Die Entstehung von Pyrit in rezenten Sedimenten des Piburger Sees

The occurrence of pyrite (FeS₂) and iron sulfide in surficial sediments of Piburger See was compared with thermodynamic calculations based on chemical analyses of iron and hydrogen sulfide in the interstitial water. The area below 17 m, where black spots were found in the sediments, showed ion products (log K_FeS=a_Fe2·a_HS/a_H+) between?3.11 and ?4.01. In areas with no visible FeS concretions logK_FeS values were in the range of ?4.74 to ?5.77, thus thermodynamic calculations seem to be in accordance with the appearance of iron sulfide. Nevertheless pyrite framboids, composed by more than 1,000 single crystals, coul be found even in shallow parts of the lake. Therefore the formation of pyrite is assumed to occur in microniches (diatom frustules, testacean shells). Inside these microcompartments high concentrations of hydrogen sulfide are reached due to the anaerobic decomposition of organic matter, whereas iron and additional sulfur are supplied by the diffusion of ferrous iron and sulfate from the anoxic environment.     

Multiple sulfur isotope chemostratigraphy across the Permian–Triassic boundary at Chaotian,China: Implications for a shoaling model of toxic deep-waters

Previous studies on multiple sulfur isotopes (³²S, ³³S, and ³⁴S) in sedimentary pyrite at the end-Permian suggested a shoaling of anoxic/sulfidic deep-water contributing to the extinction. This scenario is based on an assumption that the sedimentary sulfur cycle was largely controlled by benthos activity, though a stratigraphic correlation between the sulfur records and ichnofabrics of the sediments at the end-Permian has not yet been examined. We report the multiple sulfur isotopic composition of pyrite in the Permian–Triassic boundary interval at Chaotian, South China. Our data can be generally explained by a mixing of sulfur in sulfide from two different sources: one produced via sulfate reduction in an open system with respect to sulfate and the other produced in a closed system. In particular, the former with the substantially low δ³⁴S (<−40 ‰) and high ∆³³S (up to +0.100 ‰) values was likely produced via water-mass sulfate reduction or via sulfate reduction in oxic sediments with common burrows. The frequent occurrence of small pyrite framboids (mostly <5 μm in diameter) in the Lopingian (Late Permian) Dalong Formation of deep-water facies supports the enhanced water-mass sulfate reduction in an anoxic deep-water mass. The negative ∆³³S values are observed only in the oxic limestones, and no substantial ∆³³S change is observed across the extinction horizon despite of the disappearance of bioturbation. Our results are apparently inconsistent with the previous shoaling model. We expand the model and infer that, when the deep-water was sulfidic and its shoaling rate was high, a substantial amount of hydrogen sulfide (H₂S) was supplied onto the shelf via the shoaling; that resulted in the positive ∆³³S value of the bulk sediments. The observed ∆³³S variation on a global scale suggests a substantial variation in H₂S concentration and/or in upwelling rate of shoaling deep-waters during the Permian–Triassic transition.     

S, O and Sr isotope systematics of active vent materials from the Mariana backarc basin spreading axis at 18°N

Stable isotope ratios of S, O and Sr have been measured for active vent materials which were first found and sampled in April 1987 from the Mariana backarc spreading axis at 18°N. Chimneys consisted mostly of barite with a lesser proportion of sulfide minerals such as sphalerite, galena, chalcopyrite and pyrite. Theδ³⁴S values of sphalerite and galena taken from several chimneys and various parts of a chimney showed a narrow range from 2.1 to 3.1‰, suggesting uniform conditions of fluid chemistry during chimney growth. The sulfur isotopic results imply a contribution of hydrogen sulfide reduced from seawater sulfate in the deep hydrothermal reaction zone, considering that fresh glasses of the Mariana Trough basalts haveδ³⁴S= −0.6 ± 0.3‰. Sulfur isotopic compositions of hydrogen sulfide in the high temperature vent fluids (δ³⁴S= 3.6–4.8‰) which are higher than those of the sulfide minerals suggest the secondary addition of hydrogen sulfide partially reduced from entrained seawater SO₄²⁻ at a basal part of the chimneys. This interpretation is consistent with theδ³⁴S values of barite (21–22‰) that are higher than those of seawater sulfate. The residence time of the entrained SO₄²⁻ was an order of an hour on a basis of oxygen isotopic disequilibrium of barite. Strontium isotopic variations of barite and vent waters indicated that Sr in barite was mostly derived from the Mariana Trough basalts with a slight contribution from Sr in circulating sea-water, and that 10–20% mixing of seawater with ascending hydrothermal fluids induced precipitation of barite at the sea-floor.     

ROBUST: The ROle of BUffering capacities in STabilising coastal lagoon ecosystems

“Buffer capacities” has been defined in ecology as a holistic concept (e.g., Integration of Ecosystem Theories: A Pattern, second ed. Kluwer, Dordrecht, 1997, 388pp), but we show that it can also be worked out in mechanistic studies. Our mechanistic approach highlights that “buffering capacities” can be depleted progressively, and, therefore, we make a distinction between current and potential “buffering capacities”. We have applied this concept to understand the limited “local stability” in seagrass ecosystems and their vulnerability towards structural changes into macro-algal dominated communities. We explored the following processes and studied how they confer buffering capacities to the seagrass ecosystem: (i) net autotrophy is persistent in Zostera noltii meadows where plant assimilation acts as a sink for nutrients, this contrasted with the Ulva system that shifted back and forth between net autotrophy and net heterotrophy; (ii) the Z. noltii ecosystem possesses a certain albeit rather limited capacity to modify the balance between nitrogen fixation and denitrification, i.e., it was found that in situ nitrogen fixation always exceeded denitrification; (iii) the nitrogen demand of organoheterotrophic bacteria in the sediment results in nitrogen retention of N in the sediment and hence a buffer against release of nitrogen compounds from sediments, (iv) habitat diversification in seagrass meadows provides shelter for meiofauna and hence buffering against adverse conditions, (v) sedimentary iron provides a buffer against noxious sulfide (note: bacterial sulfide production is enhanced in anoxic sediment niches by increased organic matter loading). On the other hand, in the coastal system we studied, sedimentary iron appears less important as a redox-coupled buffer system against phosphate loading. This is because most inorganic phosphate is bound to calcium rather than to iron. In addition, our studies have highlighted the importance of plant–microbe interactions in the seagrass meadows.     

Elemental sulfur in northern South China Sea sediments and its significance

Elemental sulfur(ES) is one of the intermediates in the inorganic sulfur cycle and thus plays a key role in the fractionation of stable sulfur isotopes in different reservoirs and the marine environment. In this study, solid ES is discovered in sediments near the Jiulong Methane Reef in the northern South China Sea by scanning electron microscopy and Raman spectroscopy. Combining the morphology and distribution of ES, pyrite concentrations, and sulfur isotopes, we conclude that:(1) solid ES coexists with pyrite microcrystals and sulfide(oxyhydr)oxides as well as clay minerals, and they are mainly distributed on the surface of mineral aggregates;(2) ES mainly occurs within and near the sulfate-methane transition zone(SMTZ) despite little morphological diversity;(3) ES formation might be related to hydrogen sulfide oxidation and is therefore linked with fluctuations in the SMTZ. Within the SMTZ, hydrogen sulfide is produced and pyrite precipitates because of enhanced anaerobic oxidation of methane coupled with dissimilatory sulfate reduction. This enhances the efficiency of the inorganic sulfur cycle and provides favorable conditions for ES formation. The discovery of solid ES in sediments near the Jiulong Methane Reef suggests an important relationship with SMTZ fluctuations that could have implications for the evolution of methane hydrate in the South China Sea.     

Origin of the magnetization of Permo-Carboniferous sediments of Spitsbergen, Svalbard Archipelago

Rock magnetic investigations of Permo-Carboniferous carbonate sediments from two areas on Spitsbergen are described, conducted to identify the carriers of the NRM in these rocks. Since microscopic and magnetic separation techniques could not profitably be applied, the nature of magnetic minerals was investigated by thermal demagnetization of the NRM and decay of saturation isothermal remanence (I_rs) during heating to 600°C, as well as by the distribution of the median destructive fields of the NRM and observation of magnetic susceptibility after subsequent heatings. The results show that the NRM of these limestones resides mainly in magnetite, but creation of magnetic pyrrhotite and of fresh magnetite is observed during heating to 600°C. Presence of sulphides indicates that magnetite is an oxidation product of pyrite or of non-magnetic pyrrhotite. Examination of rock magnetic properties of limestones leads to the conclusion that most of the magnetite in the rocks of the Bellsund area is of detrital origin, whereas the rocks at Festningen contain magnetite derived from pyrite probably during an early stage of the diagenetic process.     

Arsenic Control During Aquifer Storage Recovery Cycle Tests in the Floridan Aquifer

Implementation of aquifer storage recovery (ASR) for water resource management in Florida is impeded by arsenic mobilization. Arsenic, released by pyrite oxidation during the recharge phase, sometimes results in groundwater concentrations that exceed the 10 µg/L criterion defined in the Safe Drinking Water Act. ASR was proposed as a major storage component for the Comprehensive Everglades Restoration Plan (CERP), in which excess surface water is stored during the wet season, and then distributed during the dry season for ecosystem restoration. To evaluate ASR system performance for CERP goals, three cycle tests were conducted, with extensive water‐quality monitoring in the Upper Floridan Aquifer (UFA) at the Kissimmee River ASR (KRASR) pilot system. During each cycle test, redox evolution from sub‐oxic to sulfate‐reducing conditions occurs in the UFA storage zone, as indicated by decreasing Fe²⁺/H₂S mass ratios. Arsenic, released by pyrite oxidation during recharge, is sequestered during storage and recovery by co‐precipitation with iron sulfide. Mineral saturation indices indicate that amorphous iron oxide (a sorption surface for arsenic) is stable only during oxic and sub‐oxic conditions of the recharge phase, but iron sulfide (which co‐precipitates arsenic) is stable during the sulfate‐reducing conditions of the storage and recovery phases. Resultant arsenic concentrations in recovered water are below the 10 µg/L regulatory criterion during cycle tests 2 and 3. The arsenic sequestration process is appropriate for other ASR systems that recharge treated surface water into a sulfate‐reducing aquifer.     

The solubility of iron sulphides in synthetic and natural waters at ambient temperature

A critical evaluation of literature values for the solubility products, K _sp ^NBS = [Fe²⁺][HS^–] Fe²⁺ HS^– (H _NBS ⁺ )^–1, of various iron sulphide phases results in consensus values for the pKs of 2.95 ± 0.1 for amorphous ferrous sulphide, 3.6 ± 0.2 for mackinawite, 4.4 ± 0.1 for greigite, 5.1 ± 0.1 for pyrrhotite, 5.25 ± 0.2 for troilite and 16.4 ± 1.2 for pyrite.Where the analogous ion activity products have been measured in anoxic freshwaters in which there is evidence for the presence of solid phase FeS, the values lie within the range of 2.6–3.22, indicating that amorphous iron sulphide is the controlling phase. The single value for a groundwater of 2.65 (2.98 considering carbonate complexation) agrees. In seawater four values range between 3.85 to 4.2, indicating that mackinawite or greigite may be the controlling phase. The single low value of 2.94 is in a situation where particularly high fluxes of Fe (II) and S (–II) may result in the preferential precipitation of amorphous iron sulphide. Formation of framboidal pyrite in these sulphidic environments may occur in micro-niches and does not appear to influence bulk concentrations. Calculations show that the formation of Fe₂S₂ species probably accounts for very little of the iron or sulphide in most natural waters. Previously reported stability constants for the formation of Fe (HS)₂ and (Fe (HS)₃)^– are shown to be suspect, and these species are also thought to be negligible in natural waters. In completely anoxic pore waters polysulphides also have a negligible effect on speciation, but in tidal sediments they may reach appreciable concentrations and lead to the direct formation of pyrite. Concentrations of iron and sulphide in pore waters can be controlled by the more soluble iron sulphide phase. The change in the IAP with depth within the sediment may reflect ageing of the solid phase or a greater flux of Fe (II) and S (–II) nearer the sediment surface. This possible kinetic influence on the value of IAPs has implications for their use in geochemical studies involving phase formation.     

Distribution, age and chemical composition of tephra layers in deep-sea sediments off western Indonesia

Tephra layers occur in deep-sea sediments of the northeastern Indian Ocean, adjacent to western Indonesian are. The layers range in age from Recent to Late Miocene. Relative abundance of light and heavy mineral species in all tephra layers have been determined, and pure glass shards from representative samples have been analyzed chemically for major oxides. On the basis of the chemical data, three distinct provinces can be recognized: (1) an extensive province of rhyolitic tephra layers, ranging in age back to Late Miocene, is found adjacent to Sumatra; (2) a more restricted province of dacitic layers, adjacent to Sunda Strait and western Java; and (3) a province of andesitic layers, found adjacent to eastern Java and the Lesser Sunda Islands. Chemical composition of tephra layers in each province remains constant with time. As an example, tephra layers from the rhyolitic province are characterized by a high and restricted range of SiO₂ (75–77%) when expressed on an H₂O-free basis.Tephra layers recovered from the study area were examined for chemical evidence of secondary alteration. The analyses revealed that H₂O is the only major oxide in the glass shards which increases progressively with the age of the tephra layers regardless of the bulk composition. H₂O, however, reaches a “saturation point” of 4–5% in the layers 250–400 thousands of years old and remains constant to the oldest recovered tephra layer (7.5 m.y. old).The decrease in silica content in deep-sea tephra layers eastward along the Indonesian volcanic arc coincides with a similar eastward decrease in average silica content in Indonesian lavas. A relatively high silica content in lavas from Sumatra, with associated ignimbrites and their deep-sea ash-fall equivalents is closely linked to thick pre-Cenozoic crust. In the portion of the arc to the east of Sumatra, the crust is Cenozoic and thin. Difference in silica content of both the lavas and deep-sea tephras along the Indonesian arc is considered in regard to the hypothesis of “magma filtering” which is based on the contrasting density gradients of ascending magma and the upper crust.     

Deep biological communities in the subduction zone of Japan from bottom photographs taken during “nautile” dives in the Kaiko project

Twenty-seven dives of the submersible “Nautile” in the subduction zone around Japan conducted in the French-Japanese Project Kaiko proved that fairly luxuriant benthic communities dominated by deep-sea giant clams of the genusCalyptogena (family Vesicomyidae) were consistently present on the accretionary prism at abyssal depths.Benthic communities characterized by three hitherto undescribed bivalves of the genusCalyptogena were found between depths of about 3800 and 4020 m at the mouth of Tenryu Canyon and at the top of basement swell of the Zenisu Ridge, both situated in the eastern Nankai subduction zone. Sporadic but discrete patches of organisms characterized by one more undescribed bivalve belonging to the genusCalyptogena were observed and collected between depths of 5130 and 5960 m on the landward wall of the Japan and Kouriles Trenches.Photographic inventories were prepared semiquantitatively using each series of bottom photographs taken in these areas with bow cameras of the submersible “Nautile”.Observations on the sporadic but dense distribution of the clams and other characteristic associated organisms match well with the scheme that communities sustained by chemosynthetic energy sources can be present at connate water seepages in subduction zones. These are to date the deepest record of benthic communities supposedly associated with chemosynthetic processes.     

An isotope study of the accumulation mechanisms of high-sulfur gas from the Sichuan Basin,southwestern China

The mechanism of hydrogen sulfide (H₂S) generation plays a key role in the exploration and development of marine high-sulfur natural gas, of which the major targets are the composition and isotope characteristics of sulfur-containing compounds. Hydrocarbon source rocks, reservoir rocks, natural gases and water-soluble gases from Sichuan Basin have been analyzed with an online method for the content of H₂S and isotopic composition of different sulfur-containing compounds. The results of comparative analysis show that the sulfur-containing compounds in the source rocks are mainly formed by bacterial sulfate reduction (BSR), and the sulfur compounds in natural gas, water and reservoir are mainly formed by thermal sulfate reduction (TSR). Moreover, it has been shown that the isotopically reversion for methane and ethane in high sulfur content gas is caused by TSR. The sulfur isotopic composition of H₂S in natural gas is inherited from the gypsum or brine of the same or adjacent layer, indicating that the generation and accumulation of H₂S have the characteristics of either a self-generated source or a near-source.     

Minor elements in perovskite from kimberlites and distribution of the rare earth elements: An electron probe study

We report REE and minor element distributions for perovskites from seven kimberlites (South Africa and U.S.A.). The REE (1.6–6.3 oxides wt.%) are always strongly light REE enriched, often with Ce > La (chondrite-normalized), and show an expected close correlation with whole-rock analyses. Where examined, perovskite contains far more REE than coexisting apatite, by about an order of magnitude. Calculations indicate that iron is mostly present as Fe³⁺ and is low (1.0–2.9 wt.% Fe₂O₃) compared with perovskite from carbonatite complexes such as Oka (4.4 wt.% FeO [3]). In addition to established Nb (0.3–1.7 oxide wt.%), geochemically interesting elements encountered include Zr (up to 1.5 oxide wt.%), Ba and Sr (up to 0.2, 0.4 oxide wt.% respectively). Specific geological applications suggest a possible genetic link between Wesselton pipe and Benfontein Sills kimberlites, and that carbonate-rich dikes in the Premier mine were derived from kimberlites. The overall similarities with incompatible element-rich titanates in veined mantle peridotites suggest a more direct link between kimberlite magmatism and mantle metasomatism.     

Pyrite paragenesis and multiple sulfur isotope distribution in late Archean and early Paleoproterozoic Hamersley Basin sediments

The sulfur isotope record in late Archean and early Paleoproterozoic rocks is of considerable importance because it provides evidence for changes in early Earth atmospheric oxygen levels and potentially constrains the origin and relative impact of various microbial metabolisms during the transition from an anoxic to oxic atmosphere. Mass independently fractionated (MIF) sulfur isotopes reveal late Archean and early Paleoproterozoic sulfur sources in different pyrite morphologies in Western Australia's Hamersley Basin. Multiple sulfur isotope values in late Archean pyrite vary according to morphology. Fine grained pyrite has positive sulfur MIF, indicating a reduced elemental sulfur source, whereas pyrite nodules have negative sulfur MIF, potentially derived from soluble sulfate via microbial sulfate reduction. The Hamersley Basin δ³⁴S–Δ³³S record suggests that the extent of oxygenation of the surface ocean fluctuated through the Late Archean from at least 2.6 Ga, more than 150 million yr before the Great Oxidation Event. In the early Paleoproterozoic, there is less distinction between pyrite morphologies with respect to sulfur isotope fractionation, and pyrite from the Brockman Iron Formation trends toward modern sulfur isotope values. An important exception to this is the strong negative MIF recorded in layer parallel pyrite in Paleoproterozoic carbonate facies iron formation. This may suggest that deeper water hydrothermal environments remained anoxic while shallower water environments became more oxidised by the early Paleoproterozoic. The results of the current study indicate that sulfide paragenesis is highly significant when investigating Archean and early Paleoproterozoic multiple sulfur isotope compositions and sulfur sources.     

Subaqueous geothermal activity revealed by lacustrine sediments of the acidic Nakadake crater lake, Aso Volcano, Japan

Lacustrine sediments were sampled from the inaccessible acidic (pH = 0.43) Nakadake crater lake of Aso Volcano, Japan by a simple method. The sediments contain an extremely high content (74 wt.%) of sulfur, which exits as elemental sulfur, gypsum and anhydrite. The abundant elemental sulfur is likely formed by the reaction of SO₂ and H₂S gases and by the SO₂ disproportionation reaction in magmatic hydrothermal system below the crater lake. Based on the sulfur content of sediments and measurements of elevation change of the crater bottom, the sulfur accumulation rate at the Nakadake crater lake was calculated as 250 tonne/day, which is comparable with the SO₂ emission rate (200–600 tonne/day) from the Nakadake crater. The sediments include a small amount (9%) of clear glass shards that are apparently not altered in spite of the high reactivity of hyperacid lake water. This finding suggests that the clear glass shards are fragments of recently emitted magmas from fumaroles on the bottom of the crater lake and the magma emissions continuously occur even in quiescent periods.     

Influence of metal oxides in the colorimetric determination of acid volatile sulfide in sediments

The sediment of Lagoa dos Patos‐MS, Brazil, was investigated to verify the influence of metal sulfides and oxyhydroxides of Mn and Fe on the heavy metal availability. The spectrophotometric method of methylene blue was used, with 8 interlinked tubes containing the samples with SnCl₂, where N₂ was introduced to release the H₂S extracted with 6.0 mol L^–1 HCl, and trapped in 0.05 M NaOH solution. The influence of SO₄^2–, Mn(IV) and Fe(III) oxyhydroxides was investigated with samples constituted by a mixture of MnO₂; Na₂SO₄; FeCl₃, and sediments. The presence of SnCl₂ was very important to avoid the interferences of iron and manganese oxyhydroxides. The method of standard addition was applied and the efficiency was (100.8 ± 9.4)%. The ratio among the quantities of metals potentially available and the acid volatile sulfide (AVS) indicate that the system presents small metals availability to the benthic community, by the existence of sulfide capable to immobilize the metal as insoluble sulfide.     

Distinguishing Iron-Reducing from Sulfate-Reducing Conditions

Ground water systems dominated by iron‐ or sulfate‐reducing conditions may be distinguished by observing concentrations of dissolved iron (Fe²⁺) and sulfide (sum of H₂S, HS^?, and S⁼ species and denoted here as “H₂S”). This approach is based on the observation that concentrations of Fe²⁺ and H₂S in ground water systems tend to be inversely related according to a hyperbolic function. That is, when Fe²⁺ concentrations are high, H₂S concentrations tend to be low and vice versa. This relation partly reflects the rapid reaction kinetics of Fe²⁺ with H₂S to produce relatively insoluble ferrous sulfides (FeS). This relation also reflects competition for organic substrates between the iron‐ and the sulfate‐reducing microorganisms that catalyze the production of Fe²⁺ and H₂S. These solubility and microbial constraints operate in tandem, resulting in the observed hyperbolic relation between Fe²⁺ and H₂S concentrations. Concentrations of redox indicators, including dissolved hydrogen (H₂) measured in a shallow aquifer in Hanahan, South Carolina, suggest that if the Fe²⁺/H₂S mass ratio (units of mg/L) exceeded 10, the screened interval being tapped was consistently iron reducing (H₂～0.2 to 0.8 nM). Conversely, if the Fe²⁺/H₂S ratio was less than 0.30, consistent sulfate‐reducing (H₂～1 to 5 nM) conditions were observed over time. Concomitantly high Fe²⁺ and H₂S concentrations were associated with H₂ concentrations that varied between 0.2 and 5.0 nM over time, suggesting mixing of water from adjacent iron‐ and sulfate‐reducing zones or concomitant iron and sulfate reduction under nonelectron donor–limited conditions. These observations suggest that Fe²⁺/H₂S mass ratios may provide useful information concerning the occurrence and distribution of iron and sulfate reduction in ground water systems.     

Diffusion of osmium in pyrrhotite and pyrite: implications for closure of the Re–Os isotopic system

In order to better constrain the extent to which common sulfide minerals will retain their osmium isotopic composition subsequent to crystallization, we have conducted experiments to quantify the diffusion behavior of osmium in pyrite and pyrrhotite. Experiments consisted of either (1) isothermal soaking of diffusion couples consisting of natural pyrite or pyrrhotite crystals packed against powdered Os-bearing Fe-sulfide or (2) ‘relaxation’ of initially high near-surface osmium concentrations produced in the latter experiments (pyrite only). Osmium penetration into samples was characterized by depth profiling using Rutherford backscattering spectroscopy (RBS) (pyrite) or electron microprobe analyses across sectioned run products (pyrrhotite). Results of the first type of diffusion experiment involving pyrite show only limited osmium penetration into sample surfaces, with the extent of penetration uncorrelated with run duration. Images of pyrite samples using atomic force microscopy show roughening of initially smooth surfaces as a consequence of step formation and suggest that osmium incorporation into the near-surface occurred by solute uptake during step growth and not by volume diffusion. Prolonged (1000⁺ h) ‘relaxation’ experiments revealed no additional osmium penetration into pyrite surfaces and based on the depth resolution for RBS, a maximum diffusion coefficient of 2.5×10⁻²³ m²/s at 500°C was calculated. Experiments involving pyrrhotite over the temperature range of 950–1100°C showed extensive osmium uptake and osmium concentration gradients that conform with Fickian diffusion behavior. We found that pyrrhotite Fe/S could be varied by changes in the composition of the starting material and osmium source and over the range of Fe/S produced in experiments (molar Fe/S=0.83–0.90), we observed no systematic variation in the osmium diffusion coefficient. Diffusion coefficients measured parallel to the a crystallographic axis were on average 1.4× higher than values measured parallel to c and regression of the c-axis data yielded the Arrhenius relation:

The application of these diffusion data to simple models of diffusive exchange during static or polythermal time–temperature histories is used to assess the conditions under which radiogenic osmium will be retained. During isothermal annealing, calculations indicate that the cores of millimeter-sized spherical pyrrhotite crystals undergoing diffusive exchange with an external osmium reservoir will have their initial compositions perturbed in ≤0.5 Ma at temperatures exceeding 400°C. Pyrite undergoing the same process at 500°C requires in excess of 10 Ma before crystal cores are affected. The relatively short ‘core retention’ time-scales for pyrrhotite indicates that this mineral may be prone to isotopic resetting following relatively brief crustal thermal events, thus possibly accounting for the scatter that commonly occurs in Re–Os isochrons generated from massive sulfide samples. Calculated closure temperatures (T_c) for osmium exchange in pyrrhotite yielded values of 300–400°C for grain sizes ranging from 10 to 1000 μm. These values of T_c are similar to those calculated for Ar retention in biotite, and considerably lower than for Sr in apatite and plagioclase, for example. Such low closure temperatures for pyrrhotite suggest this mineral will date the final stage in the cooling of a magmatic system and possibly be susceptible to open system osmium exchange in the presence of late-stage hydrothermal fluids. This latter result infers that caution be applied when interpreting elevated initial osmium isotopic ratios as a product of crustal assimilation at the magmatic stage.     

Lithological controls on biological activity and groundwater chemistry in Quaternary sediments

Depth profiles of solute chemistry and sulfate isotopic compositions are presented for groundwater and pore water in a sequence of Quaternary glacial outwash sediments. Sand units show evidence for hydraulic connection to the surface and thus modern sources of solutes. Finer‐grained sediments show a general pattern of increasing solute concentrations with depth, with sulfate derived from ancient rainwater and pyrite oxidation in the soil/drift. In these sediments sulfate has undergone bacterial sulfate reduction (BSR) to produce biogenic sulfide. In clay sediments, with d₁₀ ≤ 1·6 µm, high concentrations of sulfate and acetate now co‐exist, implying that BSR is inhibited. The correlation with smaller sediment grain size indicates that this is due to pore size exclusion of the sulfate reducing bacteria. Mechanical restriction of microbial function thus provides a fundamental limitation on microbial respiration in buried clay‐rich sediments, which acts as a control on the chemical evolution of their pore waters. Copyright © 2009 John Wiley & Sons, Ltd.     

Magnetic minerals in sediments at the Cretaceous/Paleogene boundary (the Gams Section,Eastern Alps)

The paper presents results of detailed magnetomineralogical and microprobe studies of sediments at the Cretaceous/Paleogene (K/T) boundary in two epicontinental sections in the Eastern Alps (Austria), where deposits, including the K/T boundary, outcrop along the Gams River and its tributaries. K/T boundary layers in these sections are similar in the set of such magnetic minerals as iron hydroxides, ferrospinels, hemoilmenite, titanomagnetite, magnetite, hematite, and metallic iron. However, the boundary layer in the Gams-1 section is distinguished by the presence of metallic nickel and its alloy with iron and by the absence of iron sulfides, whereas nickel has not been discovered in the Gams-2 section, which, however, contains iron sulfides of the pyrite type. Therefore, these minerals occur locally. It is suggested that enrichment in iron hydroxides of a common origin can be regarded as a global phenomenon inherent in the K/T boundary and unrelated to an impact event.