Fractionation of elements in sediment samples collected in rivers and harbors at Lake Balaton and its catchment area

A monitoring system has been developed to characterize the water quality of Lake Balaton. Sediment samples were collected in rivers and harbors around the lake and its catchment area. A modified four-step sequential leaching procedure was applied for determination of the distribution of elements. The fractions were: (1) exchangeable/bound to carbonate; (2) bound to Fe/Mn oxide; (3) bound to organic matter/sulfides; and (4) acid-soluble residue. Samples were taken in three seasons and the average concentration of the elements was calculated. Concentrations of elements were mostly well below the Hungarian standards set for soils and geochemical background values. Most of the elements were found in the acid-soluble residue and bound to organic matter/sulfide fractions, characterizing stable compounds in sediments. There was a difference on the elemental composition of sediments collected at rivers in the catchment area and harbors with relatively small boat traffic. Depending upon the nature of element and local pollution sources the concentration of Pb and Cu ions was found higher in sediments taken at harbors than that of small rivers. Generally, it can be stated that elemental concentration of sediments inside of the lake is smaller than at the catchment area, so the pollution from emission sources has not reached the lake yet.     

天津沿海排污河中稀土元素的地球化学特征

选择天津沿海的南、北排污河为对象，研究了城市排污河中稀土元素的某些地球化学特征。结果表明，在排污河水体中溶解态稀土含量仍很低，但与其他天然大河相比，Eu和重稀土溶解态含量明显偏高。原水中稀土元素含量较高，以悬浮态为主。轻稀土的溶解态与悬浮态分布模式随原子序递增有相反的变化趋势。沉积物与悬浮物中的稀土含量明显低于其他天然河流，而悬浮物中的稀土含量又明显低于沉积物。沉积物与悬浮物中的稀土分布模式相似，均为轻稀土富集、重稀土亏损、Eu正异常型。这种分布模式与其他天然河流不同，而与本地区含有机质丰富的土壤相似，表明其外源为附近土壤。排污河稀土元素地球化学特性与天然河流的差异可能主要由于其水体中含有大量有机污染物造成的。     

On-line measurement of intramolecular carbon isotope distribution of acetic acid by continuous-flow isotope ratio mass spectrometry

Molecular and intramolecular carbon isotope measurements of acetic acid present in natural environments have been performed by off-line procedures. The off-line method is complicated and time-consuming and requires micromolar to millimolar amounts of sample. This limits geochemical isotopic studies, especially at the intramolecular level, on acetic acid present in natural samples. Here, we examine an on-line measurement of intramolecular carbon isotope distribution of acetic acid using continuous-flow isotope ratio mass spectrometry (CF-IRMS) coupled with an on-line pyrolysis system. This is achieved by measurement of the respective carbon isotope ratios of CH4 and CO2 produced by on-line pyrolysis of acetic acid. Results for authentic standards of pure acetic acid demonstrated the practicality of this on-line method, although the carbon isotope ratio of the methyl group could not be determined directly. The precision of the carbon isotope measurements was 0.4 per thousand (1sigma). The carbon isotope distribution determined by the on-line method was identical to that determined by the conventional off-line method within analytical error. The advantages of the on-line method compared with the conventional off-line method are that it is less laborious, requires less analytical time (less than one hour per sample) and, most importantly, uses smaller sample sizes (ca. 10 nanomole). An application of this on-line method to natural geochemical samples will provide an insight into the geochemical cycle of acetic acid.     

Isotopic study of natural fission reactors at Oklo and Bangombé, Gabon

The Oklo and Bangombé uranium ores in the Republic of Gabon are fossils of natural fission reactors. Many elements in these natural fission reactors show isotopic anomalies derived from fission and neutron capture reactions. Isotopic analyses of uraninites and some other minerals provide useful information on the geochemical behavior of fission products and nuclear chemical characterization of the reactors. Integrated isotopic measurements by whole rock analysis with inductively coupled plasma mass spectrometry (ICP-MS) and thermal ionization mass spectrometry (TIMS) and by in-situ analysis with secondary ion mass spectrometry (SIMS) make it possible to clarify the migration processes of fissiogenic nuclides over a range of scales from micro meters to meters.     

Interpretation of seasonal variation of metals and abiotic properties in a tropical lake using multivariate analysis and MINTEQA2 program.

The hydrological cycle of Lake Ipê and the principal parameters that could affect its abiotic parameters and its metal (Fe, Mn, and Cd) concentrations were investigated. A detailed study of seasonal variations using Principal Components Analysis (PCA) for the most relevant metals (Fe, Mn and Cd) was performed, assisted by the MINTEQA2 geochemical equilibrium program using 15 water abiotic parameters. The abiotic variables and metals in the lake were governed by the hydrological regimen of the Parana River and by the occurrence of occasional flood pulses and rainfall. The occurrence of cadmium is a concern; its presence could be due to industrial or agricultural activities or even to a natural geochemical process.     

Use of fluorescence spectroscopy and voltammetry for the analysis of metal-organic matter interactions in the New Caledonia lagoon

Fluorescence, polarographic and potentiometric analysis of sea water from the New Caledonia lagoon (located south of Noumea) allowed the determination of the specific properties of the dissolved and particulate phases of organic matter (OM)-metal complexes according to various regions of the lagoon. In particular, OM complexes with Ni, Zn, Pb, Cu, Cd were chosen in this study due to the sensitivity of these complexes to affect biocenosis of the nearby enclosed coral reef as well as their availability to enter the coast from erosion (terrigenous OM) or human activities from nickel extraction or pollution from waste sites (anthopogenic OM) that exist throughout New Caledonia. Combined with geochemical modelling, the OM-metal complexes analysis allowed the determination of their conditional stability constants which in turn helped in predicting the fate of the metal pollution in the lagoon. For the first time, fluorescence, polarographic and potentiometric techniques combined with geochemical models that employed discrete pKa distribution on OM enabled the determination of the origin of the OM, as either natural or anthopogenic.     

Evaluation of the Potential Release Tendency of Metals and Metalloids from the Estuarine Sediments: Case Study of Raša Bay

Assessing the environmental quality of coastal systems is important not only for the management and protection of such areas, but also for improving the quality of water resources. Since sediment itself can often be a source of certain toxic elements, in addition to information on the distribution of metals in the water column and in the sediment itself, it is useful to determine the bioavailable forms of individual elements, particularly toxic ones. In this study, water and sediment geochemical data were supplemented with oxyanion mobility in sediments estimated by diffusion gradients in thin film (DGTs). The data obtained indicate that the chemical composition of the water in the Raša River estuary primarily reflects the high input of suspended sediment from the catchment, the mixing of freshwater and seawater, and to a lesser extent the effects of anthropogenic activities. Although sediment composition is primarily determined by geological and hydrodynamic conditions in the catchment, it also indicates moderate enrichment in Co, Cr, Mo and Ni. In contrast, the distribution of oxyanions in sediment pore water indicates the influence of sediment as a source of some elements in the bottom water; e.g., sediment contributes to 40% of the arsenic bottom water budget. The obtained depth profiles of the oxyanion distribution in the sediment pore water indicate an early onset of suboxic to anoxic conditions in Raša Bay, which is prone to rapid sedimentation. All this demonstrates the need to consider the bioavailable forms of elements when assessing environmental quality, as the lack of such information can lead to an incomplete assessment, especially in dynamic coastal systems such as estuaries.     

A New Model for the Genesis of Natural Gases--Multi-source Overlap, Multi-stage Continuity, Type Controlled by Main Source and Nomenclature by Main Stage (Ⅰ)--Multi-source Overlap and Type Controlled by Main Source

Based on the geochemical studies of natural gases in the past ten years in China, the authors have proposed a new model for their genesis--multi-source overlap, multi-stage continuity, main source-controlling type and nomenclature by the main stage.Multi-source refers to a diversity of material sources involved in the formation of natural gases, including abiogenic and biogenic material sources. In regard to biogenic sources, either oil-generating or coal-generating organic matter would produce gaseous hydrocarbon reservoirs of commercial importance. Generally, natural gases originating from these sources can overlap to form gas reservoirs. Under specific circumstances mantle-source abiogenic gases could overlap biogenic gases to form gas reservoirs. In nature, natural gases predominated by gaseous hydrocarbons may be formed from a single end-member source. However, multi-source overlap is more typical of the genesis of natural gases.     

Experimental study on geochemical characteristic of methane hydrate formed in porous media

The natural occurrence of methane hydrates in marine sediments has been intensively studied over the past decades, and geochemical charac-teristic of hydrate is one of the most attractive research fields. In this paper, we discussed the geochemical anomaly during hydrate formation in porous media. By doing so, we also investigated the temperature influence on hydrate formation under isobaric condition. It turns out that sub-cooling is an important factor to dominate hydrate formation. Larger subcooling provides more powerful driving force for hydrate formation. During the geochemical anomaly research, six kinds of ions and the total dissolved salt (TDS) were measured before and after the experiment in different porous media. The result is that all kinds of ionic concentration increased after hydrate formation which can be defined as salting out effect mainly affected by gas consumption. But the variation ratio of different ions is not equal. Ca2+ seems to be the most significantly influenced one, and its variation ratio is up to 80%. Finally, we theoretically made a model to calculate the TDS variation, the result is in good accordance with measured one, especially when gas consumption is large.     

A New Model for the Genesis of Natural Gases——Multi-source Overlap, Multi-stage Continuity, TypeControlled by Main Source and Nomenclature by Main Stage (Ⅱ)——Multi-stage Continuity and Nomenclature by Main Stage

The generation of natural gases involves several stages and the various stages are of continuous transition. This is another feature of natural gas generation. The term "multi-stage" is relative mainly to oil-generating threshold value and liquid window. The evolution of organic matter is affected by different epigene agencies and natural gases differing in geochemical properties such as biogenic gas (bacterial gas), thermocatalytic gas and pyrolytic gas could be produced at different stages of the evolution of organic matter. The proposal of bio-thermocatalytic transitional-zone gas presents a pattern of mutual linking and continuous transition of natural gases originated at different stages.In the genetic classification of natural gases, the nomenclature of a certain gas is based mainly on the epigene agency which is responsible for its formation, for example, biogenic gas, pyrolytic gas. That is the "nomenclature by the main stage" described in this study. On account of the continuity of gas generati     

Effects of sample preservation and storage on mercury speciation in natural stream water

Despite an increasing focus on low level methods for determination of mercury species in water over the last decades, few studies have paid attention to direct effects of different sample preparation methods (i.e. preservation techniques) on natural freshwater samples. In this study we show how different preservation techniques give significantly different concentrations of total and methylmercury in freshwaters (9 and 14% on average, respectively). Natural stream samples from a forested lake catchment were studied. Mean stream sample concentrations of total (3.6 ng/L) and methylmercury (0.06 ng/L) reflect levels typical for pristine humic boreal catchments. The main reason for the observed average differences in total and methylmercury concentrations is the use of one instead of two sample bottles and timing of sample acidification, respectively.     

褐煤超临界流体抽提产物中芳烃的组成特征

用柱色谱分离、ＧＣ／ＭＳ分析云南先锋和金所褐煤甲苯（或二甲苯）超临界流体抽提（ＳＣＦＥ）产物油段分中芳烃馏分的组成结构，鉴定出联苯、联苄型结构及它们的烷基衍生物为主要组成部分，菲、芴、芘、荧蒽、苯并芘等多环缩合芳烃的量较少，有较丰富的芳构化五环萜类，包括从三环至五环芳构化的化合物。这些结果反映了多环芳烃成煤过程中的演变情况，可为煤化学研究提供重要的信息。     

Metal content in river suspended particulate matter: data on Po River

The present study summarizes the last ten years of literature on heavy metal distribution in Suspended Particulate Matter (SPM) and dissolved phase in the Po River (Italy). The work compares different methodologies employed to collect, concentrate and fractionate the samples. The importance of metal speciation as a function of particle size is underlined and two approaches to metal speciation in the colloidal fraction of Po River SPM are presented: Sedimentation Field-Flow Fractionation (SdFFF) and pH-dependent extractions. Finally, emphasis is placed on the need for comparison with a reference "natural background level" of the metal load in Po River particulate matter in order to determine the real human contribution to river pollution. The high values of some trace transition elements, such as Cr and Ni, have been compared with clay sediments around Ferrara and with bricks in historic buildings. The highly comparable natural concentration of these metals in Po fine sedimentary rocks and in historic brick buildings of Ferrara (XII-XVI centuries) can provide information on natural geochemical anomalies.     

Geochemical study of trace vanadium in water by preconcentrational neutron activation analysis

By preconcentrational neutron activation analysis, trace vanadium was determined in natural water samples such as ground water, river water, lake water and so on. Preconcentration was accomplished by adsorption of vanadium on activated carbon surfaces using 8-quinolinol as an adjunct. As an analytical line, the 1434 keV -photopeak of⁵²V (T _1/2=3.75 m) produced in the⁵¹V (n,) ⁵²V reaction was measured with a conventional -ray spectrometer. The present analytical results show that the vanadium contents in natural water range widely from several tens ppt to about 100 ppb. A relatively larger amount of vanadium was observed in the ground water samples from the locations with basaltic soils or rocks, for example, around Mt. Fuji. This suggests that the geochemical interactions of ground water with such soils or rocks could enhance the vanadium concentrations. As an application, the vanadium contents were measured in the lake water from the five lakes surrounding Mt. Fuji in order to clarity geochemical and geological behaviors of natural water by probing vanadium as an indicator.     

Stability and Mobility of Metal-Humic Complexes Isolated from Different Soils

The contamination of potable water aquifers by heavy metals is one of the most severe environmental threats. For the transport of heavy metals from various types of contaminated sites into the ground water and also into surface water aquifers, humic substances (HS) are recognized to be of main importance. Dissolved in natural waters humic substances are readily complexed with a variety of metal ions. Therefore, humic substances are of cardinal importance for the migration and, consequently, the pollution of ground waters with heavy metals. Our paper presents the results of a comprehensive comparison of several isolated humic acids of soils of different origin (different geochemical milieu) and their metal complexes. Two polluted sites in Germany, which differ in their geochemical milieu (pH-value) were selected. The aim of our experiments was to describe the properties of terrestrial humic substances depending on their origin and genesis as well as the effects of the transport of humic substance-bound metals into the water-unsaturated soil zone. After determination of heavy metals in the soils by photon activation analysis the activated soil was used as an inherent tracer in batch experiments with the isolated humic acid. After adsorption of the loaded humic acid on an XAD-8 resin column, the partition of metals mobilized by humic acids could be quantified. There are correlations of the formation of metal-humic complexes with the soil pedogenes, with the pH-value as well as with the humic acid concentration.     

Fluorescence characterization of the natural organic matter in deep ground waters from the Canadian Shield,Ontario, Canada

Deep groundwater samples from a deep borehole in the Canadian Shield, Ontario, Canada, have been analyzed by fluorometry, to determine the difference in character of the natural organic matter (NOM) with depth. This work was done to obtain a set of geochemical characteristics of deep groundwaters at the site. The fluorescence signal is a complex signature of excitation and emission of light from fluorescent molecules which are part of all natural waters. Fluorescent components have characteristic excitation/emission components, defined as a humic-like (C1), fulvic-like (C2), and protein-like (C3); these are found in various proportions in natural samples. Changes in relative fluorescence intensities of these components have been used in the past to determine the origin and/or processes of the NOM between sampling locations. In this work, six samples were taken at different depths, from ~108 to 650 m below the surface in the borehole. The fluorescence signals of the samples showed three main patterns: (1) the shallower samples (~108, 139 and 285 m) had a pattern similar to that of surface groundwaters, dominated by components C1 and C2; (2) the samples in deep groundwaters (~620 and 650 m) had a weak overall signal, dominated by component C3; finally (3) the mid-depth sample (~503 m) had a component pattern intermediate between the shallower and deeper zones. This set of data is consistent with other data for the groundwaters from this borehole, such as chlorinity, suggesting that the three sampling intervals represent three different types of groundwaters.     

全二维气相色谱在石油地质样品分析中的应用进展

对石油地质样品的化学组成进行全面准确的剖析,可以获得丰富的地球化学信息,为油气勘探工作提供科学依据。然而,该类样品除了组成复杂之外,还易受到各种物理（如蒸发、乳化、扩散、溶解和吸附）、化学（如光降解）和生物（如微生物降解）过程的影响。这些特点给样品的分析研究工作带来了极大的困难,传统的一维气相色谱/质谱技术很难对其进行理想的分离。全二维气相色谱（GC×GC）作为新发展起来的一种分离技术,在复杂样品分析方面具有独特的优势,虽然在石油地质样品分析中的应用相对较晚,但也日益受到关注。本文主要综述了近5年来GC×GC在石油地质方面国内外的研究进展以及存在的主要问题,并对今后的研究进行了展望。     

Comprehensive study on saline-alkali soil amelioration with sediment of irrigation area in northeast China

To improve the main shortcomings of insufficient nutrients, high salinity and low productivity in saline-alkali soils, this study collected saline-alkali soil samples from Da'an City of Baicheng and sediment samples from the adjacent Qianguo irrigation district, measured their pH values and major element contents, designed and verified the improvement scheme of saline-alkali soil based on geochemical engineering principles. Results indicated that the pH value and various element contents of saline-alkali soil could be adjusted by adding sediment to make it close to reference soil. Both theoretical calculation and experimental determination (soil pH, mineral composition, functional group composition and crop growth) revealed that the optimal mixing ratio of saline-alkali soil and sediment was 2:1. The saline-alkali soil amelioration with sediment of adjacent irrigation areas was effectively, low-cost and environment-friendly. The geochemical engineering principle was applicable to the amelioration of saline-alkali soil, but the mixing ratio of saline-alkali soil and sediment in different areas should vary with the local conditions. Meanwhile, theoretical calculation could basically replace the experimental determination to simplify the actual engineering application process. This saline-alkaline soil amelioration method makes full use of the surrounding natural waste and has the advantage of adapting measures to local conditions.     

U- and Th-series radionuclides in CO2-rich geothermal systems in the French Massif Central

Uranium- and Th-series radionuclides have been analyzed in CO₂-rich geothermal waters and their associated iron hydroxide and carbonate deposits from the French Massif Central. A geochemical budget for U and Ra in water and solid deposits has been estimated. Most of the U (>75%) remains in solution, probably because of the presence of soluble U-carbonate complexes. In contrast, a large fraction of Ra (>50%) is scavenged by both deposit types. The distribution coefficient of U and Ra in calcite are 0.2 and 0.4 respectively. The D_Ra value is much higher than the experimentally determined coefficients and represents a non-equilibrium value that might be applicable to natural systems with high CaCO₃ precipitation rates.