Evolution of photoautotrophy and early atmospheric oxygen levels

Current photochemical models suggest that oxygen levels in the prebiological atmosphere were extremely low, most probably remaining in the range 10⁻⁸–10⁻¹⁴ PAL (present atmospheric level). It is, therefore, reasonable to assume that only life processes were able to overwhelm these minor O₂-pressures, with free oxygen resulting from the reduction of carbon dioxide to the carbohydrate level during photoautotrophic carbon fixation using water as an electron donor (

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). It is by now well established that reduced (organic) carbon is a common constituent of sedimentary rocks from the very start of the geological record 3.8 Ga ago. Both direct assays and inferences derived from a carbon isotope mass balance suggest that the C_org-content of Archaean sediments was not basically different from that of geologically younger rocks. This poses the problem of the existence 3.5 Ga ago of an oxidation equivalent of such a formidable ancient C_org-reservoir which, depending on the model adopted for the growth of the sedimentary mass through time, might have amounted to between 20 and 100% of the present one. Low atmospheric oxygen pressures in the Early Precambrian that are inferred from retarded oxidation reactions, notably in the ancient continental weathering cycle, are likely, therefore, to indicate extremely rapid processes of oxygen consumption in other parts of the system (e.g., hydrosphere) rather than the general absence of photosynthetic oxidation equivalents during this time.     

Geochemistry of a paleosol horizon at the base of the Sausar Group,central India: Implications on atmospheric conditions at the Archeane Paleoproterozoic boundary

A paleosol horizon is described from the contact of the Sausar Group(w2400 Ma) and its basement(Tirodi Gneiss; 2500 Ma) in Central India. Physical evidence of pedogenesis is marked by the development of stress corrosion cracks, soil peds, corestone weathering and nodular rocks. XRD and SEM-EDX data indicate the presence of siderite, ankerite, uraninite, chlorite, alumino-silicate minerals, ilmenite,rutile and magnetite, in addition to quartz, feldspar and mica. The chemical index of alteration, the plagioclase index of alteration, and the chemical index of weathering show an increasing trend from parent rock to the paleosol and indicate a moderate trend of weathering. The A-CN-K plot indicates loss of feldspars, enrichment in Al2O3 and formation of illite. Different major element ratios indicate baseloss through hydrolysis, clay formation, leaching of some elements, and more precipitation with good surface drainage. The paleosol is depleted in HREE in comparison to the parent rock indicating high fluid-rock interaction during weathering. The paleosol samples show flat Ce and Eu anomalies, low SREE, and high(La/Yb)N, indicative of a reducing environment of formation. Reducing condition can also be inferred from the concentration of elements such as V, Co, Cu, Pb, and Zn in the paleosol profile. Although enriched in Fe and Mg, the overall geochemical patterns of the paleosol indicate oxygen deficient conditions in the atmosphere and development by weathering and leaching processes associated with high precipitation and good surface drainage at the time of development of this paleosol during the Archeane Paleoproterozoic transition.     

The kinetics of the oxidation of ferrous iron in synthetic and natural waters

The rate of oxidation of ferrous iron in a seasonally anoxic lake was measured on 39 occasions with respect to both depth and time. Sample disturbance was minimal as only oxygen had to be introduced to initiate the reaction. The data were consistent with the simple rate law for homogeneous chemical kinetics previously established for synthetic solutions. The rate constant for the oxidation reaction in lake water was indistinguishable from that measured in synthetic samples. It did not appear to be influenced by changes in the microbial populations or by changes in any particulate or soluble components in the water, including iron and manganese. Analysis of the errors inherent in the kinetic measurements showed that the estimation of pH was the major source of inaccuracy and that values of the rate constant determined by different workers could easily differ by a factor of six.The present data, together with a comprehensive survey of the literature, are used to suggest a ‘universal’ rate constant of ca. 2 × 10¹³ M^?2 atm^?1 min^?1 (range 1.5–3 × 10¹³) in the rate law $\text{?d[Fe II]}\text{dt}\text{= k[Fe II]pO}{}_2\text{(OH?)}{}^2$ for natural freshwaters in the pH range 6.5–7.4. Discrepancies in the effects of ionic strength and interfering substances reported in the literature are highlighted. Generally substances have only been found to interfere at concentrations which far exceed those in most natural waters.     

SIMS analyses of silicon and oxygen isotope ratios for quartz from Archean and Paleoproterozoic banded iron formations

Banded iron formations (BIFs) are chemical marine sediments dominantly composed of alternating iron-rich (oxide, carbonate, sulfide) and silicon-rich (chert, jasper) layers. Isotope ratios of iron, carbon, and sulfur in BIF iron-bearing minerals are biosignatures that reflect microbial cycling for these elements in BIFs. While much attention has focused on iron, banded iron formations are equally banded silica formations. Thus, silicon isotope ratios for quartz can provide insight on the sources and cycling of silicon in BIFs. BIFs are banded by definition, and microlaminae, or sub-mm banding, are characteristic of many BIFs. In situ microanalysis including secondary ion mass spectrometry is well-suited for analyzing such small features. In this study we used a CAMECA IMS-1280 ion microprobe to obtain highly accurate (±0.3‰) and spatially resolved (∼10 μm spot size) analyses of silicon and oxygen isotope ratios for quartz from several well known BIFs: Isua, southwest Greenland (∼3.8 Ga); Hamersley Group, Western Australia (∼2.5 Ga); Transvaal Group, South Africa (∼2.5 Ga); and Biwabik Iron Formation, Minnesota, USA (∼1.9 Ga). Values of δ¹⁸O range from +7.9‰ to +27.5‰ and include the highest reported δ¹⁸O values for BIF quartz. Values of δ³⁰Si have a range of ∼5‰ from −3.7‰ to +1.2‰ and extend to the lowest δ³⁰Si values for Precambrian cherts. Isua BIF samples are homogeneous in δ¹⁸O to ±0.3‰ at mm- to cm-scale, but are heterogeneous in δ³⁰Si up to 3‰, similar to the range in δ³⁰Si found in BIFs that have not experienced high temperature metamorphism (up to 300 °C). Values of δ³⁰Si for quartz are homogeneous to ±0.3‰ in individual sub-mm laminae, but vary by up to 3‰ between multiple laminae over mm-to-cm of vertical banding. The scale of exchange for Si in quartz in BIFs is thus limited to the size of microlaminae, or less than ∼1 mm. We interpret differences in δ³⁰Si between microlaminae as preserved from primary deposition. Silicon in BIF quartz is mostly of marine hydrothermal origin (δ³⁰Si < −0.5‰) but silicon from continental weathering (δ³⁰Si ∼ 1‰) was an important source as early as 3.8 Ga.     

Aqueous pyrite oxidation by dissolved oxygen and by ferric iron

Rates of aqueous, abiotic pyrite oxidation were measured in oxygen-saturated and anaerobic Fe(III)-saturated solutions with initial pH from 2 to 9. These studies included analyses of sulfite, thiosulfate, polythionates and sulfate and procedures for cleaning oxidation products from pyrite surfaces were evaluated. Pyrite oxidation in oxygen-saturated solutions produced (1) rates that were only slightly dependent on initial pH, (2) linear increases in sulfoxy anions and (3) thiosulfate and polythionates at pH > 3.9. Intermediate sulfoxy anions were observed only at high stirring rates. In anaerobic Fe(III)-saturated solutions, no intermediates were observed except traces of sulfite at pH 9. The faster rate of oxidation in Fe(III)-saturated solutions supports a reaction mechanism in which Fe(III) is the direct oxidant of pyrite in both aerobic and anaerobic systems. The proposal of this mechanism is also supported by theoretical considerations regarding the low probability of a direct reaction between paramagnetic molecular oxygen and diamagnetic pyrite. Results from a study of sphalerite oxidation support the hypothesis that thiosulfate is a key intermediate in sulfate production, regardless of the bonding structure of the sulfide mineral.     

Isotopic compositions of oxygen, iron, chromium, and nickel in cosmic spherules: Toward a better comprehension of atmospheric entry heating effects

Large, correlated, mass-dependent enrichments in the heavier isotopes of O, Cr, Fe, and Ni are observed in type-I (metal/metal oxide) cosmic spherules collected from the deep sea. Limited intraparticle variability of oxygen isotope abundances, typically <5‰ in δ¹⁸O, indicates good mixing of the melts and supports the application of the Rayleigh equation for the calculation of fractional evaporative losses during atmospheric entry. Fractional losses for oxygen evaporation from wüstite, assuming a starting isotopic composition equal to that of air (δ¹⁸O = 23.5‰; δ¹⁷O = 11.8‰), are in the range 55%-77%, and are systematically smaller than evaporative losses calculated for Fe (69%-85%), Cr (81%-95%), and especially Ni (45%-99%). However, as δ¹⁸O values increase, fractional losses for oxygen approach those of Fe, Cr, and Ni indicating a shift in the evaporating species from metallic to oxidized forms as the spherules are progressively oxidized during entry heating. The observed unequal fractional losses of O and Fe can be reconciled by allowing for a kinetic isotope mass-dependent fractionation of atmospheric oxygen during the oxidation process and/or that some metallic Fe may have undergone Rayleigh evaporation before oxidation began.In situ measurements of oxygen isotopic abundances were also performed in 14 type-S (silicate) cosmic spherules, 13 from the Antarctic ice and one from the deep sea. Additional bulk Fe and Cr isotopic abundances were determined for two type-S deep-sea spherules. The isotopic fractionation of Cr isotopes suggest appreciable evaporative loss of Cr, perhaps as a sulfide. The oxygen isotopic compositions for the type-S spherules range from δ¹⁸O = −2‰ to + 27‰. The intraspherule isotopic variations are typically small, ∼5% relative, except for the less-heated porphyritic spherules which have preserved large isotopic heterogeneities in at least one case. A plot of δ¹⁷O vs. δ¹⁸O values for these spherules defines a broad parallelogram bounded at higher values of δ¹⁷O by the terrestrial fractionation line, and at lower values of δ¹⁷O by a line parallel to it and anchored near the isotopic composition of δ¹⁸O = −2.5‰ and δ¹⁷O = −5‰. Lack of independent evidence for substantial evaporative losses suggests that much of this variation reflects the starting isotopic composition of the precursor materials, which likely resembled CO, CM, or CI chondrites. However, the enrichments in heavy isotopes indicate that some mixing with atmospheric oxygen was probably involved during atmospheric entry for some of the spherules. Isotopic fractionation due to evaporation of incoming grain is not required to explain most of the oxygen isotopic data for type-S spherules. However spherules with barred olivine textures that are thought to have experienced a more intense heating than the porphyritic ones might have undergone some distillation. Two cosmic spherules, one classified as a radial pyroxene type and the other showing a glassy texture, show unfractionated oxygen isotopic abundances. They are probably chondrule fragments that survived atmospheric entry unmelted.Possible reasons type-I spherules show larger degrees of isotopic fractionation than type-S spherules include: a) the short duration of the heating pulse associated with the high volatile content of the type-S spherule precursors compared to type-I spherules; b) higher evaporation temperatures for at least a refractory portion of the silicates compared to that of iron metal or oxide; c) lower duration of heating of type-S spherules compared to type-I spherules as a consequence of their lower densities.     

Constraining atmospheric oxygen and seawater sulfate concentrations during Paleoproterozoic glaciation: In situ sulfur three-isotope microanalysis of pyrite from the Turee Creek Group, Western Australia

Previous efforts to constrain the timing of Paleoproterozoic atmospheric oxygenation have documented the disappearance of large, mass-independent sulfur isotope fractionation and an increase in mass-dependent sulfur isotope fractionation associated with multiple glaciations. At least one of these glacial events is preserved in diamictites of the ∼2.4 Ga Meteorite Bore Member of the Kungarra Formation, Turee Creek Group, Western Australia. Outcrop exposures of this unit show the transition from the Boolgeeda Iron Formation of the upper Hamersley Group into clastic, glaciomarine sedimentary rocks of the Turee Creek Group. Here we report in situ multiple sulfur isotope and elemental abundance measurements of sedimentary pyrite at high spatial resolution, as well as the occurrence of detrital pyrite in the Meteorite Bore Member. The 15.3‰ range of Δ³³S in one sample containing detrital pyrite (−3.6‰ to 11.7‰) is larger than previously reported worldwide, and there is evidence for mass-independent sulfur isotope fractionation in authigenic pyrite throughout the section (Δ³³S from −0.8‰ to 1.0‰). The 90‰ range in δ³⁴S observed (−45.5‰ to 46.4‰) strongly suggests microbial sulfate reduction under non-sulfate limiting conditions, indicating significant oxidative weathering of sulfides on the continents. Multiple generations of pyrite are preserved, typically represented by primary cores with low δ³⁴S (<−20‰) overgrown by euhedral rims with higher δ³⁴S (4-7‰) and enrichments in As, Ni, and Co. The preservation of extremely sharp sulfur isotope gradients (30‰/<4 μm) implies limited sulfur diffusion and provides time and temperature constraints on the metamorphic history of the Meteorite Bore Member. Together, these results suggest that the Meteorite Bore Member was deposited during the final stages of the “Great Oxidation Event,” when pO₂ first became sufficiently high to permit pervasive oxidative weathering of continental sulfides, yet remained low enough to permit the production and preservation of mass-independent sulfur isotope fractionation.     

Precambrian atmospheric oxygen and banded iron formations: A delayed ocean model

Evidence and arguments increasingly in favor of free oxygen in the Earth's early atmosphere renew the constraints on the environmental significance of Precambrian banded iron formations. An early moist greenhouse atmosphere with a delay in, and gradual growth of, the world oceans offers a mechanism to provide a geochemically and mechanically segregated source of iron and silica for banded iron formation, while simultaneously ‘cannibalizing’ evidence for early Archean red beds. The model supports the high rates of weathering necessary to remove initially outgassed CO₂ quickly, favors continuity in early biogenic evolution, provides a mechanism for hydrogen and strontium isotope partitioning, and is consistent with iron oxide facies that are devoid of organic carbon or stromatolites that are not encrusted by iron oxide.     

Outer-sphere electron transfer kinetics of metal ion oxidation by molecular oxygen

Density functional theory molecular orbital calculations and Marcus theory have been combined to assess the rates and physicochemical factors controlling the outer-sphere oxidation of divalent V, Cr, Mn, Fe, and Co aquo and hydroxo ions by O₂ in homogeneous aqueous solution. Key quantities in the elementary oxidation step include the inner-sphere component of the reorganization energy, the thermodynamic driving force, and electrostatic work terms describing the interactions occurring, in this case, between the net charges on the product species. Collectively, these factors and their interplay have a large influence on the rate of the oxidation cross-reaction.An inner-sphere pathway for the self-exchange reactions and oxidation by O₂ of Mn²⁺ and Cr²⁺ ions has been supported indirectly in this study by comparing predicted outer-sphere rates with the results of previous experiments. Likewise, an outer-sphere pathway is suggested for the similar sets of reactions involving the V, Fe, and Co ions. An assessment of the self-exchange reaction for the oxygen/superoxide couple has led to predicted rates in excellent agreement with direct measurements. Predicted rates of oxidation for the hexaquo Fe ion are also in agreement with experiment, while the predicted rates for the outer-sphere oxidation of its hydrolysis products are ∼2 to 3 (monohydroxo) and ∼4 (dihydroxo) orders of magnitude slower than the observed rates. This suggests an inner-sphere pathway is appropriate to explain the relatively fast rates observed for the hydrolyzed Fe species.     

Ancient graphite in the Eoarchean quartz-pyroxene rocks from Akilia in southern West Greenland II: Isotopic and chemical compositions and comparison with Paleoproterozoic banded iron formations

We present detailed petrographic surveys of apatite grains in association with carbonaceous material (CM) in two banded iron formations (BIFs) from the Paleoproterozoic of Uruguay and Michigan for comparison with similar mineral associations in the highly debated Akilia Quartz-pyroxene (Qp) rock. Petrographic and Raman spectroscopic surveys of these Paleoproterozoic BIFs show that apatite grains typically occur in bands parallel to bedding and are more often associated with CM when concentrations of organic matter are high. Carbonaceous material in the Vichadero BIF from Uruguay is generally well-crystallized graphite and occurs in concentrations around 0.01 wt% with an average δ¹³C_gra value of −28.6 ± 4.4‰ (1σ). In this BIF, only about 5% of apatite grains are associated with graphite. In comparison, CM in the Bijiki BIF from Michigan is also graphitic, but occurs in concentrations around 2.4 wt% with δ¹³C_gra values around −24.0 ± 0.3‰ (1σ). In the Bijiki BIF, more than 78% of apatite grains are associated with CM. Given the geologic context and high levels of CM in the Bijiki BIF, the significantly higher proportion of apatite grains associated with CM in this rock is interpreted to represent diagenetically altered biomass and shows that such diagenetic mineral associations can survive metamorphism up to the amphibolite facies.Isotope compositions of CM in muffled acidified whole-rock powders from the Akilia Qp rock have average δ¹³C_gra values of −17.5 ± 2.5‰ (1σ), while δ¹³C_carb values in whole-rock powders average −4.0 ± 1.0‰ (1σ). Carbon isotope compositions of graphite associated with apatite and other minerals in the Akilia Qp rock were also measured with the NanoSIMS to have similar ranges of δ¹³C_gra values averaging −13.8 ± 5.6‰ (1σ). The NanoSIMS was also used to semi-quantitatively map the distributions of H, N, O, P, and S in graphite from the Akilia Qp rock, and relative abundances were found to be similar for graphite associated with apatite or with hornblende, calcite, and sulfides. These analyses revealed generally lower abundances of trace elements in the Akilia graphite compared to graphite associated with apatite from Paleoproterozoic BIFs.Graphite associated with hornblende, calcite, and sulfides in the Akilia Qp rock was fluid-deposited at high-temperature from carbon-bearing fluids, and since this graphite has similar ranges of δ¹³C_gra values and of trace elements compared to graphite associated with apatite, we conclude that the Akilia graphite in different mineral associations formed from the same source(s) of CM. Collectively our results do not exclude a biogenic origin of the carbon in the Akilia graphite, but because some observations can not exclude graphitization of abiogenic carbon from CO₂- and CH₄-bearing mantle fluids, there remain ambiguities with respect to the exact origin of carbon in this ancient metasedimentary rock. Accordingly, there may have been several generations of graphite formation along with possibly varying mixtures of CO₂- and CH₄-bearing fluids that may have resulted in large ranges of δ¹³C_gra values. The possibility of fluid-deposited graphite associated with apatite should be a focus of future investigations as this may prove to be an alternative pathway of graphitization from phosphate-bearing fluids. Correlated micro-analytical approaches tested on terrestrial rocks in this work provide insights into the origin of carbon in ancient graphite and will pave the way for the search for life on other ancient planetary surfaces.     

Formation of iron sulfide nodules during anaerobic oxidation of methane

The biomarker compositions of iron sulfide nodules (ISNs; upper Pliocene Valle Ricca section near Rome, Italy) that contain the ferrimagnetic mineral greigite (Fe₃S₄) were examined. In addition to the presence of specific terrestrial and marine biomarkers, consistent with formation in coastal marine sediments, these ISNs contain compounds thought to originate from sulfate reducing bacteria (SRB). These compounds include a variety of low-molecular-weight and branched alkanols and several non-isoprenoidal dialkyl glycerol diethers (DGDs). In addition, archaeal biomarkers, including archaeol, macrocyclic isoprenoidal DGDs and isoprenoidal glycerol dialkyl glycerol tetraethers are also present. Both SRB and archaeal lipid δ¹³C values are depleted in ¹³C (δ¹³C values are typically less than −50‰), which suggests that the SRB and archaea consumed ¹³C depleted methane. These biomarker and isotopic signatures are similar to those found in cold seeps and marine sediments where anaerobic oxidation of methane (AOM) occurs with sulfate serving as the terminal electron acceptor. Association of AOM with formation of greigite-containing ISNs could provide an explanation for documented remagnetization of the Valle Ricca sediments. Upward migration of methane, subsequent AOM and associated authigenic greigite formation are widespread processes in the geological record that have considerable potential to compromise paleomagnetic records.     

Magnetite compositions and oxygen fugacities of the Khibina magmatic system

Most titanomagnetite in the Khibina alkaline igneous complex, sampled through 500 m of a vertical cross-section, is represented by Ti-rich varieties. The ulvöspinel component is most commonly around 55 mol%, rarely reaching up to 80 mol%.

We calculated an f_O2–T diagram for magnetite + ilmenite + titanite + clinopyroxene + nepheline + alkali feldspar and magnetite + titanite+ clinopyroxene + nepheline + alkali feldspar phase assemblages at a hedenbergite activity of 0.2. The diagram shows that magnetites with 55 mol% of ulvöspinel crystallized at oxygen fugacities just slightly below the quartz–fayalite–magnetite buffer. More Ti-rich varieties crystallized at higher temperatures and slightly lower ΔQMF values, whereas more Ti-poor magnetites crystallized at or below about 650 °C.

Under the redox conditions estimated for the apatite-bearing intrusion of the Khibina complex (close to the QFM buffer), substantial quantities of methane may only form during cooling below 400 °C in equilibrium with magma. However, even at higher orthomagmatic temperatures and redox conditions corresponding to ΔQMF = 0, the hydrogen content in the early magmatic stage is not negligible. This hydrogen present in the gas phase at magmatic temperatures may migrate to colder parts of a solidifying magma chamber and trigger Fischer-Tropsch-type reactions there. We propose therefore, that methane in peralkaline systems may form in three distinct stages: orthomagmatic and late-magmatic in equilibrium with a melt and — due to Fischer-Tropsch-type reactions — post-magmatic in equilibrium with a local mineral assemblage.     

Oxygen isotope fractionation of dissolved oxygen during reduction by ferrous iron

The oxygen isotope fractionation factor of dissolved oxygen gas has been measured during inorganic reduction by aqueous FeSO₄ at 10−54 °C under neutral (pH 7) and acidic (pH 2) conditions, with Fe(II) concentrations ranging up to 0.67 mol L⁻¹, in order to better understand the geochemical behavior of oxygen in ferrous iron-rich groundwater and acidic mine pit lakes. The rate of oxygen reduction increased with increasing temperature and increasing Fe(II) concentration, with the pseudo-first-order rate constant k ranging from 2.3 to 82.9 × 10⁻⁶ s⁻¹ under neutral conditions and 2.1 to 37.4 × 10⁻⁷ s⁻¹ under acidic conditions. The activation energy of oxygen reduction was 30.9 ± 6.6 kJ mol⁻¹ and 49.7 ± 13.0 kJ mol⁻¹ under neutral and acidic conditions, respectively. Oxygen isotope enrichment factors (ε) become smaller with increasing temperature, increasing ferrous iron concentration, and increasing reaction rate under acidic conditions, with ε values ranging from −4.5‰ to −11.6‰. Under neutral conditions, ε does not show any systematic trends vs. temperature or ferrous iron concentration, with ε values ranging from −7.3 to −10.3‰. Characterization of the oxygen isotope fractionation factor associated with O₂ reduction by Fe(II) will have application to elucidating the process or processes responsible for oxygen consumption in environments such as groundwater and acidic mine pit lakes, where a number of possible processes (e.g. biological respiration, reduction by reduced species) may have taken place.     

The ∼1100 Ma Sturgeon Falls paleosol revisited: Implications for Mesoproterozoic weathering environments and atmospheric CO2 levels

During the active rifting stage of the ∼1100 Ma Midcontinental Rift in North America, alluvial sediments were deposited intermittently between basalt flows on the north and south shores of present day Lake Superior. At times of depositional quiescence, paleosols developed in both areas on the alluvial sediments and on the antecedent basalt. New results from the Sturgeon Falls paleosol in Michigan characterizing the weathering processes at the time of its formation indicate moderate maturity, high degrees of hydrolysis and leaching, and a low degree of salinization. Geochemical provenance indices indicate a homogeneous source for the paleosols, and in contrast to earlier work, there is little evidence for K metasomatism. As a result, atmospheric CO₂ levels of 4–6× pre-industrial atmospheric levels were calculated using a mass-balance model. This result is consistent with previous calculations from nearly contemporaneous paleosols from the other side of the Keweenawan Rift and from the ∼100 Ma younger Sheigra paleosol in Scotland. The calculated CO₂ values are also consistent with the calculated weathering environment proxies that indicate weak to moderate weathering at this time frame and suggest that the higher greenhouse gas loads indicated by Paleoproterozoic paleosols had dissipated by the mid-late Mesoproterozoic.     

Genetic types of metaconglomerates at the Paleoproterozoic basement of the Krivoi Rog iron ore basin

The Paleoproterozoic basement of the Krivoi Rog iron ore basin comprises five genetically different lithopetrographic types of metaconglomerates that make up stratigraphic and lithofacies successions ranging from the proluvial to shallow-basin formations. The dominant type is represented by the basal flow (proluvial and alluvial) metaconglomerates. Variations in the lithopetrography of metaconglomerates reflect the evolution of paleofacies and paleotectonic constraints.     

Systematics of the isotopic composition of sulfur in the oceans during the Phanerozoic and its implications for atmospheric oxygen

Past treatments of the variation of δS³⁴ in marine evaporites have either assumed a steady-state ocean or have invoked rather simplified ocean input-output models. This paper derives more completely the relationships between the parameters that influence the time variation of δS³⁴ in ocean water and the relationship between δS³⁴ in ocean water and net gains and losses of atmospheric oxygen due to the operation of the sulfur cycle. The lower and mid-Paleozoic are shown to have been periods of net gain of atmospheric oxygen by the operation of the sulfur cycle; the upper Paleozoic, particularly the Permian, a period of oxygen loss. It is difficult to relate these oxygen gains and losses to variations in the oxygen content of the atmosphere, because the oxygen flux due to the operation of the carbon cycle is approximately twice as large as the flux due to the operation of the sulfur cycle. Data for the organic carbon and sulfide content of sedimentary rocks of the Russian Platform suggest that a decrease in sulfide from the Paleozoic to the Mesozoic and Cenozoic Era was roughly balanced by an increase in the proportion of organic carbon; however, such data are insufficient to define the abundance of atmospheric oxygen during the Phanerozoic. Biologic data and a better understanding of controls on atmospheric P_o2 are more likely to produce convincing evidence regarding variations of atmospheric oxygen in the past.     

内蒙古巴彦乌拉山古元古代斜长角闪岩LA-ICP-MS锆石U-Pb年龄和Hf同位素组成

巴彦乌拉山岩组形成于古元古代,而对其斜长角闪岩的精确定年数据尚缺。采用LA-MC-ICP-MS技术,对巴彦乌拉山岩组斜长角闪岩及侵入于其中的花岗岩进行了锆石U-Th-Pb和Lu-Hf同位素组成分析,确定巴彦乌拉山组斜长角闪岩原岩形成于2300Ma。根据区域地质背景,斜长角闪岩原岩可能来自叠布斯格岩群的再循环产物,并且遭受了1988~2239Ma和1892~1940Ma的变质-深熔事件,其中1892~1940Ma的年龄可能代表斜长角闪岩先期变质-深熔和花岗岩的形成时代,反映了阴山地块与鄂尔多斯地块拼接的强烈构造事件;1813~1877Ma的年龄为花岗岩的变质及先期高级变质岩退变质为斜长角闪岩的年龄,主要反映了华北板块东、西部块体的拼合事件。而斜长角闪岩中没有1813~1877Ma的年龄记录,可能是构造热事件的温度不足以引起已经发生过多次部分熔融的斜长角闪岩干体系再次发生熔融而结晶锆石。     

Paleoclimatical significance of the paleosol levels occurring in the Miocene-Pleistocene stratigraphy of the Manonga-Wembere Valley inCentral Tanzania

Micromorphological characteristics of four paleosol levels of the Manonga - Wembere deposits in Central Tanzania indicate periods of wetter climate in the Pliocene than at present. The stratigraphy of the studied section shows a series of lacustrine calcareous clay sediments alternating with gravel, sand and silt. The sediments are believed to have been deposited in the Manonga - Wembere paleolake environment. Paleosols intercalate these sediments and were formed when stable landscapes developed on former lake beds during regression periods. Micromorphological features of the paleosols indicate strong clay illuviation of red to yellow typic clay coating and some Fe-Mn hydoxide hypocoatings in voids and channels. The groundmass consists of either an accumulation of bioturbated yellow to red clay coating fragments or an argillic red to yellow groundmass of clay mass. Such an illuviation and its associated groundmass is comparable to intense clay illuviation fronts that are found in present-day calcareous sediments of warm and wet climates. The paleosol levels therefore represent wetter climatic conditions than today in the area during the Lower Pliocene.     

Fractionation of oxygen isotopes in phosphate during its interactions with iron oxides

Iron (III) oxides are ubiquitous in near-surface soils and sediments and interact strongly with dissolved phosphates via sorption, co-precipitation, mineral transformation and redox-cycling reactions. Iron oxide phases are thus, an important reservoir for dissolved phosphate, and phosphate bound to iron oxides may reflect dissolved phosphate sources as well as carry a history of the biogeochemical cycling of phosphorus (P). It has recently been demonstrated that dissolved inorganic phosphate (DIP) in rivers, lakes, estuaries and the open ocean can be used to distinguish different P sources and biological reaction pathways in the ratio of ¹⁸O/¹⁶O (δ¹⁸O_P) in PO₄³⁻. Here we present results of experimental studies aimed at determining whether non-biological interactions between dissolved inorganic phosphate and solid iron oxides involve fractionation of oxygen isotopes in PO₄. Determination of such fractionations is critical to any interpretation of δ¹⁸O_P values of modern (e.g., hydrothermal iron oxide deposits, marine sediments, soils, groundwater systems) to ancient and extraterrestrial samples (e.g., BIF’s, Martian soils). Batch sorption experiments were performed using varied concentrations of synthetic ferrihydrite and isotopically-labeled dissolved ortho-phosphate at temperatures ranging from 4 to 95 °C. Mineral transformations and morphological changes were determined by X-Ray, Mössbauer spectroscopy and SEM image analyses.Our results show that isotopic fractionation between sorbed and aqueous phosphate occurs during the early phase of sorption with isotopically-light phosphate (P¹⁶O₄) preferentially incorporated into sorbed/solid phases. This fractionation showed negligible temperature-dependence and gradually decreased as a result of O-isotope exchange between sorbed and aqueous-phase phosphate, to become insignificant at greater than ∼100 h of reaction. In high-temperature experiments, this exchange was very rapid resulting in negligible fractionation between sorbed and aqueous-phase phosphate at much shorter reaction times. Mineral transformation resulted in initial preferential desorption/loss of light phosphate (P¹⁶O₄) to solution. However, the continual exchange between sorbed and aqueous PO₄, concomitant with this mineralogical transformation resulted again in negligible fractionation between aqueous and sorbed PO₄ at long reaction times (>2000 h). This finding is consistent with results obtained from natural marine samples. Therefore, ¹⁸O values of dissolved phosphate (DIP) in sea water may be preserved during its sorption to iron-oxide minerals such as hydrothermal plume particles, making marine iron oxides a potential new proxy for dissolved phosphate in the oceans.     

Long term atmospheric deposition as the source of nitrate and other salts in the Atacama Desert, Chile: New evidence from mass-independent oxygen isotopic compositions

Isotopic analysis of nitrate and sulfate minerals from the nitrate ore fields of the Atacama Desert in northern Chile has shown anomalous ¹⁷O enrichments in both minerals. Δ¹⁷O values of 14-21 ‰ in nitrate and 0.4 to 4 ‰ in sulfate are the most positive found in terrestrial minerals to date. Modeling of atmospheric processes indicates that the Δ¹⁷O signatures are the result of photochemical reactions in the troposphere and stratosphere. We conclude that the bulk of the nitrate, sulfate and other soluble salts in some parts of the Atacama Desert must be the result of atmospheric deposition of particles produced by gas to particle conversion, with minor but varying amounts from sea spray and local terrestrial sources. Flux calculations indicate that the major salt deposits could have accumulated from atmospheric deposition in a period of 200,000 to 2.0 M years during hyper-arid conditions similar to those currently found in the Atacama Desert. Correlations between Δ¹⁷O and δ¹⁸O in nitrate salts from the Atacama Desert and Mojave Desert, California, indicate varying fractions of microbial and photochemical end-member sources. The photochemical nitrate isotope signature is well preserved in the driest surficial environments that are almost lifeless, whereas the microbial nitrate isotope signature becomes dominant rapidly with increasing moisture, biologic activity, and nitrogen cycling. These isotopic signatures have important implications for paleoclimate, astrobiology, and N cycling studies.