Kinetics of redox cycling of iron coupled with fulvic acid

The kinetics of conversion of iron(III) (hydr)oxides to ferrous iron mediated by fulvic acid have been investigated in order to improve the understanding of the redox cycling of iron at the oxic-anoxic boundary in natural waters. Under the conditions similar to natural waters, fulvic acid is able to reduce the iron(III) (hydr)oxide. The kinetics of the reaction depend on the reactivity of iron(III) (hydr)oxides and the reducing power of the fulvic acid. The rate of reaction is 60 nm/h obtained under following conditions: total concentration of Fe(III) 1.0 × 10^–4 M, pH 7.5, fulvic acid 5 mg/L. The rate is considered as a net result of reduction and oxidation in the > Fe^III-OH/Fe(II) wheel coupled with fulvic acid. In a real natural water system, reductants other than fulvic acid may be of importance. The results obtained in the laboratory, however, provide evidence that the Fe(OH)₃(s)/Fe(II) redox couple is able to act as an electron-transfer mediator for the oxidation of natural organic substances, such as fulvic acid by molecular oxygen either in the absence of microorganisms or as a supplement to microbial activity.     

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.

     

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。     

冀西北长城纪宣龙式铁矿层中微体植物化石的发现及其意义

本文研究的是笔者等在冀西北长城系串岭沟组宣龙式铁矿层中发现的微体植物化石,这些化石都保存在铁质叠层石(肾状赤铁矿)和铁质核形石(鲕状赤铁矿)的基本层中。微化石以丝状体为主,部分为球状体。归属于原核生物蓝藻门颤藻科的两个属和色球藻科的一个属。化石层同位素年龄约在1800—1757Ma。这些化石与北美冈弗林特组微化石比较,既有些相似,又有些区别。该化石的发现为研究铁矿的成因,指示沉积环境及层位对比都很有意义。     

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.     

Visualization experiments of iron precipitates: Application for in-situ arsenic remediation

Laboratory experiments were carried out to acquire more insight and understanding of the phenomena associated with the in-situ arsenic remediation. Visualization techniques are the most informative for the detection of Fe(II) while flowing in soils. Green Rust (GR) was considered as representative of in-situ iron precipitates. In a visualization flat cell, the change in color of GR to orange, due to oxidation, was monitored by a digital camera and the images were analyzed giving the spatial and temporal distribution of Fe(II). Moreover, both oxygen and pH changes in time were recorded in two sections along the flow direction in the cell. The measured and calculated concentration profiles were compared and the actual reaction rates were predicted. The reaction rate constants measured in this study, under flowing conditions, are in a good agreement with the values obtained from batch experiments reported in the literature.     

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.     

Are the South and North Liaohe Groups of North China Craton different exotic terranes? Nd isotope constraints

The Liaohe Group is an important Paleoproterozoic stratigraphic unit in the northeastern part of the North China Craton and is traditionally subdivided into the North and South Liaohe Groups. Associated with both the North and South Liaohe Groups are voluminous Paleoproterozoic granitoid rocks, named the Liaoji granitoids. Different tectonic models, including terrane amalgamation, continent–arc collision and rift closure, have been proposed to interpret the tectonic setting and evolution of the North and South Liaohe Groups and associated Liaoji granitoids. At the centre of the controversy between these models is whether or not the North and South Liaohe Groups developed on the same Archean basement. Nd isotopic geochemistry of the Liaoji granitoids provides important constraints on this controversial issue. The Liaoji granitoids associated with the North and South Liaohe Groups display similar ε_Nd values, restricted to a narrow range from 0 to 2, implying that these granitoid rocks were derived from the same or a similar magma source. Moreover, the Liaoji granitoids associated with the North and South Liaohe Groups have similar Nd model ages (T_DM), ranging from 2.4 to 2.6 Ga, suggesting that the protoliths of the Liaoji granitoids associated with both groups may have formed simultaneously, and that the basement rocks underneath the Liaoji granitoids and associated North and South Liaohe Groups belong to the same continental block rather than two different blocks. Combining lithological, structural and geochronological considerations, we interpret the North and South Liaohe Groups as having developed on a single late Archean basement that underwent Paleoproterozoic rifting associated with the intrusion of the Liaoji granitoids and the formation of the Liaohe Group, and closed upon itself in the Paleoproterozoic.     

Speciation of adsorbed arsenate on the surface of hydrous iron oxide

Adsorption of arsenate on hydrous iron oxide is an important process controlling geochemical cycling of arsenic in environment as well as the fate of arsenic-bearing mining wastes. The widely accepted view on the mechanism of adsorption is that arsenate is adsorbed via bidentate binuclear inner-sphere complexation. In this study, we characterized the arsenate-hydrous iron oxide sorption solids synthesized at pH=3-8 using Fourier transformed infrared spectroscopy （FTIR） and X-ray diffraction （XRD）. It has been determined that poorly crystalline ferric arsenate developed on the surface of iron oxide when arsenate was sorbed at acidic pH, while at alkaline pH the adsorption of arsenate was via bidentate complexation.