Boron isotope geochemistry of Paleozoic brachiopod calcite: Implications for a secular change in the boron isotope geochemistry of seawater over the Phanerozoic

Boron isotope composition of marine carbonates has been proposed as a paleo-pH proxy and potential tool to reconstruct atmospheric pCO₂. The precise knowledge of the boron isotopic composition of ancient seawater represents the fundamental prerequisite for any paleo-pH reconstruction. This contribution presents boron isotope values for Silurian to Permian brachiopod calcite that might be used to reconstruct pH or boron isotope composition of past oceans. All brachiopod shells were screened for diagenetic recrystallization by means of cathodoluminescence microscopy, trace element geochemistry (B, Fe, Mn, Sr) as well as SEM. Only nonluminescent shells revealing well-preserved microstructures, high strontium and boron concentrations as well as low iron and manganese contents were accepted for boron isotope analysis. The boron isotope ratios of Silurian, Devonian, Pennsylvanian and Permian brachiopod calcite range from 6.8 to 11.0‰, 7.3 to 14.9‰, 12.4 to 15.8‰ and 10.1 to 11.7‰, respectively. These δ¹¹B values are significantly lower in comparison to δ¹¹B values of modern biogenic carbonates and indicate that the Paleozoic oceans were depleted in ¹¹B by up to 10‰. Box modeling of the boron geochemical cycle suggests that the significant depletion of ¹¹B in the oceanic reservoir may have been initiated by an enhanced continental boron discharge. Our data support the earlier made conclusion that boron isotopes may not be used in the geological past as reliable paleo-pH proxy unless the boron isotopic composition of ancient oceans can be constrained by further studies.     

珊瑚高精度硼同位素组成分析：PTIMS与NTIMS方法的对比研究

珊瑚的B同位素组成是海水pH值记录的良好替代指标。对传统的高精度的B同位素组成分析的方法正离子热电离质谱（PTIMS）和负离子热电离质谱（NTIMS）方法进行了对比研究。结果显示,NTIMS分析方法具有极高的灵敏度,可以分析微小样品量,但由于其分馏较明显,并且我们的实验结果表明前人建议的使用O同位素进行分馏校正的方法仅在某些特定情况下适用,而对大多数的测定缺乏有效分馏校正,同时有机质或者激发剂带来的CNO-干扰难以完全排除,因此NTIMS的结果重现性稍差,δ11B外部精度约为±1．0‰（2σ）左右。PTIMS则分馏不明显,Cs2CNO^＋干扰可以有效监控并排除,可以获得很好的结果：δ11B内部精度和外部精度均优于±0．2‰（2σ）,可以满足高精度pH值重建的要求。然而PTIMS方法的灵敏度低,难以对微小样品量进行分析。因此PTIMS和NTIMS方法是相互补充的,相互无法完全取代。     

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。     

海洋Nd同位素演化及古洋流循环示踪研究

海洋Nd同位素演化已经成为示踪陆源风化输入和洋流循环改变的最重要的手段之一,得到了越来越多的应用,并取得了许多重要的成果。海水的Nd同位素组成主要受陆源输入物质控制,热液输入几乎可以忽略。由于Nd在海洋中的停留时间(约500～1000a)略小于海水的平均混合时间(约1500a),且各洋盆有不同的Nd同位素风化输入,因此现代各大洋海水具有不同的Nd同位素组成。在陆源输入稳定的情况下,可以利用海水的Nd同位素组成和演化来示踪水体的混合或洋流循环的改变。目前主要依靠对海洋中水成铁锰结壳、海洋钙质有孔虫壳体、磷酸质鱼骨头或鱼牙齿化石以及沉积物中铁锰氧化物组分等的研究来恢复和反演古海水的Nd同位素组成和演化。4种分析材料各有其优缺点。其中,通过对水成铁锰结壳的Nd同位素分析,基本建立了各大洋新生代以来的主要洋流的Nd同位素组成的长尺度演化。通过有孔虫壳体、鱼化石碎片和沉积物中Fe-Mn氧化物组分可以进行高时间分辨率的古海水Nd同位素演化示踪。利用海水Nd同位素演化可以示踪古洋流通道的开启或闭合,以及获得水体交换的直接信息,为研究构造运动与气候变化之间的关系提供指示。同时,将海水Nd同位素演化与气候变化的指标结合起来,可以用于示踪各种气候条件下洋流循环的改变,将洋流循环的改变与气候变化联系起来,研究两者之间的成因关系。对表层水体的Nd同位素组成的研究则可以示踪不同气候条件下大陆陆源风化输入的改变。     

Modelling the geochemical cycle of boron: Implications for the long-term δ11B evolution of seawater and oceanic crust

The boron geochemical cycle has been simulated using a time-dependent geochemical box model that was coupled to a one-dimension model of seawater–oceanic crust interactions. Boron elemental and isotopic compositions of oceanic rocks as a function of depth were calculated by mass balance, using the temperature and porosity profiles of the crust as well as the available experimental and empirical distribution coefficients and fractionation factors between mineral and water. Ranges of boron elemental and isotopic variations of seawater were calculated for crust–seawater interactions that take place from the ridge-axis to the off-axis closure of the hydrothermal system. The present-day δ¹¹B of seawater (40‰) could represent a steady-state value. However, depending on crustal permeability, lifetime of water–rock interactions, and expansion rate of the oceanic ridge, the δ¹¹B of seawater may vary from 30‰ to 50‰ at the 10 million year scale.Some boron isotope compositions of Cretaceous biogenic carbonates and ophiolitic serpentinites from Oman are comparable to modern rock samples, suggesting that the δ¹¹B of Cretaceous seawater was close to the present-day value. Low δ¹¹B values of some biogenic carbonates cannot be attributed to low pH values of past seawater, but more probably to δ¹¹B variations of seawater or diagenetic alteration by crustal aqueous fluids. Boron isotope composition of hydrothermally altered serpentines could be considered as a promising proxy of the seawater composition.     

Advances in Seasonal Variations and Controls of the Air-sea CO2 Flux in the South China Sea

Marine carbon cycle of the South China Sea is an important part of global carbon cycle. Researches on the air-sea CO₂ flux in the South China Sea will help us understand the global carbon cycle and improve the global carbon system parameter database. This paper concisely summarized the changes of partial pressure of CO₂ (pCO₂), air-sea CO₂ fluxes (FCO₂), and related environmental factors in four regions in domains in the South China Sea. The low-salinity area of the upper reaches of the Pearl River estuary in the northern of South China Sea shelf area acted as a strong source of atmospheric CO₂, with high pCO₂（405.3~810.6 Pa）all year round. The lower area of the Pearl River estuary (salinity > 33.7) acted as a weak sink of CO₂ in winter, with relatively low pCO₂ （35.2~37.0 Pa). The northern slope/basin in the South China Sea acted as a source of CO₂ in warm seasons with a relatively high pCO₂ (45.0 Pa), and acted as a sink of CO₂ in cold seasons with a relatively low pCO₂ (34.7 Pa). The west of the Luzon Strait acted as a sink of CO₂ in spring, while it acted as a source of CO₂ in other seasons, with relative high pCO₂ (38.4~47.5 Pa) in winter. The central/southern basin in the South China Sea acted as sources of CO₂, with relative high pCO₂ (41.0 Pa) all the year. Generally, the estimation of annual sea-air CO₂ fluxes showed that most domains in the South China Sea served as weak sources of atmospheric CO₂. In the future, more researches should be focused on the time-series of sea surface pCO₂ and the remote sensing of the sea-air CO₂ fluxes.     

硼同位素分馏的实验理论认识和矿床地球化学研究进展

硼是一种中等挥发性元素,具有¹¹B和¹⁰B两个稳定同位素。两个同位素间高达10%的相对质量差使其在地质过程中引起高达-70‰至+75‰的硼同位素变化。硼在自然界主要与氧键合形成三配位(BO₃)和四配位(BO₄)结构,因而¹¹B和¹⁰B间同位素分馏主要受控于三配体(BO₃)和四面体(BO₄)间配分。本文综述了低温和高温地质过程的硼同位素分馏的理论和实验研究进展。在溶液中B(OH)₃和${B(OH)^{-}_{4}}$间硼同位素分馏受pH和热力学p-T条件控制,实验和理论表征获得常温常压条件下的B(OH)₃和$B(OH)^{-}_{4}$间同位素分馏系数(α_3-4)变化范围为1.019 4至1.033 3。低温条件下矿物(如碳酸盐、黏土矿物(蒙脱石和伊利石)、针铁矿、水锰矿、硼酸盐)与溶液间硼同位素分馏行为除了受p-T-pH影响外,矿物表面吸附引起的分馏效应十分显著。在中高温过程(蒙脱石伊利石化、富硼电气石和白云母矿物与热液流体,以及硅酸盐熔体与流体)中硼同位素分馏行为受到硼配位构型、化学成分以及物理化学条件的控制。随着硼同位素分馏机理研究的深入以及越来越完善的地质储库硼同位素端员特征表征,硼同位素地球化学指标可以灵敏示踪成矿物质来源、探究成矿作用与成因模式和重建成矿过程物理化学条件。目前矿床硼同位素地球化学研究的难点在于实现不同赋存相(如流体、矿物和熔体)中硼配位键合结构和硼同位素组成的精细化表征。     

中北太平洋铁锰结壳钕同位素演化研究

现代海洋中的水成 Fe－Mn 结壳的 Nd 来自当时周围海水，因此利用 Fe－Mn 结壳可以恢复新生海洋 Nd 同位素演化历史，进面了解古海洋环境和古气候变迁信息。海洋中 Nd 的来源包括河流或陆源 Nd、大陆边缘沉积物和风成粉尘中的可溶 Nd，以及洋中脊热液蚀变来源的 Nd。对海水、水成成因铁锰结壳和结核、洋脊热液喷发和河流输入的 Nd 同位素研究发明，陆源物质控制着大洋中溶解的 Nd。对于风尘输入对大洋中的REE的影响还存在争议。有研究表明来自大陆和火山的风尘是某些局部大洋中的 REE 的重要来源，风尘与海水间的 REE 交换引起了某些洋区中 Nd 同位素组成的变化。相反，另有学者认为风尘对北太平洋中的溶解 Nd 总量没有影响。笔者分板子一块来自中北太平洋的铁锰结壳样品（MDD53）的 Nd，Pb 同位素，得到了该区新生代以来的 Nd，Pb 同位素演化历史。通过对比该结壳和岩心 LL44－GPC3 中粉尘的同位素演变曲线，发现二者的 Pb 同位素变化规律十分相似，证明结壳中的 Pb 主要来自粉尘。与 Pb 同位素相反，二者的 Nd 同位素演化完全不同。中国黄土的ENd值远低于中太平洋深水中的ENd值。因此，笔者认为风成粉尘对太平洋深水中溶解的 Nd 总量的影响可以忽略不计。结壳的 ENd值介于大陆和岛弧火山的值之间，说明新生代太平洋海水中的 Nd 主要来自河流、大洋边缘大陆风化及大洋环流携带大源自其他大洋的 Nd，新生代 Nd 同位素比值的增长主要是国为太平洋边缘岛弧的风化剥蚀作用和火山活动的增强。     

Assessing scleractinian corals as recorders for paleo-pH: Empirical calibration and vital effects

Laboratory experiments on the branching, symbiont-bearing coral genus Porites and Acropora have been carried out to determine the dependence of the skeletal boron isotopic composition (δ¹¹B) on the pH of seawater. The results show a clear relationship similar to previously established empirical calibrations for planktonic foraminifera and inorganic calcite. A −0.6‰ offset exists between P. cylindrica and A. nobilis which is systematic over the pH range of 7.7-8.2. To test whether the δ¹¹B of coral skeletons changes with physiological processes such as photosynthesis and respiration, corals were grown along a depth transect in their natural environment and under controlled conditions in the laboratory at varying light intensities and food supply. Although we also observe an isotopic offset between P. compressa and Montipora verrucosa, neither experimental treatment systematically changed the δ¹¹B of the two species. These findings are encouraging for using the boron isotope paleo-pH proxy in corals, because it appears that seawater pH is the dominant control on the boron isotopic composition in corals.     

土壤次生碳酸盐碳氧稳定同位素古环境意义及应用

土壤次生碳酸盐碳氧稳定同位素特征是反映古气候与古环境的重要代用指标,其碳氧稳定同位素组成分别受土壤CO2中C同位素组成和大气水的O同位素控制。在一定深度的土壤中,土壤次生碳酸盐δ^13C就主要受当地植物类型(C3植物和C4植物等)控制。土壤次生碳酸盐样预处理中剔除土壤中原生碳酸盐以及有机物污染尤为重要。土壤中次生碳酸盐C、O稳定同位素地球化学在土壤发生学、古气候恢复、古生态重建以及全球变化研究中应用日益广泛,但解译时可能受应用年代范围、成岩作用、原生和次生碳酸盐混杂、土壤碳酸盐多元发生等因素影响,其应用机理和范围还需进一步探讨。     

Tectonic progradation and plate tectonic evolution of the Alps

Rifting and spreading, trench formation, flysch deposition, subduction and nappe formation prograde from internal to external parts of the Alpine orogen. The progradation is a characteristic feature of the evolution of the Alps. A plate tectonics model based on this cognition is presented and an attempt is made to integrate the plate movements of the Alpine region during the Mesozoic and Cenozoic into the plate pattern of the Western Mediterranean.

Important events in the evolution of the Alps are the successive opening and closing of the Piedmont (South Penninic) and Valais (North Penninic) oceans, and the two continental collisions related to this. The southward drift of the Briançonian plate in the Cretaceous closes the Piedmont and opens the Valais ocean. The evolution of these oceans is related to the plate movements in the North Atlantic. The second continental collision is followed by the formation of an exogeosyncline, the molasse foredeep.

Prograding orogens like the Alps are most likely to evolve in an originally continental environment by rifting. Retrograding orogens, however, indicate an originally oceanic environment with well-developed magmatic arcs and back-arc basins.     

The Calcium Isotope Composition of Modern Seawater Determined by Thermal Ionisation Mass Spectrometry

The Ca isotopic composition of modern seawater has been determined using a ⁴³Ca-⁴⁸Ca double spike, which was calibrated using a ⁴²Ca/⁴⁴Ca seawater ratio of 0.30587 ± 0.00026. This ratio was determined from a total evaporation experiment in which the ion beam was measured from the beginning to the end of the emission. With integration of the peak intensities, the fractionation effects can be minimised, since total evaporation of the reservoir cancels out the effect of vapour enrichment in the light isotopes. This experiment avoids the gravimetric uncertainty inherent in the double spike calibration. This calibration allows the precise redetermination of the seawater isotopic composition of Ca. A mean ⁴⁰Ca/⁴⁴Ca ratio for two Atlantic water samples of 45.143 (2s_mean= 0.003) was found. The good reproducibility of the Ca isotope ratios in present seawater and the very strong isotopic homogeneity of Ca in the oceans illustrate the advantage of using seawater as the common standard, with the advantage of decreasing interlaboratory bias.     

Iron-Molybdenum Isotopes and the Chemical Evolution of Ancient-Oceans

Iron(Fe) is abundant in nature while molybdenum(Mo) is the most abundant transition metal in seawater. Due to their high sensitivity to the redox state of the environment, the isotopic compositions of Fe and Mo as well as variations have been widely used to probe the redox conditions and the evolution of ancient ocean chemistry in favor of improved analytical techniques. Here, we summarized isotopic fractionation mechanisms and natural distribution of both iron and molybdenum isotopes, and further we summarized and partially reinterpreted the redox evolution of ancient oceans through time based on available Fe-Mo data compiled in this study. The process that causes the largest iron isotope fractionation is redox reaction and the iron in oxidation state is generally enriched in ⁵⁶Fe. Biotic and abiotic pyrite formations also produce a large Fe isotope fractionations. Isotopic fractionation of molybdenum in seawater is mainly caused by the adsorption process of dissolved Mo onto ferromanganese oxides or hydroxides in sediments. Fe-Mn (hydro)oxides tend to adsorb isotopically light molybdenum resulting in the isotopic composition of Mo in seawater heavier. However, the Mo sinks in euxinic settings cause almost no molybdenum isotope fractionation. The Fe Mo isotope isotopic records through geological timegenerally suggest similar ocean redox evolution: Oceans older than 2.3 Ga was mainly dominated by ferruginous condition, and there was a slight increase in oxygen content between 2.6 and 2.5 Ga. Earth’s surface was initially oxidized during 2.3 to 1.8 Ga, during which euxinic deposition of sulfide was elevated. Euxinic waters may have expanded greatly between 1.8 and 0.8 Ga, and after that, Earth’s surface had being gradually oxidized and the euxinic waters shrank substantially.Finally, suggestions are proposed for further work on the Fe-Mo isotope research in the context of ancient ocean chemistry.     

海洋环境中的锇同位素研究现状

由于锇同位素示踪和定年具有较高的灵敏度，能提供其它同位素无法给出的重要信息，在海洋环境中应用具有独特的优越性，因此锇同位素在海洋环境中的的研究和应用引起了人们的广泛关注。近年来，国内外学者对海洋环境中的锇同位素研究取得了较大的成果，主要体现在以下几个方面：①对富钴结壳、海底铁锰结核、富有机质沉积物、富金属碳酸盐和深海远洋粘土中的锇同位素组成进行了较多研究；②对海水中锇的浓度、滞留时间，以及现代海水的锇同位素组成进行了精确测定；③初步建立了过去80Ma以来海水锇同位素组成的演化曲线；④对深海橄榄岩、大洋玄武岩、俯冲带岩石和大洋中脊喷出的热液流体的锇同位素组成进行了研究；⑤探讨了海洋环境中影响海水锇同位素组成变化的制约因素，初步揭示了海洋环境中的锇同位素组成对古海洋、古气候和古地理的指示意义。较系统地总结近年来锇同位素在海洋环境中的研究现状，对于指导以后的研究工作有着重要的意义。     

Variations in seawater osmium isotope composition since the last glacial maximum: A case study from the Japan Sea

Concentrations of Re and Os, and the isotopic composition of Os have been measured in the Japan Sea sediments to assess the response of the Japan Sea to glacial–interglacial climate change and associated weathering fluxes. The osmium concentrations in the sediment samples analyzed vary from 59 to 371 pg/g, and ¹⁸⁷Os/¹⁸⁸Os from 0.935 to 1.042. Only ¹⁸⁷Os/¹⁸⁸Os of sediment samples from dark laminations deposited under suboxic to anoxic conditions and having elevated concentrations of Re and Os, and with ≥ 80% hydrogenous Os are explained in terms of seawater composition. Lower ¹⁸⁷Os/¹⁸⁸Os were observed for sediments deposited during the last glacial maximum (LGM) when planktonic foraminifera from the Japan Sea recorded lighter oxygen isotopic composition. Decrease in dissolved Os fluxes from continents and/or change in the composition of the dissolved load to the Japan Sea are suggested as the driving mechanisms for the observed lower LGM ¹⁸⁷Os/¹⁸⁸Os. The results of this study, coupled with lower ¹⁸⁷Os/¹⁸⁸Os during the last glacial observed at other sites from ocean basins with different lithology and contrasting sediment accumulation rates, suggest that this trend is characteristic of the global oceans.

Data from this study show that the Japan Sea recorded higher ¹⁸⁷Os/¹⁸⁸Os during the current interglacial coinciding with excursions of oxygen isotopic compositions of planktonic foraminifera to heavier values. This is explained in terms of preferential release of ¹⁸⁷Os during deglacial weathering and/or higher continental Os flux driven by warm and wet climate. This study demonstrates that Os isotopic composition of reducing margin sediments has immense potential to track variations in the seawater composition. In addition, ¹⁸⁷Os/¹⁸⁸Os of reducing sediments may be used to draw inferences about local paleoceanographic processes in semi-enclosed basins such as the Japan Sea.     

The Paleoceanography during the Time with High δ13C of Phanerozoic marine carbonates

Carbon isotopic composition of marine carbonates is a record for various important geological events in the process of earth development and evolution. The carbonates of Carboniferous, Permian and Triassic, as the transition from Paleozoic to Mesozoic-Cenozoic have very high ¹³C value. Taking this as the main point, and combined with the oxygen, strontium isotopic composition in carbonates, distribution of carbonate basin area through geologic time, the correlation of carbon isotopic composition of marine carbonates to sea level change, organic carbon burial flux, exchange of CO₂ content in atmosphere and ocean, and long cycle evolution of the earth ecosystems were approached. The results are shown as follows: ①The interval of ¹³C >3‰ during Phanerozoic was concentrated in Carboniferous, Permian and the beginning of Triassic, but the beginning of Triassic was characterized by higher frequency and larger fluctuations in ¹³C value during a short time, whereas the Carboniferous-Permian presented a continuously stable high ¹³C value, indicating a larger amount of organic carbon accumulation in this time interval. Relatively high ¹⁸O values during this time was also observed, showing a long time of glaciations and cold climate, which suggest a connection among rapid organic carbon burial, cold climate, as well as pCO₂ and pO₂ states of atmosphere. ②The over consumption of atmosphere CO₂ by green plants during the time with high ¹³C of seawater forced CO₂ being transferred from ocean to atmosphere for the balance, but the decrease in the seawater amount and water column pressure caused by the global cooling could weaken dissolution capacity of CO₂ in seawater and carbon storage of marine carbonates, and also reduce the carbonate sedimentary rate and decrease the carbonate basin area globally from Devonian to Carboniferous and Permian. During the middle-late Permian carbonate was widely replaced by siliceous sediments even though in shallow carbonate platform, which resulted in the decrease of marine invertebrates, suggesting the Permian chert event should be global. ③The Phanerozoic ⁸⁷Sr/⁸⁶Sr trend of seawater showed a sharp fall in Permian and drop to a minimum at the end of the Permian, indicting input of strontium from the submarine hydrothermal systems (mantle flux). Such process should accompany with a supplement of CO₂ from deep earth to atmosphere and ocean system, but the process associated with widespread volcanism and rises of earth’s surface temperature pricked up the mass extinction during the time of end Permian. ④Cold climate and increase of continental icecap volume, the amalgamation of northern Africa and Laurentia continentals were the main reasons responsible for the sea level drop, but the water consumption result from the significantly increased accumulation of organic carbon should also be one of the reasons for the sea level drop on the order of tens of meters. ⑤The mass extinction at the end Permian was an inevitable event in the process of earth system adjustment. It was difficult for marine invertebrates to survive because of the continuously rapid burial of organic carbon, and of the decrease of sea water amount and its dissolution ability to CO₂. At last, at the end of Paleozoic, the supplement of CO₂ to atmosphere and ocean by widely magma activities resulted in a high temperature of earth surface and intensified mass extinction.     

Combined Sr,Nd, Pb and Li isotope geochemistry of alkaline lavas from northern James Ross Island (Antarctic Peninsula) and implications for back-arc magma formation

We present a comprehensive geochemical data set for a suite of back-arc alkaline volcanic rocks from James Ross Island Volcanic Group (JRIVG), Antarctic Peninsula. The elemental and isotopic (Sr, Nd, Pb and Li) composition of these Cenozoic basalts emplaced east of the Antarctic Peninsula is different from the compositions of the fore-arc alkaline volcanic rocks in Southern Shetlands and nearby Bransfield Strait. The variability in elemental and isotopic composition is not consistent with the JRIVG derivation from a single mantle source but rather it suggests that the magma was mainly derived from a depleted mantle with subordinate OIB-like enriched mantle component (EM II). The isotopic data are consistent with mantle melting during extension and possible roll-back of the subducted lithosphere of the Antarctic plate. Magma contamination by Triassic–Early Tertiary clastic sediments deposited in the back-arc basin was only localized and affected Li isotopic composition in two of the samples, while most of the basalts show very little variation in δ⁷Li values, as anticipated for “mantle-driven” Li isotopic composition. These variations are difficult to resolve with radiogenic isotope systematics but Li isotopes may prove sensitive in tracking complex geochemical processes acting through the oceanic crust pile, including hydrothermal leaching and seawater equilibration.     

硼及硼同位素地球化学在地质研究中的应用

总结了硼及硼同位素的地球化学特征：（１）硼是易溶元素,主要赋存在地球表层,尤其是海水、海相沉积物及海水交代岩石中。其同位素组成δ１１Ｂ值按顺序变化,封闭盐湖卤水（＞４０‰）＞海水（３９５‰）＞海相硼矿物（１８２‰～３１７３‰）＞海相沉积物（１３９‰～２５２‰）＞海水交代岩石（４５１‰～１０８５‰）。大陆水及陆相沉积物硼含量及硼同位素组成变化极大,并多以负值为主。海陆过渡构造带则具有过渡的硼丰度值和硼同位素组成。（２）１１Ｂ较１０Ｂ具有更活跃的地球化学性质,因此在水岩作用中具有明显的同位素交换。硅化交代作用中,岩石被硅化交代,释放硼,并优先释放重硼,同位素组成变轻;在脱硅反应中,岩石释放硅吸收硼,并优先吸收重硼,同位素组成变重。在封闭体系中,水溶液淋滤岩石中部分的硼,即可大量富集,并富集１１Ｂ;在开放体系中,岩石硼被大量淋滤流失,δ１１Ｂ值明显降低。由于水岩作用的结果,从新鲜海底玄武岩到正常海水,硼同位素值从－２９５‰到３９５‰逐渐升高。（３）变质脱水反应中硼被大量排出,并优先排出重硼同位素,进入流体相,因此随着变质程度由低到高,岩石中硼含量及同位素组成δ１１Ｂ值由高变低。（４）在成矿研究中?     

镁同位素示踪碳酸盐岩沉积—成岩过程

镁（Mg）作为主要的造岩元素及生物营养元素,是连接大陆、海洋和地球内部循环的重要纽带。碳酸盐岩作为Mg的主要储库,是全球Mg循环的重要组成环节,利用Mg同位素示踪碳酸盐岩沉积—成岩过程是有效反演深时海水Mg同位素组成（δ26Mg_海水）、恢复全球Mg循环的基本前提。近二十年来,Mg同位素在示踪碳酸盐岩沉积—成岩过程研究中取得了较大进展:1）不同类型碳酸盐矿物形成过程中的Mg同位素分馏及其影响因素的研究得到完善;2）建立了Mg同位素地球化学模型,对不同白云石化过程进行半定量—定量模拟;3）初步探索了利用Mg同位素反演早期成岩流体体系的方法。以上研究进展为利用碳酸盐岩恢复δ26Mg_海水奠定了理论基础,在选择有效的碳酸盐岩载体恢复δ26Mg_海水时,需充分考虑碳酸盐岩的沉积—成岩过程及其对Mg同位素组成的影响,并适当结合地球化学模型,消除沉积—成岩因素的影响,进而恢复δ26Mg_海水。     

Intra-shell boron isotope ratios in the symbiont-bearing benthic foraminiferan Amphistegina lobifera: Implications for δB vital effects and paleo-pH reconstructions

The boron isotope composition of marine carbonates is considered to be a seawater pH proxy. Nevertheless, the use of δ¹¹B has some limitations such as the knowledge of the fractionation factor (α_4-3) between boric acid and the borate ion and the amplitude of “vital effects” on this proxy that are not well constrained. Using secondary ion mass spectrometry (SIMS) we have examined the internal variability of the boron isotope ratio in the shallow water, symbionts bearing foraminiferan Amphistegina lobifera. Specimens were cultured at constant temperature (24 ± 0.1 °C) in seawater with pH ranging between 7.90 and 8.45. Intra-shell boron isotopes showed large variability with an upper limit value of ≈30‰. Our results suggest that the fractionation factor α_4-3 of 0.97352 (Klochko et al., 2006) is in better agreement with our experiments and with direct pH measurements in seawater vacuoles associated with the biomineralization process in these foraminifera. Despite the large variability of the skeletal pH values in each cultured specimen, it is possible to link the lowest calculated pH values to the experimental culture pH values while the upper pH limit is slightly below 9. This variability can be interpreted as follows: foraminifera variably increase the pH at the biomineralization site to about 9. This increase above ambient seawater pH leads to a range in δ¹¹B (Δ¹¹B) for each seawater pH. This Δ¹¹B is linearly correlated with the culture seawater pH with a slope of −13.1 per pH unit, and is independent of the fractionation factor α_4-3, or the δ¹¹B_sw through time. It may also be independent of the pK_B (the dissociation constant of boric acid) value. Therefore, Δ¹¹B in foraminifera can potentially reconstruct paleo-pH of seawater.