Boron isotope variations in nature: a synthesis

The large relative mass difference between the two stable isotopes of boron, ¹⁰B and ¹¹B, and the high geochemical reactivity of boron lead to significant isotope fractionation by natural processes. Published ¹¹B values (relative to the NBS SRM-951 standard) span a wide range of 90. The lowest ¹¹B values around — 30 are reported for non-marine evaporite minerals and certain tourmalines. The most ¹¹B-enriched reservoir known to date are brines from Australian salt lakes and the Dead Sea of Israel with ¹¹B values up to +59. Dissolved boron in present-day seawater has a constant world-wide ¹¹B value of + 39.5. In this paper, available ¹¹B data of a variety of natural fluid and solid samples from different geological environments are compiled and some of the most relevant aspects, including possible tracer applications of boron-isotope geochemistry, are summarized.

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Résumé La grande différence relative de masse entre les isotopes stables du bore, ¹⁰B et ¹¹B, et la grande réactivité geochimique du bore ont pour conséquence un fractionnement isotopique naturel important. Les valeurs de ¹¹B publiées (par rapport au standard NBS SRM-951) varient de 90. Les valeurs de ¹¹B les plus basses (–30) correspondent aux evaporites non-marines et à certaines tourmalines. Le réservoir le plus enrichi en ¹¹B est représenté par les saumures des lacs salés d' Australie et par la Mer Morte en Israël, qui ont des valuers de ¹¹B allent jusqu'à + 59. L'eau de mer a une valeur de ¹¹B mondialement constante de + 39.5. Des valeurs de ¹¹B des solutions naturelles ainsi que des roches et minéraux de différentes origines, publiées jusqu'à présent, sont présentées ici. En outre quelques aspects importants concernant la géochimie des isotopes du bore y compris quelques applications sont exposés.

     

Late Quaternary palaeolimnology of a tropical marl lake: Wallywash Great Pond,Jamaica

Wallywash Great Pond (17° 57 N, 77° 48 W, 7 m a.s.l.) is the largest perennial lake in Jamaica. It occupies a fault trough within the karstic White Limestone. The Great Pond is a hardwater lake with a pH of 8.2–8.6 and an alkalinity of 3.6–3.9 meq 1^–1. Its chemistry is strongly influenced by the spring discharge from the limestone. The lake water is subject to degassing, evaporation and bicarbonate assimilation by submerged plants and algae, resulting in marl precipitation. A 9.23 m core (WGP2), taken from a water depth of 2.8 m, was analysed for magnetic susceptibility, loss-on-ignition, carbonate content, mole % MgCO₃ in calcite, and stable isotopes in the fine carbonate fraction. The chronology is based on ten¹⁴C and four U/Th dates. Four main sediment types alternate in the core: marl; organic, calcareous mud; organic mud or peat; and earthy, brown, calcareous mud. The marls represent periods of wet/warm climate during sea-level highstands and the organic deposits, shallower, swampy conditions. In contrast, the brown, calcareous muds were laid down when the lake was dry or ephemeral. The last interglacial (120 000- 106 000 yr BP) is represented by three distinct marl units. After a dry interval, stable, wet/warm conditions set in from 106 000 to 93 000 yr BP. A dry/cool climate prevailed between 93 000 and at least 9500 yr BP. Three subsequent cycles of alternating wet and dry conditions culminated in flooding of the basin by the Black River during the late Holocene. These recent events cannot be accurately dated by¹⁴C due to significant and temporally-variable inputs of dead carbon from the springs.     

江西省安福地区地热水化学特征研究

为研究江西安福地区水文地球化学特征及控制因素, 本文采集了15组样品, 采用水化学、同位素分析等方法进行研究。结果表明: 研究区地热水以Na-HCO3型水为主, 地下水以HCO3-Na·Ca型为主, 地表水由西南向东北从HCO3-Na·Ca向HCO3-Ca型水演化。水化学组分演化过程主要受岩石风化作用控制, 地层封闭性较差, 水中的Na+、HCO– 3、Sr2+来源于硅酸岩风化溶解。由稳定同位素特征可知, 研究区地热水补给来源为大气降水。研究区热储温度为49.8~101.4 ℃, 地热水循环深度为1 502.6~1 513.6 m。热水在沿断裂带上升过程中与浅层冷水发生混合, 其混合比例为76.1%~87.5%。研究成果为安福地区水循环演化提供依据, 有利于地热资源的合理开采与保护。     

Fe-Cu-Zn-Mo同位素示踪氧化还原过程

非传统稳定同位素（Fe-Cu-Zn-Mo）理论与数据相结合提高了科研工作者对地质体系氧化还原过程的理解。本文对这一相对较新的领域进行了综述,包括与氧化还原过程相关的同位素分馏理论和实验约束、时空尺度下的氧逸度以及同位素示踪氧化还原过程。稳定同位素理论预测,Fe-Cu-Zn-Mo同位素应该对氧化还原状态的变化能够做出响应。结果表明,Fe同位素作为岩浆过程、表生过程、俯冲带流体性质"氧逸度计"应用前景广阔;Cu同位素在岩浆、热液、陆地系统可以很好地示踪氧化还原过程;Zn同位素由于络合过程分馏已经被用在许多不同环境中作为含硫/碳流体迁移的敏感示踪剂;Mo同位素作为古氧逸度计可有效重建古海洋-大气氧化还原状态。     

全球不同构造环境蛇纹岩全岩和矿物微量元素组成及非传统稳定同位素(Fe- Zn- Cu同位素)特征

蛇纹岩对地球深部和浅部的元素循环以及氧化还原状态调节具有非常重要的作用。蛇纹岩中的流体活动性元素(fluid- mobile element, FME)是揭示地幔岩石水化、脱水以及元素循环的关键。本文系统收集和分析了前人报道的不同构造环境的蛇纹岩矿物化学、全岩微量元素和非传统稳定同位素(Fe、Zn、Cu)的组成特征，试图从多个角度总结蛇纹岩脱水过程的元素迁移规律及流体性质。蛇纹岩主要矿物蛇纹石微量元素含量具有以下主要特征：① 不同变质程度的蛇纹岩中的蛇纹石既包含轻稀土元素(light rare earth element, LREE)富集，又包含LREE亏损的特征；② 纤蛇纹石的REE和微量元素分布在利蛇纹石和叶蛇纹石的范围内，利蛇纹石重稀土元素(heavy rare earth element, HREE)整体上略高于叶蛇纹石且更加富集FME；③ 通过中度不相容元素与REE含量相结合，能够较好地区分橄榄石和辉石蛇纹石化所形成的蛇纹石，即辉石形成的蛇纹石富集相容元素(如Sc、Zn、Cr、Y和Ti等)并具有较高的HREE，而橄榄石形成的蛇纹石则表现为平坦且整体较低的REE分布型式。在蛇纹岩全岩微量元素和稀土元素(rare earth element, REE)含量方面，不同构造环境的蛇纹岩具有较大范围的重叠，但也有一定的差异：① 慢速扩张的印度洋中脊蛇纹岩REE和微量元素含量要整体高于快速扩张的大西洋中脊和太平洋中脊的蛇纹岩；② 马里亚纳蛇纹岩泥相比于蛇纹岩和蛇纹石化纯橄岩具有更高的REE和微量元素，而蛇纹石化纯橄岩相比于蛇纹岩则具有相对低的REE及流体不活动性元素含量。因此，利用微量元素的含量在区分不同环境的蛇纹岩方面存在一定的困难。但是，碱金属元素与U元素含量及其相应的比值，则可以较明显区分出大洋蛇纹岩和弧前蛇纹岩。目前已发表的蛇纹岩Fe、Zn、Cu同位素数据表明：① 蛇绿岩中的蛇纹岩Fe和Zn同位素的分馏与其变质程度密切相关。蛇纹岩在进变质过程中δ 56Fe值与Fe 3+/∑Fe值呈负相关，而Zn含量和δ 66Zn值则呈现正相关，表明蛇纹岩变质脱水能够释放氧化性流体；② 与橄榄岩相比，蛇纹岩具有明显低的δ 65Cu值，表明橄榄岩蛇纹石化过程中存在氧化性流体的加入。蛇纹岩Fe、Zn、Cu同位素在示踪流体性质和氧化还原状态方面有很大潜力，对壳幔系统的化学循环具有重要意义。     

Research on temporal and spatial distribution, evolutionary character and mechanism of crustal deformation field before and after the Tangshan earthquake

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Ratios of stable carbon isotopes in some High Arctic plants and lake sediments

¹³C/¹²C ratios for a number of High Arctic vascular plants (51 determinations), mosses (11), and freshwater algae (11) show considerable variation, particularly among the freshwater algae (range from-6.9 to -36.3). In some cases the stable carbon ratios on modern and fossil materials provide guidance as to whether marine waters formerly occupied a given pond or lake basin. In other cases the ¹³C values for algae collected along the present-day shore of a pond or lake bear no relation to the values obtained on constituents preserved within the bottom sediments, suggesting that major changes have occurred in the last few thousand years.Geological Survey of Canada Contribution No. 17291. Contribution No. 41 from the Cape Herschel Project.     

A chlorine isotope study of DSDP/ODP serpentinized ultramafic rocks: Insights into the serpentinization process

Eight DSDP/ODP cores were analyzed for major ion concentrations and δ³⁷Cl values of water-soluble chloride (δ³⁷Cl_WSC) and structurally bound chloride (δ³⁷Cl_SBC) in serpentinized ultramafic rocks. This diverse set of cores spans a wide range in age, temperature of serpentinization, tectonic setting, and geographic location of drilled serpentinized oceanic crust. Three of the cores were sampled at closely spaced intervals to investigate downhole variation in Cl concentration and chlorine isotope composition.The average total Cl content of all 86 samples is 0.26 ± 0.16 wt.% (0.19 ± 0.10 wt.% as water-soluble Cl (X_WSC) and 0.09 ± 0.09 wt.% as structurally bound Cl (X_SBC)). Structurally bound Cl concentration nearly doubles with depth in all cores; there is no consistent trend in water-soluble Cl content among the cores. Chlorine isotope fractionation between the structurally bound Cl⁻ site and the water-soluble Cl⁻ site varies from − 1.08‰ to + 1.16‰, averaging to + 0.21‰. Samples with negative fractionations may be related to reequilibration of the water-soluble chloride with seawater post-serpentinite formation. Six of the cores have positive bulk δ³⁷Cl values (+ 0.05‰ to + 0.36‰); the other two cores (173-1068A (Leg-Hole) and 84-570) have negative bulk δ³⁷Cl values (− 1.26‰ and − 0.54‰). The cores with negative δ³⁷Cl values also have variable Cl⁻ / SO₄² ratios, in contrast to all other cores. The isotopically positive cores (153-920D and 147-895E) show no isotopic variation with depth; the isotopically negative core (173-1068A) decreases by ∼1‰ with depth for both the water-soluble and structurally bound Cl fractions.Non-zero bulk δ³⁷Cl values indicate Cl in serpentinites was incorporated during original hydration and is not an artifact of seawater infiltration during drilling. Cores with positive δ³⁷Cl values are most likely explained by open system fractionation during hydrothermal alteration, with preferential incorporation of ³⁷Cl from seawater into the serpentinite and loss of residual light Cl back to the ocean. Fluid / rock ratios were probably low as evidenced by the presence of water-soluble salts. The two isotopically negative cores are characterized by a thick overlying sedimentary package that was in place prior to serpentinization. We believe the low δ³⁷Cl values of these cores are a result of hydration of ultramafic rock by infiltrating aqueous pore fluids from the overlying sediments. The resulting serpentinites inherit the characteristic negative δ³⁷Cl values of the pore waters. Chlorine stable isotopes can be used to identify the source of the serpentinizing fluid and ultimately discern chemical and tectonic processes involved in serpentinization.     

Low temperature volatile production at the Lost City Hydrothermal Field, evidence from a hydrogen stable isotope geothermometer

Although commonly utilized in continental geothermal work, the water-hydrogen and methane-hydrogen isotope geothermometers have been neglected in hydrothermal studies. Here we report δD-CH₄ and δD-H₂ values from high-temperature, black smoker-type hydrothermal vents and low-temperature carbonate-hosted samples from the recently discovered Lost City Hydrothermal Field. Methane deuterium content is uniform across the dataset at − 120 ± 12‰. Hydrogen δD values vary from − 420‰ to − 330‰ at high-temperature vents to − 700‰ to − 600‰ at Lost City. The application of several geothermometer equations to a suite of hydrothermal vent volatile samples reveals that predicted temperatures are similar to measured vent temperatures at high-temperature vents, and 20-60 °C higher than those measured at the Lost City vents. We conclude that the overestimation of temperature at Lost City reflects 1) that methane and hydrogen are produced by serpentinization at > 110 °C, and 2) that isotopic equilibrium at temperatures < 70 °C is mediated by microbial sulfate reduction. The successful application of hydrogen isotope geothermometers to low-temperature Lost City hydrothermal samples encourages its employment with low-temperature diffuse hydrothermal fluids.     

Thermal and isotopic profiling of the Pipeline hydrothermal system: Application to exploration for Carlin-type gold deposits

New exploration techniques are vital to the search for new orebodies in mature terranes, as well as for extensions of existing orebodies. This research focused on application of low-temperature dating techniques (primarily apatite fission-tracks) and stable isotope measurements (carbon and oxygen in carbonate rocks) in and around the Pipeline deposit, a Carlin-type gold system. The primary purpose of the project was to assess whether these techniques could provide exploration vectors that might be used in conjunction with other geologic, geochemical, and geophysical techniques to determine the locus of fossil hydrothermal fluid flow, and the attendant possibility of finding economic mineral deposits.At Pipeline, measurements of apatite fission-tracks and (U − Th) / He geochronometry yield a clear indication of the elevated temperatures associated with the fossil hydrothermal system. The pattern is one of a central target (Pipeline deposit) with decreasing thermal effects as far as several kilometers laterally from the known ore zone. Because of the irregular nature of fluid flow through fractures, a significant number of samples are required to discern this pattern, but the pattern is quite clear from the 32 samples in and around the Pipeline pit.Stable isotope measurements of carbonate rocks yield patterns centered on the Pipeline pit area. Oxygen isotopes in particular are shifted toward lower values as the result of interaction between the hydrothermal fluids and carbonate rocks. Carbon isotopes show a pattern, but it is somewhat more difficult to interpret than the oxygen isotope pattern. As with the geochronometric patterns, isotopic indications of fluid flow are present several kilometers from the ore zone at Pipeline. Also as with the geochronometric data, a relatively large sample set is required to see the pattern. At Pipeline, the patterns are evident in approximately 45 surface samples and very clearly in the cross-sections containing approximately 100 samples.From these data, it is clear that thermal and stable isotopic measurements on rocks at a significant distance from the known Pipeline hydrothermal system record the passage of hot fluids through the rock. Both techniques provide a footprint of the Pipeline system that is several diameters larger than the ore zone (as presently known). Therefore, thermochronologic and stable isotopic measurements can be utilized in conjunction with other techniques as part of an overall exploration strategy for Carlin-type deposits. Although these techniques do not provide a direct indication of the metal content of the fossil hydrothermal fluids, they do provide an indication of the robustness of fluid flow and the potential size of a hydrothermal system.