The role of prokaryotes in subsurface weathering of hydrothermal sediments: A combined geochemical and microbiological investigation

A detailed geochemical and microbiological study of a ∼2 m sediment core from the inactive Alvin mounds within the TAG hydrothermal field was conducted to examine, for the first time, the role of prokaryotes in subsurface weathering of hydrothermal sediments. Results show that there has been substantial post-depositional remobilisation of metal species and diagenetic overprinting of the original high-temperature hydrothermal minerals, and aspects have involved prokaryotic processes. Prokaryotic enumeration demonstrates the presence of a population smaller than the average for deep sea sediments, probably due to the low organic carbon content, but not inhibited by (and hence adapted to) the metal rich environment. There was a small but significant increase in population size associated with the active redox boundary in an upper metal sulphide layer (50-70 cm) around which active metal remobilisation was concentrated (Cu, Au, Cd, Ag, U, Zn and Zn). Hence, subsurface prokaryotes were potentially obtaining energy from metal metabolism in this near surface zone. Close association of numbers of culturable Mn and Fe reducing prokaryotes with subsurface Fe²⁺ and Mn²⁺ pore water profiles suggested active prokaryotic metal reduction at depth in core CD102/43 (to ∼175 cm). In addition, a prokaryotic mechanism, which is associated with bacterial sulphate reduction, is invoked to explain the U enrichment on pyrite surfaces and Zn and Pb remobilisation in the upper sediment. Although prokaryotic populations are present throughout this metalliferous sediment, thermodynamic calculations indicated that the inferred low pH of pore waters and the suboxic/anoxic conditions limits the potential energy available from Fe(II) oxidation, which may restrict prokaryotic chemolithotrophic biomass. This suggests that intense prokaryotic Fe oxidation and weathering of seafloor massive sulphide deposits may be restricted to the upper portion of the deposit that is influenced by near neutral pH and oxic seawater unless there is significant subsurface fluid flow.     

A critical look at iron paleoredox proxies: New insights from modern euxinic marine basins

Enrichments in reactive iron occur under euxinic marine conditions, that is, where dissolved sulfide is present in the water column. These enrichments result primarily from the export of remobilized iron from the oxic shelf, which is scavenged from the euxinic water column during syngenetic pyrite formation and deposited in the underlying sediments. Strongly elevated ratios of highly reactive iron to total iron (Fe_HR/Fe_T) and total iron to aluminum (Fe_T/Al) and high degrees of pyritization (DOP) are each products of this enrichment process. These paleoredox proxies are among the most faithful recorders of ancient euxinia.Contrary to previous arguments, iron enrichment is decoupled from biogenic sediment inputs, but it does appear to be a uniquely euxinic phenomenon. In other words, we can rule out a major contribution from preferential physical transport of Fe_HR-rich detrital sediment to the deep basin, which could also operate under oxic conditions. Furthermore, enrichment via the shuttling of iron remobilized from oxic shelves appears to be limited by inefficient transport and trapping processes in deep oxic basins. Elevated Fe_T/Al ratios in the euxinic sediments also cannot be a product of internal enhancement of the reactivity of the detrital iron pool without net Fe_HR addition. These conclusions are supported by observations in the modern Black Sea, Orca Basin, and Effingham Inlet.Fe_T/Al ratios are unambiguous recorders of paleoredox even in sediments that have experienced high degrees of metamorphic alteration. However, this study suggests that high siliciclastic accumulation rates can swamp the enrichment mechanism, resulting in only intermediate DOP values for euxinic sediments and Fe_T/Al ratios that mimic the oxic shelf. Such dilution effects are well expressed in Black Sea basinal turbidites and rapidly accumulating muds on euxinic basin margins. Under conditions of persistent euxinia, varying extents of Fe_HR enrichment can illuminate spatial and temporal gradients in siliciclastic sedimentation. The magnitude of enrichment is a function of the source (shelf) to sink (ocean basin) areal ratio, suggesting that iron proxies can also record ocean-scale paleoenvironmental properties through muted enrichments at times of very widespread euxinia. For the first time, manganese data are interpreted in light of the redox shuttle model. As for the iron data, the Black Sea, Orca Basin, and Effingham Inlet show enrichments in total manganese in the deep euxinic basin, suggesting export from the suboxic porewaters of the oxic shelf and scavenging and burial in the basin. The Black Sea data reveal iron and manganese enrichment across the broad, deep euxinic basin, suggesting efficient lateral transport and deep-water mixing tied to the physical properties of the water column.     

Monitoring volcanic hazard using eddy covariance at Solfatara volcano, Naples, Italy

An eddy covariance (EC) station was deployed at Solfatara crater, Italy, June 8–25, 2001 to assess if EC could reliably monitor CO₂ fluxes continuously at this site. Deployment at six different locations within the crater allowed areas of focused gas venting to be variably included in the measured flux. Turbulent (EC) fluxes calculated in 30-min averages varied between 950 and 4460 g CO₂ m⁻² d⁻¹; the highest measurements were made downwind of degassing pools. Comparing turbulent fluxes with chamber measurements of surface fluxes using footprint models in diffuse degassing regions yielded an average difference of 0% (±4%), indicating that EC measurements are representative of surface fluxes at this volcanic site. Similar comparisons made downwind of degassing pools yielded emission rates from 12 to 27 t CO₂ d⁻¹ for these features. Reliable EC measurements (i.e. measurements with sufficient and stationary turbulence) were obtained primarily during daytime hours (08:00 and 20:00 local time) when the wind speed exceeded 2 m s⁻¹. Daily average EC fluxes varied by ±50% and variations were likely correlated to changes in atmospheric pressure. Variations in CO₂ emissions due to volcanic processes at depth would have to be on the same order of magnitude as the measured diurnal variability in order to be useful in predicting volcanic hazard. First-order models of magma emplacement suggest that emissions could exceed this rate for reasonable assumptions of magma movement. EC therefore provides a useful method of monitoring volcanic hazard at Solfatara. Further, EC can monitor significantly larger areas than can be monitored by previous methods.     

Optimization of the Sampling Technique for the Determination of Dissolved Hydrogen in Groundwater

In this study a field‐sampling technique for dissolved hydrogen (H₂) in groundwater will be presented which allows the transport of gaseous samples into the laboratory for further analysis. The method consists of transferring the headspace trapped in a gas‐sampling bulb which is continuously purged by groundwater into previously evacuated vials using a gas‐tight syringe. Three transfer steps with preceding evacuation of the vial led to a H₂‐recovery of 100 % in laboratory experiments. The method has been applied to determine H₂ concentrations in an aquifer contaminated with chlorinated solvents. Tests concerning the effect of different pumping techniques on H₂ concentrations revealed that most reliable values were obtained with a bladder pump, while an electrically driven submersible pump generated considerable amounts of hydrogen due to electrochemical interactions with the sampled water. Concentrations of dissolved hydrogen in field and laboratory samples were about two orders of magnitude higher when sampling was performed with the electrically driven submersible pump compared to sampling with the bladder pump and a peristaltic pump. Lab experiments with a Plexiglas reservoir to produce H₂‐enriched water were used to study the effect of two tubing materials (PVC, polyamide) on H₂ losses. PVC tubing turned out to allow transfer of H₂‐enriched water over 25 m without significant losses, while PA‐tubing was not suitable for sampling of H₂.     

The measurement of sulfate mineral solubilities in the Na-K-Ca-Cl-SO4-H2O system at temperatures of 100, 150 and 200°C

At T > 100°C development of thermodynamic models suffers from missing experimental data, particularly for solubilities of sulfate minerals in mixed solutions. Solubilities in Na⁺-K⁺-Ca²⁺-Cl⁻-SO₄²⁻/H₂O subsystems were investigated at 150, 200°C and at selected compositions at 100°C. The apparatus used to examine solid-liquid phase equilibria under hydrothermal conditions has been described.In the system NaCl-CaSO₄-H₂O the missing anhydrite (CaSO₄) solubilities at high NaCl concentrations up to halite saturation have been determined. In the system Na₂SO₄-CaSO₄-H₂O the observed glauberite (Na₂SO₄ · CaSO₄) solubility is higher than that predicted by the high temperature model of Greenberg and Møller (1989), especially at 200°C. At high salt concentrations, solubilities of both anhydrite and glauberite increase with increasing temperature. Stability fields of the minerals syngenite (K₂SO₄ · CaSO₄ · H₂O) and goergeyite (K₂SO₄ · 5 CaSO₄ · H₂O) were determined, and a new phase was found at 200°C in the K₂SO₄-CaSO₄-H₂O system. Chemical and single crystal structure analysis give the formula K₂SO₄ · CaSO₄. The structure is isostructural with palmierite (K₂SO₄ · PbSO₄). The glaserite (“3 K₂SO₄ · Na₂SO₄”) appears as solid solution in the system Na₂SO₄-K₂SO₄-H₂O. Its solubility and stoichiometry was determined as a function of solution composition.     

The constancy of galactic cosmic rays as recorded by cosmogenic nuclides in iron meteorites

We measured the He, Ne, and Ar isotopic concentrations and the ¹⁰Be, ²⁶Al, ³⁶Cl, and ⁴¹Ca concentrations in 56 iron meteorites of groups IIIAB, IIAB, IVA, IC, IIA, IIB, and one ungrouped. From ⁴¹Ca and ³⁶Cl data, we calculated terrestrial ages indistinguishable from zero for six samples, indicating recent falls, up to 562 ± 86 ka. Three of the studied meteorites are falls. The data for the other 47 irons confirm that terrestrial ages for iron meteorites can be as long as a few hundred thousand years even in relatively humid conditions. The ³⁶Cl‐³⁶Ar cosmic ray exposure (CRE) ages range from 4.3 ± 0.4 Ma to 652 ± 99 Ma. By including literature data, we established a consistent and reliable CRE age database for 67 iron meteorites. The high quality of the CRE ages enables us to study structures in the CRE age histogram more reliably. At first sight, the CRE age histogram shows peaks at about 400 and 630 Ma. After correction for pairing, the updated CRE age histogram comprises 41 individual samples and shows no indications of temporal periodicity, especially not if one considers each iron meteorite group separately. Our study contradicts the hypothesis of periodic GCR intensity variations (Shaviv 2002, 2003), confirming other studies indicating that there are no periodic structures in the CRE age histogram (e.g., Rahmstorf et al. 2004; Jahnke 2005). The data contradict the hypothesis that periodic GCR intensity variations might have triggered periodic Earth climate changes. The ³⁶Cl‐³⁶Ar CRE ages are on average 40% lower than the ⁴¹K‐K CRE ages (e.g., Voshage 1967). This offset can either be due to an offset in the ⁴¹K‐K dating system or due to a significantly lower GCR intensity in the time interval 195–656 Ma compared to the recent past. A 40% lower GCR intensity, however, would have increased the Earth temperature by up to 2 °C, which seems unrealistic and leaves an ill‐defined ⁴¹K‐K CRE age system the most likely explanation. Finally, we present new ²⁶Al/²¹Ne and ¹⁰Be/²¹Ne production rate ratios of 0.32 ± 0.01 and 0.44 ± 0.03, respectively.     

MORPHOLOGICAL DEVELOPMENT OF ANATURE-LIKE BANK PROTECTION

1 INTRODUCTIONFor the pmpose of river restoration of the river Isar in the city area of Munich several inveshgationswere cAned out at the InshtUte for Hydrosciences, German Armed Forces University Munich. The calculation ofwater level for the differnt planned variants were realized by a 2d mathematical model. Although thesesimulahons were a very helpfol basis for fuIther planing, a physical model was constrUcted in order toinvestigate detalled problems.The main interest was focussed …     

Strain localization as a key to reconciling experimentally derived flow-law data with dynamic models of continental collision

Published strength profiles predict strength discontinuities within and/or at the base of continental crust during compression. We use finite element models to investigate the effect of strength discontinuities on continental collision dynamics. The style of deformation in model crust during continued subduction of underlying mantle lithosphere is controlled by: (1) experimental flow-law data; (2) the crustal geotherm; (3) strain localization by erosion; (4) strain-softening and other localization effects. In the absence of erosion and other factors causing strain localization, numerical models with typical geothermal gradients and frictional/ductile rheologies predict diffuse crustal deformation with whole-scale detachment of crust from mantle lithosphere. This prediction is at odds with earlier model studies that only considered frictional crustal rheologies and showed asymmetric, focused crustal deformation. Without localization, model deformation is not consistent with that observed in small collisional orogens such as the Swiss Alps. This suggests that strain localization by a combination of erosion and rheological effects such as strain softening must play a major role in focusing deformation, and that strength profiles derived under constant strain rates and uniform material properties cannot be used to infer crustal strength during collision dynamics.     

Über Hiatus-Konkretionen (dargestellt an Beispielen aus dem Lias)

Zusammenfassung Als Hiatus-Konkretionen werden Kalk-Konkretionen aus dem nord- und süddeutschen Lias (Domerien) beschrieben, welche ein durch Sedimentationsunterbrechungen bedingtes mehrphasiges Wachstum erkennen lassen oder durch das Zusammenwachsen verschieden alter, durch Diskontinuitätsflächen getrennter Konkretionen entstanden sind.Der Hiatus wird dadurch bewiesen, daß die frühdiagenetisch im Sediment gebildeten Konkretionen ausgewaschen, korrodiert, angebohrt oder von Austern, Serpuliden, Bryozoen oder anderen sessilen Organismen besiedelt wurden. Nach erneuter Einbettung setzt die Konkretionsbildung wieder ein, wobei sich die jüngeren Toneisensteine um die älteren, die ihnen als Ansatzstellen dienten, herum gebildet haben.

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Calcareous concretions from the middle Lias (Domerian) of Northern and Southern Germany revealing growth in several phases conditioned by interruptions of sedimentation or by coalescence of concretions of different age are called Hiatus Concretions. The hiatuses are proved by the fact that these concretions, which were formed in the sediment by early diagenetic processes, were washed out and are corroded or bored on the surface and encrusted by oysters, serpulids, bryozoans or other sessile benthonic organisms.After a new beginning of sedimentation the growth of the concretions started again. By this process the younger concretions included the older ones which often were the starting point for a new generation of concretions.In section the ancient surfaces with incrusting shells can be observed.

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Résumé Des concrétions de CaCO₃ du lias moyen (Domérien) de l'Allemagne du Nord et de Sud laissant reconnaître une croissance en plusieurs phases conditionnées par des interruptions de la sédimentation ou qui sont formées par une fusion des concrétions separées par des surfaces de discontinuité sont appelées des «concrétions à hiatus».Le hiatus est reconnu par le fait que les concrétions formées dans le sédiment pendant la première phase d'une diagénèse sont erodées, corrodées, envahies par des organismes perforants, ou recouvertes en partie par des Huîtres, Serpulides, Bryozoaires ou autres animaux sessiles. Après une sédimentation nouvelle la croissance des concrétions s'est poursuivie. Les concrétions nouvelles ont enveloppées les anciennes qui leur ont servi de noyaux. On peut observer sur les sections des surfaces de discontinuité marquées par des organismes encroûtants.

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