Advances in Studying the Sea-Air Dimethysulphide Exchange Process in the Southern Ocean

Dimethylsulphide (DMS) is an important marine biogenic gas and can be released into atmosphere through sea air gas exchange. The oxidants of DMS in atmosphere are the main compounds of pristine marine sulphate aerosols and would affect the global climate change finally. Almost all the atmospheric DMS, about 90%, comes from the ocean. The southern ocean, which consists about 20% of the whole ocean area, is one of the largest atmospheric DMS sources. In contrast with the other oceans, the Southern Ocean appears great spatial and temporal variability of surface seawater DMS. In addition, there are the complex hydrography system, variable sea ice condition and various biologic activities in the Southern Ocean as to make survey and understand DMS as well as its controlling factors most difficult. Moreover, it is significant to integrate the DMS sea ice exchange processes and its controlling factors studies. In order to develop survey and research on the sea air DMS exchange and biogeochemistry processes, estimate methods of the sea air DMS fluxes will be reviewed, characteristics of the spatial and temporal distribution of surface seawater DMS will be discussed and the sea air DMS flux in the Southern Ocean will be assessed. Finally, major controlling factors of DMS sea air DMS processes will also be analyzed.     

Estimating the carbon transfer between the ocean, atmosphere and the terrestrial biosphere since the last glacial maximum

Carbon dioxide records from polar ice cores and marine ocean sediments indicate that the last glacial maximum (LGM) atmosphere CO₂ content was 80–90 ppm lower than the mid-Holocene. This represents a transfer of over 160 GtC into the atmosphere since the LGM. Palaeovegetation studies suggest that up to 1350 GtC was transferred from the oceans to the terrestrial biosphere at the end of the last glacial. Evidence from carbon isotopes in deep sea sediments, however, indicates a smaller shift of between 400 and 700 GtC. To understand the functioning of the carbon cycle this apparent discrepancy needs to be resolved. Thus, older data have been reassessed, new data provided and the potential errors of both methods estimated. New estimates of the expansion of terrestrial biomass between the LGM and mid-Holocene are 700 GtC ± > 300 GtC, using the ocean carbon isotope-based method, compared with of 1100 GtC ± > 500 GtC using the palaeovegetation estimate. If these estimates of the carbon shift to the terrestrial biosphere are equilibrated with the dissolved carbon in the oceans, and the CaCO₃ compensation of the ocean is taken into account, then the glacial atmospheric CO₂ would have been between 50 (± 30) ppm and 95 (± 50) ppm higher. The glacial atmosphere therefore should have had a CO₂ partial pressure of between 330 and 375 μatm. Hence, a rise of between 130 and 175 μatm in atmospheric CO₂, rather than 80 μatm, at the end of the last glacial must be accounted for.     

Boron isotope systematics in large rivers: implications for the marine boron budget and paleo-pH reconstruction over the Cenozoic

The chemical composition of the oceans and long-term climate changes are believed to be linked. Reconstruction of seawater pH evolution is desirable as pH may be related to atmospheric pCO₂, and hence to climate evolution. Boron isotopes in oceanic carbonates have been suggested to be a proxy for oceanic paleo-pH reconstruction. Nevertheless, the calculation of paleo-pH values over geological periods requires a precise knowledge of the boron isotopic composition of the oceans when calcite precipitated. We present the systematics of boron isotopic composition of the world's main rivers. We deduce a continental boron flux to the oceans of 38×10¹⁰ gB/year with a mean isotopic composition of +10‰. These results lead to a balanced boron budget in the oceans and allow the development of a model for the marine boron secular evolution over the past 100 Myr. It is shown that the oceanic boron cycle is mainly controlled by the boron continental discharge and the boron uptake from the oceans during low temperature alteration of oceanic crust. However, the recent important increase of the clastic sediment supply, linked to the Himalayan erosion, impacts the oceanic boron budget by enhancing significantly the boron uptake by adsorption on sediments. We predict a boron isotopic composition in the oceans lower during the Cenozoic and slightly higher during the Cretaceous than today. The modelled values for the marine boron isotopes follow the variations of boron isotopes in carbonates over the Cenozoic era provided by previous studies, suggesting that the variations of the seawater pH may not have been important on this time scale. If this is the case, it involves that buffering mechanisms occur in the oceans to maintain seawater pH at a roughly constant value against past atmospheric pCO₂ variations.     

Evidence for ocean acidification in the Great Barrier Reef of Australia

Geochemical records preserved in the long-lived carbonate skeleton of corals provide one of the few means to reconstruct changes in seawater pH since the commencement of the industrial era. This information is important in not only determining the response of the surface oceans to ocean acidification from enhanced uptake of CO₂, but also to better understand the effects of ocean acidification on carbonate secreting organisms such as corals, whose ability to calcify is highly pH dependent. Here we report an ∼200 year δ¹¹B isotopic record, extracted from a long-lived Porites coral from the central Great Barrier Reef of Australia. This record covering the period from 1800 to 2004 was sampled at yearly increments from 1940 to the present and 5-year increments prior to 1940. The δ¹¹B isotopic compositions reflect variations in seawater pH, and the δ¹³C changes in the carbon composition of surface water due to fossil fuel burning over this period. In addition complementary Ba/Ca, δ¹⁸O and Mg/Ca data was obtained providing proxies for terrestrial runoff, salinity and temperature changes over the past 200 years in this region. Positive thermal ionization mass spectrometry (PTIMS) method was utilized in order to enable the highest precision and most accurate measurements of δ¹¹B values. The internal precision and reproducibility for δ¹¹B of our measurements are better than ±0.2‰ (2σ), which translates to a precision of better than ±0.02 pH units. Our results indicate that the long-term pre-industrial variation of seawater pH in this region is partially related to the decadal-interdecadal variability of atmospheric and oceanic anomalies in the Pacific. In the periods around 1940 and 1998 there are also rapid oscillations in δ¹¹B compositions equivalent changes in pH of almost 0.5 U. The 1998 oscillation is co-incident with a major coral bleaching event indicating the sensitivity of skeletal δ¹¹B compositions to loss of zooxanthellate symbionts. Importantly, from the 1940s to the present-day, there is a general overall trend of ocean acidification with pH decreasing by about 0.2-0.3 U, the range being dependent on the value assumed for the fractionation factor α_(B3-B4) of the boric acid and borate species in seawater. Correlations of δ¹¹B with δ¹³C during this interval indicate that the increasing trend towards ocean acidification over the past 60 years in this region is the result of enhanced dissolution of CO₂ in surface waters from the rapidly increasing levels of atmospheric CO₂, mainly from fossil fuel burning. This suggests that the increased levels of anthropogenic CO₂ in atmosphere has already caused a significant trend towards acidification in the oceans during the past decades. Observations of surprisingly large decreases in pH across important carbonate producing regions, such as the Great Barrier Reef of Australia, raise serious concerns about the impact of Greenhouse gas emissions on coral calcification.     

海洋二氧化碳的研究进展

海洋是一个巨大的碳库,具有潜在的缓冲大气CO2增加的能力,研究CO2在海洋中的转移和归宿,对于预测未来大气CO2含量乃至全球气候变化具有重要意义。综述了海洋CO2的研究现状,着重介绍海洋CO2的源与汇、海—气CO2通量的估算以及海洋环流、生物泵和海洋生态在海洋碳循环中的作用,并对该研究领域的发展趋势进行了总结。     

Extensive and rapid changes in seawater chemistry during the Phanerozoic: evidence from Br contents in basal halite

Abstract Variation of seawater chemical composition during the Phanerozoic is still a contentious subject. Br concentration in primary marine basal halites was used to indicate variations in seawater composition during the past 550 Ma. Evaporation experiments and thermodynamic modelling suggests that the partition coefficient of Br in halite depends on the composition of the seawater. A combination of this correlation with the time-dependent models for ocean chemistry of Hardie leads to a prediction of Br in basal halite during the Phanerozoic. This prediction is in good agreement with data from different ancient evaporite basins. The Br data give evidence for rapid and massive changes in seawater chemistry during the Phanerozoic and are thus a first independent test for the Hardie model.     

Rise in seawater sulphate concentration associated with the Paleoproterozoic positive carbon isotope excursion: evidence from sulphate evaporites in the ∼2.2–2.1 Gyr shallow‐marine Lucknow Formation,South Africa

Abstract Past oceanic sulphate concentration is important for understanding how the oceans’ redox state responded to atmospheric oxygen levels. The absence of extensive marine sulphate evaporites before ～1.2 Gyr probably reflects low seawater sulphate and/or higher carbonate concentrations. Sulphate evaporites formed locally during the 2.22–2.06 Gyr Lomagundi positive δ¹³C excursion. However, the ～2.2–2.1 Gyr Lucknow Formation, South Africa, provides the first direct evidence for seawater sulphate precipitation on a carbonate platform with open ocean access and limited terrestrial input. These marginal marine deposits contain evidence for evaporite molds, pseudomorphs after selenite gypsum, and solid inclusions of Ca‐sulphate in quartz. Carbon and sulphur isotope data match the global record and indicate a marine source of the evaporitic brines. The apparent precipitation of gypsum before halite requires ≥2.5 mm L^?1 sulphate concentration, higher than current estimates for the Paleoproterozoic. During the Lomagundi event, which postdates the 2.32 Gyr initial rise in atmospheric oxygen, seawater sulphate concentration rose from Archean values of ≤200 μm L^?1, but dropped subsequently because of higher pyrite burial rates and a lower oceanic redox state.     

海洋沉积物的锌同位素地球化学及其应用

锌同位素体系是海洋地球化学研究的新示踪剂,应用于示踪海水中锌元素的来源及其运移过程.海洋沉积物作为锌元素重要的"源"与/或"汇",其锌同位素组成的研究有助于理解海洋锌元素的地球化学循环.海洋沉积物记录了海水组成的信息,可以反演古海水锌同位素组成的变化,前提是理解沉积物与海水之间的分馏.对海水及海洋不同储库锌同位素研究进行系统总结,包括河流输入、热液体系、不同类型海洋沉积物(如富碳酸盐的沉积物、陆源硅酸盐碎屑、硅质沉积物、铁锰结核、贫氧-缺氧沉积物)的锌同位素组成,阐述了海洋沉积物锌同位素组成变化在古气候、古环境重建以及古海洋学等领域的应用以及重要性.      

天然气水合物分解的甲烷对海洋生物的影响

随着海底环境的变化以及全球变暖的加剧,天然气水合物分解释放出大量甲烷到海洋中,其中一部分甲烷会穿过海水释放到大气中,导致大气中的温室气体增加,从而加剧了全球暖化。本文从甲烷的释放和运移路径角度梳理和总结了甲烷对海洋生物的直接和间接影响。首先,水合物分解释放甲烷,在海底形成冷泉渗漏区,滋养了一批特殊的生物群落,而甲烷是其形成生命元素中不可或缺的要素,由此繁衍形成了冷泉生态系统。其次,甲烷释放到海水中会引起海水酸化,海水酸化不仅会导致钙化生物合成碳酸钙外壳受阻,还会加速已生成外壳的溶解。最后,甲烷作为强温室气体释放到大气中还会加剧全球变暖;此外,极地冻土层的融化也会使得冻土区天然气水合物分解,导致大量甲烷进入大气中,从而致使海水暖化,海水的暖化又会对海洋生物的生存、代谢、繁殖、发育和免疫应答等多种生命活动造成影响。以上认识为进一步研究甲烷对未来海洋生态系统的影响提供重要参考信息。     

Earth rotation,ocean circulation and paleoclimate

During the 20 Ka glaciation maximum Earth's rate of rotation was significantly faster. The subsequent glacial eustatic rise in sea level meant an increase of the equatorial radius and hence led to a general deceleration in the Earth's rate of rotation. At about 6000 BP the glacial eustatic rise in sea level finished and a new situation began which was characterized by feedback interchanges of angular momentum between the solid Earth and the hydrosphere. There is a strong linkage between Earth's rate of rotation — total as well as differential — and the changes in ocean surface circulation. The ocean circulation changes are, in their turn, strongly linked to the paleoclimatic evolution of the boardering land masses. This is due to the high heat-storing capacity of the oceans, the ocean/ atmosphere heat flux, and the ocean/land interaction via heat transport by the winds. Consequently, we see a causal connection between Earth's rotation, oceanic circulation, ocean/atmosphere heating, atmospheric (wind) heat transport and continental paleoclimatic changes. We propose that the paleoclimatic changes on the decadal to millennial time scale are primarily driven by this mechanism. Observational data of changes in ocean water masses and paleoclimate are presented for the 20 Ka situation, for the high-amplitude changes 13-10 Ka ago, for the decadal-to-century changes during the Holocene, for the last centuries' instrumental data and for the ENSO-events. This implies that the oceanic system (the ocean surface circulation system) has a much more important role than previously appreciated.     

Advection and removal of Pb and stable Pb isotopes in the oceans: a general circulation model study

Natural Pb-isotope variability in the oceans encodes information about the sources of continental material to the oceans, about ocean circulation, and about Pb removal. In order to use this information, we must understand the natural cycle of Pb in the oceans, which is overprinted by large anthropogenic input. In this study we use ²¹⁰Pb, which has not been significantly anthropogenically perturbed, to investigate oceanic Pb. GEOSECS ²²⁶Ra and model-derived atmospheric fluxes of ²¹⁰Pb are used to input ²¹⁰Pb into an ocean general circulation model. Irreversible scavenging of this ²¹⁰Pb onto settling biogenic particles and at the seafloor are tuned so that the model replicates the observed pattern of ²¹⁰Pb in the oceans. The best-fit model run provides a map of the variability of residence time for Pb. The global average residence time of Pb in this model is 48 yr, but there is over an order of magnitude variation between areas of high and low productivity. This is expected to enhance provinciality of Pb isotope ratios in the oceans. Because stable Pb isotopes are expected to behave in seawater in a similar fashion to ²¹⁰Pb, the pattern of removal of ²¹⁰Pb derived by the model can be used to investigate the behavior of stable Pb isotopes. We use a simplified input of Pb consisting of five point sources representing major rivers and a disseminated dust input. Although this simplified input scheme does not allow precise reconstruction of Pb concentration and isotopes in the oceans, it allows us to answer some first-order questions about the behavior of Pb as an ocean tracer. With a total Pb input of 6.3 × 10⁷ mol/yr (Chow T. J. and Patterson C. C., “The occurrence and significance of Pb isotopes in pelagic sediments,” Geochim. Cosmochim. Acta26, 263-308, 1962), the model predicts natural seawater Pb concentrations averaging 2.2 pmol/kg. Even in the absence of anthropogenic input, the model ocean exhibits a near-surface maximum in Pb concentration. And the model suggests natural Pb concentrations in the Northern Hemisphere an order of magnitude higher than in the Southern Hemisphere. A point source of Pb is suggested to dominate the seawater Pb inventory close to the source but is reduced to typically less than 10% of the inventory by the time that Pb is advected out of the originating ocean. This length scale of advection for Pb isotope signals confirms their potential as tracers of ocean circulation. Assuming an 8% dissolution of dust, their input to the open ocean are seen to be a significant portion of Pb inventory throughout the oceans and make up >50% of the Pb inventory in the model’s Southern Ocean. Finally, a preliminary investigation of the response of Pb-isotope distributions to changes in boundary conditions between glacial and interglacial times illustrates that significant variation in the Pb isotopes are expected in some regions, even for reasonably small changes in climate conditions.     

Major perturbation of ocean chemistry and a 'Strangelove Ocean' after the end-Permian mass extinction

The severe mass extinction of marine and terrestrial organisms at the end of the Permian Period (c. 251 Ma) was accompanied by a rapid (<100 000 years and possibly <10 000 years) negative excursion of c. 3‰ in the δ¹³C of the global surface oceans and atmosphere that persisted for some 500 000 years into the Early Triassic. Simulations with an ocean–atmosphere/carbon-cycle model suggest that the isotope excursion can be explained by collapse of ocean primary productivity, and changes in the delivery and cycling of carbon in the oceans and on land. Model results suggest that severe reduction of marine productivity led to an increase in surface-ocean dissolved inorganic carbon and a rapid, short-term increase in atmospheric pCO₂ (from a Late Permian base of 850 ppm to c. 2500 ppm). Increase in surface ocean alkalinity may have stimulated the widespread microbial and abiotic shallow-water carbonate deposition seen in the earliest Triassic. The model is also consistent with a long-term (>1 Ma) decrease in sedimentary burial of organic carbon in the early Triassic.     

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.     

西太平洋上层海水溶解甲烷浓度及碳同位素特征研究

对西太平洋上层海水溶解甲烷浓度的研究结果表明，该海域海水甲烷相对于大气甲烷是强烈过饱和的。甲烷浓度及碳同位素组成特征表明这部分甲烷为生物成因。该海域海－气交换过程中甲烷通量在０．７～１０．４ｎｍｏｌｍ－２ｓ－１，明显高于其它开放海域。     

古海水pH值代用指标——海洋碳酸盐硼同位素研究进展

仪器测量的海水pH记录太短，无法评估海水pH自然变化的频率和幅度,并预测未来大气CO₂急剧增加后海水酸度的响应。海相碳酸盐的硼同位素是目前恢复古海洋pH的有效途径，倍受古气候—环境学家的重视。评述了近年来海洋碳酸盐的硼同位素的最新研究成果和研究现状，重点探讨了海相碳酸盐的硼同位素的测定方法、硼同位素—pH模型和古海水pH恢复等前沿内容，旨在提供一个系统的海洋碳酸盐硼同位素—pH系统的基本概念及研究思路，以利于气候学、地质学界了解这一交叉领域的发展动态。     

Ice ages and the thermal equilibrium of the earth,II

The energy required to sustain midlatitude continental glaciations comes from solar radiation absorbed by the oceans. It is made available through changes in relative amounts of energy lost from the sea surface as net outgoing infrared radiation, sensible heat loss, and latent heat loss. Ice sheets form in response to the initial occurrence of a large perennial snowfield in the subarctic. When such a snowfield forms, it undergoes a drastic reduction in absorbed solar energy because of its high albedo. When the absorbed solar energy cannot supply local infrared radiation losses, the snowfield cools, thus increasing the energy gradient between itself and external, warmer areas that can act as energy sources. Cooling of the snowfield progresses until the energy gradients between the snowfield and external heat sources are sufficient to bring in enough (latent plus sensible) energy to balance the energy budget over the snowfield. Much of the energy is imported as latent heat. The snow that falls and nourishes the ice sheet is a by-product of the process used to satisfy the energy balance requirements of the snowfield. The oceans are the primary energy source for the ice sheet because only the ocean can supply large amounts of latent heat. At first, some of the energy extracted by the ice sheet from the ocean is stored heat, so the ocean cools. As it cools, less energy is lost as net outgoing infrared radiation, and the energy thus saved is then available to augment evaporation. The ratio between sensible and latent heat lost by the ocean is the Bowen ratio; it depends in part on the sea surface temperature. As the sea surface temperature falls during a glaciation, the Bowen ratio increases, until most of the available energy leaves the oceans as sensible, rather than latent heat. The ice sheet starves, and an interglacial period begins. The oscillations between stadial and interstadial intervals within a glaciation are caused by the effects of varying amounts of glacial meltwater entering the oceans as a surface layer that acts to reduce the amount of energy available for glacial nourishment. This causes the ice sheet to melt back, which continues the supply of meltwater until the ice sheet diminishes to a size consistent with the reduced rate of nourishment. The meltwater supply then decreases, the rate of nourishment increases, and a new stadial begins.     

Land–sea carbon and nutrient fluxes and coastal ocean CO2 exchange and acidification: Past,present, and future

Epochs of changing atmospheric CO₂ and seawater CO₂–carbonic acid system chemistry and acidification have occurred during the Phanerozoic at various time scales. On the longer geologic time scale, as sea level rose and fell and continental free board decreased and increased, respectively, the riverine fluxes of Ca, Mg, DIC, and total alkalinity to the coastal ocean varied and helped regulate the C chemistry of seawater, but nevertheless there were major epochs of ocean acidification (OA). On the shorter glacial–interglacial time scale from the Last Glacial Maximum (LGM) to late preindustrial time, riverine fluxes of DIC, total alkalinity, and N and P nutrients increased and along with rising sea level, atmospheric PCO₂ and temperature led, among other changes, to a slightly deceasing pH of coastal and open ocean waters, and to increasing net ecosystem calcification and decreasing net heterotrophy in coastal ocean waters. From late preindustrial time to the present and projected into the 21st century, human activities, such as fossil fuel and land-use emissions of CO₂ to the atmosphere, increasing application of N and P nutrient subsidies and combustion N to the landscape, and sewage discharges of C, N, P have led, and will continue to lead, to significant modifications of coastal ocean waters. The changes include a rapid decline in pH and carbonate saturation state (modern problem of ocean acidification), a shift toward dissolution of carbonate substrates exceeding production, potentially leading to the “demise” of the coral reefs, reversal of the direction of the sea-to-air flux of CO₂ and enhanced biological production and burial of organic C, a small sink of anthropogenic CO₂, accompanied by a continuous trend toward increasing autotrophy in coastal waters.     

海洋环境Fe同位素地球化学研究进展

Fe是海洋“生物泵”中限制浮游生物生长和控制海洋初级生产力的主要因素之一,也可间接影响大气中CO2含量,反馈于全球的气候变化。近年来基于多接收电感耦合等离子体质谱仪(MC ICP MS)分析方法的改进及测试精度的提高,应用Fe同位素组成、变化及其分馏机制,为研究海水中Fe的主要来源以及示踪海洋环境中Fe的循环过程等,提供了一个有效地球化学指标,也对示踪地球不同演化阶段的海洋沉积环境变化具有指示意义。较为详细地介绍了海洋环境中不同储库的Fe同位素组成,洋中脊热液流体—玄武岩、海水—大洋玄武岩等水—岩反应影响Fe同位素分馏效应的主要因素及地球不同演化阶段古海洋沉积环境中的Fe同位素变化。认为海洋环境下Fe同位素可以产生较为明显的分馏作用,轻铁同位素具有更易活动、易迁移的特征,并进一步提出不同相态、不同矿物间Fe同位素分馏系数的确定等相关问题仍是今后Fe同位素研究的主要方向。     

Global weathering variations inferred from marine radiogenic isotope records

Determining the past record of chemical weathering is essential for understanding changes in climate and atmospheric CO₂, such as those that occur throughout the Cenozoic (the last 65 my). Many natural radiogenic isotopes in seawater are sensitive to variations in chemical weathering, but taken alone cannot distinguish such changes from those caused by variations in erosional source (such as composition, geographical location or ocean circulation). However, comparison of isotope systems with different sources and different behaviour in seawater can resolve such effects, and the relationship between weathering and climate change can be examined on both long and short timescales.     

海洋中溶存甲烷研究进展

CH₄是大气中的重要微量气体，对全球变暖和大气化学有重要作用。海洋是大气甲烷的重要源和汇。开展海洋中溶存甲烷的研究，有助于了解海洋对大气甲烷和全球变化的贡献。综述了海洋中溶存甲烷的研究现状，着重介绍了海洋中溶存甲烷的分布特征、海气交换通量的估算及其生物地球化学循环，并探讨了该领域研究中存在的问题。