Geochemical and isotopic constraints on the interaction between saline lakes and groundwater in southeast Australia

Major ion and stable isotope geochemistry allow groundwater/surface-water interaction associated with saline to hypersaline lakes from the Willaura region of Australia to be understood. Ephemeral lakes lie above the water table and locally contain saline water (total dissolved solids, TDS, contents up to 119,000 mg/L). Saline lakes that lack halite crusts and which have Cl/Br ratios similar to local surface water and groundwater are throughflow lakes with high relative rates of groundwater outflows. Permanent hypersaline lakes contain brines with TDS contents of up to 280,000 mg/L and low Cl/Br ratios due to the formation of halite in evaporite crusts. These lakes are throughflow lakes with relatively low throughflow rates relative to evaporation or terminal discharge lakes. Variations in stable isotope and major ion geochemistry show that the hypersaline lakes undergo seasonal cycles of mineral dissolution and precipitation driven by the influx of surface water and evaporation. Despite the generation of highly saline brines in these lakes, leakage from the adjacent ephemeral lakes or saline throughflow lakes that lack evaporite crusts is mainly responsible for the high salinity of shallow groundwater in this region.     

Interaction between zinc and freshwater and marine diatom species: Surface complexation and Zn isotope fractionation

This work is devoted to characterization of zinc interaction in aqueous solution with two marine planktonic (Thalassiosira weissflogii = TW, Skeletonema costatum = SC) and two freshwater periphytic species (Achnanthidium minutissimum = AMIN, Navicula minima = NMIN) by combining adsorption and electrophoretic measurements with surface complexation modeling and by assessing Zn isotopes fractionation during both long term uptake and short term adsorption on diatom cells and their frustules. Reversible adsorption experiments were performed at 25 and 5 °C as a function of exposure time (5 min to 140 h), pH (2 to 10), zinc concentration in solution (10 nM to 1 mM), ionic strength (I = 0.001 to 1.0 M) and the presence of light. While the shape of pH-dependent adsorption edge is almost the same for all four species, the constant-pH adsorption isotherm and maximal Zn binding capacities differ by an order of magnitude. The extent of adsorption increases with temperature from 5 to 25 °C and does not depend on light intensity. Zinc adsorption decreases with increase of ionic strength suggesting competition with sodium for surface sites. Cell number-normalized concentrations of sorbed zinc on whole cells and their silica frustules demonstrated only weak contribution of the latter (10-20%) to overall zinc binding by diatom cell wall. Measurements of electrophoretic mobilities (μ) revealed negative diatoms surface potential in the full range of zinc concentrations investigated (0.15-760 μmol/L), however, the absolute value of μ decreases at [Zn] > 15 μmol/L suggesting a change in surface speciation. These observations allowed us to construct a surface complexation model for Zn binding by diatom surfaces that postulates the constant capacitance of the electric double layer and considers Zn complexation with carboxylate and silanol groups. Thermodynamic and structural parameters of this model are based on previous acid-base titration and spectroscopic results and allow quantitative reproduction of all adsorption experiments. Although Zn adsorption constants on carboxylate groups are almost the same, Zn surface adsorption capacities are very different among diatom species which is related to the systematic differences in their cell wall composition and thickness. Measurements of Zn isotopic composition (⁶⁶Zn/(⁶⁴Zn)) performed using a multicollector ICP MS demonstrated that irreversible incorporation of Zn in cultured diatom cells produces enrichment in heavy isotope compared to growth media (Δ⁶⁶Zn(solid-solution) = 0.27 ± 0.05, 0.08 ± 0.05, 0.21 ± 0.05, and 0.19 ± 0.05‰ for TW, SC, NMIN, and AMIN species, respectively). Accordingly, an enrichment of cells in heavy isotopes (Δ⁶⁶Zn(solid-solution) = 0.43 ± 0.1 and 0.27 ± 0.1‰ for NMIN and AMIN, respectively) is observed following short-term Zn sorption on freshwater cells in nutrient media at pH ∼ 7.8. Finally, diatoms frustules are enriched in heavy isotopes compared to solution during Zn adsorption on silica shells at pH ∼ 5.5 (Δ⁶⁶Zn(solid-solution) = 0.35 ± 0.10‰). Measured isotopes fractionation can be related to the structure and stability of Zn complexes formed and they provide a firm basis for using Zn isotopes for biogeochemical tracing.     

沙茨基海隆(ShatskyRise)白垩纪玄武岩的地球化学特征及其地幔柱-洋中脊相互作用过程

沙茨基海隆(Shatsky Rise)是白垩纪早期形成的西北太平洋大火成岩省, 其成因和演化过程目前仍存在较大争议。本次研究对沙茨基海隆白垩纪玄武岩进行了全岩主量、微量元素、Sr-Nd-Pb同位素的分析。沙茨基海隆玄武岩主要属于拉斑玄武岩, 具有较亏损的大离子亲石元素和轻稀土元素以及较富集的重稀土元素的特征, 没有明显的Eu异常(δEu=0.99~1.29), 与正常洋中脊玄武岩(N-MORB)的微量元素配分模式较为相似。然而该系列玄武岩却具有相对较富集的初始⁸⁷Sr/⁸⁶Sr(0.702986~0.703991)和¹⁴³Nd/¹⁴⁴Nd(0.513034~0.513194)同位素比值、较富集的²⁰⁷Pb/²⁰⁴Pb(15.439~15.508)和²⁰⁸Pb/²⁰⁴Pb(37.853~38.488)同位素比值, 与富集的洋岛玄武岩(OIB)和岛弧火山岩的同位素成分较为相似, 且源区混入高U/Pb比值(HIMU型)的富集地幔成分。稀土元素部分熔融模拟反演表明沙茨基海隆火山岩的原始岩浆可能起源于尖晶石相二辉橄榄岩源区, 且具有较高程度的部分熔融作用(>10%)。在以上研究基础上, 本文提出地幔柱-洋中脊相互作用模型来解释沙茨基海隆拉斑玄武岩较亏损的不相容元素成分和较富集的同位素成分这一特殊地球化学特征。由于来自扩张洋中脊的强大拉张应力的影响, 地幔柱岩浆物质将流向洋中脊并发生减压部分熔融, 导致不相容元素的高度亏损, 但由于放射成因元素(Sm、Rb和U)的半衰期相对较长, 同位素成分则难以在较短时间内被改变, 因此本文推测沙茨基海隆同位素富集的N-MORB拉斑玄武岩可能是地幔柱-洋中脊相互作用的产物。

     

海相沉积氧化还原环境的地球化学识别指标

全球海洋在10-5.4亿年间演变成氧化环境,此后历经多次全球性的缺氧事件后演变到现在的氧化环境.海水和沉积物中多种无素的循环、分异和富集明显受氧化还原条件的影响.Mn、Mo、Cr、V和U等变价元素的溶解度随氧化还原条件的改变产生极大变化,导致沉积物中的元素含量分异:Ni、Co、Cu和Zn等在还原条件下形成硫化物沉淀,导致沉积物中对应元素的富集.这些元素的地球化学行为是古海洋氧化还原条件的灵敏指示剂,作为恢复古海洋氧化还原条件环境变化的地球化学指标.黄铁矿化程度(DOP)、生物樗化合物和Ce异常等也是沉积物氧化还原条件的常用判别指标.泥岩石研究中通常采用DOP、U/Th、自生U、V/Cr、Ni/Co和生物标志化合物等指标,碳酸盐岩则主要采用Ce异常指标.当前各种指标的定性分析都取得比较一致的结果,但是用一种或几种定量的地球化学指标来恢复整个古海洋的氧化还原环境目前还有很大的问题.     

Several unexpected marine sterols in a freshwater sediment

Some unexpected stanols, 22,23-methylene-23,24-dimethyl-5α(H)-cholestan-3β-ol (gorgostanol and the related stenol), 24,26-dimethyl-5α(H)-cholestan-3β-ol (aplystanol) and most probably 24-isopropyl-5α(H)-cholest-22-en-3β-ol, have been found in the sediment of a eutrophic pond. These compounds possess side chains which have until now been considered to belong exclusively to sterols of marine origin. The presence of these stanols in a freshwater sediment suggests that considering their side chain structures as specific marine input markers can lead to erroneous conclusions. The vertical distribution of these compounds along a 6 m core shows that they arise from organisms which still exist except for aplystanol which was found only in the sections below 5 m.     

Geochemical processes and solute transport at the seawater/freshwater interface of a sandy aquifer

Geochemical processes occurring at a seawater/freshwater interface were studied in a shallow coastal siliclastic aquifer containing minor amounts of calcite. Data were collected from 106 piezometers in a 120-m transect from the coastline and landward. In the first 40 m from the coastline, a wedge of saltwater is intruding below the freshwater aquifer. The aquifer is strongly reduced with mineralization of organic matter by methanogenesis in the freshwater aquifer, and sulfate reduction dominating in the most seaward part of the saline aquifer. The spatial separation of cations in the aquifer indicated a slow freshening process where Ca²⁺ from freshwater displaced the marine cations Na⁺ and Mg²⁺ from the exchanger complex. The resulting loss of Ca²⁺ from solution decreases the saturation state for calcite and possibly causes calcite dissolution. A storm-flooding event was recorded where pulses of dense seawater sank through the fresh aquifer. As a result, the terminal electron accepting process switched from methanogenesis to sulfate reduction. The pulses of sinking seawater also triggered cation exchange reactions where Ca²⁺ was expelled from the exchanger by seawater Na⁺ and Mg²⁺. The released Ca²⁺ is being flushed from the aquifer by groundwater flow, and this export of Ca²⁺ will, in the long term, cause decalcification of the sediment. The water composition in the aquifer is in a transient state as the result of various processes that operate on different timescales. Oxidation of organic matter occurs continuously but at a rate decreasing on a geological time scale. The freshening of the aquifer operates on the timescale of a few years. The episodic flooding and sinking of seawater through the aquifer proceeds in the course of days to weeks, but occurs irregularly with years in between.     

Resistant biomacromolecules in marine microalgae of the classes Eustigmatophyceae and Chlorophyceae: Geochemical implications

Non-hydrolysable macromolecular constituents (i.e. algaenans) were isolated from two out of seven marine microalgae investigated. Nannochloropsis salina and Nannochloropsis sp. from the class of Eustigmatophyceae produce highly aliphatic algaenans. Flash pyrolysis and chemical degradations with HI and RuO₄ allowed for the identification of their chemical structure, which is mainly composed of polyether-linked long-chain (up to C₃₆) n-alkyl units. The building blocks of this polymer were also recognized in lipid fractions. The green microalgae (Chlorophyceae) Chlorella spaerckii, Chlorococcum sp. and Nannochloris sp. were earlier thought to biosynthesize algaenans comprising aliphatic and/or aromatic moieties. However, a new isolation method utilizing trifluoroacetic acid (TFA) prior to the other hydrolyses revealed that the macromolecular material isolated from these three chlorophytes was either hydrolysable with TFA or artefacts from the former method. Similar to algaenans from fresh water green microalgae, the aliphatic eustigmatophyte algaenans are likely to be selectively preserved in depositional environments and might ultimately serve as source rock organic matter of marine crude oils. Furthermore, they may play an important role in the cycling of carbon.     

Stratiform copper deposits and interactions with co-existing atmospheres, hydrospheres, biospheres and lithospheres

Fundamental evidence from world-class stratiform copper deposits repeatedly indicates that they originated by a two-stage mineralization process: a syn-diagenetic enrichment of the host sediment in iron sulfide, followed by a sub-surface addition of copper during early diagenesis of the sediment. In contrast to the previously favored syngenetic hypothesis, which suggested an open equilibration between atmosphere, hydrosphere, biosphere and upper lithosphere during mineralization, the two-stage model implies that only the initial deposition of iron sulfides should take place with open exchanges between the upper “spheres”. The sub-surface emplacement of copper should occur in relative isolation from surface environments and, therefore, the occurrence and distribution of stratiform copper deposits through time and space should not be used to make direct interpretations of contemporaneous conditions in the upper “spheres”.     

克拉玛依侏罗纪玄武岩地球化学特征及其壳幔作用过程研究

新疆北部中新生代岩石圈深部过程一直备受关注但研究较少。在详细的野外地质和室内岩相学的研究基础上,对西准噶尔克拉玛依侏罗纪玄武岩开展了全岩主元素、微量元素和Sr-Nd同位素以及锆石U-Pb年代学和Hf同位素分析。这些玄武岩与下伏下石炭统太勒古拉组地层呈角度不整合接触关系,具有明显柱状节理、块状构造、斑状结构,斑晶主要由富Ca斜长石、普通辉石和橄榄石组成,部分含有菱铁矿,基质为间粒间隐结构。玄武岩属于碱性玄武岩系列(σ=3.87~4.68),强烈富集大离子亲石元素(如Rb、Ba、K等)和轻稀土元素,没有Eu的负异常(δEu=1.02~1.06),具有相对较低的正εNd(t)值(+2.95~+3.02)和较高的(87Sr/86Sr)i值(0.7048~0.7049),暗示其具有与OIB型源区相似但较为亏损的源区特征。这些玄武岩可能来源于80 km以下深处的石榴石二辉橄榄岩的低程度部分熔融作用。玄武岩中获得锆石的U-Pb谐和年龄为(357.3±5.1)Ma,这一年龄与围岩太勒古拉组的时代相当,指示这些锆石主要来自早期岩浆作用。与晚古生代岛弧及后碰撞基性火山岩不同,侏罗纪玄武岩形成于相对稳定的板内构造环境,其地幔源区亏损程度不及晚古生代火山岩源区。这样的源区可能与俯冲下沉洋壳和拆层岩石圈发生变质重熔形成富集熔体并不断交代亏损地幔有关。     

Geochemical fingerprint of the primary magma composition in the marine tephras originated from the Baegdusan and Ulleung volcanoes

The intraplate Baegdusan (Changbai) and Ulleung volcanoes located on the border of China, North Korea, and East/Japan Sea, respectively, have been explained by appeals to both hotspots and asthenospheric mantle upwelling (wet plume) caused by the stagnant Pacific plate. To understand the origin of the Baegdusan and Ulleung volcanism, we performed geochemical analyses on the tephra deposits in the East/Japan Sea basins originating from the Baegdusan and Ulleung volcanoes. The volcanic glass in the tephra from the Baegdusan and Ulleung volcanoes ranged from alkaline trachyte to peralkaline rhyolite and from phonolite to trachyte, respectively. The tephra from the two intraplate volcanoes showed highly enriched incompatible elements, such as Tb, Nb, Hf, and Ta, distinct from those of the ordinary arc volcanoes of the Japanese islands. The straddle distribution of the Th/Yb and Ta/Yb ratios of the tephra deposits from the Baegdusan volcano may originate from the alkali basaltic magma resulting from mixing between the wet plume from the stagnant Pacific plate in the transition zone and the overlying shallow asthenospheric mantle. In contrast, the deposits from the Ulleung volcano show a minor contribution of the stagnant slab to the basaltic magma, implying either partial melting of a more enriched mantle, smaller degrees of partial melting of a garnet-bearing mantle source, or a combination of both processes as the magma genesis. Our study indicated that the Baegdusan and Ulleung volcanoes have different magma sources and evolutionary histories.     

俯冲型和碰撞型含矿斑岩地球化学组成的差异

Cu-Mo-Au含矿斑岩不仅可以形成于与洋壳俯冲相联系的弧环境,而且也产于碰撞造山带内。通过对比俯冲型和碰撞型含矿斑岩的地球化学特征,发现它们特别在微量元素上具有较大差别,暗示它们有着不同的物源区组成或形成机制。同冈底斯带碰撞型含矿斑岩相比,太平洋东岸俯冲型含矿斑岩有着明显高的HREE和Y含量,低的Sr/Y、(La/Yb)_N以及(Dy/Yb)_N比值,表明其物质源区不含或含有少量的石榴子石并可能以角闪石组成为主。统计发现这些俯冲型含矿斑岩部分样品具有埃达克岩地球化学特征,但大部分样品却显示出具有与正常岛弧系列火山岩相似的特征,它们很可能是板片释放流体交代地幔楔形成的熔体并在后期经历MASH过程的产物。冈底斯带碰撞型含矿斑岩具有典型埃达克岩地球化学特征,指示其形成条件达到了石榴子石相变,可能形成于增厚的下地壳,其物质源区很可能与前期的洋壳俯冲有着密切的联系。普朗-雪鸡坪含矿斑岩具有与俯冲型含矿斑岩十分相似的地球化学特征,它们有可能是西向俯冲的甘孜-理塘洋发生断离,进而诱发前期俯冲流体交代的富集地幔楔发生部分熔融的产物,而并非是俯冲洋壳直接发生部分熔融的产物。     

The transition of a freshwater karst aquifer to an anoxic marine system

Jewfish Sink is located in the shallow seagrass flats of the Gulf of Mexico in west central Florida. Jewfish Sink was a submarine spring until the drought of 1961–1962 when it ceased flowing. Today, the sink is an anaerobic marine basin and provides the opportunity to study the implications of saltwater intrusion in coastal karstic areas. The biogeochemistry of Jewfish Sink was studied from summer 2001 through spring 2004. A distinct feature of the sink is the uniform cold temperature (16–17°C) of the deeper anoxic water that does not match groundwater found nearshore or onshore (22–24°C). There are four zones within the sink: oxic zone, transition zone, upper anoxic zone, and anoxic bottom water. The anoxic bottom water does not mix with water from above but may be linked to deep Gulf shelf water through ancient aquifer conduits. The other three zones vary seasonally in oxygen, salinity, and temperature because of limited mixing in the winter due to cooding and sinking of surface water. The walls of the anoxic zones have characteristic microbial mats that are found in other sulfidic karstic features in the area. Bacterial activity appears to be carbon, limited in the anoxic zones where sulfate reduction appears to be the major metabolic process. The reduction of sulfate to sulfide appears to be driven by irregular influexes of organic matter including macroalgae, horseshoe crabs, and stingrays that become entrapped within the sink. Bacterial activity in the oxic zones appears to be phosphate limited. Although the system is partially isolated from the overlying marine ecosystem, organic input from above drives the bacterial anaerobic ecosystem, resulting in a sulfide pump. In this model, sulfide percolates up through the karst and removes oxygen from the overlying sediment, which has likely caused changes in the shallow benthic ecosystem. Jewfish Sink appears to be part of an extensive anoxic subterranean estuary that extends under parts of at least three coastal counties in Florida and serve as a model for the effects of rising sea levels or aquifer mining.     

Geochemical behavior of Pt and Pd in coastal marine sediments,southeastern margin of the Japan Sea

Eighty-one argillaceous marine sediments collected from the southeastern coastal margin of the Japan Sea were analyzed for Pt and Pd by atomic absorption spectrometry using a graphite furnace atomizer after solvent extraction separation. The average Pt (1.2 ± 0.5 ppb) and Pd(1.6 ± 0.9 ppb) contents are generally similar to those of the published crustal abundances. The Pt or Pd is generally enriched in the fine sediment fraction, and positively correlated with Cu, Pb and water depth. The inverse correlation between the Pt or Pd content and redox potential of the sediment suggests that significant amounts of Pt and Pd are supplied in their dissolved forms, and reduced to their metallic states. It is concluded that the Pt and Pd distributions in the coastal marine sediments are controlled by the geological characteristics of the studied area, grain size and redox potential of sediments, water depths, and dissolved O₂ concentration of sea water.     

Nutrient exchange between subtropical lagoons and the marine environment

The tidal exchange of ammonia-nitrogen, nitrate-nitrogen, total nitrogen, total phosphorus, and total organic carbon between coastal lagoons and the marine environment were determined. Constituent measurements were made in Huizache-Caimanero Lagoon in Northwest Mexico over 24-h sampling periods during both dry and wet seasons. The exchange of these nutrients was also compared to exchanges in estuarine marshes of other latitudes. High exchange rates were found to be associated to extreme climatic events.     

柑桔品质与地球化学背景关系的初步研究

通过不同品质柑桔土壤的母质母岩及地球化学条件对比，发现优质者产于矿物和化学成分复杂的母质母岩区，其Ｍｎ、Ｍｏ、Ｚｎ、Ｃａ等的含量及Ｃａ／Ｋ、Ｍｏ／Ｎ等比值与柑桔品质呈复杂的相关关系。     

塔里木盆地海相油藏具有高热稳定性的地球化学条件探讨

塔里木盆地在埋深超过8000 m、油藏经历200℃以上高温改造仍然发现液态烃类流体稳定存在,目前勘探工作正在面向深层-超深层拓展,塔里木盆地海相原油具有的高热稳定性来自其较好的保存条件。本文总结了近年来塔里木盆地海相油藏研究进展,结合宏观地质背景演化,主要从微观过程入手探讨塔里木盆地海相油藏热稳定性的地球化学特征。认为宏观上塔里木盆地目前的低地温梯度有利于油藏的稳定保存;而油藏储层中普遍缺乏氧化性矿物,石膏类等含硫矿物也贫乏,使得油藏储层中的烃-水-岩相互作用(包括热化学硫酸盐还原反应)发生的程度有限;同时,塔里木盆地海相油藏中地层水广泛发育、分布复杂,这对油藏中的液态烃类,特别是大分子烃类的热裂解具有抑制作用,从而有利于油藏的稳定保存。有必要进一步开展针对塔里木盆地海相原油热稳定性的微观地球化学特征探讨,特别是烃-水-岩相互作用中有利于原油烃类流体稳定保存的物理化学机理分析,研究成果将有助于深化塔里木盆地深层-超深层油气藏的勘探研究工作。     

地球化学填图与地球化学勘查

在中国与西方国家，地球化学填图的目的与做法并不相同，西方的地球化学填图是由研究机构开展的，使用等离子焰光量计、X射线荧光光谱仪等大型仪器进行多元素分析，目的是取得多种元素在地球表层分布的基础性资料。地球化学勘查则由矿业公司主要分析少量成矿元素，目的是为了找矿。而中国的地球化学填图计划却做出了巨大努力，使地球化学填图取得的资料既有学术价值又对矿产勘查具有重大的实用意义。本文详细讨论了西方国家与中国地球化学填图与地球化学勘查的思路、方法与技术的演变，并瞻望了地球化学填图在21世纪的巨大发展前景。     

Microbial mercury transformations in marine,estuarine and freshwater sediment downstream of the Idrija Mercury Mine,Slovenia

The Idrija Mine, the second largest Hg mine in the world, ceased operation in 1995, but still delivers large quantities of Hg downstream including into the northern Adriatic Sea, 100 km away. Transformation of Hg species in sediment in sites over 60 km from the mine, including marine sites in the Adriatic Sea, was measured to determine the ability of the system to transform and mobilize Hg and to produce methylmercury (MeHg). Cores from a freshwater impoundment, a brackish estuarine site, and three marine sites in the Gulf of Trieste were sectioned anaerobically, and Hg methylation and MeHg demethylation activities determined using radio-techniques (²⁰³Hg for methylation and ¹⁴C-MeHg for demethylation). Total and dissolved Hg and MeHg were determined as were other geochemical parameters. In addition, rates of SO₄ reduction were determined in marine sediment using a ³⁵S technique. Mercury was readily methylated and demethylated at all sites. Marine sediment was investigated in winter and summer with rates of Hg transformation and SO₄ reduction corresponding only in winter. Methylation of Hg in summer displayed subsurface peaks that may have been influenced by bioturbation. Total Hg and MeHg were most abundant in the freshwater, estuarine, and near-shore marine sites, but dissolved pore water Hg and MeHg were highest in the estuarine region where S cycling appeared ideal for the mobilization of Hg. The impoundment sediment also seemed to be a ‘hotspot’ of Hg transformations. MeHg demethylation occurred via the oxidative demethylation pathway (CO₂ produced from MeHg), except in surficial sediment offshore in the Gulf during winter, where sediment was more oxidizing and significant amounts of CH₄ were liberated during MeHg degradation via reductive demethylation. The CH₄ formation was likely due to an increased influence from the expression of MeHg degradative enzymes encoded by the mer detoxification bacterial genetic system. The freshwater site also liberated CH₄ from MeHg, but it appeared to be due to oxidative demethylation by methanogenic bacteria.