The effects of liquid immiscibility and thermal diffusion on oxygen isotopes in silicate liquids

Differences between the δ¹⁸O values of Si- and Fe-rich immiscible liquids in the system Fe₂SiO₄-KAlSi₂O₆-SiO₂ (Fa-Lc-Q) in isothermal experiments at 0.1 MPa have been determined experimentally to be 0.6 permil. The observed partition of ¹⁸O into the Si-rich liquid is consistent with previous experience with the preferential partition of ¹⁸O into Si-rich minerals in isothermal equilibrium with minerals of less polymerized structure. Crystallochemical principles affect the distribution of oxygen isotopes in coexisting isothermal liquids in the same way as they apply to isothermally coexisting crystals. The effects of Soret (thermal) diffusion on the distribution of oxygen isotopes in silicate liquids above the solvus in the system Fa-Lc-Q under conditions of an imposed temperature gradient of ca. 250 °C over 4 mm and at 2 GPa have also been investigated experimentally. Both the magnitude and the direction of separation of oxygen isotopes as a result of Soret diffusion are unexpected. For each of the silicate liquids, the cold end of the charge is enriched in ¹⁸O by up to 4.7 permil, and the highest δ¹⁸O values are associated with the most silica-poor compositions. The distribution of oxygen isotopes appears to be similar in each liquid, regardless of their chemical compositions, which is in contrast to the behaviour of cations whose distributions are compositionally dependent and characterized by strong crystallochemical effects wherein network-forming species such as Si and Al separate to the hot end and Mg, Fe and Ca are segregated preferentially to the cold end. Structural units in the melts are evidently less selective between oxygen isotopes than between cations, because oxygen redistribution over all possible sites in these units proceeds according to mass. Self-diffusion coefficients of oxygen in basaltic liquids estimated from the Soret experiments are in accord with those from other isotope tracer experiments, and comparable to those of Si. The possible effects of Soret diffusion on the oxygen isotopic composition of metasomatic veins in the mantle are examined in light of these data, and indicate that decay of the thermal gradients in the veins exceeds that of the diffusion of oxygen needed to produce variations in the δ¹⁸O values of mantle minerals. Variations in oxygen isotope ratios in most natural systems as a result of Soret effects are unlikely. Received: 6 January 1997 /  Accepted: 28 June 1998     

Sulfides,oxides and sphene in high-pressure schists from New Caledonia

In the New Caledonia high-pressure schists pyrite, pyrrhotite, chalcopyrite, rutile and sphene are common phases while hematite and ilmenite are rare and magnetite is absent. The parageneses of these minerals were clarified from their occurrence as inclusions in garnet, from phase relations in the Cu-Fe-S and Fe-Ti-O-S systems, and from phase rule considerations for the multi-component system. The sulfur fugacity estimated for pelites and basites containing pyrrhotite, pyrite and rutile increased with increasing metamorphic grade; the oxygen fugacity in these schists was less than 10^–27.6 bars at 400° C, 10 kb and 10^–22.3 bars at 500° C, 11 kb. Among the other components of the metamorphic fluid in pelites, H₂O was major, CH₄, CO₂ and H₂S minor, and H₂, CO, COS and SO₂ rare. The fluid composition altered with advancing metamorphic grade, such that H₂O decreased while CO₂, CH₄ and H₂S increased, and this change was linked to concurrent massive decarbonization in the rock matrices.     

Processes controlling precipitation of carbonate cement and dissolution of silica in reef and near-reef settings

Carbonate cementation in the surface layer of reefs and beachrock eliminates porosity and partially replaces detrital quartz grains. The uptake and release of CO₂ by photosynthesis and respiration in reef communities cause a shift in the carbonate buffer system of seawater. Field studies and experimentation simulating the natural settings show minimum values of CO₂ (1.9 mmoles 1^?1) and HCO₃^? (2.4 meq 1^?1) in association with maximum values of pH (9.8) and O₂ (> 100% oxygen saturation) in waters covering corals and algae prior to sunset. The converse is true for these variables prior to sunrise, when minimum values of pH (7.6) and O₂ (<66% oxygen saturation) occur with maximum values of CO₂ (2.7 mmoles 1^?1) and HCO₃^? (2.7 meq 1^?1). Experimental tanks containing plain seawater showed almost no diurnal variability in pH (a constant 7.5–7.6) or O₂ (80–90% oxygen saturation) measurements. Seawater adjacent to reef biomass, with elevated pH and supersaturated with calcium carbonate, is periodically pumped into the underlying reef and beach sediments due to pressure-buildups between the reef framework or algal zones and open waters. Carbonate precipitation and quartz dissolution follow. As the system equilibrates, pH values progressively decrease.     

Oxygen isotope mapping of the Archean Sturgeon Lake caldera complex and VMS-related hydrothermal system, Northwestern Ontario, Canada

The hydrothermal and magmatic evolution of the Sturgeon Lake caldera complex is graphically documented by a regional-scale (525 km²) analysis of oxygen isotopes. Spatial variations in whole-rock oxygen isotope compositions provide a thermal map of the cumulative effects of multiple stages of hydrothermal metasomatism before, during, and after volcanogenic massive sulfide (VMS) mineralization. There is a progressive, upward increase in δ¹⁸O from less than 2‰ to greater than 15‰ through a 5-km-thick section above the Biedelman Bay subvolcanic intrusive complex. This isotopic trend makes it clear that at least the earlier phases of this intrusive complex were coeval with the overlying VMS-hosting cauldron succession and provided thermal energy to drive a convective hydrothermal circulation system. The sharp contrast in δ¹⁸O values between late stage phases of the Biedelman Bay intrusion and immediate hanging wall strata indicates that the main phase of VMS-related hydrothermal activity took place before late-stage resurgence in the cauldron-related magmatic activity. Mineralogical and isotopic evidence indicates the presence of both syn- and postmineralization hydrothermal activity defined by the presence of widespread semiconformable and more restricted discordant alteration zones that affect the pre- and syncauldron strata. The semiconformable alteration zones formed during early stages of hydrothermal circulation and are defined by widespread silicification and carbonatization in association with relatively high δ¹⁸O values. The discordant alteration assemblages, containing Al-silicate minerals with chloritoid and/or Fe-rich carbonate or chlorite, centered on synvolcanic faults represent restricted zones of both seawater inflow and hydrothermal fluid upflow. A rapid increase in δ¹⁸O values (∼7–9‰) over a short distance (<200 m) suggests marked cooling of hydrothermal fluid from ∼350°C to less than 130°C either just before or during discharge onto the seafloor. Late emplacement of diorite sills and a dacite dome disrupted the isotopic imprint of cauldron-stage hydrothermal activity. The abrupt lowering of δ¹⁸O values at the transition from explosive to passive volcanism (andesite flows and dacite domes) indicates postcauldron emergence. Subsequently, thrust faulting disrupted the older synvolcanic hydrothermal isotopic patterns.     

Carbonate diagenesis of the upper Jurassic successions in the west of Binalud — Eastern Alborz (NE Iran)

The upper Jurassic carbonate settings in Iran are widely exposed in north and northeastern parts. Five stratigraphic columns were selected in the north eastern Iran. Their thickness ranges from 330 to 500 m. The various diagenetic processes identified include, micritization, cementation, compaction (physical and chemical), dissolution, neomorphism, pyritization, hematitization, silicification and dolomitization, which affected these carbonates. Elemental and stable isotopes analysis indicated that these deposits have undergone both meteoric and burial diagenesis in a relatively open system with moderate water-rock interaction. The positive trend between trace elements and oxygen isotope depletion also support these burial conditions. Lighter δ^l8O values of the dolomite samples may be related to an increase in temperature during the burial, which correspond to coarser euhedral crystals. Relatively higher δ¹⁸O values in finer dolomite crystals indicate their formation at lower burial depths relative to coarser crystals. Petrographic evidences such as coarse euhedral crystals with bright and dull zonation prove this interpretation. Chert nodules also have lighter ¹⁸O values relative to carbonate host rock, thus indicating the influence of burial diagenetic processes in their formation. The average environmental palaeotemperature was estimated to be 26°C on the basis of oxygen isotope values of less altered lime-mudstones.     

Oxygen isotope heterogeneity in chondrules from the Mokoia CV3 carbonaceous chondrite

We report a study of the oxygen isotope ratios of chondrules and their constituent mineral grains from the Mokoia, oxidized CV3 chondrite. Bulk oxygen isotope ratios of 23 individual chondrules were determined by laser ablation fluorination, and oxygen isotope ratios of individual grains, mostly olivine, were obtained in situ on polished mounts using secondary ion mass spectrometry (SIMS). Our results can be compared with data obtained previously for the oxidized CV3 chondrite, Allende. Bulk oxygen isotope ratios of Mokoia chondrules form an array on an oxygen three-isotope plot that is subparallel to, and slightly displaced from, the CCAM (carbonaceous chondrite anhydrous minerals) line. The best-fit line for all CV3 chondrite chondrules has a slope of 0.99, and is displaced significantly (by δ¹⁷O ∼ −2.5‰) from the Young and Russell slope-one line for unaltered calcium-aluminum-rich inclusion (CAI) minerals. Oxygen isotope ratios of many bulk CAIs also lie on the CV-chondrule line, which is the most relevant oxygen isotope array for most CV chondrite components. Bulk oxygen isotope ratios of most chondrules in Mokoia have δ¹⁸O values around 0‰, and olivine grains in these chondrules have similar oxygen isotope ratios to their bulk values. In general, it appears that chondrule mesostases have higher δ¹⁸O values than olivines in the same chondrules. Our bulk chondrule data spread to lower δ¹⁸O values than any ferromagnesian chondrules that have been measured previously. Two chondrules with the lowest bulk δ¹⁸O values (−7.5‰ and −11.7‰) contain olivine grains that display an extremely wide range of oxygen isotope ratios, down to δ¹⁷O, δ¹⁸O around -50‰ in one chondrule. In these chondrules, there are no apparent relict grains, and essentially no relationships between olivine compositions, which are homogeneous, and oxygen isotopic compositions of individual grains. Heterogeneity of oxygen isotope ratios within these chondrules may be the result of incorporation of relict grains from objects such as amoeboid olivine aggregates, followed by solid-state chemical diffusion without concomitant oxygen equilibration. Alternatively, oxygen isotope exchange between an ¹⁶O-rich precursor and an ¹⁶O-poor gas may have taken place during chondrule formation, and these chondrules may represent partially equilibrated systems in which isotopic heterogeneities became frozen into the crystallizing olivine grains. If this is the case, we can infer that the earliest nebular solids from which chondrules formed had δ¹⁷O and δ¹⁸O values around -50‰, similar to those observed in refractory inclusions.     

Hydrogen incorporation in enstatite in the system MgO–SiO2–H2O–NaCl

The incorporation of hydrogen in enstatite in a hydrous system containing various amounts of NaCl was investigated at 25 kbar. The hydrogen content in enstatite shows a clear negative correlation to the NaCl-concentration in the system. The most favourable explanation is the reduction of water fugacity due to dilution. Other reasons for the limited hydrogen incorporation at high NaCl levels, such as a significant influence of Na⁺ on the defect chemistry or an exchange between OH^- and Cl⁻in enstatite, appear much less important. A partition coefficient D _Na ^En/Fluid = 0.0013 could be determined, demonstrating that Na is less incompatible in enstatite than H. The new results support the idea that dissolved components have to be considered when the total hydrogen storage capacity in nominally anhydrous minerals is estimated, especially in geological settings with high levels of halogens, such as subduction zones.     

Stable isotopes of cherts and carbonate cements in the Lake Valley Formation (Mississippian), Sacramento Mts, New Mexico

Oxygen isotopic compositions of chert and calcite cements in the Lake Valley Formation indicate that these diagenetic features cannot be equilibrium co-precipitates in spite of their coexistence in the same interstices. Petrography of megaquartz and non-ferroan calcite cements indicates that both are original precipitates that formed during pre-Pennsylvanian time at shallow burial depths (< 215m) implying precipitation temperatures less than 30°C. Under these constraints the δ¹⁸Os of megaquartz (mean =+27.0^0/00 SMOW; range =+ 24.8 to + 28.9^0/00) and calcite (mean =+ 28.0^0/00 SMOW; range =+ 27.3 to + 28.4^0/00) are best interpreted as unaltered since precipitation; thus, they must reflect the oxygen isotopic composition of pre-Pennsylvanian pore waters. Microquartz and chalcedony are interpreted to have formed from recrystallization of pre-Pennsylvanian opal-CT precursors, and therefore probably re-equilibrated during recrystallization in late or post-Mississippian time. We propose a model integrating the isotopic data with regional petrographic and sedimentological data that explains the greater consistency and generally greater δ¹⁸Os values of the calcites compared to those of the cherts. This model is one of chertification and calcite cementation in a regional meteoric phreatic ground-water system, the seaward terminus of which moved southward during lowering of pre-Pennsylvanian sea level. The calcite cements and some of the opal-CT precursor to microquartz and chalcedony are interpreted to have formed in the more seaward portions of the groundwater system. The megaquartz precipitated in the more inland parts of the phreatic groundwater system where rainfall was isotopically lighter and more variable. As such, the δ¹⁸Os of the megaquartz reflect the isotopic composition of groundwaters in areas undersaturated with respect to calcite.     

Al environment in tectosilicate and peraluminous glasses: A Al MQ-MAS NMR, Raman, and XANES investigation

Tecto-aluminosilicate and peraluminous glasses have been prepared by conventional and laser heating techniques, respectively, in the CaO-Al₂O₃-SiO₂ system. The structure of these glasses were studied using Raman spectroscopy, X-ray absorption at the Al K-edge and ²⁷Al NMR spectroscopy with two different high fields (400 and 750 MHz). Raman spectroscopy and X-ray absorption are techniques sensitive to the network polymerization and, in particular, show different signal as a function of silica content. However, these two techniques are less sensitive than NMR to describe the local aluminium environment. For tectosilicate glasses, aluminium in five-fold coordination, ^[5]Al, was found and a careful quantification allows the determination of a significant amount of ^[5]Al (7% in the anorthite glass). The proportion of ^[5]Al increases for the peraluminous glasses with small amounts (<2%) of six-fold coordination, ^[6]Al. The presence of ^[5]Al agrees with previous observations of the existence of nonbridging oxygens (NBOs) in tectosilicate compositions. However, the proportion of ^[5]Al in the present study indicates that no major proportion of triclusters (oxygen coordinated to three (Si,Al)O₄ tetrahedra) is required to explain these NBOS.     

The effects of multiple stressors on the balance between autotrophic and heterotrophic processes in an estuarine system

Responses of autotrophic and heterotrophic processes to nutrients and trace elements were examined in a series of experimental estuarine food webs of increasing trophic complexity using twenty 1-m³ mesocosms. Nutrients (nitrogen and phosphorus) and trace elements (a mix of arsenic, copper, cadmium) were added alone and in combination during four experimental runs spanning from spring 1997 to spring 1998. Diel changes in dissolved oxygen were used to examine whole system gross primary production (WS-GPP), respiration (WS-RESP), and net ecosystem metabolism (NEM). Nutrient and trace element additions had the greatest effect on WS-GPP, WS-RESP, and NEM; trophic complexity did not significantly affect any of these parameters (p>0.3). Effects of trophic complexity were detected in nutrient tanks where bivalves significantly (p=0.03) reduced WS-GPP. Nutrient additions significantly enhanced WS-GPP and to a lesser extent WS-RESP during most mesocosm runs. The system shifted from net heterotrophy (−17.2±1.8 mmol C m⁻³ d⁻¹) in the controls to net autotrophy (29.1±7.6 mmol C m⁻³ d⁻¹) in the nutrient tanks. The addition of trace elements alone did not affect WS-GPP and WS-RESP to the same extent as nutrients, and their effects were more variable. Additions of trace elements alone consistently made the system more net heterotrophic (−24.9±1.4 mmol C m⁻³ d⁻¹) than the controls. When trace elements were added in combination with nutrients, the nutrient-enriched system became less autotrophic (1.6±3.1 mmol C m⁻³ d⁻¹). The effects of trace elements on NEM occurred primarily through reductions in WS-GPP rather than increases in WS-RESP. Our results suggest that autotrophic and heterotrophic processes respond differently to these stressors.     

Aquaculture intensification under land and water limitations

Two intensive aquaculture systems are described in which high yields are obtained for relatively low inputs of land area, water and supplementary feed. The one is a polyculture of a number of fish species in deep cotton irrigation reservoires (5–7 m deep) in Israel. The large volume of water in these reservoirs improves the oxygen regime and dilutes catabolites excreted by the fish. This allows the increase of fish density to 10,000–18,000 fish ha^–1. It also enables the increase of the resevoir's productivity by manuring with liberal amounts of animal wastes. Yields obtained in this system reach over 10 ton ha^–1 yr^–1 at very low feed conversion rates. The second system is practiced in Taiwan for the culture of red tilapia. Pond water is stirred mechanically by paddlewheels to create a gentle current around a central water outlet. This supplies ample oxygen and concentrates wastes in the center of the pond, from where it is removed twice daily, thus alleviating the build-up of catabolite concentration in the pond. Densities of fish amount to 215,000 to 430,000 fish ha^–1, and the yields are accordingly high reaching more than 200 ton ha^–1 yr^–1. The ecological principles involved in these systems are discussed.     

Kinetic oxygen isotope effects during dissimilatory sulfate reduction: A combined theoretical and experimental approach

Kinetic isotope effects related to the breaking of chemical bonds drive sulfur isotope fractionation during dissimilatory sulfate reduction (DSR), whereas oxygen isotope fractionation during DSR is dominated by exchange between intercellular sulfur intermediates and water. We use a simplified biochemical model for DSR to explore how a kinetic oxygen isotope effect may be expressed. We then explore these relationships in light of evolving sulfur and oxygen isotope compositions (δ³⁴S_SO4 and δ¹⁸O_SO4) during batch culture growth of twelve strains of sulfate-reducing bacteria. Cultured under conditions to optimize growth and with identical δ¹⁸O_H2O and initial δ¹⁸O_SO4, all strains show ³⁴S enrichment, whereas only six strains show significant ¹⁸O enrichment. The remaining six show no (or minimal) change in δ¹⁸O_SO4 over the growth of the bacteria. We use these experimental and theoretical results to address three questions: (i) which sulfur intermediates exchange oxygen isotopes with water, (ii) what is the kinetic oxygen isotope effect related to the reduction of adenosine phosphosulfate (APS) to sulfite (SO₃²⁻), (iii) does a kinetic oxygen isotope effect impact the apparent oxygen isotope equilibrium values? We conclude that oxygen isotope exchange between water and a sulfur intermediate likely occurs downstream of APS and that our data constrain the kinetic oxygen isotope fractionation for the reduction of APS to sulfite to be smaller than 4‰. This small oxygen isotope effect impacts the apparent oxygen isotope equilibrium as controlled by the extent to which APS reduction is rate-limiting.     

Abundance of marine resources in relation to dissolved oxygen in Long Island Sound

This study was designed to examine effects of low dissolved oxygen on finfish, lobster, and squid under field conditions in western Long Island Sound. The relationship between bottom dissolved oxygen (DO) and catch was examined for effects on abundance, numbers of species, and mean length, for trawl sites throughout the sound. Examination of mean catch per tow, and species number per tow, showed that both abundance and diversity decreased markedly with bottom DO, with dramatic declines at sites with DO<2 mg l^?1. Of 18 species examined, 15 were found to occur with greater frequency at sites with DO>3 mg l^?1 compared to sites with <2 mg l^?1, and three of these species occurred significantly less frequency at a DO of 2–3 mg l^?1. Trawl samples taken in the Narrows west of Greenwich, an area which chronically experiences summer hypoxia (DO<3 mg l^?1) consistently yielded below average species number during hypoxic events. However, when DO was>3 mg l^?1, 13 of 14 tows had above average species number. Abundance of five common species at sites>3 mg l^?1 DO were significantly higher than at sites <3 mg l^?1 DO in this area. Lobster was the only species not showing this DO threshold. Patterns in abundance vs DO for squid, bluefish, and butterfish suggest that these species are among the most sensitive to hypoxia. Only one of the four examined species, winter flounder, showed a decrease in mean length with DO. Scup, bluefish, and lobster lengths did not vary significantly with respect to dissolved oxygen.     

The oxygen isotope composition of nitrate generated by nitrification in acid forest floors

The oxygen isotope composition of nitrate is used increasingly for identifying the origin of nitrate in terrestrial and aquatic ecosystems. This novel isotope tracer technique is based on the fact that nitrate in atmospheric deposition, in fertilizers, and nitrate generated by nitrification in soils appear to have distinct oxygen isotope ratios. While the typical ranges of δ¹⁸O values of nitrate in atmospheric deposition and fertilizers are comparatively well known, few experimental data exist for the oxygen isotope composition of nitrate generated by nitrification in soils. The objective of this study was to determine δ¹⁸O values of nitrate formed by microbial nitrification in acid forest floors.Evidence from laboratory incubation experiments and field studies suggests that during microbial nitrification in acid forest floor horizons, up to two of the three oxygen atoms in newly formed nitrate are derived from water, particularly if ammonium is abundant and nitrification rates are high. It was, however, also observed that in ammonium-limited systems with low nitrification rates, significantly less than two thirds of the oxygen in newly formed nitrate can be derived from water oxygen, presumably as a result of heterotrophic nitrification. It can be concluded from the presented data that the δ¹⁸O values of nitrate formed by microbial nitrification in acid forest floors typically range between +2 and +14‰, assuming that soil water δ¹⁸O values vary between −15 and −5‰. Hence, oxygen isotope ratios of nitrate formed by nitrification in forest floors are usually distinct from those of other nitrate sources such as atmospheric deposition and synthetic fertilizers and, therefore, constitute a valuable qualitative tracer for distinguishing among these sources of nitrate. A quantitative source apportionment appears, however, difficult because of the wide range of δ¹⁸O values, particularly for atmospheric nitrate deposition and for nitrate from microbial nitrification.     

Oxygen diffusion in basalt and andesite melts: experimental results and discussion of chemical versus tracer diffusion

Chemical diffusion coefficients for oxygen in melts of Columbia River basalt (Ice Harbor Dam flow) and Mt. Hood andesite have been determined at 1 atm. The diffusion model is that of sorption or desorption of oxygen into a sphere of uniform initial concentration from a constant and semi-infinite atmosphere. The experimental design utilizes a thermogravimetric balance to monitor the rate of weight change arising from the response of the sample redox state to an imposed fO₂. Oxygen diffusion coefficients are approximately an order-ofmagnitude greater for basaltic melt than for andesitic melt. At 1260° C, the oxygen diffusion coefficients are: D=1.65×10^–6cm²/s and D=1.43×10^–7cm²/s for the basalt and andesite melts, respectively. The high oxygen diffusivity in basaltic melt correlates with a high ratio of nonbridging oxygen/tetrahedrally coordinated cations, low melt viscosity, and high contents of network-modifying cations. The dependence of the oxygen diffusion coefficient on temperature is: D=36.4exp(–51,600±3200/RT)cm²/s for the basalt and D=52.5exp(–60,060±4900/RT)cm²/s for the andesite (R in cal/deg-mol; T in Kelvin). Diffusion coefficients are independent of the direction of oxygen diffusion (equilibrium can be approached from extremely oxidizing or reducing conditions) and thus, melt redox state. Characteristic diffusion distances for oxygen at 1260° C vary from 10^-2 to 10² m over the time interval of 1 to 10⁶ years. A compensation diagram shows two distinct trends for oxygen chemical diffusion and oxygen tracer diffusion. These different linear relationships are interpreted as supporting distinct oxygen transport mechanisms. Because oxygen chemical diffusivities are generally greater than tracer diffusivities and their Arrhenius activation energies are less, transport mechanisms involving either molecular oxygen or vacancy diffusion are favored.     

Mass-independent fractionation of oxygen isotopes in the mesostasis of a chondrule from the Semarkona LL3.0 ordinary chondrite

A large chondrule from Semarkona, the most primitive ordinary chondrite known, has been discovered to contain a record of mass transport during its formation. In most respects, it is a normal Type I, group A1, low-FeO chondrule that was produced by reduction and mass-loss during the unidentified flash-heating event that produced the chondrules, the most abundant structural component in primitive meteorites. We have previously measured elemental abundances and abundance profiles in this chondrule. We here report oxygen isotope ratio abundances and ratio abundance profiles. We have found that the mesostasis is zoned in oxygen isotope ratio, with the center of the chondrule containing isotopically heavier oxygen than the outer regions, the outer regions being volatile rich from the diffusion of volatiles into the chondrule during cooling. The δ¹⁷O values range from −2.0‰ to 9.9‰, while δ¹⁸O range from −1.9‰ to 9.6‰. More importantly, a plot of δ¹⁷O against δ¹⁸O has a slope of 1.1 ± 0.2 (1σ) and 0.88 ± 0.10 (1σ) when measured by two independent methods. Co-variation of δ¹⁷O with δ¹⁸O that does not follow mass-dependent fractionation has often been seen in primitive solar system materials and is usually ascribed to the mixing of different oxygen reservoirs. We argue that petrographic and compositional data indicate that this chondrule was completely melted at the time of its formation so that relic grains could not have survived. Furthermore, there is petrographic and compositional evidence that there was no aqueous alteration of this chondrule subsequent to its formation. Although it is possible to formulate a series of exchanges between the chondrule and external ¹⁶O-rich and ¹⁶O-poor reservoirs that may explain the detailed oxygen isotope systematics of this chondrule, such a sequence of events looks very contrived. We therefore hypothesize that reduction, devolatilization, and crystallization of the chondrule melt may have produced ¹⁶O-rich olivines and ¹⁶O-poor mesostasis plotting on a slope-one line as part of the chondrule-forming process in an analogous fashion to known chemical mass-independent isotopic fractionation mechanisms. During cooling, volatiles and oxygen near the terrestrial line in oxygen isotope composition produced the outer zone of volatile rich and ¹⁶O-rich mesostasis. The chondrule therefore not only retains a record of considerable mass transport accompanying formation, but also may indicate that the isotopes of oxygen underwent mass-independent fractionation during the process.     

Strontium and oxygen isotope profiles across marble-silicate contacts,Lizzies Basin,East Humboldt Range,Nevada: constraints on metamorphic permeability contrasts and fluid flow

 Sr isotope profiles across marble-silicate rock contacts are used in conjunction with previously published oxygen isotope profiles to constrain fluid movement, porosity and permeability contrasts in migmatitic rocks from Lizzies Basin in the East Humboldt Range, Nevada. The ¹⁸O/¹⁶O systematics in the high-grade sequence have been interpreted to reflect infiltration of ∼2×10² m³/m² of a relatively low ¹⁸O hydrous fluid through the sequence, but with preservation of δ¹⁸O anomalies in thin marble bands due to a 30-fold lower porosity in the marble compared with silicate rocks (Wickham and Peters 1992). The Sr isotope profiles confirm that tracer exchange between marble and silicate rock was primarily by diffusion, and in one case, indicate that porosities differed by less than a factor of four in the ∼10 cm boundary layer which exhibits diffusive modification of ⁸⁷Sr/⁸⁶Sr ratios. This contrasts with modelling of the oxygen isotope profiles which imply porosity contrasts >10 for one marble band and >50 for a second marble band. Either strontium and oxygen isotope diffusion reflect different events (possible if fluid Sr contents varied with time) or porosity varied substantially with the silicate rocks. Oxygen isotope profiles in the deeper part of the metamorphic section in which δ¹⁸O values of silicate rocks have been homogenised and lowered, indicate similar diffusion distances (and thus porosity-time evolution) to oxygen isotopic profiles higher in the section. Comparison of strontium and oxygen isotope diffusion distances constrains fluid Sr contents to between ∼50 and ∼500 ppm deep in the section, but less than ∼10 ppm higher in the section. The difference is related to release of relatively saline, Sr-rich fluids, by the abundant leucogranites and associated skarns deep in the section (cf. Peters and Wickham 1995). Received: 9 December 1994/Accepted: 13 April 1995     

Effect of oxygen fugacity on sulfur isotope compositions and magnetite concentrations in the Kirkpatrick Basalt,Mount Falla,Queen Alexandra Range,Antarctica

The δ³⁴S-values of total sulfur in the Jurassic tholeiite flows on Mt. Falla in Antarctica range from ?1.45 to +11.73‰. The concentrations of sulfur range from 80 to 480 ppm, which is typical of subaerial lava flows that lose varying proportions of sulfur by out-gassing of SO₂. The concentrations of magnetite range from less than 1% to more than 4% and appear to correlate inversely with the total Fe content of the flows. However, the five flows which are anomalously enriched in ³⁴S also have elevated magnetite concentrations. We suggest that the elevated magnetite concentrations and the ³⁴S enrichment were both caused by high oxygen fugacities (f_O2) in the melt. The magnetite concentrations are affected by the fugacity of oxygen through equilibrium in the FMQ buffer whereas the enrichment of the flows in ³⁴S resulted from outgassing of SO₂ at f_O2 greater than ～ 10^?8 atm. The dependence of δ³⁴S and the magnetite concentrations of the flows on f_O2 is supported by the stratigraphic variation of these parameters and by their direct linear correlation.     

Pyrite oxidation in moist air

The rate of pyrite oxidation in moist air was determined by measuring, over time, the pressure difference between a sealed chamber containing pyrite plus oxygen and a control. The experiments carried out at 25°C, 96.7% fixed relative humidity, and oxygen partial pressures of 0.21, 0.61, and 1.00 atm showed that the rate of oxygen consumption is a function of oxygen partial pressure and time. The rates of oxygen consumption (r, mol/m²sec) fit the expression

(A)     

Decomposition of alkyl dixanthogens in aqueous solutions

Alkyl dixanthogens, (ROCSS)₂, decompose in aqueous solution in the presence of nucleophiles in many ways.It is proposed here that in alkaline solution the principal methods of decomposition of ethyl dixanthogen are by simultaneous attack of OH^? ions on the sulphur-sulphur bond to give products which include xanthate ion (ROCSS^?) and peroxide (H₂O₂) and on the carbon-sulphur bond to give products which include monothiocarbonate ion (ROSCO^?), sulphide ion (S^2?), and sulphur (S⁰). Above pH 12 reaction is complete in a few minutes, and more monothiocarbonate than xanthate is formed. At pH 9 the reaction takes over 20 h and more xanthate than monothiocarbonate is formed.The primary products react further to give various ions which depend in part on the pH of the system. In alkaline solution some of the xanthate and peroxide react to give perxanthate (ROCSSO^?). In acid solution both xanthate and monothiocarbonate decompose rapidly; CS₂ is formed from xanthate and OCS from monothiocarbonate.In the presence of other nucleophiles at pH 9.2, dissolved dixanthogen decomposes much more quickly than with OH^? alone, and other reactions occur. With thiosulphate a higher proportion of xanthate is formed together with some xanthyl thiosulphate and monothiocarbonate but no perxanthate. With sulphite (in the absence of oxygen) or cyanide the products include xanthate and monothiocarbonate but no perxanthate. With sulphite in the presence of oxygen, perxanthate is also formed.Suspensions of dixanthogens react slowly but in a similar fashion to dissolved dixanthogens.Longer-chain dixanthogens are much less soluble than ethyl dixanthogen but, in general, react in a similar way. Higher temperatures increase the rate of decomposition by OH^?.This work has various implications in operating plants.