Molybdenum isotope fractionation in pelagic euxinia: Evidence from the modern Black and Baltic Seas

Here we present stable isotope data for vertical profiles of dissolved molybdenum of the modern euxinic water columns of the Black Sea and two deeps of the Baltic Sea. Dissolved molybdenum in all water samples is depleted in salinity-normalized concentration and enriched in the heavy isotope (δ98Mo values up to + 2.9‰) compared to previously published isotope data of sedimentary molybdenum from the same range of water depths. Furthermore, δ98Mo values of all water samples from the Black Sea and anoxic deeps of the Baltic Sea are heavier than open ocean water. The observed isotope fractionation between sediments and the anoxic water column of the Black Sea are in line with the model of thiomolybdates that scavenge to particles under reducing conditions. An extrapolation to a theoretical pure MoS42− solution indicates a fractionation constant between MoS42− and authigenic solid Mo of 0.5 ± 0.3‰. Measured waters with all thiomolybdates coexisting in various proportions show larger but non-linear fractionation. The best explanation for our field observations is Mo scavenging by the thiomolybdates, dominantly — but not exclusively — present in the form of MoS42−. The Mo isotopic compositions of samples from the sediments and anoxic water column of the Baltic Sea are in overall agreement with those of the Black Sea at intermediate depth and corresponding sulphide concentrations. The more dynamic changes of redox conditions in the Baltic deeps complicate the Black Sea-derived relationship between thiomolybdates and Mo isotopic composition. In particular, the occasional flushing/mixing, of the deep waters, affects the corresponding water column and sedimentary data. δ98Mo values of the upper oxic waters of both basins are higher than predicted by mixing models based on salinity variations. The results can be explained by non-conservative behaviour of Mo under suboxic to anoxic conditions in the shallow bottom parts of the basin, most pronounced on the NW shelf of the Black Sea.

"Death may come on like a stroke of lightening ..." : Phenomenological and morphological aspects of fatalities caused by manure gas

Due to the decomposition of biological material, hydrogen sulphide (H(2)S) is produced. In low concentrations, the well-known smell of "rotten eggs" is associated with H(2)S. In higher concentrations, H(2)S is an odourless and colourless gas that may cause rapid loss of consciousness, neurological and respiratory depression and imminent death-"... like a stroke of lightening". Hydrogen sulphide poisoning is an un-common incident that is often associated with colleague fatalities. In this study, 4 fatal accidents with 10 deceased victims are reported and the morphological and phenomenological aspects are presented. In these cases, the morphological findings, namely, discolouration of the livores, pulmonary pathologies and sub-mucosal or sub-serosal congestion bleeding were found in nearly all cases. Also the impending threat for colleagues, first aid helpers and professional rescue teams is demonstrated. The suspicion of a fatal H(2)S intoxication should be based on a precise scene analysis with respect to the possibility of life-threatening H(2)S intoxication for the helpers, the typical scent of rotten eggs, which may be noted on the corpses and the abovementioned morphological findings. The diagnosis should be confirmed by a qualitative and, if possible, quantitative analysis of H(2)S.

Magmatic–hydrothermal molybdenum isotope fractionation and its relevance to the igneous crustal signature

We analysed the Mo isotope composition of a comprehensive series of molybdenite samples from the porphyry- type Questa deposit (NM, USA), as well as one rhyolite and one granite sample, directly associated with the Mo mineralization. The δ98Mo of the molybdenites ranges between −0.48‰ and +0.40‰, with a median at −0.05‰. The median Mo isotope composition increases from early magmatic (−0.29‰) to hydrothermal (−0.05‰) breccia mineralization (median bulk breccia = −0.17‰) to late stockwork veining (+0.22‰). Moreover, variations of up to 0.34‰ are found between different molybdenite crystals within an individual hand specimen. The rhyolite sample with 0.12 μg g−1 Mo has δ98Mo = −0.57‰ and is lighter than all molybde- nites from the Questa deposit, interpreted to represent the igneous leftover after aqueous ore fluid exsolution. We recognize three Mo isotope fractionation processes that occur between about 700 and 350 °C, affecting the Mo iso- tope composition of magmatic–hydrothermal molybdenites. Δ1Mo: Minerals preferentially incorporate light Mo isotopes during progressive fractional crystallization in subvolcanic magma reservoirs, leaving behind a melt enriched in heavy Mo isotopes. Δ2Mo: Magmatic–hydrothermal fluids preferentially incorporate heavy Mo iso- topes upon fluid exsolution. Δ3Mo: Light Mo isotopes get preferentially incorporated in molybdenite during crys- tallization from an aqueous fluid, leaving behind a hydrothermal fluid that gets heavier with progressive molybdenite crystallization. The sum of all three fractionation processes produces molybdenites that record heavier δ98Mo compositions than their source magmas. This implies that the mean δ98Mo of molybdenites published so far (~0.4‰) likely represents a maximum value for the Mo isotope composition of Phanerozoic igneous upper crust.

Pelagic molybdenum concentration anomalies and the impact of sediment resuspension on the molybdenum budget in two tidal systems of the North Sea

The seasonal dynamics of molybdenum (Mo) were studied in the water column of two tidal basins of the German Wadden Sea (Sylt-Rømø and Spiekeroog) between 2007 and 2011. In contrast to its conservative behaviour in the open ocean, both, losses of more than 50% of the usual concentration level of Mo in seawater and enrichments up to 20% were observed repeatedly in the water column of the study areas. During early summer, Mo removal by adsorption on algae-derived organic matter (e.g. after Phaeocystis blooms) is postulated to be a possible mechanism. Mo bound to organic aggregates is likely transferred to the surface sediment where microbial decomposition enriches Mo in the pore water. First δ98/95Mo data of the study area disclose residual Mo in the open water column being isotopically heavier than MOMo (Mean Ocean Molybdenum) during a negative Mo concentration anomaly, whereas suspended particulate matter shows distinctly lighter values. Based on field observations a Mo isotope enrichment factor of ε = −0.3‰ has been determined which was used to argue against sorption on metal oxide surfaces. It is suggested here that isotope fractionation is caused by biological activity and association to organic matter. Pelagic Mo concentration anomalies exceeding the theoretical salinity-based concentration level, on the other hand, cannot be explained by replenishment via North Sea waters alone and require a supply of excess Mo. Laboratory experiments with natural anoxic tidal flat sediments and modelled sediment displacement during storm events suggest fast and effective Mo release during the resuspension of anoxic sediments in oxic seawater as an important process for a recycling of sedimentary sulphide bound Mo into the water column.

Reactive mass transport modelling of a three-dimensional vertical fault zone with a finger-like convective flow regime

For a three-dimensional vertically-oriented fault zone, we consider the coupled effects of fluid flow, heat transfer and reactive mass transport, to investigate the patterns of fluid flow, temperature distribution, mineral alteration and chemically induced porosity changes. We show, analytically and numerically, that finger-like convection patterns can arise in a vertically-oriented fault zone. The onset and patterns of convective fluid flow are controlled by the Rayleigh number which is a function of the thermal properties of the fluid and the rock, the vertical temperature gradient, and the height and the permeability of the fault zone. Vigorous fluid flow causes low temperature gradients over a large region of the fault zone. In such a case, flow across lithological interfaces becomes the most important mechanism for the formation of sharp chemical reaction fronts. The degree of rock buffering, the extent and intensity of alteration, the alteration mineralogy and in some cases the formation of ore deposits are controlled by the magnitude of the flow velocity across these compositional interfaces in the rock. This indicates that alteration patterns along compositional boundaries in the rock may provide some insights into the convection pattern. The advective mass and heat exchanges between the fault zone and the wallrock depend on the permeability contrast between the fault zone and the wallrock. A high permeability contrast promotes focussed convective flow within the fault zone and diffusive exchange of heat and chemical reactants between the fault zone and the wallrock. However, a more gradual permeability change may lead to a regional-scale convective flow system where the flow pattern in the fault affects large-scale fluid flow, mass transport and chemical alteration in the wallrocks

The Yanque prospect (Peru): from polymetallic Zn-Pb mineralization to a nonsulfide deposit

The Yanque nonsulfide Pb-Zn deposit (inferred resources 12.5 Mt @ 3.7% Pb and @ 3.5% Zn) is located in the Andahuaylas-Yauri ore province (Cuzco, southern Peru). The deposit occurs within a base metal mineralized district, centered on the medium-sized Dolores porphyry copper. A thorough geological, mineralogical and geochemical study has carried out in order to define: the relationships between the Dolores Cu-porphyry ore and the Yanque Zn-Pb polymetallic mineralization, and the characteristics of the economic nonsulfide concentrations. Both sedimentary and igneous rocks constitute the backbone of the Yanque-Dolores area. The sedimentary lithologies belong to the Soraya, Mara and Ferrobamba Fms. (upper Jurassic-middle Cretaceous). The Yanque orebody is hosted by the Mara Fm., which prevailingly consists of a siliciclastic sedimentary breccia. The original sulfide mineralization consisted of galena, pyrite and sphalerite. The host rock has been affected by a strong hydrothermal alteration, characterized by prevailing sericite/illite, as in the typical porphyry-related phyllic-argillic alteration stage, and by minor kaolinite, dolomite and quartz. Minor element geochemistry, characterized by Sb, As, Mn, Ag and locally also by Cu, points to magmatic-hydrothermal related mineralizing fluids. The Pb isotopic compositions from Dolores and Yanque sulfides are similar, and are typical of the Tertiary magmatically-derived ores in this part of Peru. The hydrothermally altered rocks at Yanque have the same Pb isotopic compositions as the sulfides, thus confirming the hypothesis that the Yanque primary Zn-Pb mineralization may have been produced by hydrothermal circulation related to the emplacement of the Dolores Cu-porphyry, as it is the case of other porphyry Cu systems associated with polymetallic mineralization elsewhere. However, no simple genetic model for the mineralization involving just one fluid circulation episode is able to explain the data. The Yanque economic nonsulfide ore association consists of sauconite, hemimorphite, smithsonite and cerussite, which result from the weathering and alteration of the original sulfide mineralization. Zinc is allocated mainly in sauconite (Zn-smectite), rather than in carbonates: a factor strictly related to the prevailing siliciclastic character of the host rock. Distinctive features of the Yanque orebody are the comparable ore grades for both Pb and Zn (3.5% Zn and 3.7% Pb), and the inverse supergene chemical zoning. In fact, contrary to other supergene ores of this type, zinc prevails in the top zone of the Yanque deposit, whereas lead content increases with depth. Considering the different mobility of the two metals in solution, it may be assumed that most of the primary zinc that was the source for the Yanque nonsulfides was originally located far from the position occupied by the galena mineralization, whose remnants have been observed on site. Zinc sulfides may have been originally contained in the eroded rock volumes that surrounded the actual deposit: the zinc-rich solutions have possibly migrated through the siliciclastic Mara Fm. and precipitated the nonsulfide minerals by porosity filling and replacement processes. In this sense, the Yanque secondary Zn-Pb deposit could be considered as a special type of “Exotic” mineralization.

Elemental and Lead Isotopic Data of Copper Finds from the Singen Cemetery, Germany – a Methodological Approach to Investigate Early Bronze Age Trade Networks

We report a trace element - Pb isotope analytical (LIA) database on the "Singen Copper", a peculiar type of copper found in the North Alpine realm, from its type locality, the Early Bronze Age Singen Cemetery (Germany). What distinguishes “Singen Copper” from other coeval copper types? (i) is it a discrete metal lot with a uniform provenance (if so, can its provenance be constrained)? (ii) was it manufactured by a special, unique metallurgical process that can be discriminated from others? Trace element concentrations can give clues on the ore types that were mined, but they can be modified (more or less intentionally) by metallurgical operations. A more robust indicator are the ratios of chemically similar elements (e.g. Co/Ni, Bi/Sb, etc.), since they should remain nearly constant during metallurgical operations, and are expected to behave homogeneously in each mineral of a given mining area, but their partition amongst the different mineral species is known to cause strong inter-element fractionations. We tested the trace element ratio pattern predicted by geochemical arguments on the Brixlegg mining area. Brixlegg itself is not compatible with the Singen Copper objects, and we only report it because it is a rare instance of a mining area for which sufficient trace element analyses are available in the literature. We observe that As/Sb in fahlerz varies by a factor 1.8 above/below median; As/Sb in enargite varies by a factor of 2.5 with a 10 times higher median. Most of the 102 analyzed metal objects from Singen are Sb-Ni-rich, corresponding to “antimony-nickel copper” of the literature. Other trace element concentrations vary by > 100 times, ratios by factors > 50. Pb isotopic compositions are all significantly different from each other. They do not form a single linear array and require > 3 ore batches that certainly do not derive from one single mining area. Our data suggest a heterogeneous provenance of “Singen copper”. Archaeological information limits the scope to Central European sources. LIA requires a diverse supply network from many mining localities, including possibly Brittany. Trace element ratios show more heterogeneity than LIA; this can be explained either by deliberate selection of one particular ore mineral (from very many sources) or by processing of assorted ore minerals from a smaller number of sources, with the unintentional effect that the quality of the copper would not be constant, as the metallurgical properties of alloys would vary with trace element concentrations.

Promising anchoring groups for single-molecule conductance measurements

The understanding of the charge transport through single molecule junctions is a prerequisite for the design and building of electronic circuits based on single molecule junctions. However, reliable and robust formation of such junctions is a challenging task to achieve. In this topical review, we present a systematic investigation of the anchoring group effect on single molecule junction conductance by employing two complementary techniques, namely scanning tunneling microscopy break junction (STM-BJ) and mechanically controllable break junction (MCBJ) techniques, based on the studies published in the literature and important results from our own work. We compared conductance studies for conventional anchoring groups described earlier with the molecular junctions formed through π-interactions with the electrode surface (Au, Pt, Ag) and we also summarized recent developments in the formation of highly conducting covalent Au–C σ-bonds using oligophenyleneethynylene (OPE) and an alkane molecular backbone. Specifically, we focus on the electron transport properties of diaryloligoyne, oligophenyleneethynylene (OPE) and/or alkane molecular junctions composed of several traditional anchoring groups, (dihydrobenzo[b]thiophene (BT), 5-benzothienyl analogue (BTh), thiol (SH), pyridyl (PY), amine (NH2), cyano (CN), methyl sulphide (SMe), nitro (NO2)) and other anchoring groups at the solid/liquid interface. The qualitative and quantitative comparison of the results obtained with different anchoring groups reveals structural and mechanistic details of the different types of single molecular junctions. The results reported in this prospective may serve as a guideline for the design and synthesis of molecular systems to be used in molecule-based electronic devices.