors for a variety of isotope systems including H, O, Mg, Ca, Si, S, Fe, Ge and Se (Balan et al, 2014;Blanchard et al, 2009;Feng et al, 2014;Huang et al, 2014;Liu, 2010, 2011;Liu et al, 2014Liu et al, , 2015Méheut et al, 2009Méheut et al, , 2010Méheut and Schauble, 2014;Reynard and Caracas, 2009;Schauble, 2011;Wu et al, 2015). In this study, this approach is used to investigate the equilibrium S isotope fractionation in the sulpharsenides and sulphantimonides of Fe, Co and Ni.…”

Section: Introductionmentioning

confidence: 99%

First-principles calculations of sulphur isotope fractionation in MX2 minerals, with M= Fe, Co, Ni and X2= AsS, SbS

Liu

Gong

et al. 2016

Chemical Geology

View full text Add to dashboard Cite

Iron, Co and Ni are first row transition metals and are all able to combine with S, As, and Sb to form disulphides, sulpharsenides and sulphantimonides, respectively, all of which exhibit substitutions of metal and metalloid elements in their structures. As an important tracer in the geochemistry of ore deposits, S isotope fractionation in sulphides can be used to analyse the ore-forming process and the source of ore-forming elements. However, there have been few studies of S isotope fractionation in sulpharsenides and sulphantimonides. Studying the isotope fractionation of the various members of this structural group can provide systematic information regarding S isotope fractionation in transition metal disulphides, sulpharsenides and sulphantimonides. In this paper, the S isotope fractionation parameters for Fe, Co and Ni sulpharsenides and sulphantimonides were calculated using first-principles methods based on density functional theory in the temperature range of 0-1000 ºC. Our calculations show that the order of heavy S isotope enrichment is arsenopyrite > cobaltite > gudmundite > costibite >

show abstract

The Light Stable Isotope (Hydrogen, Boron, Carbon, Nitrogen, Oxygen, Silicon, Sulfur) Composition of Orogenic Gold Deposits

Quesnel

Scheffer

Beaudoin

2023

Mineral Resource Reviews

View full text Add to dashboard Cite

Orogenic gold deposits formed in various terranes of most ages since the Paleoarchean and generally consist of quartz veins hosted in shear zones formed at the ductile brittle transition under greenschist to lower amphibolite metamorphic conditions. Vein mineralogy is dominated by quartz with various amounts of silicates, carbonates, phyllosilicates, borates, tungstates, sulfides, and oxides. The isotopic composition of these minerals and fluid inclusions has been investigated since the 1960s to constrain the characteristics of orogenic fluid systems involved in the formation of gold deposits worldwide. This review is based on 8580 stable isotope analyses, including δ18O, δD, δ13C, δ34S δ15N, δ11B, and δ30Si values, from 5478 samples from 558 orogenic gold deposits reported in the literature from 1960 to 2010. This contribution describes the variability of the light stable isotopic systems as function of the minerals, the age of the deposits, their regional setting, and their country rocks. The temperature of isotopic equilibrium of orogenic gold veins is estimated from mineral pairs for oxygen and sulfur isotopes. Based on these temperatures, and on fractionation between mineral and fluid components (H2O, CO2 and H2S), the isotopic composition of fluids is estimated to better constrain the main parameters shared by most of auriferous orogenic fluid systems. Orogenic gold deposits display similar isotopic features through time, suggesting that fluid conditions and sources leading to the formation of orogenic gold deposits did not change significantly from the Archean to the Cenozoic. No consistent secular variations of mineral isotope composition for oxygen (−8.1‰ ≤ δ18O ≤ 33‰, n = 4011), hydrogen (−187‰ ≤ δD ≤ −4‰, n = 246), carbon (−26.7‰ ≤ δ13C ≤ 12.3‰, n = 1179), boron (−21.6‰ ≤ δ11B ≤ 9‰, n = 119), and silicon (−0.5‰ ≤ δ30Si ≤ 0.8‰, n = 33) are documented. Only nitrogen (1.6‰ ≤ δ15N ≤ 23.7‰, n = 258) and sulfide sulfur from deposits hosted in sedimentary rocks (−27.2‰ ≤ δ34S ≤ 25‰, n = 717) display secular variations. For nitrogen, the change in composition is interpreted to record the variation of δ15N values of sediments devolatilized during metamorphism. For sulfur, secular variations reflect incorporation of local sedimentary sulfur of ultimate seawater origin. No significant variation of temperature of vein formation is documented for orogenic gold deposits of different ages. Quartz-silicate, quartz-carbonate and sulfide-sulfide mineral pairs display consistent temperatures of 360 ± 76 °C (1σ; n = 332), in agreement with the more common greenschist facies hostrocks and fluid inclusion microthermometry. Fluid sources for orogenic gold deposits are complex but the isotopic systems (hydrogen, boron, carbon, nitrogen, oxygen, sulfur) are most consistent with contributions from metamorphic fluids released by devolatilization of igneous, volcano-sedimentary and/or sedimentary rocks. The contribution of magmatic water exsolved from magma during crystallization is not a necessary component, even if permissible in specific cases. Isotopic data arrays can be interpreted as the result of fluid mixing between a high T (~550 °C)—high δ18O (~10‰)—low δD (~−60‰) deep-seated (metamorphic) fluid reservoir and a low T (~200 °C)—low δ18O (~2‰)—high δD (~0‰) upper crustal fluid reservoir in a number of orogenic gold deposits. The origin of the upper crustal fluid is most likely sea- or meteoric water filling the host rock porosity, with a long history of water–rock isotope exchange. Mixing of deep-seated and upper crustal fluids also explains the large variation of tourmaline δ11B values from orogenic gold veins. Regional spatial variations of oxygen and hydrogen isotope compositions of deep-seated fluid reservoirs are documented between orogenic gold districts. This is the case for the Val-d’Or (Abitibi), Coolgardie and Kalgoorlie (Yilgarn) where the oxygen isotope composition of the deep-seated fluid end-member is 4‰ lower compared to that from the Timmins, Larder Lake, and Kirkland Lake districts (Abitibi). However, both mixing trends converge towards a common, low δ18O upper crustal fluid end-member. Such variations cannot be related to fluid buffering at the site of deposition and suggest provinciality of the fluid source. The contribution of meteoric water is mainly recorded by fluid inclusions from Mesozoic and Cenozoic age deposits, but micas are not systematically in isotopic equilibrium with fluid inclusions trapped in quartz from the same vein. This suggests late involvement of meteoric water unrelated to deposit formation. Yet, a number of deposits with low δD mica may record infiltration of meteoric water in orogenic gold deposits. Isotope exchange between mineralizing fluid and country rocks is documented for oxygen, carbon, sulfur and silicon isotopes. Large variations (> 10‰) of sulfide δ34S values at the deposit scale are likely related to evolving redox conditions of the mineralizing fluid during reaction with country rocks. Deposits hosted in sedimentary rocks show a shift to higher δ18O values as a result of fluid/rock oxygen exchange with the regional sedimentary country rocks.

show abstract

First-principles study of sulfur isotope fractionation in pyrite-type disulfides

Cited by 18 publications

References 55 publications

Iron and sulfur isotope factors for pyrite from experimental gamma-resonant studies and heat capacity

Iron and sulfur isotope factors for pyrite from experimental gamma-resonant studies and heat capacity

First-principles calculations of sulphur isotope fractionation in MX2 minerals, with M= Fe, Co, Ni and X2= AsS, SbS

The Light Stable Isotope (Hydrogen, Boron, Carbon, Nitrogen, Oxygen, Silicon, Sulfur) Composition of Orogenic Gold Deposits

Contact Info

Product

Resources

About