An X-ray absorption fine structure and nuclear magnetic resonance spectroscopy study of gallium-silica complexes in aqueous solution

The influence of aqueous silica on gallium(III) hydrolysis in dilute (2 × 10⁻⁴ ≤ m_Ga ≤ 5 × 10⁻³) and moderately concentrated (0.02 ≤ m_Ga ≤ 0.3) aqueous solutions was studied at ambient temperature, using high resolution X-ray absorption fine structure (XAFS) and nuclear magnetic resonance (NMR) spectroscopies, respectively. Results show that, in Si-free acidic solutions (pH < 3), Ga is hexa-coordinated with oxygens of H₂O molecules and/or OH groups in the first coordination sphere of the metal. With increasing pH, these hydroxyl groups are progressively replaced by bridging oxygens (-O-), and polymerized Ga-hydroxide complexes form via Ga-O-Ga chemical bonds. In the 2.5-3.5 pH range, both XAFS and NMR spectra are consistent with the dominant presence of the Ga₁₃ Keggin polycation, which has the same local structure as A1₁₃. Under basic pH (pH > 8), Ga exhibits a tetrahedral coordination, corresponding to Ga(OH)₄⁻ species, in agreement with previous NMR and potentiometric studies. Major changes in Ga hydrolysis have been detected in the presence of aqueous silica. Ga is tetra-coordinated, both in basic and acid (i.e., at pH > 2.7) Si-bearing solutions (0.01 ≤ m_Si ≤ 0.2), and forms stable gallium-silicate complexes. In these species, Ga binds via bridging oxygen to 2 ± 1 silicons, with an average Ga-Si distance of 3.16 ± 0.05 Å, and to 2 ± 1 silicons, with an average Ga-Si distance of 3.39 ± 0.03 Å. These two sets of Ga-Si distances imply the formation of two types of Ga-silicate aqueous complex, cyclic Ga-Si_2-3 species (formed by the substitution of Si in its tri-, tetra- or hexa-cyclic polymers by Ga atoms), and chainlike GaSi_2-4 species (similar to those found for A1), respectively. The increase in the number of Si neighbors (a measure of the complex concentration and stability), in alkaline media, with increasing SiO₂(aq) content and decreasing pH is similar to that for A1-Si complexes found in neutral to basic solutions. At very acid pH and moderate silica concentrations, the presence of another type of Ga-Si complex, in which Ga remains hexa-coordinated and binds to the silicon tetrahedra via the GaO₆ octahedron corners, has also been detected. These species are similar to those found for Al³⁺ in acid solutions. Thus, as for aluminum, silicic acid greatly hampers Ga hydrolysis and enhances Ga mobility in natural waters via the formation of gallium-silicate complexes.     

Siberian river run-off and Late Quaternary glaciation in the southern Kara Sea, Arctic Ocean: preliminary results

The extent of the Barents-Kara Ice Sheet during the eastern Last Glacial Maximum (LGM) is not yet fully known. A detailed echo-sounding survey performed during the Boris Petrov Expedition 2001 permitted the detailed mapping of part of it. Based on the profiling results, a southern connection between the LGM Barents-Kara Ice Sheet and a local ice sheet on Taymyr Peninsula appears to be unlikely. Based on sediment core data and profiling results, most of the terrigenous river-derived material accumulated in the estuaries during late Holocene times, whereas during early Holocene times of lowered sea level major amounts were transported further offshore and accumulated on the shelf. During the post-glacial sea level rise, the main depocentre migrated southward, reaching its present position no earlier than about 6 cal. Ky BP (or 5.2 Kya). Future studies of accelerator mass spectrometry (AMS) ¹⁴C-dated sediment cores will allow a detailed reconstruction of the variability of fluvial sediment discharge and the history of glaciation in the Kara Sea during late Quaternary times.     

Argo floats revealing bimodality of large-scale mid-depth circulation in the North Atlantic

Analysis of Argo float trajectories at 1 000 m and temperature at 950 m in the North Atlantic between November 2003 and January 2005 demonstrates the existence of two different circulation modes with fast transition between them. Each mode has a pair of cyclonic - anticyclonic gyres. The difference is the location of the cyclonic gyre. The cyclonic gyre stretches from southeast to northwest in the first mode and from the southwest to the northeast in the second mode. The observed modes strongly affect the heat and salt transport in the North Atlantic. In particular, the second mode slows down the westward transport of the warm and saline water from the Mediterranean Sea.     

Compositional variation in Hg-bearing sphalerite from the polymetallic Eskay Creek deposit, British Columbia, Canada

The Eskay Creek, British Columbia, Canada, is a polymetallic, gold- and silver-rich, volcanic-hosted, massive sulfide deposit. The ore in the deposit is divided into subzones distinguished by mineralogy, texture, grade and metallurgical characteristics. This study presents the results of a mineralogical examination of three composite field samples, with emphasis on the chemistry of sphalerite. Sphalerite is associated with variable amounts of Hg-tetrahedrite and cinnabar, and an array of sulfides, sulphosalts and non-opaque minerals. Electron micro probe analyses of sphalerite in the three composite samples reveal wide variations in compositions. The Hg content in sphalerite in the three samples varies between 0.08 and 16.35 wt%, whereas the Fe content ranges from 0.33 to 2.29 wt%. The chemical formula of the sphalerite shows the compositional range (Zn_0.89–0.98Hg_0.01–0.09.Fe_0.005–0.02)S. Sphalerite exhibits an almost perfect substitution of Hg and Zn, as shown by the negative covariance between them. Sphalerite with the highest Hg contents tends to have the lowest Fe concentrations. The highest Hg contents in sphalerite are recorded in the samples with the highest bulk Hg concentrations and with the highest cinnabar contents.

The compositional variations of sphalerite are important because they can be used in mapping ore forming fluids and indicate possible temporal variations. Second, determination of the compositional variation of the sphalerite in the mine has metallurgical implications because the mineral is an important Zn source. The mineralogical data indicate that non-physical processes (e.g. pyrometallurgy) must be used to separate Hg from Zn concentrates, with direct environmental implications, that is, release of metals, such as Hg, into the environment during mining and processing.     

Impacts of Present and Future Climate Variability on Agriculture and Forestry in the Temperate Regions: Europe

Agriculture and forestry will be particularly sensitive to changes in mean climate and climate variability in the northern and southern regions of Europe. Agriculture may be positively affected by climate change in the northern areas through the introduction of new crop species and varieties, higher crop production and expansion of suitable areas for crop cultivation. The disadvantages may be determined by an increase in need for plant protection, risk of nutrient leaching and accelerated breakdown of soil organic matter. In the southern areas the benefits of the projected climate change will be limited, while the disadvantages will be predominant. The increased water use efficiency caused by increasing CO₂ will compensate for some of the negative effects of increasing water limitation and extreme weather events, but lower harvestable yields, higher yield variability and reduction in suitable areas of traditional crops are expected for these areas. Forestry in the Mediterranean region may be mainly affected by increases in drought and forest fires. In northern Europe, the increased precipitation is expected to be large enough to compensate for the increased evapotranspiration. On the other hand, however, increased precipitation, cloudiness and rain days and the reduced duration of snow cover and soil frost may negatively affect forest work and timber logging determining lower profitability of forest production and a decrease in recreational possibilities. Adaptation management strategies should be introduced, as effective tools, to reduce the negative impacts of climate change on agricultural and forestry sectors.     

Authigenic rhodochrosite from a gas hydrate-bearing structure in Lake Baikal

International Journal of Earth Sciences - Early diagenetic carbonates are rare in Lake Baikal. Siderite (Fe carbonate) concretions in the sediments were discovered only recently. Here, we discuss...     

Ziminaite,Fe3+VO4, a new howardevansite-group mineral from the Bezymyannyi volcano,Kamchatka, Russia

Mineralogy and Petrology - The new mineral ziminaite, ideally Fe3+VO4, was found in fumarole sublimates at the Bezymyannyi volcano, Kamchatka, Russia. Ziminaite occurs as lamellar, tabular or...     

Molecular and isotopic characteristics of gas hydrate-bound hydrocarbons in southern and central Lake Baikal

We investigated the molecular composition (methane, ethane, and propane) and stable isotope composition (methane and ethane) of hydrate-bound gas in sediments of Lake Baikal. Hydrate-bearing sediment cores were retrieved from eight gas seep sites, located in the southern and central Baikal basins. Empirical classification of the methane stable isotopes (δ¹³C and δD) for all the seep sites indicated the dominant microbial origin of methane via methyl-type fermentation; however, a mixture of thermogenic and microbial gases resulted in relatively high methane δ¹³C signatures at two sites where ethane δ¹³C indicated a typical thermogenic origin. At one of the sites in the southern Baikal basin, we found gas hydrates of enclathrated microbial ethane in which ¹³C and deuterium were both highly depleted (mean δ¹³C and δD of –61.6‰ V-PDB and –285.4‰ V-SMOW, respectively). To the best of our knowledge, this is the first report of C₂ δ¹³C–δD classification for hydrate-bound gas in either freshwater or marine environments.     

Geochemical and microbiological characteristics of sediments near the Malenky mud volcano (Lake Baikal, Russia), with evidence of Archaea intermediate between the marine anaerobic methanotrophs ANME-2 and ANME-3

Detailed lithological, biogeochemical and molecular biological analyses of core sediments collected in 2002–2006 from the vicinity of the Malenky mud volcano, Lake Baikal, reveal considerable spatial variations in pore water chemical composition, with total concentrations of dissolved salts varying from 0.1 to 1.8‰. Values of methane δ¹³С in the sediments suggest a biogenic origin (δ¹³С_min. ?61.3‰, δ¹³С_max. ?72.9‰). Rates of sulphate reduction varied from 0.001 to 0.7 nmol cm^?3 day^?1, of autotrophic methanogenesis from 0.01 to 2.98 nmol CH₄ cm^?3 day^?1, and of anaerobic oxidation of methane from 0 to 12.3 nmol cm^?3 day^?1. These results indicate that methanogenic processes dominate in gas hydrate-bearing sediments of Lake Baikal. Based on clone libraries of 16S rRNA genes amplified with Bacteria- and Archaea-specific primers, investigation of microbial diversity in gas hydrate-bearing sediments revealed bacterial 16S rRNA clones classified as Deltaproteobacteria, Gammaproteobacteria, Chloroflexi and OP11. Archaeal clone sequences are related to the Crenarchaeota and Euryarchaeota. Baikal sequences of Archaea form a distinct cluster occupying an intermediate position between the marine groups ANME-2 and ANME-3 of anaerobic methanotrophs.     

Chemical Mechanism Development: Laboratory Studies and Model Applications

Within the German Tropospheric Research Programme (TFS) numerous kinetic and mechanistic studies on the tropospheric reaction/degradation of the following reactants were carried out: oxygenated VOC, aromatic VOC, biogenic VOC, short-lived intermediates, such as alkoxy and alkylperoxy radicals.At the conception of the projects these selected groups were classes of VOC or intermediates for which the atmospheric oxidation mechanisms were either poorly characterised or totally unknown. The motivation for these studies was the attainment of significant improvements in our understanding of the atmospheric chemical oxidation processes of these compounds, particularly with respect to their involvement in photooxidant formation in the troposphere. In the present paper the types of experimental investigations performed and the results obtained within the various projects are briefly summarised. The major achievements are highlighted and discussed in terms of their contribution to improving our understanding of the chemical processes controlling photosmog formation in the troposphere.