Sulfide Grains Research Articles

Analytical modeling of localized surface plasmon resonance in heterostructure copper sulfide nanocrystals.

Localized surface plasmon resonance (LSPR) in semiconductor nanocrystals is a relatively new field of investigation that promises greater tunability of plasmonic properties compared to metal nanoparticles. A novel process by which the LSPR in semiconductor nanocrystals can be altered is through heterostructure formation arising from solution-based cation exchange. Herein, we describe the development of an analytical model of LSPR in heterostructure copper sulfide-zinc sulfide nanocrystals synthesized via a cation exchange reaction between copper sulfide (Cu(1.81)S) nanocrystals and Zn ions. The cation exchange reaction produces dual-interface, heterostructure nanocrystals in which the geometry of the copper sulfide phase can be tuned from a sphere to a thin disk separating symmetrically-grown sulfide (ZnS) grains. Drude model electronic conduction and Mie-Gans theory are applied to describe how the LSPR wavelength changes during cation exchange, taking into account the morphology evolution and changes to the local permittivity. The results of the modeling indicate that the presence of the ZnS grains has a significant effect on the out-of-plane LSPR mode. By comparing the results of the model to previous studies on solid-solid phase transformations of copper sulfide in these nanocrystals during cation exchange, we show that the carrier concentration is independent of the copper vacancy concentration dictated by its atomic phase. The evolution of the effective carrier concentration calculated from the model suggests that the out-of-plane resonance mode is dominant. The classical model was compared to a simplified quantum mechanical model which suggested that quantum mechanical effects become significant when the characteristic size is less than ~8 nm. Overall, we find that the analytical models are not accurate for these heterostructured semiconductor nanocrystals, indicating the need for new model development for this emerging field.

Factors Controlling In Situ Biogeochemical Transformation of Trichloroethene: Field Survey

AbstractWe have previously defined in situ biogeochemical transformation as the biogenic formation of reactive minerals that are capable of abiotically degrading chlorinated solvents such as trichloroethene without accumulation of degradation products such as vinyl chloride (AFCEE et al. ). This process has been implemented in biowalls used to intercept contaminated groundwater. Abiotic patterns of contaminant degradation were observed at Altus Air Force Base (AFB) and in an associated column study, but not at other sites including Dover AFB. These abiotic patterns were associated with biogenic formation of reactive iron sulfide minerals. Iron sulfides in the form of small individual grains, coatings on magnetite, and sulfur‐deficient pyrite framboids were observed in samples collected from the Altus AFB biowalls and one of the EPA columns. Larger iron sulfide grains coated with oxide layers were observed in samples collected from Dover AFB. Altus AFB and the EPA column differed from Dover AFB in that groundwater flow at Dover AFB was relatively slow and potentially reversing. High volumetric sulfate consumption rates, an abiotic pattern of trichloroethene (TCE) degradation, and the formation of small, high surface area iron sulfide particles were associated with relatively high rates of TCE removal via an abiotic pattern. Geochemical modeling demonstrated that iron monosulfides such as mackinawite were near saturation, and iron disulfides such as pyrite were supersaturated at all sites. This environmental condition can be supportive of nucleation of small particles rather than crystal growth leading to larger particles. When nucleation is dominant, small, high surface area, and reactive particles result. When crystal growth dominates the crystals are larger and have lower specific surface area and reactivity. These results taken together suggest that creation of a dynamic environment can promote biogeochemical transformation based on generation of reactive iron sulfides.

Significance of ancient sulfide PGE and Re–Os signatures in the mantle beneath Calatrava, Central Spain

Spinel lherzolite and wehrlite xenoliths from the Cenozoic Calatrava volcanic field carry the geochemical imprint of metasomatic agents that have affected the subcontinental lithospheric mantle beneath Central Iberia. Some xenoliths (mainly wehrlites) were enriched in REE, Sr, P, and CO2 by silicic-carbonate-rich metasomatic melts/fluids, while others record the effects of subduction-related hydrous silicate fluids that have precipitated amphibole and induced high Ti/Eu in primary clinopyroxene. The petrographic observations and geochemical data suggest that interstitial glass in the xenoliths represent the quenched products of Si-rich melts that infiltrated the mantle peridotite shortly before the entrainment of the xenoliths in the host magmas that erupted ca 2 million years ago. During their infiltration, the metasomatic melts reacted with peridotite, resulting in silica enrichment, while remobilizing grains of iron-rich monosulfide solid solution (Fe-rich Mss) initially enclosed in, or intergranular to, primary olivine and pyroxenes. In situ laser ablation inductively coupled plasma-mass spectrometry analysis of single sulfide grains reveals that the Fe-rich Mss in glass shows platinum-group element (PGE) patterns and 187Os/188Os compositions identical to the Fe-rich Mss occurring as inclusions in, or at grain boundaries of primary silicates. Moreover, independent of its microstructural position, Fe-rich Mss exhibits PGE and 187Os/188Os signatures typical of Mss either residual after partial melting or crystallized directly from sulfide melts. Our findings reveal that young metasomatic melt(s)/fluid(s) may carry remobilized sulfides with PGE and Os-isotopic signatures identical to those of texturally older sulfides in the peridotite xenolith. These sulfides thus still provide useful information about the timing and nature of older magmatic events in the subcontinental mantle.

Recovery of copper sulphides mineral grains at coarse rock fragments size

Assuming the random distribution of sulphide mineral grains and random rock breakage, a relatively small percentage of sulphide grains will be exposed on the rock surface. Early liberation of sulphide grains needs to be considered in terms of the mechanical properties of such grains relative to the properties of the host rock matrix.Clustering of sulphide mineral grains, will make early liberation possible. Depending on the nature of mineral associations, crushing of such rocks will result in different outcomes. Where clustering is manly of very soft copper minerals, with the host rock being moderately strong feldspars or quartzite’s, the copper rich parts of rock are likely to fragment first, resulting in relatively small size being rich in copper minerals. However, in the case of moderately strong chalcopyrite, the difference in elastic properties between chalcopyrite and feldspar or quartz, will not be significant enough to cause a propensity for early liberation.Where clustering of copper minerals occurs with grains of pyrite (or magnetite), the stronger part of the rock fragment will be one rich in valuable minerals. During crushing of such rock, the sulphides rich zones will fragment in a different way than gangue. Stress concentration within pyrite (or magnetite) will result in failure of the relatively soft surrounding matrix, thus promoting liberation of chalcopyrite or chalcocite grains. Therefore, textural information about the associations of sulphide minerals (copper sulphides vs. pyrite/magnetite/garnet) will be of critical significance in the evaluation of the propensity for coarse liberation of copper sulphide minerals. An absence of close spatial associations will significantly reduce the possibility of early liberation of copper sulphides.During blasting ore is exposed to sufficiently intense, high-strain rate loading to be able to induce micro-fracturing originating from individual sulphides mineral grains as well as their clusters. Due to the high rate of loading, a substantial amount of energy can be dissipated with embryonic rock fragment, before macro-failure of rock, which will relieve rock of blast induced stress. Created micro-cracks will play a significant role in subsequent comminution, where rock fragments with enhanced density of micro-cracks will be crushed more easily. Extensive micro-cracking is also likely to play a significant role during heap or dump leaching, stimulating infiltration/diffusion of leaching fluids into the interiors of rock fragments.

Shock and annealing in the amphibole‐ and mica‐bearing R chondrites

AbstractMIL 11207 (R6) and LAP 04840 (R6) contain hornblende and phlogopite; MIL 07440 (R6) contains accessory titan‐phlogopite and no hornblende. All three meteorites have been shocked: MIL 11207 contains extensive sulfide veins, pyroxene that formed from dehydrated hornblende, and an extensive network of plagioclase glass; MIL 07440 contains chromite‐plagioclase assemblages, chromite veinlets and blebs, pincer‐shaped plagioclase patches, but no sulfide veins; LAP 04840 contains olivine grains with chromite‐bleb‐laden cores and opaque‐free rims, rare grains of pyroxene that formed from dehydrated hornblende, and no sulfide veins. These meteorites appear to have been heated to maximum temperatures of approximately 700–900 °C under conditions of moderately high PH2O (perhaps 250–500 bars). All three samples underwent postshock annealing. During this process, olivine crystal lattices healed (giving the rocks the appearance of shock‐stage S1), and diffusion of Fe and S from thin sulfide veins to coarse sulfide grains caused the veins to disappear in MIL 07440 and LAP 04840. This latter process apparently also occurred in most S1–S2 ordinary chondrites of high petrologic type. The pressure–temperature conditions responsible for forming the amphibole and mica in these rocks may have been present at depths of a few tens of kilometers (as suggested in the literature). A giant impact or a series of smaller impacts would then have been required to excavate the hornblende‐ and biotite‐bearing rocks and bring them closer to the surface. It was in that latter location where the samples were shocked, deposited in a hot ejecta blanket of low thermal diffusivity, and annealed.

Chlorine distribution and its isotopic composition in “rusty rock” 66095. Implications for volatile element enrichments of “rusty rock” and lunar soils, origin of “rusty” alteration, and volatile element behavior on the Moon

An interesting characteristic of the pyroclastic glass bead deposits, select impact produced lithologies such as the “rusty rock” 66095, and unique lunar soils from the Apollo 16 landing site, is their unusual enrichments in 204Pb, Cd, Bi, Br, I, Ge, Sb, Tl, Zn, and Cl which indicates that portions of these sample contain a substantial volatile component. Sample 66095, a fine-grained, subophitic to ophitic polymict melt breccia, also hosts a pervasive low-temperature, volatile-rich, oxyhydrated mineral assemblage. The volatile element enrichments in these assorted lunar lithologies have been attributed to a variety of extra-lunar and lunar processes, whereas the oxyhydration in 66095 has long been thought to represent either terrestrial alteration of lunar chlorides and Fe–Ni metal to βFeO(OH,Cl) or indigenous lunar processes. In 66095, Cl is accommodated in FeO(OH,Cl), phosphates, and chlorides and is heterogeneously distributed. The low-temperature alteration occurs as rims around Fe–Ni metal and sulfide grains, and as dispersed grains in the adjacent matrix. Micro-Raman and transmission electron microscope (TEM) imaging indicate that akaganéite (βFeO(OH,Cl)) is the dominant FeO(OH) polymorph and is intergrown with goethite (αFeO(OH)) and hematite (αFe2O3). TEM observations indicate a well-defined “nanometer-scale” stratigraphy” to the alteration. For example, kamacite (body centered cubic)→face-centered cubic (fcc) Fe–Ni alloy→lawrencite (FeCl2)→akaganéite. The lunar lawrencite (Fe,Ni)Cl2 in 66095 does not react directly to akaganéite on Earth. Rather, lawrencite exposed to terrestrial conditions reacts to form an amorphous Fe- and Cl-bearing phase, nano-crystalline goethite, and hematite. The morphology of these terrestrial alteration products is significantly different than that of the akaganéite occurring in 66095. The chlorine isotopic compositions of these volatile-rich samples are enriched in heavy Cl. For 66095, the δ37Cl ranges from +14.0‰ to +15.6‰, whereas the δ37Cl for the volatile-rich A16 soils ranges from +5.6‰ to +15.7‰. Based on these data it appears likely that the volatile element enrichments and the Cl isotopic fractionation observed in 66095 and the Apollo 16 soils did not result from extra-lunar additions, but are most likely indigenous to the Moon. Lawrencite was deposited on mineral surfaces at approximately 650°C to 570°C from a metal-chloride-bearing, H-poor gas phase. This gas phase was also responsible for the transport of other metals (e.g. Zn, Cu, Pb, Fe). The fractionation of Cl isotopes in the rusty rock can be attributed to fumarole processes in a low-H system. The origin and formation of the akaganéite is more enigmatic. The Cl-isotopes are consistent with it replacing lawrencite. However, numerous nanometer-scale observations are not consistent with a terrestrial origin and indicate multiple episodes of oxyhydration.

Diavik Waste Rock Project: Evolution of Mineral Weathering, Element Release, and Acid Generation and Neutralization during a Five-Year Humidity Cell Experiment

A five-year, humidity-cell experiment was used to study the weathering evolution of a low-sulfide, granitic waste rock at 5 and 22 °C. Only the rock with the highest sulfide content (0.16 wt %) released sufficient acid to overcome a limited carbonate acid-neutralization capacity and produce a substantial decline in pH. Leached SO4 and Ca quickly increased then decreased during the first two years of weathering. Sulfide oxidation continued to release acid and SO4 after carbonate depletion, resulting in an increase in acid-soluble elements, including Cu and Zn. With the dissolution of Al-bearing minerals, the pH stabilized above 4, and sulfide oxidation continued to decline until the end of the experiment. The variation in activation energy of sulfide oxidation correlates with changes in sulfide availability, where the lowest activation energies occurred during the largest releases of SO4. A decrease in sulfide availability was attributed to consumption of sulfide and weathered rims on sulfide grains that reduced the oxidation rate. Varying element release rates due to changing carbonate and sulfide availability provide identifiable geochemical conditions that can be viewed as neutralization sequences and may be extrapolated to the field site for examining the evolution of mineral weathering of the waste rock.

Column bioleaching of a polymetallic ore: Effects of pH and temperature on metal extraction and microbial community structure

A complex, polymetallic ore with approximately 6wt% organic carbon and 3wt% inorganic carbon (calcite) was bioleached using mixed cultures of mesophilic and moderately thermophilic microorganisms enriched from materials obtained from an auto-heating coal mine. The microorganisms adapted readily to the ore despite the organic carbon content. Two characteristics of the pyrite-rich ore, a porous organic-sericite phase that allowed the lixiviant and oxidant to penetrate particles and contact sulfide grains and a quartz-feldspar phase that partly occluded the acid-consuming carbonate phase, facilitated rapid and efficient metal (Co, Ni, Cu and Zn) extraction. Metal extractions showed little temperature or acid dependence. Extractions of Co, Ni, Cu and Zn in inoculated tests were higher than in uninoculated tests under the same conditions, indicating at least partial association of the metals with sulfide minerals and highlighting the roles of microorganisms in enhancing bioleaching. Approximately 40–60wt% of the metals were acid soluble. The oxidation of pyrite with concomitant acid generation was a key parameter in lessening acid consumption during leaching. On the basis of solution monitoring data and leached residue analyses of the carbonate contents and sulfur speciation, it is concluded that leachate free acidity is also an important parameter in metal extraction. Both parameters relate directly to acid use in bioleaching systems and impact on the economics of proposed processes. The microbial communities in the inocula and bioleaching samples contained three archaeal and five bacterial species. The archaeal species detected were related to Ferroplasma (Fp.) acidiphilum, Thermogymnomonas (T.) acidicola and Metallosphaera (M.) hakonensis. The bacterial species detected were related to Leptospirillum (L.) ferriphilum, Acidithiobacillus (At.) thiooxidans, Ferrimicrobium (Fm.) acidiphilum, At. caldus and Acidimicrobium (Am.) ferrooxidans. The Ferrimicrobium acidiphilum-related species was the only species present in the 35°C and possibly the 50°C columns thought to be native to the ore.

Effect of water quality on the leaching of a low-grade copper sulfide ore

Copper extractions from a low-grade, ground copper sulfide ore (0.7% Cu) leached in three media were freshwater<seawater>double-strength seawater and pH 1.5⩾pH 2; 84% extraction was achieved in pH 1.5 seawater in 28days at 23°C. Cu-oxide and carbonate dissolved completely and chalcocite was altered to secondary covellite, some of which persisted in all media for the duration of the 28-day experiment. Chalcopyrite and bornite were both oxidised more readily in saline water. Iron, sodium, potassium and sulfur (sulphate) concentrations in leach solutions diminished and the amounts of insoluble iron(III) reaction products increased with increased salinity and increased solution pH. While, overall, silicate dissolution was small, the amounts of poorly crystalline phases (both iron(III) and silica-rich phases) increased with increased salinity and were greater in pH 1.5 media. In the context of heap leaching, the increased amounts of secondary precipitates formed if saline water was used could result in lower extraction efficiency and the increased total dissolved solids, density and viscosity could result in increased energy costs for solution management at operations.The software package Geochemist’s Workbench was evaluated by modelling the synthetic seawater – pH 2 test. It was possible to predict the evolution of the solution composition, the main species and phase boundaries at the start and end of leaching, and the formation of three reaction products in accord with experimental data by applying the React sliding function.The tests were conducted using a pulverised ore sample to increase dissolution reaction kinetics, particularly for chalcopyrite. Future tests should be conducted using ore particle sizes appropriate to heap leaching. The copper distribution within particles indicated that the test ore may not be suited to heap leaching because the surface exposure of copper sulfide grains is limited. Therefore reactor designs better suited to smaller sized particles with/without pre-treatment should be considered.

In-situ Pb isotopic analysis of sulfides in abyssal peridotites: New insights into heterogeneity and evolution of the oceanic upper mantle

Abyssal peridotites and mid-oceanic ridge basalts (MORBs) represent complementary residue-liquid products of melting and melt migration in the oceanic mantle. Because MORBs are mixtures of melts from different mantle depths, their isotopic signature does not directly describe the isotopic composition of the mantle source, but instead describes the local average composition of different parts of the mantle. In contrast, abyssal peridotites, the residues of fractional melting and melt-rock reaction, should shed more light on the distribution of isotopic heterogeneities. We analyzed Pb isotopic compositions in sulfide grains from the Southwest Indian Ridge and the Gakkel Ridge (Arctic Ocean) using the high-resolution Cameca 1280 ion microprobe. Sulfide Pb isotope ratios show very large variations, with 16 grains from 1 sample covering ∼25% of the entire range observed in the oceanic mantle. Pb isotopes in sulfides preserve a record of mantle compositions not seen in whole-rock MORBs from the same area. Sulfides from the Atlantis II Fracture Zone (Southwest Indian Ridge) confirm the presence of ancient refractory material scatter in the oceanic upper mantle. Gakkel Ridge sulfides define a high degree of isotopic variability, suggesting that oceanic mantle, not subcontinental lithospheric mantle, is the main source of such heterogeneity. Our results confirm that the source of MORBs, as represented by abyssal peridotites, is very heterogeneous and that other mantle end-member components are intimately mixed in. In-situ sulfide analysis is a powerful tool to detect the isotopic diversity of the MORB mantle source.

Upgrading valuable mineralization and rejecting magnesium silicates by pre-concentration of mafic ores

Amenability of mafic ores to pre-concentration was investigated with respect to ore mineraliza- tion characteristics. For the pre-concentration tests seven ores from various nickel-copper operations at Sudbury, Ontario were subjected to dense medium separation. Size assays of metal values, i.e. distribu- tion of nickel and copper with respect to size fractions, were also determined. The ores were assessed in three categories of valuable mineralization as massive pure sulphides, coarse massive sulphide grains and disseminated sulphides. For ores with massive pure sulphides and coarse massive sulphide grains even a size classification based pre-concentration route could be sought since a clear trend of metal enrichment was identified towards finer fractions. Orebodies of similar mineralogy had similar responses to pre- concentration tests. The best results were for those ore bodies with a distinct differentiation between mineralization and gangue, i.e. the ores with massive pure sulphides, where nickel recoveries of 97% and mass rejections of 38-53% were achieved. Similar results were obtained for ores with coarse massive sulphides. For disseminated sulphide mineralogy relatively lower mass rejection was attained with ac- ceptable recoveries of metals. Rejection of magnesium bearing gangue, such as talc, was identified as another benefit of pre-concentration. The extent of magnesium rejection occurred as a function of ore mineralogy. Clear distinction between valuable mineralization and gangue provided preferential magnesi- um rejection at high levels with no or minor metal losses.

Insights into subduction zone sulfur recycling from isotopic analysis of eclogite-hosted sulfides

Subduction of sulfur in ocean crust makes a significant but poorly understood contribution to the global sulfur cycle. Part of the uncertainty arises from a lack of knowledge about the metamorphic changes that affect subducted sulfur-bearing minerals, and the ultimate source of sulfur that is subducted to depth. Sulfur δ34S varies both as a function of the original sulfur source, and as a consequence of processes subsequent to sulfide crystallisation such as devolatilisation, redox reactions, and fluid loss. To investigate sulfur liberation during subduction, secondary ion mass spectroscopy (SIMS) was used to measure δ34S in grains of pyrite, chalcopyrite and pyrrhotite in eclogites from the Zermatt–Saas zone in the Western Alps, and the Pouébo terrane of New Caledonia. Trace element mapping on selected sulfide grains was also performed.Sulfides in these rocks are generally associated with greenschist retrogression assemblages, but also occur as inclusions in garnet, associated with glaucophane and omphacite, and as polysulfide grains with typical magmatic combinations of minerals. δ34S varies significantly within individual pyrite grains, with striking correlations, in some cases, between Co zoning and changes in δ34SVCDT. δ34SVCDT is, in many cases, greater than 13‰, consistent with derivation from seawater-derived sulfate. The dataset suggests that sulfur isotopes in pyrite experienced little or no post-crystallisation re-equilibration, that pyrite grew under open system conditions with heterogeneous fluid flow on a thin section scale, and that sulfide growth involved sulfur addition. Prograde subduction processes most likely involved sulfur loss. Sulfide growth occurred in some samples at the very earliest stages of exhumation. Therefore these sulfides provide useful information on the fluids present in slabs at great depths.

PRE-ACCRETIONAL SORTING OF GRAINS IN THE OUTER SOLAR NEBULA

Despite their micrometer-scale dimensions and nanogram masses, chondritic porous interplanetary dust particles (CP IDPs) are an important class of extraterrestrial material since their properties are consistent with a cometary origin and they show no evidence of significant post-accretional parent body alteration. Consequently, they can provide information about grain accretion in the comet-forming region of the outer solar nebula. We have previously reported our comparative study of the sizes and size distributions of crystalline silicate and sulfide grains in CP IDPs, in which we found these components exhibit a size-density relationship consistent with having been sorted together prior to accretion. Here we extend our data set and include GEMS (glass with embedded metal and sulfide), the most abundant amorphous silicate phase observed in CP IDPs. We find that while the silicate and sulfide sorting trend previously observed is maintained, the GEMS size data do not exhibit any clear relationship to these crystalline components. Therefore, GEMS do not appear to have been sorted with the silicate and sulfide crystals. The disparate sorting trends observed in GEMS and the crystalline grains in CP IDPs present an interesting challenge for modeling early transport and accretion processes. They may indicate that several sorting mechanisms operated on these CP IDP components, or alternatively, they may simply be a reflection of different source environments.

Podiform chromitite formation in a low-Cr/high-Al system: An example from the Southwest Indian Ridge (SWIR)

Recent reassessment of abyssal peridotites obtained during the dredging of the oblique supersegment and the easternmost subsection of the Southwest Indian Ridge by the R/V Knorr Cruise 162 and the R/V Yokosuka YK98-07 revealed the occurrence of dunites containing podiform chromitites and dunites with variable chromite concentration closely associated with lherzolite and harzburgite. The size of the chromitite pods varies from a few mm to 2 cm in width. Chromites in the podifom chromitites have very low Cr# (=0.22–0.23) and low TiO2 (<0.17 wt%). They are almost free of silicate inclusions except for a few euhedral sulfide grains which occur far from cracks and lamellae and are considered primary in origin. The lherzolite which possibly represents the wallrock hosting the dunites with podiform chromitites also show low spinel Cr#(=0.16) and low Cr# in the clinopyroxenes (=0.09–0.10) and orthopyroxenes (=0.07–0.09). The small size of the SWIR podiform chromitites is strongly controlled by the low Cr/Al available in the wallrock and the invading melt. The presence of sulfide inclusions and the absence of PGEs further attest to the low Cr/Al (i.e. low refractoriness) in the system involved in the genesis of the SWIR podiform chromitites. Lastly, the discovery of podiform chromitites in the SWIR implies that the formation of podiform chromitite at mid-oceanic ridges, regardless of its spreading rate, is highly possible.

The nanoscale mineralogy of Fe,Ni sulfides in pristine and metamorphosed CM and CM/CI‐like chondrites: Tapping a petrogenetic record

AbstractWe have sampled sulfide grains from one pristine CM2 chondrite (Yamato [Y‐] 791198), one thermally metamorphosed CM2 chondrite (Y‐793321), and two anomalous, metamorphosed CM/CI‐like chondrites (Y‐86720 and Belgica [B‐] 7904) by the focused ion beam (FIB) technique and studied them by analytical transmission electron microscopy (TEM). Our study aims at exploring the potential of sulfide assemblages and microstructures to decipher processes and conditions of chondrite petrogenesis. Complex exsolution textures of pyrrhotite (crystallographic NC‐type with N ≈ 6), troilite, and pentlandite occur in grains of Y‐791198 and Y‐793321. Additionally, polycrystalline 4C‐pyrrhotite‐pentlandite‐magnetite aggregates occur in Y‐791198, pointing to diverse conditions of gas–solid interactions in the solar nebula. Coarser exsolution textures of Y‐793321 grains indicate higher long‐term average temperatures in the &lt;100 °C range compared to Y‐791198 and other CM chondrites. Sulfide mineralogy of Y‐86720 and B‐7904 is dominated by aggregates of pure troilite and metal, indicating metamorphic equilibration at sulfur fugacities (fS2) of the iron‐troilite buffer. Absence of magnetite in equilibrium with sulfide and metal in Y‐86720 indicates higher peak temperatures compared with B‐7904, in which coexistence of troilite, metal, and magnetite constrains metamorphic temperature to less than 570 °C. NC‐pyrrhotite occurs in both meteorites as nm‐wide rims on troilite grains and, together with frequent anhydrite, indicates a retrograde metamorphic stage at higher fS2 slightly above the fayalite‐magnetite‐quartz‐pyrrhotite buffer. Fine‐grained troilite‐olivine intergrowths in both meteorites suggest the pre‐metamorphic presence of tochilinite‐serpentine interlayer phases, pointing to mineralogical CM affinity. Pseudomorphs after euhedral pyrrhotite crystals in Y‐86720 in turn suggest CI affinity as do previously published O isotopic data of both meteorites.

Study on Tribological Behaviors of FeS Solid Lubrication Duplex Layer under n-Fe&lt;sub&gt;3&lt;/sub&gt;O&lt;sub&gt;4&lt;/sub&gt; Additive Lubricating

FeS solid lubrication duplex layer was prepared on the surface of 45 steel by ion nitrocarburizing and ion sulphurizing process. The sulphide grains in micron and nano scale and holes distributing equably on the duplex layer. The duplex layer is composed of FeS, FeS2 and Fe3N. Under liquid paraffin oil with 0.2wt%n-Fe3O4 lubricating, the synergistic effect between n-Fe3O4 and the duplex layer is produced, and the chemical reaction films including sulphide, sulphate and nitride is formed, which makes the friction factor of the duplex layer keep being the lowest and about 0.075, and the volume loss is reduced by 91% than that of the plain surface, and reduced by 89% and 21% than that of the sulphurized surface and the nitrocarburized surface, respectively.

Lead and osmium isotopic constraints on the oceanic mantle from single abyssal peridotite sulfides

Single sulfides from abyssal peridotites have been analyzed for Pb and Re-Os to constrain the evolution of oceanic mantle composition. These represent the first analyses of Pb and Os isotopic compositions in the same sulfide grain. The sulfides are from Gakkel and Southwest Indian ridge peridotites, occur at <0.1% modal abundances, and contain 0.001–0.4ppm Re, 0.003–5ppm Os, and 0.12–12ppm Pb. Sulfide Pb isotopic compositions extend from depleted (e.g., 206Pb/204Pb=17.0) to enriched (19.6), covering a larger range than associated basalts. The Os isotopic range of sulfides is more restricted, but extends from depleted (187Os/188Os=0.116) to enriched (0.150). Pb and Os concentrations and isotopic compositions co-vary, with correlation coefficients of 0.76–0.94. Both Pb and Re–Os isotopic data follow ∼2Ga isochrons, with isotopic compositions varying down to small (⪡1km) length-scales and some sulfides containing supra-chondritic 187Re/188Os and 187Os/188Os. These observations are best explained by long-term recycling of oceanic lithosphere combined with melt extraction and refertilization at ancient ocean ridges, rather than a specific event at 2Ga.The concentration of Pb in sulfides indicates that they host <4% of the mantle Pb budget. A re-evaluation of the mass balance of Pb in peridotites indicates that most mantle Pb is stored in silicate phases. The Pb partition coefficient between sulfide melt and silicate melt is estimated to be ∼3, based on the correlation of Pb–Os concentrations in this study and measured Os partition coefficients from the literature. These observations indicate that sulfides do not exert a strong control on the fractionation of Pb during mantle melting, but they can be used to constrain mantle Pb isotopic composition.Sulfides in this study, combined with literature data for Pb isotopes in peridotite whole rocks and pyroxene separates, provide evidence for ultra-depleted mantle, as 24% of peridotites are unradiogenic (i.e., 207Pb/204Pb <15.440 and 206Pb/204Pb <17.726), compared to only 3% of ridge basalts. This suggests that the mantle contains volumetrically significant reservoirs of ultra-depleted material, probably derived from recycled oceanic lithospheric mantle. These depleted reservoirs contribute in only small amounts to oceanic crust generation, both due to a limited ability to melt and to the dilution of any melt by more enriched melts during crust formation.

GRAIN SORTING IN COMETARY DUST FROM THE OUTER SOLAR NEBULA

Most young stars are surrounded by a disk of gas and dust. Close to the hot stars, amorphous dust grains from the parent molecular cloud are reprocessed into crystals that are then distributed throughout the accretion disk. In some disks, there is a reduction in crystalline grain size with heliocentric distance from the star. We investigated crystalline grain size distributions in chondritic porous (CP) interplanetary dust particles (IDPs) believed to be from small, icy bodies that accreted in outer regions of the solar nebula. The grains are Mg-rich silicates and Fe-rich sulfides, the two most abundant minerals in CP IDPs. We find that they are predominantly <0.25 {mu}m in radius with a mean grain size that varies from one CP IDP to another. We report a size-density relationship between the silicates and sulfides. A similar size-density relationship between much larger silicate and sulfide grains in meteorites from the asteroid belt is ascribed to aerodynamic sorting. Since the silicate and sulfide grains in CP IDPs are theoretically too small for aerodynamic sorting, their size-density relationship may be due to another process capable of sorting small grains.

Implications of sulfur isotope fractionation in fracture-filling sulfides in crystalline bedrock, Olkiluoto, Finland

A detailed investigation of 34S/32S ratios in fracture-bound pyrite and marcasite was conducted at Olkiluoto, western Finland, in order to gain information on paleohydrogeochemical conditions in a deep groundwater (0–400m b.s.l.) environment. The bedrock at Olkiluoto is being considered for a final repository of spent nuclear fuel. The 34S/32S ratios were measured in situ on individual sulfide grains, using secondary ion mass spectrometry (SIMS) supplemented by analyses from bulk sulfide material. The δ34S values of pyrite and marcasite show considerable variations, from −50‰ to +82‰ VCDT. Using published records and new data from fracture filling minerals, the pyrite fillings were classified into groups representing distinct episodes of fracture mineral formation. The δ34S values of these groups record a transition from hydrothermal activity to a low temperature groundwater environment. The δ34S values of hydrothermal pyrite vary between −18‰ and +34‰. However, hydrothermal pyrite that definitively precipitated at 128–245°C, evidenced by fluid inclusion data from co-genetic calcite, is characterized by a more limited variation in δ34S from −8.6‰ to +3.9‰. The high variability of δ34S within the hydrothermal pyrite precipitates indicates that biogenic fractionation effects cannot be completely excluded. Hydrothermal pyrite precipitation is likely related to hydrothermal systems produced by Mesoproterozoic rapakivi granite and diabase intrusions. Subsequent pyrite generations show a wider spread of δ34S values. Pyrite types representing formation temperatures from ca. 50 to 90°C have δ34S values ranging from −40‰ to +82‰, and the latest low temperature (<80°C) pyrite precipitates are characterized by δ34S from −50‰ to +78‰. The wide range of δ34S values is attributed to bacterial SO42- reduction, affected by Rayleigh fractionation under restricted SO42- input. It can be calculated that the highest δ34S values in pyrite represent consumption of ca. 90% of the original SO42- in the deep groundwater in a fracture section. Furthermore, in situ variations of the δ34S values in pyrite grains indicate that pulses of fresh SO42- with relatively non modified S-isotopic composition have periodically entered the fractures. The latest low temperature pyrite formation event most likely occurred during the Holocene period when brackish, SO42--rich waters of the Litorina Sea infiltrated the fracture network at 8000–4000 BP, providing substrate for SO42--reducing bacteria. Due to the complex Quaternary history of the site and low temperature conditions existing for millions of years, latest fracture filling calcite and pyrite may represent a compilation of several low temperature precipitation events. The records of δ13C in calcite and δ34S in coexisting pyrite indicate that paleogroundwaters have been influenced by the migration of a redox front between methanic and sulfidic environments. These findings can be used to consider the possible geochemical changes that may affect the materials used to contain spent nuclear fuel.

Sulfur- and oxygen-isotope constraints on the sedimentary history of apparent conglomerates from the Nuvvuagittuq Greenstone Belt (Nunavik, Québec)

Mafic igneous rocks of the Nuvvuagittuq Greenstone Belt (NGB) crystallized before 3.8Ga and possibly as early as 4.3Ga, potentially making the belt the oldest known supracrustal sequence on Earth. However, detrital zircons from a rare quartz-biotite schist in the NGB yield significantly younger ages of ≈3.77Ga or less. These appear to be inconsistent with the ages of the mafic igneous rocks, as the quartz-biotite schist has been interpreted as a metaconglomerate, formed by the dismantling of preexisting lithologies. In order to assess this genetic interpretation, we performed a sulfur and oxygen isotope study of the quartz-biotite schist. Sulfide grains found in quartz clasts and the matrix show significant mass-independent fractionation of sulfur isotopes (+0.2‰≤Δ33S‰≤+1.0‰; mean Δ33S=+0.5±0.1‰). Secondary sulfides from crosscutting veins do not show mass-independent fractionation of sulfur isotopes (−0.1‰≤Δ33S≤+0.3‰; mean Δ33S=+0.1±0.1‰). Oxygen isotope compositions of quartz from clasts, matrix and a fine-grained lens are highly enriched in 18O (16.9‰≤δ18O≤26.7‰). Non-zero Δ33S values indicate a surficial origin for sulfur, probably the Eoarchean atmosphere, while high δ18O values suggest a low-temperature (65±18°C) origin for the quartz, likely as chemical precipitation of a chert precursor from Si-saturated seawater. Therefore, the coupled S- and O-isotope measurements show that primary isotopic signatures characteristic of surficial environments survived the protracted metamorphic history of the NGB, and suggest that the quartz-biotite schist contains material that originated as chemical metasediments. The near mono-mineralic compositions of the clasts (quartz) and their shared 18O-enrichment suggest that they had a common protolith, which was deposited prior to the formation of the schist, and subsequently reworked. Whether the quartz-biotite schist represents a metaconglomerate or a structural melange, it preserves remnants of some of the oldest chemical sediments on Earth.