硼掺入Mg(OH)2形式及机理

采用pH=9.5～13.0的无镁合成海水进行了Mg(OH)₂沉积时B的掺入实验,证实了B(OH)₃优先掺入Mg(OH)₂的硼同位素分馏特征。在所研究的pH范围内,Mg(OH)₂沉积的δ11B均高于无镁合成海水的δ11B,它们之间的硼同位素分馏系数α沉积/海水为1.017 7~1.056 9,平均为1.032 9±0.009 32(SD)。硼同位素的这种分馏特征与无机碳酸盐沉积时的硼同位素分馏存在明显差异,表明B掺入Mg(OH)₂沉积具有不同的机理。B在Mg(OH)₂沉积上的吸附以及B(OH)₃与Mg(OH)₂的沉积反应同时存在并相互制约是其主要特征,造成了B(OH)₃优先掺入的总结果,这并不意味B(OH)₃在掺入的分数上占有优势,相反在所研究的pH范围内,Mg(OH)₂沉积的B(OH)₃/B(OH)-₄大都小于1,因此吸附作用决定了Mg(OH)₂沉积中B浓度的变化特征。采用这种模型能很好地解释沉积中B浓度、B在沉积和海水间的分配系数Kd以及沉积与海水间的分馏系数α随海水pH的变化特征。石珊瑚中Mg(OH)₂的普遍存在和Mg(OH)₂中B(OH)₃的优先掺入也许会影响珊瑚的硼同位素组成与海水pH的定量对应关系,给δ11B作为古海水pH的代用指标带来一定的不确定性。     

海水蒸发时的硼同位素分馏

采用立式亚沸石英蒸馏器，在非流动条件下进行了海水蒸发实验，以研究海水一空气界面硼同位素的行为。将具有不同pH值的天然海水在不同温度下平静地蒸发，采用冷水收集海水蒸汽，实现了无流动空气的真实的蒸发过程，共进行了3种类型的实验。 实验1 将不同pH值（(7.71-8.49)的海水在27℃，33℃和40℃下蒸发，蒸发时连续地补充高纯水以维持蒸发液体的体积恒定。收集海水蒸汽，进行蒸汽的硼同位素组成、硼和氯浓度的测定。 实验2将天然海水在33℃下蒸发，蒸发时不补加高纯水．搏派承药蒸干。分捌收集海水蒸汽和蒸干后的固体盐，进行蒸汽和固体盐的硼同位素组成测定。并同时测定不同蒸发阶段海水的pH值。 实验3 将加人不同硼量的天然海水在40℃下蒸发.蒸发时连续地补充高纯水以维持蒸发液体的体积恒定，收集海水蒸汽，进行硼同位素和硼浓度的测定。 硼浓度的结果表明：①在实验1中，蒸汽的硼浓度变化范围是1.51-10.7 μg/L，平均值为5.16 μg/L，随海水pH值升高而降低，但与蒸发温度无关；②在实验2和3中蒸汽硼的浓度要远远高于实验1，而且蒸汽硼浓度与海水硼浓度具有线性的正相关关系；③蒸汽相的Cl/B比（摩尔比值：平均23.4)远远低于海水的Cl/B比（摩尔比值：1485)，这表明蒸发时没有将海水喷雾的细珠引人蒸汽中。 硼同位素结果表明： (1)在实验1中，蒸汽的δ11B值除一个以外均低于海水B(OH)3的δ11B值，而高于海水B(OH)4-的δ11B值，而且都比海水的δ11B值高，蒸汽与海水间的平均硼同位素分馏系数为1.0019，这表明在海水蒸发时，11B富集在蒸汽相中。此结果与以前所进行的硼溶液蒸发实验结果一致，但与以前所进行的海水蒸发实验结果完全相反。以前的海水蒸发实验结果表明，10B在蒸汽相富集。这种截然相反的结果要归结于蒸发条件的差异，以前蒸发的海水蒸汽是由流动空气带出，此时非平衡的动力因素将起到重要作用，造成质量轻的10B优先进人蒸汽相。而本次实验在非空气流动条件下进行，B(OH)3和B(OH)-4间的同位素平衡将起主导作用。显然，燕汽的δ11B值与海水的pH值没有明显的关系。 (2)在实验2中，蒸汽与海水间的硼同位素分馏系数要远远高于实验1，特别当海水蒸干前的500 mL蒸汽，分馏系数高达1.0182。而蒸干后的固体盐的δ11B值明显低于原始海水，分馏系数为0.9973。这充分表明，在海水蒸发时，11B优先被蒸发而进人燕汽相。海水蒸发时蒸汽相的δ11B值随蒸发程度呈平方指数形式增加，这与蒸发时残留海水的δ11B值急剧升高有关。 (3）实验3中，蒸汽的δ11B值随海水硼浓度的增加而升高，当硼浓度为19.7 μg/mL和63.5 μg/mL时，硼同位素分馏系数分别为1.0072和1.0107。 海水蒸发时的硼同位素分馏可用于对大气降雨硼来源的研究。在不同时期采集的西宁雨水的δ11B值为12.1‰和9.0‰，受风向的影响甚微，表明西宁地区的大气环境受海洋影响较小，大气中的硼主要来源于陆地。但南海西江石油平台大气降雨的δ11B值明显受风向所控制，高δ11B值（33.2‰）表明其海洋来源，而低δ11B值（8.4‰）表明其陆地来源。以往文献所报道的陆地及其沿海大气降雨的δ11B值变化范围很宽(0.8‰~35‰)，但是它们都低于海水的δ11B值，这表明陆地及其沿海大气中的硼主要来源于陆地。 海水中的硼将因洋壳低温蚀变、沉积物吸附以及生物碳酸盐共沉淀从海洋中迁出，这些过程均造成海水10B的贫化。惟独海水蒸发时会造成海水10B的富集，但由于此时硼同位素分馏小，而且与其他因素相比，被海水蒸汽迁出的硼量低，根据计算，海水燕发对古海洋硼同位素组成的影响完全可以忽略不计。     

南海北部珊瑚高分辨率硼同位素组成及其对珊瑚礁海水pH变化的指示意义

造礁珊瑚是研究热带海洋高分辨率气候环境演变的重要载体。对采自海南岛南部三亚湾的活体滨珊瑚SY10进行了约为月分辨率的碳、氧、硼同位素组成分析,并利用珊瑚δ11B重建了海水pH。结果显示,所测量样品的δ13C变化范围为–3.32‰~–1.76‰,δ18O为–6.13‰~–4.78‰,δ11B为23.51‰~26.23‰,且这些珊瑚样品的碳、氧、硼同位素组成均存在明显的季节性周期波动。其中pH与δ18O之间存在明显的正相关关系,高的pH值更倾向于在低温的季节出现,这意味着短时间尺度该处珊瑚礁海水pH可能主要不是受海水CO2溶解度控制,而是与生物活动有密切的关系。利用SY10珊瑚样品硼同位素组成重建的海水pH值变化范围为7.77~8.37,并呈季节性周期波动,这种大幅度的周期波动与我们对三亚珊瑚礁海水pH进行现场观测所得到的结果以及前人的研究成果相符,说明了利用珊瑚δ11B重建海水pH记录是可靠的。     

海洋生物碳酸盐δ11B-pH技术研究进展

利用海洋生物碳酸盐硼同位素组成重建古海水pH的研究通常被称为δ11B-pH技术.近年来,该领域的研究取得了许多重要的成果.但由于理论上尚不完善,随着研究的深入,提出的问题也逐渐增多,如δ11Bcarb=δ11B4的假设能否成立,理论的α4-3值也尚未确定.本文综述了近年来的研究成果,重点讨论海洋生物碳酸盐硼同位素恢复古海水pH三个主要理论基础的研究进展,展望了利用海洋生物碳酸盐硼同位素恢复古海水pH的前景.     

理论计算阳离子对水体中B(OH)_3和B(OH)_4~-间硼同位素平衡分馏的影响

采用密度泛函方法模拟了阳离子对水体中B(OH)3和B(OH)4-的影响,计算海水的硼同位素平衡分馏参数。模拟海水环境时,选择基于分子簇模型的"水滴"法,以最多12个水分子环绕兴趣分子的方式构建"水滴"。对海水环境的计算结果显示,B(OH)3和B(OH)4-的硼同位素平衡分馏系数在25?C时为1.031,与纯水环境下的该分馏值并无明显差别。研究表明前人对B(OH)3和B(OH)4-间硼同位素平衡分馏参数的实验测定可能存在问题。研究结果为精进硼同位素古环境重建工作和硼同位素平衡分馏测定提供了理论制约。     

硼同位素在矿床学中的应用研究

硼在自然界有两种稳定同位素11B和10B,常采用δ(11B)/10-3来表示不同地质体的同位素组成。由于硼同位素在不同地质体中的分馏作用大,在较大温度范围内岩浆-热液流体中的高活动性和化学性质稳定等方面的优势,使硼同位素在地球科学研究中的作用越来越广泛。控制硼同位素分馏的主要因素是硼源。一般情况下,非海相的硼酸盐矿物和与之相关的电气石的δ(11B)值为负值,而在某些盐湖卤水和与海相环境有关的硼酸盐矿物的δ(11B)值则为正值。目前,硼同位素示踪主要应用于块状硫化物矿床、与花岗岩有关的热液矿床以及盐湖矿床的研究。随着硼同位素分馏机制及其在不同环境地质样品中分布特征的深入研究,硼同位素在解决矿床的成矿物质来源、矿床成因和成矿作用等方面将发挥更大的作用。     

硼同位素及其地质应用研究

硼的两个稳定同位素（10B 和11B）相对质量差较大,因此,硼同位 素分馏较显著。由于分析测量技术方面的改进和创新, 硼同位素地球化学近年来有了长足 的发展。业已查明,自然界中δ11B值变化为 －37‰～+58‰。其中,较负的 δ11B值见于非海相蒸发硼酸盐矿物和某些电气石,而较正的δ11B值见 于某些盐湖卤水和蒸发海水。现代大洋水的δ11B值十分恒定 (+39,5‰)。原始 地幔的δ11B值估测为－10‰±2‰。陨石的δ11B值很不均一,变化 可达90‰。而月岩的δ11B值变化较小（－6‰～+4‰）。由于硼同位素存在大的 分馏和不同地质体中截然不同的δ11B值,硼同位素地质应用范围十分广泛。目 前,硼同位素在研究星云形成过程和宇宙事件,壳-幔演化和板块俯冲作用过程,判别沉积 环境,研究矿床成因,示踪古海洋和古气候条件,和判断环境污染源区等方面的研究中成效显著。     

长江口咸淡水混合过程中溶解态硼的含量及同位素组成特征

采用Cs2BO2^ -石墨技术对长江口咸淡水混合过程中溶解态的硼同位素组成进行了测定，得到混合水的δ^11B的变化范围是39．9‰～12．δ^11‰，硼浓度的变化范围是2．07～O．0429μg／mL。结果表明，混合水的硼浓度和δ^11B均随离长江口岸距离的增加而增加，但硼浓度与其它所有水化学成分一样，只呈线性关系而增加。而δ^11B值是呈对数关系而增加，即在混合的初期，混合水的δ^11B值随海水的掺入而急剧增加至海水的δ^11B值后趋于稳定。混合水δ^11B值的这种变化是长江淡水与海水简单混合的结果。     

北海涠洲岛珊瑚多色性分布规律初步研究

正涠洲岛位于北部湾中部(中国新闻网,2015),属亚热带季风气候,远离大陆,海水清洁,广泛发育珊瑚礁群落(王欣等,2009)。涠洲岛具有丰富多彩的海蚀、海积与海滩地貌(北海涠洲岛网,2015)。作者于2018年3月1日～3月4日赴涠洲岛进行为期4天的调研工作,通过观察发现,海滩砂主要由珊瑚和贝壳碎屑构成,珊瑚碎块大量呈白色,但也见有少量的灰色、粉色等,本文探究不同颜色     

西藏错那洞电气石花岗岩中电气石化学组成、硼同位素特征及意义

为了对西藏错那洞电气石花岗岩源区进一步约束,利用显微镜、电子探针和激光剥蚀多接收等离子质谱仪,对错那洞电气石花岗岩中电气石的形态、成分及硼同位素组成进行了研究.结果表明,错那洞电气石花岗岩中的电气石为碱族黑/铁电气石,直接结晶自富硼熔体,与熔体之间未发生明显的硼同位素分馏.电气石δ11B值主要在-6.91‰^-9.17‰之间,与大陆地壳平均δ11B值(-10‰±3‰)相近,表明错那洞电气石花岗岩主要源自变质沉积岩的部分熔融.然而,与起源于变质沉积岩的花岗岩相比,样品的δ11B值明显偏高,而与前人报道的雅拉香波淡色花岗岩(源自石榴石角闪岩部分熔融)的δ11B值相似.因此,错那洞电气石花岗岩源区中,除了变质沉积岩外,可能还混入了少量石榴石角闪岩.     

Instability of seawater pH in the South China Sea during the mid-late Holocene: Evidence from boron isotopic composition of corals

We used positive thermal ionization mass spectrometry (PTIMS) to generate high precision δ¹¹B records in Porites corals of the mid-late Holocene from the South China Sea (SCS). The δ¹¹B values of the Holocene corals vary significantly, ranging from 22.2‰ to 25.5‰. The paleo-pH records of the SCS, reconstructed from the δ¹¹B data, were not stable as previously thought but show a gradual increase from the Holocene thermal optimal and a sharp decrease to modern values. The latter is likely caused by the large amount of anthropogenic CO₂ emissions since the Industrial Revolution but variations of atmospheric pCO₂ cannot explain the pH change of the SCS before the Industrial Revolution. We suggest that variations of monsoon intensity during the mid-late Holocene may have driven the sea surface pH increase from the mid to late Holocene. Results of this study indicate that the impact of anthropogenic atmospheric CO₂ emissions may have reversed the natural pH trend in the SCS since the mid-Holocene. Such ocean pH records in the current interglacial period can help us better understand the physical and biological controls on ocean pH and possibly predict the long-term impact of climate change on future ocean acidification.     

Boron isotopes as pH proxy: A new look at boron speciation in deep-sea corals using B MAS NMR and EELS

Dissolved boron in modern seawater occurs in the form of two species, trigonal boric acid B(OH)₃ and tetrahedral borate ion . One of the key assumption in the use of boron isotopic compositions of carbonates as pH proxy is that only borate ions, , are incorporated into the carbonate. Here, we investigate the speciation of boron in deep-sea coral microstructures (Lophelia pertusa specimen) by using high field magic angle spinning nuclear magnetic resonance (¹¹B MAS NMR) and electron energy-loss spectroscopy (EELS). We observe both boron coordination species, but in different proportions depending on the coral microstructure, i.e. centres of calcification versus fibres. These results suggest that careful sampling is necessary before performing boron isotopic measurements in deep-sea corals. By combining the proportions of B(OH)₃ and determined by NMR and our previous ion microprobe boron isotope measurements, we propose a new equation for the relation between seawater pH and boron isotopic composition in deep-sea corals.     

Incorporation of uranium in modern corals

Uranium occurs in corals at three sites: 1, in organic matter; 2, adsorbed on the surfaces of skeletal aragonite; and 3, in the aragonite lattice. Organic matter incorporates from sea water by chelation 40–70 ppm uranium; skeletal aragonite incorporates only 3 ppm. However, as the organic fraction is low (0·1%), its high concentration of uranium does not significantly affect the total concentration of uranium in the coral. A negligible concentration of uranium, 40–60 ppb, is adsorbed on skeletal aragonite from which it is readily leached or exchanged. This low concentration of adsorbed uranium (<2% of the total uranium in skeletal aragonite) is related to the very small specific surface area (1·5–1·8 m²/g of the corals.     

Monitoring of terrestrial input by massive corals

Human-induced pollution in coastal areas can significantly increase the concentration of some trace elements in the marine environment. In the tropics, scleractinian corals incorporate these trace elements in their living parts and skeleton. The potential of corals to monitor pollution through time is reviewed in this contribution. The strength and weakness of corals as pollution indicators are discussed, and a few examples are shown. Although some progress should be made in the understanding of the processes ruling the incorporation of trace elements in coralline aragonite, it is concluded that large environmental changes are well recorded by coral skeletons.     

Laser ablation ICP-MS screening of corals for diagenetically affected areas applied to Tahiti corals from the last deglaciation

Fossil corals are unique archives of past seasonal climate variability, providing vital information about seasonal climate phenomena such as ENSO and monsoons. However, submarine diagenetic processes can potentially obscure the original climate signals and lead to false interpretations. Here we demonstrate the potential of laser ablation ICP-MS to rapidly detect secondary aragonite precipitates in fossil Porites colonies recovered by Integrated Ocean Drilling Program (IODP) Expedition 310 from submerged deglacial reefs off Tahiti. High resolution (100 μm) measurements of coralline B/Ca, Mg/Ca, S/Ca, and U/Ca ratios are used to distinguish areas of pristine skeleton from those afflicted with secondary aragonite. Measurements of coralline Sr/Ca, U/Ca and oxygen isotope ratios, from areas identified as pristine, reveal that the seasonal range of sea surface temperature in the tropical south Pacific during the last deglaciation (14.7 and 11 ka) was similar to that of today.     

The isotopic composition of respired carbon dioxide in scleractinian corals: Implications for cycling of organic carbon in corals

The origin of δ¹³C variations within the skeletons of zooxanthellate scleractinian corals is still a matter of considerable debate. In particular, the role respired CO₂ plays in controlling the eventual δ¹³C of the skeleton remains unclear. In this study, the temporal variability of the δ¹³C of respired CO₂ produced by Montastraea faveolata has been measured at approximately monthly intervals over a 1-year period. In these experiments, three corals maintained on a platform at 8 m depth near Molasses Reef in the Florida Keys were incubated in closed chambers for 24-h periods and samples of the incubation water analyzed for the δ¹³C of the dissolved inorganic carbon (ΣCO₂) at ∼3-h intervals. Throughout the incubation, the concentration of O₂ was measured continuously within the chamber. Our results show that during daylight, the δ¹³C of the ΣCO₂ in the incubation water becomes enriched in ¹³C as a result of fractionation during the fixation of C by photosynthesis, whereas at night the δ¹³C of the ΣCO₂ becomes more negative. The δ¹³C of the respiratory CO₂ ranges from −9‰ in the late spring to values as low as −17‰ in the autumn. The lighter values are significantly more negative than those reported by previous workers for coral tissue and zooxanthellae. An explanation for this discrepancy may be that the corals respire a significant proportion of isotopically negative substances, such as lipids, which are known to have values up to 10‰ lighter compared to the bulk δ¹³C of the tissue. The clear seasonal cycle in the δ¹³C of the respiratory CO₂ suggests that there is also seasonal variability in either the δ¹³C of the coral tissue or the type and/or amount of organic material being respired. A similar temporal pattern and magnitude of change was observed in the δ¹³C of the coral tissue samples collected from a nearby reef at monthly intervals between 1995 and 1997. These patterns are similar in timing to the δ¹³C measured in the coral skeletons. We have also calculated an annual mean value for the fractionation factor between dissolved CO₂⁻ in the external environment and photosynthate fixed by the zooxanthellae of 1.0121 (±0.003). This value is inversely correlated with the ratio of photosynthesis to respiration (P/R) of the entire organism and shows the highest values during the summer months.     

Dating Indian corals by U-decay-series methods

Nine samples of corals collected from seven locations in the Saurashtra Coastal region of India were dated by ²³⁸U series disequilibrium methods. Of the three age groups (6000, 30,000, and 120,000 yr) reported for this region by the earlier studies of S. K. Gupta and B. S. Amin (1974, Marine Geology16, 79–83), we could confirm only the 6000-yr group. Instead of a 120,000-yr group, we found a scatter of ages between 118,000 and 176,000 yr. There appears to be no evidence for 30,000-yr-old corals from this region.     

Palaeozoic corals: their evolution and palaeoecology

In recent years, our understanding of Palaeozoic corals has increased enormously. Several new groups have been discovered, extending the range of corals back to the early Cambrian, and we now have a clearer idea of the relationships between them. None of them was a direct ancestor to the post‐Palaeozoic corals. Similarly, the ecology of Palaeozoic corals differed from that of their living relatives in important respects. Palaeozoic corals were principally adapted for life on soft substrates and were not the spectacular reef‐builders that modern corals have become. However, their contribution to Palaeozoic ecosystems is nonetheless fascinating. Their structural adaptations and growth‐forms can tell us much about life and processes on Palaeozoic sea floors.     

Calcium isotope fractionation in modern scleractinian corals

The ⁴⁴Ca/⁴⁰Ca ratios of cultured (Acropora sp.) and open ocean (Pavona clavus, Porites sp.) tropical reef corals are positively correlated with growth temperature. The slope of the temperature-fractionation relation is similar to inorganic aragonite precipitates. However, δ^44/40Ca of the coral aragonite is offset from inorganic and sclerosponge aragonite by about +0.5‰. This offset can neither be explained by the very fast, biologically controlled calcification of scleractinian corals, nor as a consequence of calcification from a partly closed volume of fluid. As corals actively transport calcium through several cell layers to the site of calcification, the most likely explanation for the offset is a biologically induced fractionation. Our results indicate a limited use of Ca isotopes in scleractinian corals as temperature proxy.