Low marine sulphate and protracted oxygenation of the Proterozoic biosphere

Progressive oxygenation of the Earth's early biosphere is thought to have resulted in increased sulphide oxidation during continental weathering, leading to a corresponding increase in marine sulphate concentration. Accurate reconstruction of marine sulphate reservoir size is therefore important for interpreting the oxygenation history of early Earth environments. Few data, however, specifically constrain how sulphate concentrations may have changed during the Proterozoic era (2.5-0.54 Gyr ago). Prior to 2.2 Gyr ago, when oxygen began to accumulate in the Earth's atmosphere, sulphate concentrations are inferred to have been <1 mM and possibly <200 microM, on the basis of limited isotopic variability preserved in sedimentary sulphides and experimental data showing suppressed isotopic fractionation at extremely low sulphate concentrations. By 0.8 Gyr ago, oxygen and thus sulphate levels may have risen significantly. Here we report large stratigraphic variations in the sulphur isotope composition of marine carbonate-associated sulphate, and use a rate-dependent model for sulphur isotope change that allows us to track changes in marine sulphate concentrations throughout the Proterozoic. Our calculations indicate sulphate levels between 1.5 and 4.5 mM, or 5-15 per cent of modern values, for more than 1 Gyr after initial oxygenation of the Earth's biosphere. Persistence of low oceanic sulphate demonstrates the protracted nature of Earth's oxygenation. It links biospheric evolution to temporal patterns in the depositional behaviour of marine iron- and sulphur-bearing minerals, biological cycling of redox-sensitive elements and availability of trace metals essential to eukaryotic development.     

Exploitation of syndecan-1 shedding by Pseudomonas aeruginosa enhances virulence

Cell-surface heparan sulphate proteoglycans (HSPGs) are ubiquitous and abundant receptors/co-receptors of extracellular ligands, including many microbes. Their role in microbial infections is poorly defined, however, because no cell-surface HSPG has been clearly connected to the pathogenesis of a particular microbe. We have previously shown that Pseudomonas aeruginosa, through its virulence factor LasA, enhances the in vitro shedding of syndecan-1-the predominant cell-surface HSPG of epithelia. Here we show that shedding of syndecan-1 is also activated by P. aeruginosa in vivo, and that the resulting syndecan-1 ectodomains enhance bacterial virulence in newborn mice. Newborn mice deficient in syndecan-1 resist P. aeruginosa lung infection but become susceptible when given purified syndecan-1 ectodomains or heparin, but not when given ectodomain core protein, indicating that the ectodomain's heparan sulphate chains are the effectors. In wild-type newborn mice, inhibition of syndecan-1 shedding or inactivation of the shed ectodomain's heparan sulphate chains prevents lung infection. Our findings uncover a pathogenetic mechanism in which a host response to tissue injury-syndecan-1 shedding-is exploited to enhance microbial virulence apparently by modulating host defences.     

高浓度硫酸盐废水厌氧生物脱硫研究

本文对高浓度硫酸盐废水厌氧生物脱硫技术进行了探讨,研究了单相上流式污泥床（UASB）反应器处理高浓度硫酸盐废水启动条件和稳定运行的全过程。利用人工配水成功启动和稳定运行的UASB反应器在硫酸盐容积负荷1.8kg.（m3.d）-1,COD容积负荷5.0kg.（m3.d）-1时相应的硫酸盐和COD去除率分别达到95%左右和35%左右。温度低于20℃或者硫化物浓度高于300mg/L时都会抑制硫酸盐还原,导致硫酸盐和COD去除率降低。温度高于20℃或者硫化物浓度低于300mg/L时,硫酸盐去除率可以保持稳定在90%以上。反应器功能微生物驯化富集成功后,可以保持稳定的硫酸盐和COD去除率,提高进水负荷对其影响不大,能短时间内提高到较高的进水负荷。合理的对反应器进行气体吹脱可以有效脱除废水中游离的H2S降低硫化物对微生物的抑制作用,从而提高硫酸盐去除率和COD去除率。     

Early oxygenation of the terrestrial environment during the Mesoproterozoic

Geochemical data from ancient sedimentary successions provide evidence for the progressive evolution of Earth's atmosphere and oceans. Key stages in increasing oxygenation are postulated for the Palaeoproterozoic era (～2.3?billion years ago, Gyr ago) and the late Proterozoic eon (about 0.8?Gyr ago), with the latter implicated in the subsequent metazoan evolutionary expansion. In support of this rise in oxygen concentrations, a large database shows a marked change in the bacterially mediated fractionation of seawater sulphate to sulphide of Δ(34)S?相似文献   

Aerobic bacterial pyrite oxidation and acid rock drainage during the Great Oxidation Event

The enrichment of redox-sensitive trace metals in ancient marine sedimentary rocks has been used to determine the timing of the oxidation of the Earth's land surface. Chromium (Cr) is among the emerging proxies for tracking the effects of atmospheric oxygenation on continental weathering; this is because its supply to the oceans is dominated by terrestrial processes that can be recorded in the Cr isotope composition of Precambrian iron formations. However, the factors controlling past and present seawater Cr isotope composition are poorly understood. Here we provide an independent and complementary record of marine Cr supply, in the form of Cr concentrations and authigenic enrichment in iron-rich sedimentary rocks. Our data suggest that Cr was largely immobile on land until around 2.48?Gyr ago, but within the 160?Myr that followed--and synchronous with independent evidence for oxygenation associated with the Great Oxidation Event (see, for example, refs 4-6)--marked excursions in Cr content and Cr/Ti ratios indicate that Cr was solubilized at a scale unrivalled in history. As Cr isotope fractionations at that time were muted, Cr must have been mobilized predominantly in reduced, Cr(III), form. We demonstrate that only the oxidation of an abundant and previously stable crustal pyrite reservoir by aerobic-respiring, chemolithoautotrophic bacteria could have generated the degree of acidity required to solubilize Cr(III) from ultramafic source rocks and residual soils. This profound shift in weathering regimes beginning at 2.48?Gyr ago constitutes the earliest known geochemical evidence for acidophilic aerobes and the resulting acid rock drainage, and accounts for independent evidence of an increased supply of dissolved sulphate and sulphide-hosted trace elements to the oceans around that time. Our model adds to amassing evidence that the Archaean-Palaeoproterozoic boundary was marked by a substantial shift in terrestrial geochemistry and biology.     

Biomarker evidence for green and purple sulphur bacteria in a stratified Palaeoproterozoic sea

The disappearance of iron formations from the geological record approximately 1.8 billion years (Gyr) ago was the consequence of rising oxygen levels in the atmosphere starting 2.45-2.32 Gyr ago. It marks the end of a 2.5-Gyr period dominated by anoxic and iron-rich deep oceans. However, despite rising oxygen levels and a concomitant increase in marine sulphate concentration, related to enhanced sulphide oxidation during continental weathering, the chemistry of the oceans in the following mid-Proterozoic interval (approximately 1.8-0.8 Gyr ago) probably did not yet resemble our oxygen-rich modern oceans. Recent data indicate that marine oxygen and sulphate concentrations may have remained well below current levels during this period, with one model indicating that anoxic and sulphidic marine basins were widespread, and perhaps even globally distributed. Here we present hydrocarbon biomarkers (molecular fossils) from a 1.64-Gyr-old basin in northern Australia, revealing the ecological structure of mid-Proterozoic marine communities. The biomarkers signify a marine basin with anoxic, sulphidic, sulphate-poor and permanently stratified deep waters, hostile to eukaryotic algae. Phototrophic purple sulphur bacteria (Chromatiaceae) were detected in the geological record based on the new carotenoid biomarker okenane, and they seem to have co-existed with communities of green sulphur bacteria (Chlorobiaceae). Collectively, the biomarkers support mounting evidence for a long-lasting Proterozoic world in which oxygen levels remained well below modern levels.     

干旱区污染绿洲土壤中Cd和Zn形态分布与生物有效性

利用盆栽试验研究了干旱区污染绿洲土壤中Cd和Zn形态分布与生物有效性。结果表明:少量的Cd和Zn有促进油菜生长的作用,但高质量分数的Cd和Zn对油菜的生长有明显抑制作用;原状绿洲土壤中Cd和Zn形态以残渣态为主,随着绿洲土壤中Cd和Zn污染程度的加深,Cd和Zn各形态分布发生了显著变化,其中碳酸盐结合态Cd和Zn和铁锰氧化物结合态Cd和Zn质量分数大幅增加,并逐渐占据绝对优势,而残渣态Cd和Zn质量分数则几乎不变。相关分析表明土壤中的铁锰氧化物结合态Cd质量分数与油菜叶和根部的Cd质量分数呈极显著相关,表明土壤中的铁锰氧化物结合态Cd对油菜叶和根部累积Cd有最大贡献;铁锰氧化物结合态Zn和有机物结合态Zn分别与油菜根部和叶部的Zn质量分数呈极显著相关,表明土壤中铁锰氧化物结合态Zn和有机物结合态Zn分别对油菜根和叶部累积Zn贡献最大;油菜叶和根部Cd的富集系数均大于Zn的,表明油菜吸收Cd的能力大于Zn的;两种金属的富集系数叶部的均大于根部的,表明Cd和Zn的迁移性较强,且Cd在油菜中的迁移能力大于Zn的,其毒害作用也相应大于Zn的。两种金属主要累积在油菜可食用的叶部,因此对人体健康有潜在威胁。     

Evidence for iron, copper and zinc complexation as multinuclear sulphide clusters in oxic rivers

The availability and toxicity of trace metals in fresh water are known to be regulated by the complexation of free metal ions with dissolved organic matter. The potential role of inorganic sulphides in binding trace metals has been largely ignored because of the reduced persistence of sulphides in these oxic waters. However, nanomolar concentrations of copper and zinc sulphides have been observed in four rivers in Connecticut and Maryland. Here we report dissolved (< 0.2 microm particle diameter) sulphide concentrations ranging up to 600 nM, with more than 90% being complexed by copper, iron and zinc. These complexes account for up to 20% of the total dissolved Fe and Zn and 45% of the total dissolved Cu. Fourier transform mass spectrometry reveals that these complexes are not simple M(HS)+ protonated species but are higher-order unprotonated clusters (M3S3, M4S6, M2S4), similar to those found in laboratory solutions and bio-inorganic molecules. These extended structures have high stability constants and are resistant to oxidation and dissociation, which may help control the toxicity of these and other less abundant, but more toxic, trace metals, such as silver, cadmium and mercury.     

Late Proterozoic rise in atmospheric oxygen concentration inferred from phylogenetic and sulphur-isotope studies

The evolution of non-photosynthetic sulphide-oxidizing bacteria was contemporaneous with a large shift in the isotopic composition of biogenic sedimentary sulphides between 0.64 and 1.05 billion years ago. Both events were probably driven by a rise in atmospheric oxygen concentrations to greater than 5-18% of present levels--a change that may also have triggered the evolution of animals.     

Two episodes of microbial change coupled with Permo/Triassic faunal mass extinction

Microbial expansion following faunal mass extinctions in Earth history can be studied by petrographic examination of microbialites (microbial crusts) or well-preserved organic-walled microbes. However, where preservation is poor, quantification of microbial communities can be problematic. We have circumvented this problem by adopting a lipid biomarker-based approach to evaluate microbial community changes across the Permo/Triassic (P/Tr) boundary at Meishan in South China. We present here a biomarker stratigraphic record showing episodic microbial changes coupled with a high-resolution record of invertebrate mass extinction. Variation in the microbial community structure is characterized by the 2-methylhopane (2-MHP) index (a ratio of the abundance of cyanobacterial biomarkers to more general bacterial biomarkers). Two episodes of faunal mass extinction were each preceded by minima in the 2-MHP index, followed by strong maxima, likely reflecting microbial responses to the catastrophic events that caused the extinction and initiated ecosystem changes. Hence, both cyanobacterial biomarker and invertebrate fossil records provide evidence for two episodes of biotic crisis across the P/Tr boundary.     

Isotopic evidence for Mesoarchaean anoxia and changing atmospheric sulphur chemistry

The evolution of the Earth's atmosphere is marked by a transition from an early atmosphere with very low oxygen content to one with an oxygen content within a few per cent of the present atmospheric level. Placing time constraints on this transition is of interest because it identifies the time when oxidative weathering became efficient, when ocean chemistry was transformed by delivery of oxygen and sulphate, and when a large part of Earth's ecology changed from anaerobic to aerobic. The observation of non-mass-dependent sulphur isotope ratios in sedimentary rocks more than approximately 2.45 billion years (2.45 Gyr) old and the disappearance of this signal in younger sediments is taken as one of the strongest lines of evidence for the transition from an anoxic to an oxic atmosphere around 2.45 Gyr ago. Detailed examination of the sulphur isotope record before 2.45 Gyr ago also reveals early and late periods of large amplitude non-mass-dependent signals bracketing an intervening period when the signal was attenuated. Until recently, this record has been too sparse to allow interpretation, but collection of new data has prompted some workers to argue that the Mesoarchaean interval (3.2-2.8 Gyr ago) lacks a non-mass-dependent signal, and records the effects of earlier and possibly permanent oxygenation of the Earth's atmosphere. Here we focus on the Mesoarchaean interval, and demonstrate preservation of a non-mass-dependent signal that differs from that of preceding and following periods in the Archaean. Our findings point to the persistence of an anoxic early atmosphere, and identify variability within the isotope record that suggests changes in pre-2.45-Gyr-ago atmospheric pathways for non-mass-dependent chemistry and in the ultraviolet transparency of an evolving early atmosphere.     

磷酸盐浓度对微生物铁还原过程的影响

微生物铁还原过程对淹水稻田中水体富营养化调控具有重要的作用,但高浓度磷酸盐对氧化铁的微生物过程是否产生抑制尚不清楚．为此采用土壤泥浆厌氧培养、接种水稻土浸提液混合培养和铁还原菌纯培养等方法,探讨了磷酸盐浓度对微生物铁还原过程的影响程度．结果表明：在水稻土泥浆培养过程中,Fe（Ⅲ）还原速率随磷酸盐浓度增加而降低,淹水后期高浓度磷酸盐处理中的Fe（Ⅱ）累积量呈下降趋势;磷营养为4～16mmol／L时,四川水稻土中的微生物群落能较好地利用葡萄糖和丙酮酸盐进行Fe（OH）3还原反应,江西水稻土中的铁还原微生物群落对葡萄糖的响应时间有所延迟,2种水稻土浸提液的微生物群落对乳酸盐的利用较差,反应40d后才有明显的Fe（OH）1还原现象在接种铁还原茵的纯培养试验中,磷酸盐浓度在小于1mmol／L或大于16mmol／L时均不能进行铁还原反应,表明铁还原过程对磷酸盐的调控存在浓度阂值．     

Effects of 2,3,7,8-TCDD and benzo[a]pyrene on modulating vitellogenin expression in primary culture of crucian carp （Carassius auratus） hepatocytes

Vitellogenin (Vtg) is the precursor of yolk protein. Its expression and secretion are estrogen-regulated and are crucial for oocyte maturation. An in ritro xenoestrogen screening model was established by measuring Vtg induction in cultured primary hepatocytes from crucian carp. Vtg production was detected by biotin-avidin sandwich ELISA method while Vtg and cytochrome P4501A1 (CYP1A1) mRNA induction were measured by semi- quantitative PCR-primer dropping technique. Vtg and Vtg mRNA were dose-dependently induced by diethylstilbestrol (DES, 0.2-200 ng/mL) in hepatocytes of crucian carp. Co-treatment of the DES-induced hepatocytes with either 2,3,7,8-TCDD (TCDD, 0.1-4 pg/mL) or benzo[a]pyrene (B[a]P, 5-1000 ng/mL) resulted in a reduction of Vtg production and an increment of CYP1A1 mRNA expression both in a dose dependent manner, indicating the anti-estrogenic effects of the compounds. However, at lower tested concentrations, TCDD (0.1, 0.2 pg/mL), B[a]P (5 ng/mL)seemed to have a potentiating effect on Vtg expression and secretion, although by their own these compounds had no observable estrogenic effect on Vtg induction. Tamoxifen (a selective estrogen receptor modulators, 1 nmol/L-1μmol/L),and β-naphtho-flavone (β-NF, an aryl hydrocarbon receptor inducing compounds, 2.5-1000 ng/mL) also were employed to study the possible interactions in DES-induced Vtg expression. In co-treatment of the DES-induced hepatocytes with β-NF or tamoxifen, the decrease in Vtg production did parallel induction of CYP1A1 for β-NF, but tamoxifen inhibited Vtg induction did not parallel induced CYP1A1 expression in all test concentrations. On the contrary, it was found that in co-treatment of the TCDD-induced hepatocytes with DES, TCDD induced CYP1A1 mRNA production was inhibited by DES also. These results implicated a possible cross talk between estrogen receptor- and aryl hydrocarbon receptor-mediated pathways in the hepatocytes.     

汞与铁、镓、铑、铈和锌的绿色析相萃取富集和分离研究

研究水-溴化钾-正丙醇-硫酸铵体系绿色析相萃取汞的行为及与一些金属离子分离的条件.结果表明,硫酸铵能使正丙醇的水溶液分成两相,HgBr24-与质子化正丙醇(C3H7OH2+)形成的缔合物[HgBr24-][C3H7OH2+]2能被正丙醇相完全萃取.当溶液中溴化钾、硫酸铵和正丙醇的浓度分别为7.0 mmol/L,200 g/L和30%(v/v)时,Hg2+的萃取率达到97.3%以上,而Fe2+、Ga3+、Rh3+、Ce3+和Zn2+基本不被萃取,实现了Hg2+与上述金属离子的分离.     

高粱种子醇溶蛋白的提取条件

以高粱种子为材料,研究了不同提取剂、提取剂用量、浓度和还原剂浓度对高粱种子醇溶蛋白提取的影响.蛋白浓度测定和SDS PAGE电泳表明,DDT浓度为4%的60％叔丁醇溶液,样品质量比提取剂用量为1∶8（g/mL）是提取高粱种子醇溶蛋白的最佳条件.该条件下,提取高粱属不同种的种子醇溶蛋白,得到的高粱属种子醇溶蛋白的“指纹”图谱,可以用来区分高粱属内的种间差异.     

Evidence for low sulphate and anoxia in a mid-Proterozoic marine basin

Many independent lines of evidence document a large increase in the Earth's surface oxidation state 2,400 to 2,200 million years ago, and a second biospheric oxygenation 800 to 580 million years ago, just before large animals appear in the fossil record. Such a two-staged oxidation implies a unique ocean chemistry for much of the Proterozoic eon, which would have been neither completely anoxic and iron-rich as hypothesized for Archaean seas, nor fully oxic as supposed for most of the Phanerozoic eon. The redox chemistry of Proterozoic oceans has important implications for evolution, but empirical constraints on competing environmental models are scarce. Here we present an analysis of the iron chemistry of shales deposited in the marine Roper Basin, Australia, between about 1,500 and 1,400 million years ago, which record deep-water anoxia beneath oxidized surface water. The sulphur isotopic compositions of pyrites in the shales show strong variations along a palaeodepth gradient, indicating low sulphate concentrations in mid-Proterozoic oceans. Our data help to integrate a growing body of evidence favouring a long-lived intermediate state of the oceans, generated by the early Proterozoic oxygen revolution and terminated by the environmental transformation late in the Proterozoic eon.     

High-resolution carbon dioxide concentration record 650,000-800,000 years before present

Changes in past atmospheric carbon dioxide concentrations can be determined by measuring the composition of air trapped in ice cores from Antarctica. So far, the Antarctic Vostok and EPICA Dome C ice cores have provided a composite record of atmospheric carbon dioxide levels over the past 650,000 years. Here we present results of the lowest 200 m of the Dome C ice core, extending the record of atmospheric carbon dioxide concentration by two complete glacial cycles to 800,000 yr before present. From previously published data and the present work, we find that atmospheric carbon dioxide is strongly correlated with Antarctic temperature throughout eight glacial cycles but with significantly lower concentrations between 650,000 and 750,000 yr before present. Carbon dioxide levels are below 180 parts per million by volume (p.p.m.v.) for a period of 3,000 yr during Marine Isotope Stage 16, possibly reflecting more pronounced oceanic carbon storage. We report the lowest carbon dioxide concentration measured in an ice core, which extends the pre-industrial range of carbon dioxide concentrations during the late Quaternary by about 10 p.p.m.v. to 172-300 p.p.m.v.     

硫铁化物自燃性的研究

储罐内壁铁的腐蚀产物之一Fe2O3与湿H2S发生反应生成不同形式的硫铁化物,硫铁化物的氧化放热是引起含硫油品储罐着火的主要原因。研究了在75℃条件下,硫化时间对Fe2O3硫化产物的生成及其自燃性的影响。通过X-射线衍射对硫化时间为6h、3d．6d以及17d条件下生成的硫铁化物成分进行了鉴定,并对3d和6d条件下的硫铁化物进行了定量分析。结果表明,在高温条件下,随着硫化时间的延长,有更多的FeS2和Fe3S4生成,并且Fe3S4不断向FeS2转化,自燃性增强,对储罐安全运行构成威胁。     

Efficient mixing of the solar nebula from uniform Mo isotopic composition of meteorites

The abundances of elements and their isotopes in our Galaxy show wide variations, reflecting different nucleosynthetic processes in stars and the effects of Galactic evolution. These variations contrast with the uniformity of stable isotope abundances for many elements in the Solar System, which implies that processes efficiently homogenized dust and gas from different stellar sources within the young solar nebula. However, isotopic heterogeneity has been recognized on the subcentimetre scale in primitive meteorites, indicating that these preserve a compositional memory of their stellar sources. Small differences in the abundance of stable molybdenum isotopes in bulk rocks of some primitive and differentiated meteorites, relative to terrestrial Mo, suggest large-scale Mo isotopic heterogeneity between some inner Solar System bodies, which implies physical conditions that did not permit efficient mixing of gas and dust. Here we report Mo isotopic data for bulk samples of primitive and differentiated meteorites that show no resolvable deviations from terrestrial Mo. This suggests efficient mixing of gas and dust in the solar nebula at least to 3 au from the Sun, possibly induced by magnetohydrodynamic instabilities. These mixing processes must have occurred before isotopic fractionation of gas-phase elements and volatility-controlled chemical fractionations were established.     

Origins of sulphate in Antarctic dry-valley soils as deduced from anomalous 17O compositions

The dry valleys of Antarctica are some of the oldest terrestrial surfaces on the Earth. Despite much study of soil weathering and development, ecosystem dynamics and the occurrence of life in these extreme environments, the reasons behind the exceptionally high salt content of the dry-valley soils have remained uncertain. In particular, the origins of sulphate are still controversial; proposed sources include wind-blown sea salt, chemical weatherings, marine incursion, hydrothermal processes and oxidation of biogenic sulphur in the atmosphere. Here we report measurements of delta18O and delta17O values of sulphates from a range of dry-valley soils. These sulphates all have a large positive anomaly of 17O, of up to 3.4/1000. This suggests that Antarctic sulphate comes not just from sea salt (which has no anomaly of 17O) but also from the atmospheric oxidation of reduced gaseous sulphur compounds, the only known process that can generate the observed 17O anomaly. This source is more prominent in high inland soils, suggesting that the distributions of sulphate are largely explained by differences in particle size and transport mode which exist between sea-salt aerosols and aerosols formed from biogenic sulphur emission.