The application of isotopic and biogeochemical markers to the study of the biochemistry of organic matter in a macrotidal estuary, the Loire, France

The biogeochemistry of organic matter in a macrotidal estuary, the Loire, France, has been studied for two years during different seasons. Both particulate matter and sediment have been sampled in the riverine zone, in the maximum turbidity zone and in the ocean near the river mouth. Two techniques have been used: carbon isotopic ratio determination and analysis of lipid-marker signatures in the n-alkane, n-alkene and fatty acid series. For the period corresponding to the output of the maximum turbidity zone in the ocean, the complete change of organic matter, continental in nature in the inner estuary, pure marine in the outer estuary is well illustrated by the decrease of δ¹³C values and of carbon preference index of n-alkanes. Input sources of organic matter by continental plants, plankton and micro-organisms are discussed from biogeochemical-marker analyses data along with the processes of accumulation of particles and their evolution with the season. Some criteria for evidencing the nature of various organic-matter pools are assessed and compared in different chemical-marker series as follows: high molecular weight n-alkanes and fatty acids, perylene for continental imprints, polyunsaturated 18-, 20- and 22-carbon fatty acids, n-C₁₇, n-alkenes and squalene for algae imprints, branched iso and anteiso fatty acids, Δ11-C_18:1 for microbial imprints.     

东太平洋下中新统氧同位素地层与古海洋学意义

研究取自于东太平洋CC48柱状样的钙质超微化石和底栖有孔虫的氧同位素成分变化的结果表明,该区下中新统至少可分出九个氧同位素地层(期),反映该区在早中新世期间至少经历了4次气温上升和5次下降的古气候变化。南极大陆冰川应是形成于早中新世而不是前人认为的中中新世。在早中新世,南极冰体体积有较大的变化。受古气候变化的影响,在早中新世期间东太平洋水柱热结构或温度梯度有比较大的变化,海平面出现多次上升与下降。     

Factors influencing the oxidation,reduction, methylation and demethylation of mercury species in coastal waters

The objective of this study was to examine the redox reactions and other transformations of mercury (Hg) species in surface waters, and the factors determining the rates of these reactions. For the redox studies completed at the Chesapeake Biological Laboratory (CBL), two isotopes (¹⁹⁹Hg^II and ²⁰²Hg⁰) were added into different types of filtered water (fresh to seawater) to examine the oxidation and reduction reactions. Further studies of both the redox reactions and methylation/demethylation reactions of Hg were conducted with unfiltered water on board research vessels during cruises in May and July 2005 on the Chesapeake Bay and shelf. While CH₃¹⁹⁹Hg^II was added to allow the examination of demethylation, ²⁰¹Hg^II was used to examine both reduction and methylation, and ²⁰²Hg⁰ was used to examine oxidation. Overall, the results showed that both Hg oxidation and reduction were simultaneously occurring and were photochemically mediated in the waters investigated. In contrast to the previously assumed “unreactive” nature of Hg⁰, the studies found that the magnitude of the rate constant for Hg⁰ oxidation was greater than that for reduction, indicating its importance in estuarine and coastal waters. In addition, both experiments at CBL and on board ship showed that Hg^II reduction was similar in magnitude, suggesting that biotic processes were relatively unimportant. While no measurable methylation occurred during the incubation period during the on board studies, concentration of CH₃¹⁹⁹Hg^II decreased over the time during the experiments. It appeared that the demethylation processes were not dominantly photochemically driven, but could be microbially mediated. Further studies are needed in order to help better understand Hg redox and transformations in natural water systems.     

A Stable Carbon Isotope Study of the Food-web in a Freshwater-deprived South African Estuary, with Particular Emphasis on the Ichthyofauna

The importance of macrophytes as food sources for estuarine nekton is unclear. Previous carbon isotope investigations in the macrophyte-dominated, freshwater-deprived Kariega Estuary showed that the bivalveSolen cylindraceusdid not utilize the dominant estuarine macrophytes found within the estuary as a primary food source. This finding prompted questions as to what the nekton of this estuary utilize as primary energy sources. δ¹³C analyses of the principal autochthonous and allochthonous primary carbon sources, as well as the dominant invertebrate and fish species, indicate that there are two main carbon pathways within the Kariega Estuary. The littoral community, which incorporates the majority of crustaceans, gobies, mullet and a sparid, utilizes δ¹³C enriched primary food sources namelySpartina maritima,Zosteracapensis and epiphytes. The channel fauna, which includes the zooplankton, zooplanktivorous and piscivorous fish, utilizes a primary food source depleted in δ¹³C, which is most likely a mixture of phytoplankton, terrestrial plant debris and C₄macrophyte detritus. The C₃saltmarsh macrophytesSarcocornia perennisandChenolea diffusa, as well as benthic microalgae, appear to be less important as primary food sources to the nekton of the Kariega Estuary.     

太平洋三海区热液烟囱物的氧同位素特征及形成温度

使用氧同位素方法 ,测试了西太平洋马里亚纳岛弧、马里亚纳海槽、冲绳海槽和东太平洋加拉帕戈斯裂谷的海底热液烟囱和硫化物全岩样品。结果表明 :马里亚纳岛弧上的埃斯梅拉尔达破火山口的热液硫化物的形成温度最高 (达 2 75℃ ) ,而成为高温产物的代表 ;冲绳海槽和加拉帕戈斯裂谷烟囱 ,表现为中高温类型 ,其氧同位素温度在 1 5 0℃左右 ;马里亚纳海槽以蛋白石为主要矿物的烟囱物 ,则显示出典型的低温热液类型 ,少量黄铁矿砂试样则表现出中温类型特征。但上述区域大都不同程度地存在有闪锌矿、黄铁矿、黄铜矿等中高温热液矿物 ,说明研究区除马里亚纳海槽明显有中低温热液活动类型外 ,其它区域皆具备中高温热液活动特征     

Environmental tracers as indicators of karst conduits in groundwater in South Dakota,USA

Environmental tracers sampled from the carbonate Madison aquifer on the eastern flank of the Black Hills, South Dakota, USA indicated the approximate locations of four major karst conduits. Contamination issues are a major concern because these conduits are characterized by direct connections to sinking streams, high groundwater velocities, and proximity to public water supplies. Objectives of the study were to estimate approximate conduit locations and assess possible anthropogenic influences associated with conduits. Anomalies of young groundwater based on chlorofluorocarbons (CFCs), tritium, and electrical conductivity (EC) indicated fast moving, focused flow and thus the likely presence of conduits. δ¹⁸O was useful for determining sources of recharge for each conduit, and nitrate was a useful tracer for assessing flow paths for anthropogenic influences. Two of the four conduits terminate at or near a large spring complex. CFC apparent ages ranged from 15 years near conduits to >50 years in other areas. Nitrate-N concentrations >0.4 mg/L in groundwater were associated with each of the four conduits compared with concentrations ranging from <0.1 to 0.4 mg/L in other areas. These higher nitrate-N concentrations probably do not result from sinking streams but rather from other areas of infiltration.     

Application of environmental groundwater tracers at the Sulphur Bank Mercury Mine, California, USA

Boron, chloride, sulfate, δD, δ¹⁸O, and ³H concentrations in surface water and groundwater samples from the Sulphur Bank Mercury Mine (SBMM), California, USA were used to examine geochemical processes and provide constraints on evaporation and groundwater flow. SBMM is an abandoned sulfur and mercury mine with an underlying hydrothermal system, adjacent to Clear Lake, California. Results for non-³H tracers (i.e., boron, chloride, sulfate, δD, and δ¹⁸O) identify contributions from six water types at SBMM. Processes including evaporation, mixing, hydrothermal water input and possible isotopic exchange with hydrothermal gases are also discerned. Tritium data indicate that hydrothermal waters and other deep groundwaters are likely pre-bomb (before ~1952) in age while most other waters were recharged after ~1990. A boron-based steady-state reservoir model of the Herman Impoundment pit lake indicates that 71–79% of its input is from meteoric water with the remainder from hydrothermal contributions. Results for groundwater samples from six shallow wells over a 6–month period for δD and δ¹⁸O suggests that water from Herman Impoundment is diluted another 3% to more than 40% by infiltrating meteoric water, as it leaves the site. Results for this investigation show that environmental tracers are an effective tool to understand the SBMM hydrogeologic regime.

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Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users.

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Résumé Les concentrations en bore, chlorure, sulfate, δD, δ¹⁸O, et ³H d’échantillons d’eaux de surface et souterraine prélevés dans le banc de soufre de la mine de mercure (SBMM en anglais) en Californie, USA, ont été utilisées pour étudier les processus géochimiques et pour fournir des contraintes à l’évaporation et à l’écoulement des eaux souterraines. La SBMM est une mine de soufre et de mercure abandonnée, adjacente au lac Clear en Californie et sous laquelle se trouve un système hydrothermal.Les résultats des traceurs autres que le tritium (bore, chlorure, sulfate, δD, et δ¹⁸O) ont permis d’identifier des contributions de six types d’eaux à SBMM. Des processus tels que l’évaporation, le mélange, l’entrée d’eau hydrothermale et de possibles échanges isotopiques avec des gaz hydrothermaux ont également été identifiés. Les données de tritium montrent que les eaux hydrothermales et d’autres eaux profondes sont probablement d’age antérieure à la bombe (avant ~1952), alors que la plupart des autres eaux sont issues de la recharge après ~1990. Un modèle de réservoir représentant le lac situé dans la partie Herman Impoundment de l’ancienne mine, en régime permanent et basé sur le bore, montre que 71–79% de l’eau provient des précipitations, le reste provenant de contributions hydrothermales. Les résultats de δD et δ¹⁸O pour des échantillons d’eau souterraine de six puits peu profonds sur une période de 6 mois suggèrent que l’eau de Hermann Impoundment est encore diluée entre 3% jusqu’à plus de 40% lorsqu’elle quitte le site du fait de l’infiltration d’eau météorique. Les résultats de cette étude montrent que les traceurs environnementaux constituent un outil efficace pour comprendre le régime hydrogéologique de la SBMM.

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Resumen Se han utilizado datos de concentraciones de boro, cloruros, sulfatos, δD, δ¹⁸O, y ³H en muestras de aguas superficiales y subterráneas procedentes de la Mina de Mercurio Sulphur Bank (SBMM), California, USA, para estudiar los procesos geoquímicos y caracterizar la evaporación y el flujo del agua subterránea. SBMM es una mina abandonada de azufre y mercurio con un sistema hidrotermal subyacente, cercano al Lago Clear, California.Los resultados de los trazadores que no son ³H (por ejemplo, boro, cloruros, sulfatos δD, y δ¹⁸O) identifican las contribuciones de seis tipos de agua en la SBMM. Se han identificado diversos procesos, como evaporación, mezcla, entrada de agua hidrotermal y la posibilidad de intercambios isotópicos con gases hidrotermales. Los datos de tritio indican que las aguas hidrotermales y otras aguas subterráneas profundas son probablemente pre-bombas (previas a ~1952) en edad mientras que la mayoría de las otras aguas se han recargado después de ~1990. Un modelo estacionario basado en el boro de la fosa del lago Herman Impoundment indica que el 71–79% de su entrada procede de agua meteórica con restos de contribución hidrotermal. Los resultados para las muestras de aguas subterráneas procedentes de seis pozos superficiales en un periodo de 6 meses para δD y δ¹⁸O sugieren que el agua procedente de Herman Impoundment se diluye en otro 3% hasta más del 40% debido a la infiltración de agua meteórica., que sale del sitio. Los resultados de esta investigación muestran que los trazadores ambientales son una herramienta efectiva para entender el régimen hidrogeológico de la SBMM.

     

Hydrogeochemistry and isotope analyses used to determine groundwater recharge and flow in low-gradient catchments of the province of Buenos Aires,Argentina

The region known as Pampa Plain, in Argentina, is a vast area characterized by slopes of less than 0.05%. The surface sediment is silty sand, mainly Aeolian, referred to as Pampean Loess, which is a phreatic aquifer unit of utmost importance for the water supply of the region. On account of the slight gradient, hydrogeological analyses using only hydraulic measurements are difficult to perform, often leading to confusing results. Thus, the study presented relies on hydrochemical modeling and isotopic determinations as well. The study area comprises three catchments in the inter-mountainous area corresponding to El Moro, Tamangueyú and Seco creeks, and covering 2,570 km² in the province of Buenos Aires. Measurements of piezometric levels and samples of groundwater, surface water and rainwater were carried out between January and March 2005. Major ion results were analyzed by means of hydrochemical graphs and hydrogeochemical modelling using NETPATH. The resulting data show that it is possible to identify local changes in recharge, flow direction and stream/groundwater relationship by using hydrochemical and isotopic information, which may become a useful and more precise tool for the study of particularly flat landscapes.     

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.

     

Stable isotope study of carbonate-cemented rocks from the Pobitite Kamani area,north-eastern Bulgaria

The Precipitation of carbonate cements in the Pobitite Kamani area (Lower Eocene) began during early diagenesis of sediments. There is evidence, however, that calcite is still forming today.The negative ¹³C values to –29.2 suggest that the carbonate formed during degradation of ¹²C-enriched organic matter (perhaps partly from oxidation of methane). The ¹⁸O values of –0.9 to –1.6 reflect the marine origin of the early diagenetic carbonate cements. Most of the carbonates, however, formed during late diagenesis (at approximately 1300 m burial depth) and/or recently (after uplift) from percolating groundwaters. These carbonates have an isotopic composition characteristic of carbonates which precipitated from meteoric waters under normal sedimentary temperatures in isotopic equilibrium with ¹²C-enriched soil carbon dioxide.