俯冲带硫的地球化学行为及硫循环SCIEI北大核心CSCD

俯冲带是全球最大的物质循环系统,控制着硫(S)在地球内部圈层及表层的循环,影响着大气圈、水圈、生物圈、岩石圈的稳定性以及地球的宜居性。厘清S在俯冲带中的地球化学行为和循环特征对理解地球各储库的氧化还原状态、岩浆作用与演化、成矿物质聚集、以及地球大气成分等具有重要意义。本文首先总结了进入俯冲带之前的大洋岩石圈的S结构模型,对S在大洋板片中的分布状态和地球化学特征进行了系统归纳。随后,系统阐述了俯冲带高压-超高压变质岩记录的板片变质及脱水过程中硫的地球化学行为。岩石学研究表明俯冲板片中的S多以硫化物相存在,硫酸盐矿物在弧前深度就已被释放或分解。相较于熔体,俯冲带流体中S的溶解度更高,是运移硫的更有效方式。DEW模型计算结果显示,流体中S含量总体较低,但在俯冲板片~90km处其含量有一个峰值(浓度0.5%~1.0%)。岩相学证据、地球化学测试结果、磷灰石S近边吸收结构(S-XANES)特征以及模拟结果都显示俯冲深部流体中S多以HS^(-)及H_(2)S形式存在,不含大量的SO_(4)^(2-)及硫酸盐;中f_(S_(2))流体有利于S迁移出俯冲板片,从而促进俯冲带大规模S循环,而高f_(S_(2))流体在流-岩交换过程沿流体通道发生S的锁固作用而不利于俯冲带S循环。质量平衡计算显示全球俯冲带S输入通量为4.65×10^(13)g/yr,弧下深度板片S输出通量为2.91×10^(12)g/yr,板片-岛弧S循环效率仅6.3%。俯冲板片在弧下深度可能存在一个短暂高效的S释放窗口,释放流体的δ^(34)S值为-2.1±3.0‰。基于高压-超高压变质岩中硫化物的研究,初步厘清了俯冲板片中S的地球化学行为,首次从板片角度全面、定量地限定了俯冲带的脱硫通量、效率、种型和同位素特征,提出俯冲带循环的S不是岛弧岩浆的氧化剂,与岛弧环境的正δ^(34)S值也无直接因果联系,对解析俯冲带S循环和理解地球长期的S循环具有重要意义。最后,本文还展望了俯冲带S循环的未来发展方向,应在俯冲带流体氧化还原性质(硫酸盐的命运)、俯冲沉积物对S循环的制约、俯冲带环境下多硫同位素的分馏效应、S循环与其它挥发分(如C等)循环之间的耦合关系、地球历史上深部S循环等方向做出探索,更深入地理解俯冲带及全球S循环过程。     

Transnational linkages and the spillover of environment-efficiency into developing countries

Arguments about the “positive” influence of growing transnational linkages have typically focused on their role in diffusing environmentally superior innovations which help to raise countries’ environment-efficiency. The present article empirically tests these claims by examining whether developing countries’ linkages with more CO₂- and SO₂-efficient economies contribute to domestic improvements in CO₂- and SO₂-efficiency. Our large-N, statistical findings caution against some of the efficiency-oriented optimism voiced by supporters of globalization. Although imports ties with more pollution-efficient countries are found to spillover into improved domestic CO₂- and SO₂-efficiency, neither transnational linkages via exports, inward foreign direct investment (FDI) nor telephone calls appear to have any influence on domestic pollution-efficiency.     

Landscape-scale patterns of sediment sulfur accumulation in Swedish lakes

Sulfur has played a central role in the acidification of many lakes in Scandinavia and other regions. As part of the research into sulfur cycling, numerous studies have analyzed the sediment record in order to develop insights into past in-lake cycling of sulfur, particularly in the context of reconstructing past deposition rates. Although many of these studies have shown that it is not easy to interpret the sediment record in terms of past sulfur deposition rates, analyses of sulfur in sediment still provide valuable information on the response of lakes to anthropogenic sulfur deposition. Here, we have analyzed sulfur in top and bottom samples from short surface cores (25–35 cm, representing ≥250 years) as well as bulk cores from ∼110 lakes located throughout Sweden, which were collected during 1986, as well as in more-detailed profiles from six lakes. The lakes with the highest surface sediment concentrations (9–24 mg S g⁻¹ dry mass) and the highest calculated inventories of ‘excess’ sulfur (20–180 g S m⁻²) are found in southern Sweden and around one industrial area along the northeastern coast where sulfur deposition rates and lake-water concentrations have been highest. For many lakes in the central and northern inland region it is common that the sediment cores exhibit either no enrichment or even a decline in sulfur concentrations in near-surface sediments, which we suggest was the pre-pollution norm for lakes. Although interpreting sulfur sediment profiles is problematic for reconstructing deposition, a more-comprehensive spatial sampling approach shows that there is a good geographic agreement between sulfur deposition, lake-water chemistry and sediment sulfur accumulation.     

The role of iron and sulfur in the visual appearance of lake sediment varves

Easily discernible sediment varves (annual laminations) may be formed in temperate zone lakes, and reflect seasonal changes in the composition of the accumulating material derived from the lake and its catchment (minerogenic and organic material). The appearance of varves may also be influenced by chemical processes. We assessed the role of iron (Fe) and sulfur (S) in the appearance of varves in sediments from Lake Nylandssjön in northern Sweden. We surveyed Fe in the lake water and established whether there is internal transport of Fe within the sediment. We used a unique collection of seven stored freeze cores of varved sediment from the lake, collected from 1979 to 2004. This suite of cores made it possible to follow long-term changes in Fe and S in the sediment caused by processes that occur in the lake bottom when the sediment is ageing. We compared Fe and S concentrations using X-ray fluorescence spectroscopy (XRF) in specific years in the different cores. No diagenetic front was found in the sediment and the data do not suggest that there is substantial vertical transport of Fe and S in the sediment. We also modeled Fe and S based on thermodynamic, limnological, and sediment data from the lake. The model was limited to the five components H⁺, e^?, Fe³⁺, SO₄ ^2?, H₂CO₃ and included the formation of solid phases such as Fe(OH)₃ (amorphous), FeOOH (aged, microcrystalline), FeS and FeCO₃. Modeling showed that there are pe (redox) ranges within which either FeS or Fe(OH)₃/FeOOH is the only solid phase present and there are pe ranges within which the two solid phases co-exist, which supports the hypothesis that blackish and grey-brownish layers that occur in the varves were formed at the time of deposition. This creates new possibilities for deciphering high-temporal-resolution environmental information from varves.     

胶西北大尹格金矿床成矿机理:载金黄铁矿标型及硫同位素地球化学约束

胶东是我国最重要的金矿集中区,破碎带蚀变岩型金矿床是区内最主要的金矿床类型,该类型金矿床已探明金资源量占全区的90%以上,其巨量金的来源是引人瞩目的关键科学问题。招平断裂带是该区内规模最大的断裂-成矿带,位于招平金矿带中段的大尹格庄金矿床是该金矿带最具代表性的破碎带蚀变岩型金矿床之一,已探明金金属量约283t。大尹格庄金矿床严格受沿胶东群与玲珑花岗岩接触带发育的NNE向招平断裂带控制,矿体赋存在招平断裂下盘黄铁绢英岩化和碎裂岩化玲珑花岗岩中,主要由Ⅰ号和Ⅱ号矿体组成,其具有相似的矿物组成,矿石主要矿物是绢云母、石英、黄铁矿,次要矿物是钾长石、斜长石、黑云母、方解石、黄铜矿、方铅矿、闪锌矿、磁黄铁矿、黝铜矿和自然金、自然银、金银矿、碲银矿等;其中黄铁矿是最主要的载金矿物。根据穿插关系和矿物共生组合,大尹格庄金矿床内成矿作用可划分为4个成矿阶段,分别是黄铁矿-石英-绢云母阶段(I)、石英-黄铁矿阶段(Ⅱ)、石英-多金属硫化物阶段(Ⅲ)和石英-方解石-多金属硫化物阶段(Ⅳ)。各个成矿阶段的黄铁矿的晶体形态标型研究表明,成矿Ⅰ阶段黄铁矿以粗粒自形立方体为主,含有少量五角十二面体;成矿Ⅱ和Ⅲ阶段黄铁矿以细粒五角十二面体为主,且具有更多五角十二面体、八面体和立方体形成的聚形;成矿Ⅳ阶段主要为细粒立方体晶形。不同矿体各个成矿阶段的硫化物的δ~(34)S值集中在4.58‰~7.54‰,具有一定的塔式效应,正向偏离陨石硫,与胶东地区胶东群变质岩、围岩花岗岩类δ~(34)S比较接近,指示大尹格庄金矿床各个成矿阶段的矿石硫源总体一致,与胶东群变质岩和中生代花岗岩间具有继承演化关系。此外,从成矿Ⅰ阶段→Ⅱ阶段→Ⅲ阶段→Ⅳ阶段,大尹格庄金矿床矿石硫化物δ~(34)S呈现出逐渐降低的趋势,反映了成矿过程中物理化学条件的演化趋势:Ⅰ阶段为较高温度(330~350℃)、快速冷却、低过饱和度、低氧逸度和硫逸度的成矿环境;Ⅱ和Ⅲ阶段黄铁矿形成于中-低温(200~300℃)、成矿流体过饱和度高、高氧逸度和硫逸度、缓慢冷却同时物质供应充分的成矿环境;Ⅳ阶段处于较低温度(200℃)、热液流体过饱和度较低、低氧逸度和硫逸度、同时物质供应不足的成矿环境。     

Neoproterozoic chemostratigraphy

Chemostratigraphy has diverse applications to investigating the rock record, such as reconstructing paleoenvironments, determining the tectonic setting of sedimentary basins, indirect dating, and establishing regional or global correlations. Chemostratigraphy is thus an integral component of many investigations of the ancient sedimentary record. In this contribution, we review the principle inorganic geochemical methods that have been applied to the Neoproterozoic sedimentary record. Analysis of the traditional stable and radiogenic isotope systems, such as δ¹³C, δ¹⁸O, δ³⁴S, and ⁸⁷Sr/⁸⁶Sr, is routine, particularly in successions rich in carbonate. These mainstay applications have yielded invaluable data and information bearing on the chronology and evolution of this eventful era in Earth history. Alongside the growing database of traditional data, a series of novel geochemical techniques have given rise to important new models and constraints on Neoproterozoic biogeochemical change. In particular, a range of proxies for water column redox, mainly obtained from black shales, have shed light on the pace and tempo of Neoproterozoic oxygenation and its link to the appearance of early animal evolution. Increased integration of diverse geochemical, sedimentological, and paleontological datasets, and the gradual radiometric calibration of the stratigraphic record promise to bring the details of the evolution of the Neoproterozoic Earth system into ever greater focus.     

气态SO_2转化及其数值模型研究

本文基于对室外烟雾箱实验,探讨了SO_2的转化机制及影响SO_2转化的因素,由此并借助于烟团模型,建立了SO_2转化和硫酸盐气溶胶细粒子生成的数值模型,用于估算从排放源排入大气的SO_2浓度及其转化成硫酸盐细粒子的浓度以及它们的空间分布,与实测结果相比,两者有较好的一致性.同时指出,由于大气中细粒子(粒径小于1μm)可通过人体呼吸进入并沉积在肺泡中而对健康有不利影响,从而说明研究大气中细粒子污染的迫切性.     

新元古代—寒武纪硫同位素异常事件(Yudomski事件)的起源与结束

新元古代晚期—寒武纪早期是地球历史演化的关键时期,整个生物圈、大气圈和水圈在此期间都发生了巨大的变化,海水成分在其间也发生了明显的变化。而石盐流体包裹体恰恰记录了该时段海水主要离子成分的转变:海水成分从新元古代晚期的“文石海”,快速转化为寒武纪的“方解石海”;同时海水中的碳、锶、硫同位素都发生了剧烈的改变,其中海水硫酸根的硫同位素从新元古代冰期前的20‰左右,迅速升高到新元古代冰期后的35‰左右,甚至可以到45‰,海相蒸发岩沉积中的硫酸盐沉积(主要是石膏、硬石膏)则直接记录了当时海水中硫酸根的硫同位素变化。现有研究表明,新元古代晚期——寒武纪时期的海相蒸发岩沉积记录了当时海洋中存在着地质历史时期最大的硫同位素异常,即“Yudomski事件”。塔里木盆地的寒武纪早期、中期蒸发岩记录了“Yudomski事件”的硫同位素异常高值(35‰左右,甚至更高),表明这一起源于新元古代晚期的同位素异常事件持续到了寒武纪的早期和中期;塔里木盆地奥陶纪早期的蒸发岩、鄂尔多斯盆地奥陶纪中期蒸发岩和美国Williston盆地奥陶纪晚期地层的蒸发岩的硫同位素数据相似,都在+25‰左右则记录了较低的海洋硫同位素值,表明起源于新元古代冰期之后的“Yudomski事件”的硫同位素异常,持续到了寒武纪的中期,而结束于寒武纪的晚期。     

Seasonal variations of atmospheric sulfur dioxide and dimethylsulfide concentrations at Amsterdam Island in the southern Indian Ocean

Daily measurements of atmospheric sulfur dioxide (SO₂) concentrations were performed from March 1989 to January 1991 at Amsterdam Island (37°50 S–77°30 E), a remote site located in the southern Indian Ocean. Long-range transport of continental air masses was studied using Radon (²²²Rn) as continental tracer. Average monthly SO₂ concentrations range from less than 0.2 to 3.9 nmol m^-3 (annual average = 0.7 nmol m^-3) and present a seasonal cycle with a minimum in winter and a maximum in summer, similar to that described for atmospheric DMS concentrations measured during the same period. Clear diel correlation between atmospheric DMS and SO₂ concentrations is also observed during summer. A photochemical box model using measured atmospheric DMS concentrations as input data reproduces the seasonal variations in the measured atmospheric SO₂ concentrations within ±30%. Comparing between computed and measured SO₂ concentrations allowed us to estimate a yield of SO₂ from DMS oxidation of about 70%.