Seasonal DOC accumulation in the Black Sea: a regional explanation for a general mechanism

During three cruises in the Black Sea, organised in July 1995 and April–May 1997, biological and chemical parameters that can influence the carbon budget were measured in the water column on the NW shelf, particularly in the mixing zone with Danube River waters. We observed in early spring (end of April–May) conditions an important input of freshwater organisms that enhanced the microbial activity in the low salinity range. High bacterial activity regenerates nitrogen in the form of nitrates, but is also responsible for an important consumption of ammonium and phosphate, leading to a high N/P ratio and a strong deficit in phosphorus. The consequence is a limitation of phytoplankton development but also a production of carbohydrates that accumulate all along the salinity gradient. These mechanisms are responsible for a seasonal accumulation of dissolved organic carbon (DOC) that increases from 210 μM in winter to about 280 μM in summer. All this excess DOC disappears during winter, probably degraded by bacterial activity. The degradation of carbon-rich organic matter increases the phosphorus demand by bacteria bringing limitation to phytoplankton primary production.     

Pb and other ore metals in modern seafloor tectonic environments: Evidence from melt inclusions

Many modern seafloor tectonic environments are host to hydrothermal systems and associated polymetallic sulfide deposits. Metal transport and precipitation are controlled by magmatic processes such as pre-eruptive degassing and the hydrothermal cycle. The original availability of Pb and other ore metals in a given setting is dependent on concentrations in the original magmatic source or additional enrichment processes. We have examined the Pb budget of melt inclusions from nine modern seafloor settings representing back-arcs, mid-ocean ridges and seamounts. Melt inclusions provide information on the characteristics of parental magmas, including insights into metal budgets. Trace element data in melt inclusions hosted in plagioclase, olivine and pyroxene were obtained by laser-ablation inductively-coupled mass-spectrometry.Results from back-arcs emphasize the impact of slab-subduction and dehydration processes on the chemical characteristics of generated magmas. Volatile- and fluid-mobile element-rich melt inclusions at Manus basin and Okinawa trough reflect a robust contribution of elements from the subducting slab as evidenced by relatively low Ce/Pb ratios. At Bransfield strait, on the other hand, melt inclusions are volatile poor, and fluid-mobile element ratios are similar to mid-ocean ridge values indicating little or no contribution from the slab. High Cu concentrations at Manus basin and Okinawa trough can be explained by fluxing of ferric iron from the subducting slab benefiting the production of sulfate over sulfide.Metal budgets for seamounts located on and nearby the axis of mid-ocean ridge segments appear to be independent of any input of mantle plume material. Results from the southern Explorer ridge (strong lower mantle influence, transitional- and enriched-MORBs), Pito and Axial seamounts (moderate lower mantle influence, transitional-MORBs) and a Foundation near-ridge seamount (little to no mantle influence, normal-MORB) show that, despite similar tectonic environments and varying contributions of mantle plume material, Cu, Zn and Pb values do not vary significantly between the enriched and non-enriched magma components of a given setting.     

Dynamical evolution of NEAs: Close encounters, secular perturbations and resonances

We discuss the main mechanisms affecting the dynamical evolution of Near-Earth Asteroids (NEAs) by analyzing the results of three numerical integrations over 1 Myr of the NEA (4179) Toutatis. In the first integration the only perturbing planet is the Earth. So the evolution is dominated by close encounters and looks like a random walk in semimajor axis and a correlated random walk in eccentricity, keeping almost constant the perihelion distance and the Tisserand invariant. In the second integration Jupiter and Saturn are present instead of the Earth, and the 3/1 (mean motion) and v ₆ (secular) resonances substantially change the eccentricity but not the semimajor axis. The third, most realistic, integration including all the three planets together shows a complex interplay of effects, with close encounters switching the orbit between different resonant states and no approximate conservation of the Tisserand invariant. This shows that simplified 3-body or 4-body models cannot be used to predict the typical evolution patterns and time scales of NEAs, and in particular that resonances provide some fast-track dynamical routes from low-eccentricity to very eccentric, planet-crossing orbits.On leave from the Department of Mathematics, University of Pisa, Via Buonarroti 2, 56127 Pisa, Italy, thanks to the G. Colombo fellowships of the European Space Agency.     

3D numerical modelling of fluid flow in the Val-d’Or orogenic gold district: major crustal shear zones drain fluids from overpressured vein fields

Fluid flow patterns have been determined using oxygen isotope isopleths in the Val-d’Or orogenic gold district. 3D numerical modelling of fluid flow and oxygen isotope exchange in the vein field shows that the fluid flow patterns can be reproduced if the lower boundary of the model is permeable, which represents middle or lower crustal rocks that are infiltrated by a metamorphic fluid generated at deeper levels. This boundary condition implies that the major crustal faults so conspicuous in vein fields do not act as the only major channel for upward fluid flow. The upper model boundary is impermeable except along the trace of major crustal faults where fluids are allowed to drain out of the vein field. This upper impermeable boundary condition represents a low-permeability layer in the crust that separates the overpressured fluid from the overlying hydrostatic fluid pressure regime. We propose that the role of major crustal faults in overpressured vein fields, independent of tectonic setting, is to drain hydrothermal fluids out of the vein field along a breach across an impermeable layer higher in the crust and above the vein field. This breach is crucial to allow flow out of the vein field and accumulation of metals in the fractures, and this breach has major implications for exploration for mineral resources. We propose that tectonic events that cause episodic metamorphic dehydration create a short-lived pulse of metamorphic fluid to rise along zones of transient permeability. This results in a fluid wave that propagates upward carrying metals to the mineralized area. Earthquakes along crustal shear zones cause dilation near jogs that draw fluids and deposit metals in an interconnected network of subsidiary shear zones. Fluid flow is arrested by an impermeable barrier separating the hydrostatic and lithostatic fluid pressure regimes. Fluids flow through the evolving and interconnected network of shear zones and by advection through the rock matrix. Episodic breaches in the impermeable barrier along the crustal shear zones allow fluid flow out of the vein field.     

Does stress transmission in forelands depend on structural style? Distinctive stress magnitudes during Sevier thin‐skinned and Laramide thick‐skinned layer‐parallel shortening in the Bighorn Basin (USA) revealed by stylolite and calcite twinning paleopiezometry

The Sheep Mountain‐Little Sheep Mountain Anticlines, Bighorn Basin (USA) formed as basement‐cored Laramide structures in the formerly undeformed foreland of the thin‐skinned Sevier orogen. We take advantage of the well‐constrained microstructural network there to reconstruct differential stress magnitudes that prevailed during both Sevier and Laramide layer‐parallel shortening (LPS), before the onset of large‐scale folding. Differential stress magnitudes determined from tectonic stylolites are compared and combined to previous stress estimates from calcite twinning paleopiezometry in the same formations. During stress loading related to LPS, differential stress magnitudes transmitted from the distant Sevier thin‐skinned orogen into the sedimentary cover of the Bighorn basin (11–43 MPa) are higher than the differential stress magnitudes accompanying the early stage of LPS related to the thick‐skinned Laramide deformation (2–19 MPa). This study illustrates that the tectonic style of an orogen affects the transmission of early orogenic stress into the stable continental interior.     

Chemical and textural equilibration of garnet during amphibolite facies metamorphism: The influence of coupled dissolution–reprecipitation

Metamorphic equilibration requires chemical communication between minerals and may be inhibited through sluggish volume diffusion and or slow rates of dissolution in a fluid phase. Relatively slow diffusion and the perceived robust nature of chemical growth zoning may preclude garnet porphyroblasts from readily participating in low‐temperature amphibolite facies metamorphic reactions. Garnet is widely assumed to be a reactant in staurolite‐isograd reactions, and the evidence for this has been assessed in the Late Proterozoic Dalradian pelitic schists of the Scottish Highlands. The 3D imaging of garnet porphyroblasts in staurolite‐bearing schists reveals a good crystal shape and little evidence of marginal dissolution; however, there is also lack of evidence for the involvement of either chlorite or chloritoid in the reaction. Staurolite forms directly adjacent to the garnet, and its nucleation is strongly associated with deformation of the muscovite‐rich fabrics around the porphyroblasts. “Cloudy” fluid inclusion‐rich garnet forms in both marginal and internal parts of the garnet porphyroblast and is linked both to the production of staurolite and to the introduction of abundant quartz inclusions within the garnet. Such cloudy garnet typically has a Mg‐rich, Mn‐poor composition and is interpreted to have formed during a coupled dissolution–reprecipitation process, triggered by a local influx of fluid. All garnet in the muscovite‐bearing schists present in this area is potentially reactive, irrespective of the garnet composition, but very few of the schists contain staurolite. The staurolite‐producing reaction appears to be substantially overstepped during the relatively high‐pressure Barrovian regional metamorphism reflecting the limited permeability of the schists in peak metamorphic conditions. Fluid influx and hence reaction progress appear to be strongly controlled by subtle differences in deformation history. The remaining garnet fails to achieve chemical equilibrium during the reaction creating distinctive patchy compositional zoning. Such zoning in metamorphic garnet created during coupled dissolution–reprecipitation reactions may be difficult to recognize in higher grade pelites due to subsequent diffusive re‐equilibration. Fundamental assumptions about metamorphic processes are questioned by the lack of chemical equilibrium during this reaction and the restricted permeability of the regional metamorphic pelitic schists. In addition, the partial loss of prograde chemical and textural information from the garnet porphyroblasts cautions against their routine use as a reliable monitor of metamorphic history. However, the partial re‐equilibration of the porphyroblasts during coupled dissolution–reprecipitation opens possibilities of mapping reaction progress in garnet as a means of assessing fluid access during peak metamorphic conditions.     

Spatial patterns of groundwater‐lake exchange – implications for acid neutralization processes in an acid mine lake

Exchange of groundwater and lake water with typically quite different chemical composition is an important driver for biogeochemical processes at the groundwater‐lake interface, which can affect the water quality of lakes. This is of particular relevance in mine lakes where anoxic and slightly acidic groundwater mixes with oxic and acidic lake water (pH < 3). To identify links between groundwater‐lake exchange rates and acid neutralization processes in the sediments, exchange rates were quantified and related to pore‐water pH, sulfate and iron concentrations as well as sulfate reduction rates within the sediment. Seepage rates measured with seepage meters (?2.5 to 5.8 L m^‐2 d^‐1) were in reasonable agreement with rates inverted from modeled chloride profiles (?1.8 to 8.1 L m^‐2 d^‐1). Large‐scale exchange patterns were defined by the (hydro)geologic setting but superimposed by smaller scale variations caused by variability in sediment texture. Sites characterized by groundwater upwelling (flow into the lake) and sites where flow alternated between upwelling and downwelling were identified. Observed chloride profiles at the alternating sites reflected the transient flow regime. Seepage direction, as well as seepage rate, were found to influence pH, sulfate and iron profiles and the associated sulfate reduction rates. Under alternating conditions proton‐consuming processes, for example, sulfate reduction, were slowed. In the uppermost layer of the sediment (max. 5 cm), sulfate reduction rates were significantly higher at upwelling (>330 nmol g^‐1 d^‐1) compared to alternating sites (<220 nmol g^‐1 d^‐1). Although differences in sulfate reduction rates could not be explained solely by different flux rates, they were clearly related to the prevailing groundwater‐lake exchange patterns and the associated pH conditions. Our findings strongly suggest that groundwater‐lake exchange has significant effects on the biogeochemical processes that are coupled to sulfate reduction such as acidity retention and precipitation of iron sulfides. Copyright © 2012 John Wiley & Sons, Ltd.