Vienna Canyon Diablo Troilite Research Articles

Isotopic constraints on the sulfur cycle of the Bottom Convective Layer in the Black Sea

The Black Sea is the largest euxinic seawater basin with H2S at depths of below 90 m. Previously found that the presence of H2S in water was caused by microbial sulfate reduction. Herein, we report the sulfur isotopic composition of sulfate and sulfide in seawater at stations in the central part of the Black Sea, especially from the Bottom Convective Layer (BCL) located below a water depth of 1750 m. Our study shows that the sulfur isotopic composition of sulfate (δ34S(SO4)) in the surface layer of the oxic zone is +21.1‰ ± 0.1‰ relative to the Vienna Canyon Diablo troilite (VCDT), and does not differ from sulfate in the Mediterranean Sea. In the BCL, the average δ34S(SO4) value is +23.0‰ ± 0.2‰, which does not change vertically or laterally owing to effective convective mixing. The sulfur isotopic composition of H2S varies from −40.0‰ to −41.9‰ between 200 m water depth down to the seafloor with an average δ34S(H2S) value of −40.6‰ ± 0.4‰ for the BCL.Based on the water mass balance and sulfur isotopic composition of sulfate in the relevant water masses affecting the BCL, we have formulated a model to calculate the sulfate reduction rate in the BCL. After evaluating the sulfate and sulfide sources in the BCL, we assumed that the only apparent sulfide source is a bacterial sulfate reduction in the water column, and the main sulfate source is a mixture of water from the Black Sea and the lower Bosporus current with an initial sulfate isotopic composition of +21‰. The weak water exchange in the BCL leads to the largest observed isotopic difference ΔSR = δ34S(SO4) − δ34S(H2S) of 63.6‰ between sulfate and sulfide in the sulfidic water column of the Black Sea. To achieve a steady state with respect to the sulfate isotopic composition +23‰ in the BCL, an average sulfate reduction (SR) rate of 1.1 ± 0.1 nmol L−1 day−1 is required. A steady state relative to sulfur isotopic composition of sulfate in the BCL water was established 4200 years ago. The estimated residence time of H2S was 1.5 times shorter (946 years) than that of sulfate (1390 years). The latter is close to the water renewal time of the BCL (1432 years). Different residence times of sulfide and sulfate in the BCL are explained using their different fluxes from the BCL. Sulfate is mainly removed from the BCL via vertical advection, while a considerable part of the sulfide generated in the BCL (1/3 of total annual production) is probably spent on the sulfidation (FeS → FeS2) of muddy turbidites. The estimated annual H2S production in the BCL is 0.78 ± 0.07 Tg. The developed model predicts that the sulfide concentration in the BCL remains practically unchanged (380 ± 5 μM) over the last 1800 years (after 5700 years from the onset of anoxia).

The Characteristics and Origin of Barite in the Giant Mehdiabad Zn-Pb-Ba Deposit, Iran

Abstract Mehdiabad is the world’s largest Mississippi Valley-type (MVT) Zn-Pb deposit (394 million tonnes [Mt] of metal ore at 4.2% Zn, 1.6% Pb) and contains significant barite resources (>40 Mt). Such large accumulations of barite are not common in carbonate-hosted Zn-Pb deposits. Therefore, the origin of the barite and its association with the Zn-Pb mineralization is of significant interest for further investigation. Field work and petrographic studies indicate that the Zn-Pb-Ba orebodies in the Mehdiabad deposit are hosted by Lower Cretaceous carbonate units of the Taft and Abkuh Formations. Fine- to coarse-grained barite with lesser siderite formed in three stages (S1, S2, and S4), along with a quartz-sulfide stage (S3) with minor quartz, sphalerite, galena, chalcopyrite, and pyrite, and the main Zn-Pb sulfide stage (S5) with massive sphalerite and galena. The barites have δ34S values from 17.7 to 20.6‰, δ18O values from 13.2 to 16.8‰, Δ33SV-CDT values from –0.001 to 0.036‰, and initial 87Sr/86Sr ratios from 0.707327 ± 0.000008 to 0.708593 ± 0.000008 (V-CDT = Vienna-Canyon Diablo Troilite). The siderites have δ13CV-PDB values from –3.8 to –2.7‰, and δ18OV-SMOW values from 18.2 to 20.9‰ (V-PDB = Vienna-Pee Dee Belemnite, V-SMOW = Vienna-standard mean ocean water). These geochemical data, and the barite morphology, point to a diagenetic origin for all stages of barite. We suggest that S1 and S2 barite precipitated from pore fluids at the sulfate-methane transition zone in a methane-diffusion-limited environment with increasing methane content. S4 barite precipitated when the methane- and barium-bearing cold-seep fluid migrated to the shallow carbonate sediments and formed a methane-in-excess setting. For the three stages, the SO42- in barite came from the residual SO42- in pore fluids undergoing sulfate-driven anaerobic oxidation of methane, and the Ba2+ came from dissolved biogenic barite and terrigenous materials in the Taft and Sangestan Formations. Primary fluid inclusions trapped in S3 quartz have salinities of 5.6 to 8.1 wt % NaCl equiv and homogenization temperatures of 143.8° to 166.1°C. The quartz has δ18OV-SMOW values ranging from 9.8 to 22.5‰ and δ30Si values from –1.3 to –0.9‰. These data indicate hydrothermal fluid flow occurred between the diagenetic S2 and S4 events. Secondary fluid inclusions with salinities of 17.70 to 19.13 wt % NaCl equiv and homogenization temperatures of 123.0° to 134.0°C are found in the S3 quartz, too. They might represent the hydrothermal event formed by basinal brines in S5. According to the ore textures and the comparison of the sulfur isotopes between S5 Zn-Pb sulfides and the digenetic barites, the barite provided a host and a sulfur source for the later Zn-Pb mineralization. The relationship between barite and the Zn-Pb mineralization indicates that significant accumulations of sulfates may be a critical exploration target for this kind of giant deposit.

New Potential Sphalerite, Chalcopyrite, Galena and Pyrite Reference Materials for Sulfur Isotope Determination by Laser Ablation‐MC‐ICP‐MS

The sulfur isotope system is important in tracing a variety of geochemical processes. However, the availability of matrix‐matched reference materials for in situ sulfur isotope ratio measurement is limited. This study analysed four sulfide specimens to investigate their potential as reference materials for in situ sulfur isotope determination, including three natural sulfide minerals (sphalerite SPH‐1, chalcopyrite GC‐1 and galena NWU‐GN), and one resin preserved pyrite powder (RPPY). These four sulfides were analysed independently in four laboratories using both bulk and microbeam analysis techniques, all of which gave equivalent results within uncertainty with comparable accuracy and precision. The sulfur isotopes of these four sulfides are homogeneous based on a large number of isotope determinations by solution nebulisation multi‐collector inductively coupled plasma‐mass spectrometry (MC‐ICP‐MS) and laser ablation (LA) MC‐ICP‐MS. The mean δ34S values for SPH‐1, RPPY, GC‐1 and NWU‐GN determined by gas source isotope ratio mass spectrometry (GS‐IRMS) and solution nebulisation MC‐ICP‐MS are −7.13 ± 0.41‰ (2s), 3.66 ± 0.24‰ (2s), −0.65 ± 0.28‰ (2s), 28.21 ± 0.17‰ (2s) relative to the Vienna‐Canyon Diablo troilite (V‐CDT) reference value, respectively, and which are proposed as potential preferred values. Over 400 spot analyses performed on randomly selected fragments of each sulfide by LA‐MC‐ICP‐MS yielded highly consistent δ34S values with the preferred values. Thus, SPH‐1, GC‐1, NWU‐GN and RPPY are considered a set of candidate matrix‐matched sulfide reference materials for in situ sulfur isotope determination.

Microscopic and NanoSIMS characterization of black shale-hosted pre-kinematic pyrites: Possible gold source of the orogenic gold deposits in the Truchas Syncline (Variscan Iberian Massif)

The Truchas Syncline contains orogenic gold deposits (OGDs), hosted mainly by the Armorican Quartzite Fm. In order to look for the source of gold in these deposits, pre-kinematic sulphides from black shales from the overlying Luarca Fm. were studied using both optical and scanning electron (SEM) microscopy, as well as nanoscale secondary ion mass spectrometry (NanoSIMS). NanoSIMS images allowed the observation of relevant structures (pyrite with high As content nodules) hidden to SEM.Microscopy and 36S, 75As32S, 75As, 75As34S, and 197Au mappings, as well as δ34S analysis (‰ Vienna-Canyon Diablo Troilite) allowed 4 types of pyrite to be characterized. According to their sequence of deposition, the pyrite types identified are the following: (1) framboid nuclei (FmPy), with δ34S between +4.1‰ and +57.5‰; (2) overgrowths (OgPy), with presence of Au, As and δ34S of approximately +20.5‰; (3) pyrite with high As content (AsPy), replacing previous pyrites, with δ34S of approximately +23‰, nodular shapes and non-detected Au; (4) subhedral pyrite (ShPy), with δ34S of approximately +19.7‰ and Au and As distribution showing (a) nuclei, (b) rims with Au and As and (c) structures interpreted as replacements of previous pyrite. Luarca Fm. pyrite framboids reach 75 µm in size, larger than framboids described in most previous NanoSIMS work, with microcrystals sufficiently large to be analyzed without contamination from edge effects. The FmPy formed in early diagenetic conditions by dissimilatory reduction of marine sulphate plus Rayleigh distillation or anaerobic oxidation of methane processes. The first FmPy nuclei formed in the periphery of framboids, and then started to form in the central region until completion of the framboidal structure. Growth of OgPy, AsPy and ShPy corresponded to more advanced diagenetic conditions, although the last stage of ShPy growth followed an aggregation model, in which ShPy metamorphic pyrites grew over ShPy diagenetic pyrites.The sulphur isotopic signature of the four types of pyrite is in good agreement with a source from Ordovician marine sulphate. A hypothesis stating that the source of Au in OGDs in the district could be in Luarca Fm. is supported by the results of the present research. Firstly, a source of Au in the district could have been the replacement of previous pyrites by AsPy and the release of Au to the system, instead of the framboidal to euhedral pyrite recrystallization process observed in other gold deposits. Secondly, by the correspondence between δ34S isotopic signature of the pyrites from Luarca Fm. and those from sulphides in OGDs. However, these results do not rule out other possible sources.

Tracing sulfur sources in the crust via SIMS measurements of sulfur isotopes in apatite

We present a refined approach for acquiring sulfur (S) isotope compositions (33S/32S, 34S/32S) in apatite by secondary ion mass spectrometry (SIMS), including the characterisation of new reference materials. In order to test the method, we analyzed potential apatite reference samples for their S isotope ratios via three different bulk methods. The investigated apatite samples contain S concentrations between ~160 μg/g and 3100 μg/g and their 34S/32S (δ34S) ratios deviate by more than 25‰ from the Vienna-Canyon Diablo Troilite (VCDT) standard. We identified four candidates as new primary reference materials for routine SIMS S isotope measurements of apatite. Based on ICP-MS, EA-IRMS, and fluorination analyses, recommended S isotope values are +12.27± 0.22 (2σ) ‰ δ34S for SAP1, +14.02 ± 0.22 (2σ) ‰ δ34S for Big1, −1.06 ± 0.80 (2σ) ‰ δ34S for Durango-A, and −1.39 ± 0.48 (2σ) ‰ for Durango-B. By selecting one of those four primary standards for SIMS analysis, the S isotope values of the other reference materials and additional tested apatite specimens can be reproduced to within 1‰. Under optimized SIMS conditions, single spot uncertainty for δ34S that combines the within-spot precision and the repeatability of measurements of the primary apatite reference material during an analytical session is ±0.4‰ (95% CI). We also show that in apatite with S > 1000 μg/g, SIMS analysis permits the detection of mass-independent S isotope signatures (i.e., Δ33S) that are larger than ~1.0‰ if an average of multiple grains is used, and larger than ~1.5‰ for a single analytical point. Furthermore, our study shows that apatite can record S isotope signatures from extremely diverse environments, making this near-ubiquitous mineral a key candidate for tracing S source reservoirs and to track the pathway of magmatic-hydrothermal fluids in a wide range of geological settings.

Genesis of sediment‐hosted stratiform Cu–Co deposits of the Zambia Copperbelt: Geochemistry and S–Pb isotopes constraints from the Chambishi deposit

In this study, we present new field geology, whole‐rock geochemical and S–Pb isotope data for the Chambishi deposit in the Zambia Copperbelt (ZCB), in order to constrain the mineralization process and ore sulphur and metal source. The Lower Roan Subgroup clastic rocks are compositionally similar to the Post‐Archean Australian Shale and have low Chemical Index of Alteration, indicating a felsic and slightly weathered source, which we proposed to be the felsic Lufubu Metamorphic Complex (LMC). The Th, Ti, and Zr elemental features suggest that the Lower Roan Subgroup was deposited in a rift basin of passive margin. The 34S values of early‐stage diagenetic Cu‐Co sulphide (−6.2 to +6.6‰, Vienna Canyon Diablo Troilite [V‐CDT]) from the nodular and layered ores are lower than those of the late‐stage vein‐type hydrothermal Cu–Co sulphides and disseminated molybdenites (3.9–11.9‰, V‐CDT), indicating different sulphur precipitation mechanism in the two mineralization stages. Integrated with previous fluid inclusion studies, we suggest that the sulphur for the diagenetic sulphides was from bacterial reduction of sedimentary anhydrite and seawater sulphates, whereas that for the orogenic‐stage sulphides was from both diagenetic sulphide remobilization and from thermochemical sulphate reduction. The mean 238U/204Pb ratios of the diagenetic‐ and orogenic‐stage sulphides are 10.21 and 10.44, respectively, overlapping with those of the average Lufubu schist (10.38) and the Mufulira granodiorite (10.21), and suggest the LMC as the main ore metal source.

Geochronology and Stable Isotope Analysis of Fracture-Fill and Karst Mineralization Reveal Sub-Surface Paleo-Fluid Flow and Microbial Activity of the COSC-1 Borehole, Scandinavian Caledonides

The deep biosphere hosted in fractured rocks within the upper continental crust is one of the least understood and studied ecological realms on Earth. Scarce knowledge of ancient life and paleo-fluid flow within this realm is owing to the lack of deep drilling into the crust. Here we apply microscale high spatial-resolution analytical techniques to fine-grained secondary minerals in a deep borehole (COSC-1) drilled into the Silurian-Devonian Scandinavian Caledonide mountain range in central Sweden. The aim is to detect and date signs of ancient microbial activity and low-temperature fluid circulation in micro-karsts (foliation-parallel dissolution cavities in the rock) and fractures at depth in the nappe system. Vein carbonates sampled at 684 to 2210 m show a decreased C isotope variability at depths below 1050 m; likely due to decreased influence of organic-C at great depth. Micro-karsts at 122–178 m depth feature at least two generations of secondary calcite and pyrite growth in the voids as shown by secondary ion mass spectrometry analytical transects within individual grains. The younger of these two precipitation phases shows 34S-depleted δ34Spyrite values (−19.8 ± 1.6‰ vs. Vienna-Canyon Diablo Troilite (V-CDT)) suggesting microbial sulfate reduction in situ. The calcite of this late phase can be distinguished from the older calcite by higher δ18Ocalcite values that correspond to precipitation from ambient meteoric water. The late stage calcite gave two separate laser ablation inductively coupled mass spectrometry-derived U-Pb ages (9.6 ± 1.3 Ma and 2.5 ± 0.2 Ma), marking a minimum age for widespread micro-karst formation within the nappe. Several stages of fluid flow and mineral precipitation followed karst formation; with related bacterial activity as late as the Neogene-Quaternary; in structures presently water conducting. The results show that our combined high spatial-resolution stable isotope and geochronology approach is suitable for characterizing paleo-fluid flow in micro-karst; in this case, of the crystalline crust comprising orogenic nappe units.

Sulfur isotope analysis for representative regional background atmospheric aerosols collected at Mt. Lulin, Taiwan

Air pollution resulted from fossil fuel burning has been an environmental issue in developing countries in Asia. Sulfur-bearing compounds, in particular, are species that are regulated and monitored routinely. To assess how the species affect at local and global scales, regional background level has to be defined. Here, we report analysis of sulfur isotopes in atmospheric sulfate, the oxidation end product of sulfur species, in particulate phase collected at the Lulin observatory located at 2862 m above mean sea level in 2010. The averaged sulfate concentration for 44 selected samples is 2.7 ± 2.3 (1-σ standard deviation) μg m−3, and the averaged δ34S is 2.2 ± 1.6‰, with respect to the international standard Vienna Canyon Diablo Troilite. Regardless of the origins of air masses, no noticeable difference between the low-altitude Pacific and high-altitude free troposphere sulfate aerosols is observed. Also, no identifiable seasonal cycle in seen. Correlation analysis with respect to coal burning tracers such as lead and oil industry tracers such as vanadium shows sulfate concentration is in better correlation with vanadium (R2 = 0.86, p-value < 0.001) than with lead (R2 = 0.45, p-value < 0.001) but no statistically significant correlation is found in δ34S with any of physical quantities measured. We suggest the sulfate collected at Lulin can best represent the regional background level in the Western Pacific, a quantity that is needed in order to quantitatively assess the budget of sulfur in local to country scales.

Sulfur Isotope Ratios from VMS Deposits in the Penokean Volcanic Belt, Great Lakes Region, USA: Constraints on the Source of Sulfur in a Paleoproterozoic Intra-Arc Rift

The Paleoproterozoic (~1.8 Ga) Penokean Volcanic Belt (PVB) in the Great Lakes Region of North America hosts several polymetallic volcanogenic massive sulfide (VMS) deposits. These deposits were formed by back-arc extensional volcanism during the accretion of island-arc terranes along the southern margin of the Archean Superior Craton. This study reports δ34S values obtained from sulfide minerals collected from eight VMS deposits in the PVB: Back Forty, Bend, Eisenbrey, Flambeau, Horseshoe, Lynne, Reef, and Schoolhouse. The average δ34S values from most of these deposits lie within the mantle-range between −2 and 2‰, relative to Vienna Canyon Diablo Troilite (V-CDT). Average δ34S values from Back Forty and Lynne deposits are slightly higher, at 2.5 and 2.4‰, respectively. No systematic variation in δ34S was observed based on factors such as the kind of sulfide mineral, ore-texture, type of host rock, or the nature of host-rock alteration. The narrow observed range from the PVB offers a clear indication that sulfur in the mineralizing fluid, originated predominantly from a magmatic source. If there was a significant contribution of sulfur from seawater, the δ34S of seawater sulfur must also have been close to the mantle range. Slightly higher values from Back Forty and Lynne indicate minor involvement of oxidized sulfur at shallow water levels, possibly derived from the continental margin.

Pyrite sulfur isotopes constrained by sedimentation rates: Evidence from sediments on the East China Sea inner shelf since the late Pleistocene

Isotopic compositions of coeval sulfide and sulfate have been widely employed to reconstruct the seawater chemistry evolution over geologic time; however, these signals can be modulated by other factors, such as the sedimentation rate. Here, we present a data set of pyrite sulfur isotopes (δ34Spy) derived from 60-m drilled core sediments deposited on the inner shelf of the East China Sea since 16.5 ka. The resulting δ34Spy values range from −38.2 to 15.0‰ (Vienna Canyon Diablo Troilite; V-CDT), representing a range of 53.2‰. Freshwater deposition before 12.3 ka produced a limited pyrite abundance and δ34Spy values that fall within the typical range of freshwater environments. After the marine incursion in the study area at 12.3 ka, variations in the δ34Spy values become significantly correlated with sedimentation rates (SRs; r = 0.78, p < 0.01), which were controlled by the intensity of coastal currents in response to the East Asian winter monsoon. Specifically, pyrite sulfur is markedly depleted in 34S during the intervals with low SRs (δ34Spy < −30‰) relative to that observed during the intervals with high SRs (δ34Spy > 0‰), suggesting that SRs exert controls on δ34Spy values. We propose that these sedimentary controls are expressed by modulating the connectivity between porewaters and the overlying seawater. Low SRs tend to form an open diagenetic system, in which the pyrites are able to preserve the large biological fractionations associated with microbial sulfate reduction (and disproportionation). In contrast, high SRs favour a restricted diagenetic system, in which the distillation of porewater sulfate produces pyrites enriched in 34S, masking the magnitude of biological fractionation during microbial sulfur cycling. These findings highlight the critical effect of the local sedimentation regime on pyrite sulfur isotopic compositions, especially within shallow depositional environments, over geologic time.

Sources of sulphate minerals in limestone cave-a possible evidence of anthropogenic activity: a case study in Črna Jama Cave (Slovenia).

In the caves, the formation of cave minerals is a consequence of a variety of chemical reactions, some of them also due to human activity. There are many caves in Slovenia, but sulphate minerals are not very often reported and analysed. In this study, the presence of sulphate minerals is detected by SEM/EDS analysis of speleothems from Črna Jama, a cave near Kočevje (southern Slovenia). The cave is characterised by its dark, almost black colour on cave walls, floor and speleothems. Anthropogenic influence in the cave is still visible, including the remains of a fireplace, some inscriptions on the walls and wooden containers. The analyses of some of the black-coated speleothems reveal the presence of calcium sulphate, confirmed by XRD as gypsum. Gypsum crystals are around 50μm in size, and they occur in thin crusts. Additionally, some rare authigenic baryte crystals a few micrometres in size are detected. The sulphates δ34S value in gypsum found on dark coloured speleothems is +10.4‰ Vienna Canyon Diablo Troilite (VCDT), while the sulphate δ34S of the bedrock is +8.6‰ VCDT. The more likely source of sulphate ions is thus biomass burning rather than bedrock. Also, bedrock and biomass ash are a very probable source of calcium and barium. The highly probable pyrogenous origin of sulphates draws attention to human impact on cave mineralogy.

Sulphur isotope mass-independent fractionation observed in comet 67P/Churyumov–Gerasimenko by Rosetta/ROSINA

The knowledge about sulphur isotopic fractionation in volatile cometary species is limited as only measurements in five comets have been done and only for ³⁴S/³²S. The lack of information about the fractionation of ³³/³²S makes it impossible to compare them with what is known from refractories. We present results of ³⁴S/³²S and for the first time ³³S/³²S isotopic ratio in H₂S, OCS, and CS₂ in the coma of comet 67P/Churyumov–Gerasimenko. Observations used for this study were performed with Rosetta Orbiter Spectrometer for Ion and Neutral Analysis/Double Focusing Mass Spectrometer during 2014 October and 2016 May. Bulk isotopic ³³S/³²S and ³⁴S/³²S ratios derived from these three species yield δ³³S = (−302 ± 29)‰ and δ³⁴S = (−41 ± 17)‰, respectively. The observed isotopic fractionation is significantly different from the assumed Solar system standard [Vienna-Canyon Diablo Troilite (V-CDT)] and all other reported values for Solar system objects, except other comets. Furthermore, we show that neither mass-dependent nor mass-independent fractionation due to photodissociation as it has been observed in recent laboratory studies can be the cause of the significant depletion compared to Solar system standard. In addition, we conclude that there seems to be an intrinsic difference in sulphur isotopic fractionation in cometary volatiles and refractories while the difference between molecules is most likely due to different chemical pathways. The significant fractionation of sulphur isotopes together with a high D₂O/HDO versus HDO/H₂O and non-solar isotopic ratio for xenon as well as for Si point towards a non-homogeneously mixed protosolar nebula.

Biogenic overgrowth on detrital pyrite in ca. 3.2 Ga Archean paleosols

Regionally traceable paleosols in the lower Moodies Group of the Barberton greenstone belt (ca. 3.22 Ga, northeastern South Africa and Swaziland) contain locally abundant silicified nodules, originally composed of pedogenic carbonates and sulfates, interbedded with heavy-mineral laminae dominated by pyrite. Pyrite grains show rounded detrital cores and secondary idiomorphic rims with trace element concentrations and δ 34 S ratios clearly different from those of the cores. While cores have low Co and Ni concentrations and high Co/Ni ratios, rims show as much as 5.5 wt% of these elements and low Co/Ni ratios, reflecting the weathering of nearby ultramafic rocks. In-situ sulfur isotope analyses of pyrite cores show δ 34 S VCDT (Vienna Canyon Diablo troilite) values between +5‰ and −5‰, while the rims show δ 34 S VCDT values between −20‰ and −24.5‰, suggesting biogenic fractionation of sulfur. The close spatial association and microtextural evidence for nearly contemporaneous formation of the pedogenic sulfate nodules and the secondary pyrite rims suggests microbial processing of sulfur in the paleosols, which provided reduced and 34 S-depleted sulfur for the growth of authigenic pyrite. This indicates that vadose-zone soil-forming processes in the Archean involved not only physical and chemical modification of moist, unconsolidated sediment in a terrestrial environment but also already included its microbiological modification.

Sulfur isotope homogeneity of lunar mare basalts

We present a new set of high precision measurements of relative 33S/32S, 34S/32S, and 36S/32S values in lunar mare basalts. The measurements are referenced to the Vienna-Canyon Diablo Troilite (V-CDT) scale, on which the international reference material, IAEA-S-1, is characterized by δ33S=−0.061‰, δ34S≡−0.3‰ and δ36S=−1.27‰. The present dataset confirms that lunar mare basalts are characterized by a remarkable degree of sulfur isotopic homogeneity, with most new and published SF6-based sulfur isotope measurements consistent with a single mass-dependent mean isotopic composition of δ34S=0.58±0.05‰, Δ33S=0.008±0.006‰, and Δ36S=0.2±0.2‰, relative to V-CDT, where the uncertainties are quoted as 99% confidence intervals on the mean. This homogeneity allows identification of a single sample (12022, 281) with an apparent 33S enrichment, possibly reflecting cosmic-ray-induced spallation reactions. It also reveals that some mare basalts have slightly lower δ34S values than the population mean, which is consistent with sulfur loss from a reduced basaltic melt prior to eruption at the lunar surface. Both the sulfur isotope homogeneity of the lunar mare basalts and the predicted sensitivity of sulfur isotopes to vaporization-driven fractionation suggest that less than ≈1–10% of lunar sulfur was lost after a potential moon-forming impact event.

In situ LA–MC–ICP–MS boron isotope and zircon U–Pb age determinations of Paleoproterozoic borate deposits in Liaoning Province, northeastern China

A large number of Paleoproterozoic borate deposits are hosted by the lower units of a volcanic-sedimentary sequence in Liaoning Province, northeastern China, and are a major source of boron in China. The ore-bearing wall rocks in the deposits are serpentinized ultrabasic rocks and carbonates, with layered leptynites, leptites, amphibolites, and migmatites adjacent to the ore. Both the borate ores and country rocks contain tourmaline, although the country rocks have much lower abundances of the mineral. Based on in situ boron isotope measurements using laser ablation–multi-collector–inductively coupled plasma–mass spectrometry (LA–MC–ICP–MS), boron isotope data show that: (1) δ11B values of borate ores range from +6.8‰ to +13.9‰ (mean +10.8‰); (2) tourmalines from the borate ores have δ11B values from +9.5‰ to +12.7‰; and (3) the wall rocks within the borate ores yield slightly lower δ11B values ranging from +5.7‰ to +7.6‰, and those outside the deposits from −9.9‰ to −5.9‰. Positive δ11B values in borates as well as in tourmalines inside the mining area indicate that boron in these Paleoproterozoic borate deposits was derived from marine evaporites. δ34SV-CDT (where V-CDT is Vienna Canyon Diablo Troilite) values of borate ores, serpentinized marbles, and anhydrites range from +16.1‰ to +24.7‰, whereas δ13CV-PDB (where V-PDB is Vienna Pee Dee Belemnite) values of marbles range from +3.2‰ to +5.9‰. These isotopic characteristics are interpreted to reflect formation in a marine evaporative environment. LA–MC–ICP–MS zircon weighted207Pb/206Pb ages of leptite and serpentinized olivine basalt from the hanging wall of the borate deposits are 2139±13Ma and 2130±19Ma, respectively. Therefore, the (~2.2Ga) borate deposits may have originated from marine evaporative boron-bearing sediments, which were interbedded within bimodal volcanic rocks during the early stages of development of the Liaoji rift.

Genesis of the Au–Bi–Cu–As, Cu–Mo ± W, and base–metal Au–Ag mineralization at the Mountain Freegold (Yukon, Canada): constraints from Ar–Ar and Re–Os geochronology and Pb and stable isotope compositions

The genesis of mineralized systems across the Mountain Freegold area, in the Dawson Range Cu–Au ± Mo Belt of the Tintina Au province was constrained using Pb and stable isotope compositions and Ar–Ar and Re–Os geochronology. Pb isotope compositions of sulfides span a wide compositional range (206Pb/204Pb, 18.669–19.861; 208Pb/204Pb, 38.400–39.238) that overlaps the compositions of the spatially associated igneous rocks, thus indicating a magmatic origin for Pb and probably the other metals. Sulfur isotopic compositions of sulfide minerals are broadly similar and their δ34S (Vienna-Canyon Diablo Troilite (V-CDT)) values range from −1.4 to 3.6 ‰ consistent with the magmatic range, with the exception of stibnite from a Au–Sb–quartz vein, which has δ34S values between −8.1 and −3.1 ‰. The δ34S values of sulfates coexisting with sulfide are between 11.2 and 14.2 ‰; whereas, those from the weathering zone range from 3.7 to 4.3 ‰, indicating supergene sulfates derived from oxidation of hypogene sulfides. The δ13C (Vienna Peedee Belemnite (VPDB)) values of carbonate range from −4.9 to 1.1 ‰ and are higher than magmatic values. The δ18O (V-SMOW) values of magmatic quartz phenocrysts and magmatic least-altered rocks vary between 6.2 and 10.1 ‰ and between 5.0 and 10.1 ‰, respectively, whereas altered magmatic rocks and hydrothermal minerals (quartz and magnetite) are relatively 18O-depleted (4.2 to 7.9 ‰ and −6.3 to 1.5 ‰, respectively). Hydrogen isotope compositions of both least-altered and altered igneous rock samples are D-depleted (from −133 to −161 ‰ Vienna-Standard Mean Ocean Water (V-SMOW)), consistent with differential magma degassing and/or post-crystallization exchange between the rocks and meteoric ground water. Zircon from a chlorite-altered dike has a U–Pb crystallization age of 108.7 ± 0.4 Ma; whereas, the same sample yielded a whole-rock Ar–Ar plateau age of 76.25 ± 0.53 Ma. Likewise, molybdenite Re–Os model ages range from 75.8 to 78.2 Ma, indicating the mineralizing events are genetically related to Late Cretaceous volcano-plutonic intrusions in the area. The molybdenite Re–Os ages difference between the nearby Nucleus (75.9 ± 0.3 to 76.2 ± 0.3 Ma) and Revenue (77.9 ± 0.3 to 78.2 ± 0.3 Ma) mineral occurrences suggests an episodic mineralized system with two pulses of hydrothermal fluids separated by at least 2 Ma. This, in combination with geological features suggest the Nucleus deposit represents the apical and younger portion of the Revenue–Nucleus magmatic-hydrothermal system and may suggest an evolution from the porphyry to the epithermal environments.

Sulfur isotope evidence for a Paleoarchean subseafloor biosphere, Barberton, South Africa

The Archean sub-seafloor has been proposed as an environment for the emergence of life, with septate clusters of titanite microtextures in pillow lava rims argued to be the earliest traces of microbial microboring. Here we use nanoscale secondary ion mass spectrometry (NanoSIMS) to test possible geochemical traces of life in ca. 3.45 Ga pillow lavas of the Barberton Greenstone Belt, South Africa. Sulfide inclusions in the titanite microtextures record strongly negative sulfur isotope fractionations of δ 34 S VCDT –39.8‰ to –3.2‰ (VCDT—Vienna Canyon Diablo Troilite). These represent the largest range and most negative δ 34 S values so far reported from the Archean, and are consistent with an early biogenic origin for the sulfides. Extensive in situ elemental mapping did not find any organic linings associated with the microtextures, despite the high spatial resolution and sensitivity of the NanoSIMS. The absence of organic linings thus excludes a key line of evidence previously used to support the biogenicity of the microtextures. In contrast, in situ sulfur isotope analysis of basalt-hosted sulfides provides an alternative approach to investigating the existence and nature of an Archean subseafloor biosphere.

Evolution of a Carboniferous carbonate-hosted sphalerite breccia deposit, Isle of Man

A newly discovered, extensive sphalerite-bearing breccia (~7.5 wt.% Zn) is hosted in dolomitised Carboniferous limestones overlying Ordovician–Silurian metasedimentary rocks on the Isle of Man. Although base metal sulphide deposits have been mined historically on the island, they are nearly all quartz vein deposits in the metamorphic basement. This study investigates the origin of the unusual sphalerite breccia and its relationship to basement-hosted deposits, through a combination of petrographic, cathodoluminescence, fluid inclusion, stable isotope and hydrogeologic modelling techniques. Breccia mineralisation comprises four stages, marked by episodes of structural deformation and abrupt changes in fluid temperature and chemistry. In stage I, high-temperature (T h > 300°C), high-salinity (20–45 wt.% equiv. NaCl) fluid of likely basement origin deposited a discontinuous quartz vein. This vein was subsequently dismembered during a major brecciation event. Stages II–IV are dominated by open-space filling sphalerite, quartz and dolomite, respectively. Fluid inclusions in these minerals record temperatures of ~105–180°C and salinities of ~15–20 wt.% equiv. NaCl. The δ34S values of sphalerite (6.5–6.9‰ Vienna-Canyon Diablo troilite) are nearly identical to those of ore sulphides from mines in the Lower Palaeozoic metamorphic rocks. The δ18O values for quartz and dolomite indicate two main fluid sources in the breccia’s hydrothermal system, local Carboniferous-hosted brines (~0.5–6.0‰ Vienna standard mean ocean water) and basement-involved fluids (~5.5–11.5‰). Ore sulphide deposition in the breccia is compatible with the introduction and cooling of a hot, basement-derived fluid that interacted with local sedimentary brines.

Two coexisting sulfur metabolisms in a ca. 3400 Ma sandstone

A sandstone from the ca. 3400 Ma Strelley Pool Formation of Western Australia contains pristine micron-sized pyrite intimately associated with organic material coating framework quartz grains. A synsedimentary to early diagenetic origin for this pyrite is indicated by its occurrence in black, bedded sandstone at the base of the formation, and in reworked black clasts higher up in the formation. High-resolution multiple sulfur isotope analysis (32S, 33S, 34S) using secondary ion mass spectrometry (NanoSIMS and large-radius ion microprobe) reveals δ34SVCDT (Vienna Canyon Diablo troilite) values between ∼–12‰ and +6‰, and Δ33S values between –1.65‰ and +1.43‰, from pyrite grains within a single thin section. A large spread of δ34S values over only 5–10 μm, together with the spatial association of pyrite with carbon and nitrogen, indicates biological processing of sulfur. The presence of both +Δ33S and –Δ33S signals overprinted by significant mass-dependent δ34S fractionation in this pyrite population indicates for the first time that both microbial sulfate reduction of aqueous sulfate (–Δ33S) and microbial disproportionation of elemental sulfur (+Δ33S) were co-occurring in an open-marine, sedimentary hosted ecosystem in the Paleoarchean.

Measurement of the δ34S value in methionine by double spike multi‐collector thermal ionization mass spectrometry using Carius tube digestion

Methionine is an essential amino acid and is the primary source of sulfur for humans. Using the double spike ((33)S-(36)S) multi-collector thermal ionization mass spectrometry (MC-TIMS) technique, three sample bottles of a methionine material obtained from the Institute for Reference Materials and Measurements have been measured for delta(34)S and sulfur concentration. The mean delta(34)S value, relative to Vienna Canyon Diablo Troilite (VCDT), determined was 10.34 +/- 0.11 per thousand (n = 9) with the uncertainty reported as expanded uncertainties (U). These delta(34)S measurements include a correction for blank which has been previously ignored in studies of sulfur isotopic composition. The sulfur concentrations for the three bottles range from 56 to 88 microg/g. The isotope composition and concentration results demonstrate the high accuracy and precision of the DS-MC-TIMS technique for measuring sulfur in methionine.