Preparation of sulfur dioxide for mass spectrometer analyses by combustion of sulfides with copper oxide

Fritz, P.; Drimmie, R.J.; Nowicki, V. K.

doi:10.1021/ac60337a044

Cited by 90 publications

(33 citation statements)

References 3 publications

(1 reference statement)

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“…The drill was cleaned between each sample extraction to ensure no crosssample contamination. Hand-picked or drilled mineral separates were combusted with excess CuO in vacuo to produce SO 2 by the method of Fritz et al (1974). Sulfur-isotope analyses were performed in the Central Science Laboratory at the University of Tasmania on a VG ISOGAS stable isotope mass spectrometer.…”

Section: Methodsmentioning

confidence: 99%

Detailed sulfurisotope investigation of the TAG hydrothermal mound and stockwork zone, 26°N, Mid-Atlantic Ridge

Gemmell¹,

Sharpe²

1998

Proceedings of the Ocean Drilling Program

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Drilling of the Trans-Atlantic Geotraverse (TAG) hydrothermal mound and underlying stockwork zone has revealed a complex internal stratigraphy consisting of, with increasing depth, massive pyrite and pyrite breccias, with significant chalcopyrite and sphalerite in places, pyrite-anhydrite breccias, pyrite-silica breccias, silicified wallrock breccias, and chloritized basalt breccias. Several stages of quartz pyrite ± chalcopyrite veins occur in the stockwork zone and lower portions of the mound whereas anhydrite ± pyrite ± chalcopyrite veins are common within the central and upper parts of the mound.A detailed sulfur-isotope investigation of sulfides and sulfates within mound and the underlying stockwork zone has revealed that the overall range of sulfide δ 34 S analyses is from 0.35‰ to 10.27‰, with a mean of 7.20‰. Anhydrite has a mean δ 34 S value of 21.10‰ within a tight range of 20.55‰-21.56‰.There are distinct differences in δ 34 S values between the different textural types of pyrite (massive sulfide, breccia clasts, disseminations associated with alteration, and veins) within the hydrothermal mound and stockwork zone. The massive sulfide and breccia clasts have a similar distribution of isotope values (δ 34 S = 6‰-8‰), however the δ 34 S values of the disseminated pyrite associated with the alteration are distinctly heavier (δ 34 S = 8‰-10‰). Vein sulfides have the lightest δ 34 S values (δ 34 S = 5‰-7‰) at TAG. The sulfur-isotope values measured at TAG are, in general, the heaviest reported for unsedimented mid-ocean ridge deposits.A sulfur-isotope model is proposed to account for the heavy δ 34 S signature (compared to other sediment-free hydrothermal systems), the distribution of δ 34 S values from the various textural styles and the spatial distribution of the δ 34 S values both laterally and vertically throughout the hydrothermal mound and underlying stockwork zone. The two initial sources of sulfur during the life of the TAG hydrothermal system are seawater sulfate (δ 34 S = 21‰) and mid-ocean ridge basalt (MORB) derived sulfur (δ 34 S = 0‰-1‰). Variations in δ 34 S values at TAG can be explained in a model where totally to partially reduced seawater sulfate of shallow origin mixes with a deep hydrothermal fluid dominated by MORB sulfur and interacts with previously formed sulfide and sulfate minerals in the upper parts of the stockwork zone and within the mound. Deep subseafloor processes cause the initial hydrothermal fluids entering the TAG system at depth to have a δ 34 S value of approximately 0‰-1‰. This fluid mixes with locally entrained partially reduced seawater in the upper parts of the subseafloor stockwork system (created by local hydrothermal convection though the porous and permeable mound and stockwork zone) and creates a modified hydrothermal fluid with a δ 34 S value of approximately 6‰−7‰. The fluid rises to the seafloor, precipitating pyrite in the quartz-pyrite veins (δ 34 S = 6‰−7‰) in the upper parts of the stockwork, and mixes with cold seawater, which causes rapid pr...

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Section: Methodsmentioning

confidence: 99%

Detailed sulfurisotope investigation of the TAG hydrothermal mound and stockwork zone, 26°N, Mid-Atlantic Ridge

Gemmell¹,

Sharpe²

1998

Proceedings of the Ocean Drilling Program

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“…Robinson and Kusakabe (1975) used Cu2O for direct oxidation of sulphide minerals to SO,. They noted, as did Fritz et al (1974) using CuO, that difficulties were experienced burning certain minerals, e.g., ZnS, PbS. This does not appear to be the case for the current technique, although the yields seem slightly lower for pyrite and pyrrhotite.…”

Section: Resultsmentioning

confidence: 71%

“…Direct combustion of Ag2S and other sulphide minerals to SO2 has been carried out using 02 (e.g., Thode et al, 1961), 02-N2 mixtures (e.g., Sakai and Yamamoto, 1966), and solid oxidants such as PbO (Vinogradov et al, 1956), V205 (Gavelin et al, 1960;Ricke, 1964), CuO (Grinenko, 1962;Fritz et al, 1974) or Cu2O (Robinson and Kusakabe, 1975). In these combustions, the yields of SO, were often below 95% and proper corrections were not always made for oxygen isotope variations in the SO2.…”

Section: Introductionmentioning

confidence: 99%

Direct conversion of sulphide and sulphate minerals to SO2 for isotope analyses.

Ueda

Krouse

1986

Geochem. J.

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Sulphide and sulphate minerals mixed with V205 and Si02, were heated in a vacuum at 950°C for 15 minutes. The evolved S03 was converted to S02 by reaction with metallic Cu for sulphur isotope determinations. This technique yields S02 of consistent oxygen isotope composition regardless of whether sulphide or sulphate is converted. The reproducibilities of sulphur conversion and S34S values were 98 ±5% and ±0.2%d, respectively. The technique is particularly suitable for small samples. Successful isotope determinations have been obtained with natural samples containing less than 1 mg S. In some cases, varia tions in S34S of 2% have been found for single grains analysed from a small specimen.

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“…Oxygen and hydrogen were released from milky, clear and smoky quartz using the BrF 5 extraction technique of Clayton and Mayeda (1963) and Friedman and O'Neil (1977), whereas carbon and oxygen in calcite by using the CO 2 treating of Clayton et al (1972). Sulfur was released as SO 2 after the method of Fritz et al (1974). The isotopic ratios are reported in standard δ notation per mil relative to SMOW for oxygen and hydrogen, Pee Dee belemnite for carbon, and Cañon Diablo troilite for sulfur.…”

Section: Methodsmentioning

confidence: 99%

Later stages of evolution of an epithermal system: Au–Ag mineralizations at Apigania Bay, Tinos Island, Cyclades, Hellas, Greece

et al. 2008

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Precious metals accompany all types of epithermal deposits. In general, the largest of these deposits occur in intrusive or extrusive rocks of alkaline or calc-alkaline affinity. The Apigania Bay vein system and Au-Ag mineralization is hosted in Mesozoic marbles and schists, and is composed primarily of five nearly parallel, high-angle quartz veins that extend for at least 200 m. Gold-silver mineralization, in association with more than thirty ore and vein minerals, is developed in three stages and occurs at the contact of marbles and schists. Zones of epidote-chlorite-calcite and sericite-albite alteration are associated with precious metal-bearing milky and clear quartz veins. Fluid inclusion studies suggest that hydrothermal mineralization was deposited under hydrostatic pressures of~100 bars, at temperature of 120-235°C, from low to moderate, calcium-bearing, saline fluids of 0.2 to 6.8 equiv. wt.% NaCl. Calculated isotope compositions (δ 18 O=−4.7‰ to 1.7‰ and δD= −120‰ to −80‰) for waters in equilibrium with milky and clear quartz are consistent with mixing with dilute, low temperature meteoric ore fluids. Calculated δ 13 C CO2 (0.6‰ to 1.1‰) and δ 34 S H2S (−7.3 to −0.3‰) compositions of the ore fluids indicate exchange, in an open system, with a metasedimentary source. Gold and silver deposition was associated with degassing of hydrogen due to intense uplift of the mineralizing area. The physicochemical conditions of mineralization stages I to III range between 200°C and 150°C, f S 2 ¼ 10

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Preparation of sulfur dioxide for mass spectrometer analyses by combustion of sulfides with copper oxide

Cited by 90 publications

References 3 publications

Detailed sulfurisotope investigation of the TAG hydrothermal mound and stockwork zone, 26°N, Mid-Atlantic Ridge

Detailed sulfurisotope investigation of the TAG hydrothermal mound and stockwork zone, 26°N, Mid-Atlantic Ridge

Direct conversion of sulphide and sulphate minerals to SO2 for isotope analyses.

Later stages of evolution of an epithermal system: Au–Ag mineralizations at Apigania Bay, Tinos Island, Cyclades, Hellas, Greece

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Preparation of sulfur dioxide for mass spectrometer analyses by combustion of sulfides with copper oxide

Cited by 90 publications

References 3 publications

Detailed sulfurisotope investigation of the TAG hydrothermal mound and stockwork zone, 26°N, Mid-Atlantic Ridge

Detailed sulfurisotope investigation of the TAG hydrothermal mound and stockwork zone, 26°N, Mid-Atlantic Ridge

Direct conversion of sulphide and sulphate minerals to SO2 for isotope analyses.

Later stages of evolution of an epithermal system: Au–Ag mineralizations at Apigania Bay, Tinos Island, Cyclades, Hellas, Greece

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Detailed sulfurisotope investigation of the TAG hydrothermal mound and stockwork zone, 26°N, Mid-Atlantic Ridge

Detailed sulfurisotope investigation of the TAG hydrothermal mound and stockwork zone, 26°N, Mid-Atlantic Ridge