Rapid biotic molecular transformation of fulvic acids in a karst aquifer

The study of molecular transformation processes of dissolved organic carbon (DOC) in the environment significantly contributes to a better understanding of the global biogeochemical organic matter cycle. In an oxic karst groundwater system, in which the most powerful abiotic DOC degradative reactions, photodegradation and metal-mediated redox chemistry, are at best marginal contributors, a near complete turnover of fulvic acids (FAs) has been observed within decades (∼60 years). Depletion of oxygen for a very extensive range of aliphatic and aromatic carbon chemical environments has been confirmed as well as the formation of novel classes of compounds, suggesting a major contribution from biotic processes. From these results we infer that FAs must be perceived as a rather active participant in the global carbon cycle. Molecular-level alterations of such magnitude and rapidity on such short-time scales ought to be considered as widespread in the processing of “refractory” DOC in the environment.     

Middle Pleistocene environments,landscapes and tephrostratigraphy of the Armenian Highlands: evidence from Bird Farm 1, Hrazdan Valley

The significance of the southern Caucasus in understanding Pleistocene hominin expansions is well established. However, the palaeoenvironments in which Palaeolithic occupation of the region took place are presently poorly defined. The Hrazdan river valley, Armenian Highlands, contains a rich Palaeolithic record alongside Middle Pleistocene volcanic, fluvial and lacustrine strata, and thus offer exciting potential for palaeoenvironmental reconstruction. We present the first results of sedimentological, geochemical, tephrostratigraphical and biological (diatoms) study of the sequence of Bird Farm 1, located in the central part of the valley. These data show six phases of landscape development during the interval 440–200 ka. The sequence represents the first quantitative Pleistocene diatom record from the Armenian Highlands and the southern Caucasus, and indicates the persistence of a deep, stratified lacustrine system, with evidence for changing lake productivity that is tentatively linked to climate. Furthermore, major element chemical characterization of visible and crypto-tephra horizons in the sequence enables the first stages of the development of a regional tephrostratigraphy. Together, the evidence from Bird Farm 1 demonstrates the importance of lacustrine archives in the region for palaeoenvironmental reconstruction and highlights the potential for linkages between archives on both a local and regional scale.     

Pseudotachylytes in the southern border fault of the Cenozoic intracontinental Teletsk basin (Altai, Russia)

The Cenozoic intracontinental Teletsk basin in the Central Asian Altai Mountains is composed of a complexly structured northern and a more simple southern sub-basin. These sub-basins formed in two distinct kinematic stages when first the NNW-striking Teletsk- and then the NE-striking West-Sayan shear zones became reactivated in the Cenozoic under dominant NS-oriented horizontal compression. Although the entire Teletsk basin strikes roughly NS, the southern sub-basin is parallel to the NNW-trending, amphibolite facies Teletsk ductile shear zone, while the northern sub-basin is NS-striking and flanked by differently structured, greenschist facies basement. Basement reactivation closely controlled the southern sub-basin formation, but this is less clear for the northern sub-basin. Contrasts between northern and southern basement and the exclusive occurrence of pseudotachylytes along the margins of the southern basin are explored for their contribution to the formation of the Teletsk basin with two distinct sub-basins.In the ductile shear fabric of the basement flanking the southern sub-basin, concordantly interleaved pseudotachylytes and isolated breccia lenses reflect local brittle deformation along the ductile fabric. The genetic link between breccia lenses and pseudotachylyte occurrences was defined by microstructural investigation. It allows to explore their possible development in a dextral strike–slip zone. These rocks occur in a large fault-bounded segment of the basement. The geometry of the structures in the segment is comparable with a dextral strike–slip sidewall-ripout structure along the Teletsk shear zone. Seismic slip related to pseudotachylytes is attributed to the sudden stress release on the NNW-striking Teletsk shear zone, when the latter became unconstrained by reactivation of the NE-trending West-Sayan fault zone at its northern boundary. The boundary of the sidewall-ripout structure was reactivated as a large listric fault in a later stage. The northern sub-basins roughly develop along an NS strike and are assumed to reflect reactivation of the ductile shear zone underneath the variably structured greenschist facies basement outcropping along the flanks of the sub-basin.     

Quantification of adamantane in organic media via infrared attenuated total reflection spectroscopy

In the present study, the quantitative determination of the diamondoid compound adamantane in organic solvents via infrared attenuated total reflection (IR-ATR) spectroscopy at unmodified waveguide surfaces was established. Limits of detection (LOD) and quantification (LOQ) of adamantane in dichloromethane, hexane and carbon tetrachloride were determined. Quantitative IR-ATR measurements additionally facilitated the determination of adamantane solubility limit in dichloromethane, hexane and carbon tetrachloride. The developed analytical strategy further enabled the successful detection and quantification of adamantane in crude oil matrices. Consequently, IR-ATR spectroscopy provides a promising strategy for on ship and in situ diamondoid analysis in harsh real world environments.     

Contrasting patterns of precipitation seasonality during the Holocene in the south‐ and north‐central Mediterranean

Pollen‐based quantitative estimates of seasonal precipitation from Lake Pergusa and lake‐level data from Lake Preola in Sicily (southern Italy) allow three successive periods to be distinguished within the Holocene: an early Holocene period before ca. 9800 cal a BP with rather dry climate conditions in winter and summer, a mid‐Holocene period between ca. 9800 and 4500 cal a BP with maximum winter and summer wetness, and a late Holocene period after 4500 cal a BP with declining winter and summer wetness. This evolution observed in the south‐central Mediterranean shows strong similarities to that recognized in the eastern Mediterranean. But, it contrasts with that reconstructed in north‐central Italy, where the mid‐Holocene appears to be characterized by a winter (summer) precipitation maximum (minimum), while the late Holocene coincided with a decrease (increase) in winter (summer) precipitation. Maximum precipitation at ca. 10 000–4500 cal a BP may have resulted from (i) increased local convection in response to a Holocene insolation maximum at 10 000 cal a BP and then (ii) the gradual weakening of the Hadley cell activity, which allowed the winter rainy westerlies to reach the Mediterranean area more frequently. After 4500 cal a BP, changes in precipitation seasonality may reflect non‐linear responses to orbitally driven insolation decrease in addition to seasonal and inter‐hemispheric changes of insolation. Copyright © 2011 John Wiley & Sons, Ltd.     

The significance of isotope specific diffusion coefficients for reaction-transport models of sulfate reduction in marine sediments

Modeling isotopic signatures in systems affected by diffusion, advection, and a reaction which modifies the isotopic abundance of a given species, is a discipline in its infancy. Traditionally, much emphasis has been placed on kinetic isotope effects during biochemical reactions, while isotope effects caused by isotope specific diffusion coefficients have been neglected. A recent study by Donahue et al. (2008) suggested that transport related isotope effects may be of similar magnitude as microbially mediated isotope effects. Although it was later shown that the assumed differences in the isotope specific diffusion coefficients were probably overstated by one or two orders of magnitude (Bourg, 2008), this study raises several important issues: (1) Is it possible to directly calculate isotopic enrichment factors from measured concentration data without modeling the respective system? (2) Do changes in porosity and advection velocity modulate the influence of isotope specific diffusion coefficients on the fractionation factor α? (3) If one has no a priori knowledge whether diffusion coefficients are isotope specific or not, what is the nature and magnitude of the error introduced by either assumption? Here we argue (A) That the direct substitution of measured data into a differential equation is problematic and cannot be used as a replacement for a reaction-transport model; (B) That the transport related fractionation scales linearly with the difference between the respective diffusion coefficients of a given isotope system, but depends in a complex non-linear way on the interplay between advection velocity, and downcore changes of temperature and porosity. Last but not least, we argue that the influence of isotope specific diffusion coefficients on microbially mediated sulfate reduction in typical marine sediments is considerably smaller than the error associated with the determination of the fractionation factor.     

Experimental study of gold-hydrosulphide complexing in aqueous solutions at 350-500°C, 500 and 1000 bars using mineral buffers

The solubility of gold was measured in KCl solutions (0.001-0.1 m) at near-neutral to weakly acidic pH in the presence of the K-feldspar-muscovite-quartz, andalusite-muscovite-quartz, and pyrite-pyrrhotite-magnetite buffers at temperatures 350 to 500°C and pressures 0.5 and 1 kbar. These mineral buffers were used to simultaneously constrain pH, f(S₂), and f(H₂). The experiments were performed using a CORETEST flexible Ti-cell rocking hydrothermal reactor enabling solution sampling at experimental conditions. Measured log m(Au) (mol/kg H₂O) ranges from −7.5 at weakly acid pH to −5.9 in near-neutral solutions, and increases slightly with temperature. Gold solubility in weakly basic and near-neutral solutions decreases with decreasing pH at all temperatures, which implies that Au(HS)₂ is the dominant Au species in solution. In more acidic solutions, solubility is independent of pH. Comparison of the experimentally measured solubilities with literature values for Au hydrolysis constants demonstrates that at 350°C dominates Au aqueous speciation at the weakly acidic pH and f(S₂)/f(H₂) conditions imposed by the pyrite-pyrrhotite-magnetite buffer. In contrast, at temperatures >400°C becomes less important and predominates in weakly acid solutions. Solubility data collected in this study were used to calculate the following equilibrium reaction constants:

     

Spatial variation in fluid flow and geochemical fluxes across the sediment-seawater interface at the Carlos Ribeiro mud volcano (Gulf of Cadiz)

Submarine mud volcanism is an important pathway for transfer of deep-sourced fluids enriched in hydrocarbons and other elements into the ocean. Numerous mud volcanoes (MVs) have been discovered along oceanic plate margins, and integrated elemental fluxes are potentially significant for oceanic chemical budgets. Here, we present the first detailed study of the spatial variation in fluid and chemical fluxes at the Carlos Ribeiro MV in the Gulf of Cadiz. To this end, we combine analyses of the chemical composition of pore fluids with a 1-D transport-reaction model to quantify fluid fluxes, and fluxes of boron, lithium and methane, across the sediment-seawater interface. The pore fluids are significantly depleted in chloride, but enriched in lithium, boron and hydrocarbons, relative to seawater. Pore water profiles of sulphate, hydrogen sulphide and total alkalinity indicate that anaerobic oxidation of methane occurs at 34-180 cm depth below seafloor. Clay mineral dehydration, and in particular the transformation of smectite to illite, produces pore fluids that are depleted in chloride and potassium. Profiles of boron, lithium and potassium are closely related, which suggests that lithium and boron are released from the sediments during this transformation. Pore fluids are expelled into the water column by advection; fluid flow velocities are 4 cm yr⁻¹ at the apex of the MV but they rapidly decrease to 0.4 cm yr⁻¹ at the periphery. The associated fluxes of boron, lithium and methane vary between 7-301, 0.5-6 and 0-806 mmol m⁻² yr⁻¹, respectively. We demonstrate that fluxes of Li and B due to mud volcanism may be important on a global scale, however, release of methane into the overlying water column is suppressed by microbial methanotrophy.     

Carbonatite diversity in the Central Andes: the Ayopaya alkaline province,Bolivia

The Ayopaya province in the eastern Andes of Bolivia, 100 km NW of Cochabamba, hosts a Cretaceous alkaline rock series within a Palaeozoic sedimentary sequence. The alkaline rock association comprises nepheline-syenitic/foyaitic to ijolitic intrusions, carbonatite, kimberlite, melilititic, nephelinitic to basanitic dykes and diatremes, and a variety of alkaline dykes. The carbonatites display a wide petrographic and geochemical spectrum. The Cerro Sapo area hosts a small calciocarbonatite intrusion and a multitude of ferrocarbonatitic dykes and lenses in association with a nepheline-syenitic stock. The stock is crosscut by a spectacular REE-Sr-Th-rich sodalite-ankerite-baryte dyke system. The nearby Chiaracke complex represents a magnesiocarbonatite intrusion with no evidence for a relationship to igneous silicate rocks. The magnesiocarbonatite ( REE up to 1.3 wt%) shows strong HREE depletion, i.e. unusually high La/Yb ratios (520–1,500). Calciocarbonatites ( REE up to 0.5 wt%) have a flatter REE distribution pattern (La/Yb 95–160) and higher Nb and Zr contents. The sodalite-ankerite-baryte dyke system shows geochemical enrichment features, particularly in Na, Ba, Cl, Sr, REE, which are similar to the unusual natrocarbonatitic lavas of the recent volcano of Oldoinyo Lengai, Tanzania. The Cerro Sapo complex may be regarded as an intrusive equivalent of natrocarbonatitic volcanism, and provides an example for carbonatite genesis by late-stage crystal fractionation and liquid immiscibility. The magnesiocarbonatite intrusion of Chiaracke, on the other hand, appears to result from a primary carbonatitic mantle melt. Deep seated mantle magmatism/metasomatism is also expressed by the occurrence of a kimberlite dyke. Neodymium and strontium isotope data (_Nd 1.4–5.4, ⁸⁷Sr/⁸⁶ Sr<Bulk Earth) indicate a depleted mantle source for the alkaline magmatism. The magmatism of the Ayopaya region is attributed to failed rifting of western South America during the Mesozoic and represents the only occurrence of carbonatite and kimberlite rocks in the Andes.