Chemical and isotopic equilibrium between CO2 and CH4 in fumarolic gas discharges: Generation of CH4 in arc magmatic-hydrothermal systems

The chemical and isotopic composition of fumarolic gases emitted from Nisyros Volcano, Greece, and of a single gas sample from Vesuvio, Italy, was investigated in order to determine the origin of methane (CH₄) within two subduction-related magmatic-hydrothermal environments.Apparent temperatures derived from carbon isotope partitioning between CH₄ and CO₂ of around 340°C for Nisyros and 470°C for Vesuvio correlate well with aquifer temperatures as measured directly and/or inferred from compositional data using the H₂O-H₂-CO₂-CO-CH₄ geothermometer. Thermodynamic modeling reveals chemical equilibrium between CH₄, CO₂ and H₂O implying that carbon isotope partitioning between CO₂ and CH₄ in both systems is controlled by aquifer temperature.N₂/³He and CH₄/³He ratios of Nisyros fumarolic gases are unusually low for subduction zone gases and correspond to those of midoceanic ridge environments. Accordingly, CH₄ may have been primarily generated through the reduction of CO₂ by H₂ in the absence of any organic matter following a Fischer-Tropsch-type reaction. However, primary occurrence of minor amounts of thermogenic CH₄ and subsequent re-equilibration with co-existing CO₂ cannot be ruled out entirely. CO₂/³He ratios and δ¹³C_CO2 values imply that the evolved CO₂ either derives from a metasomatized mantle or is a mixture between two components, one outgassing from an unaltered mantle and the other released by thermal breakdown of marine carbonates. The latter may contain traces of organic matter possibly decomposing to CH₄ during thermometamorphism.     

Evolution of a hydrothermal fluid-rock interaction system as recorded by Sr isotopes: A case study from the Schwarzwald, SW Germany

Metasomatic and Sr-isotopic changes, associated with formation of zoned alteration halos along hydrothermal veins, are documented for a gneiss from the Artenberg quarry near Steinach (Kinzigtal, Schwarzwald, SW Germany). Veins are postorogenic, SW-NE-oriented, and cut straight through metaquartzdioritic Variscan gneiss, where flow of low-temperature fluids (～100–200°C) caused adularia-quartz-sericite-type alteration. Fluid-rock interaction occurred nearly 50 Ma after Variscan metamorphism, as constrained by a Rb–Sr multimineral isochron for unaltered gneiss of 327.1?±?3.1 Ma, and by two independent ages of 279.2?±?3.1 Ma and 274?±?13 Ma, based on Rb–Sr systematics of late-stage quartz from the veins. In a profile from unaltered gneiss towards a vein, alteration-induced mineralogical changes correlate with metasomatic net addition of K, Rb, and Cl to the alteration zone, combined with net loss of Na, Ca, and Sr. Strontium isotopes give a more detailed insight into the fluid-rock interaction process. ⁸⁷Sr/⁸⁶Sr ratios in a profile across the alteration zone are incompatible with simple Sr leaching but reflect partial replacement of the rocks’ Sr by fluid-derived Sr, the isotopic composition of which varied with time. Early fluids, with high ⁸⁷Sr/⁸⁶Sr ratios compared to unaltered gneiss, evolved into fluids with somewhat lower ratios, and finally reached a second maximum in ⁸⁷Sr/⁸⁶Sr ratios. This Sr-isotopic fluid evolution is equally revealed by the mineral sequence of the vein mineralization. It appears that the compositional evolution of the fluids correlates with the sequence of mineral breakdown reactions in the gneissic host rock, and that the Sr-isotopic evolution of the fluids can be fully explained as the result of internal, progressive reaction of fluid with the local rocks. Results also show that the spatial distributions of Sr isotopes in metasomatic alteration zones may reflect the complex evolution of fluid-rock interaction systems, and ultimately constrain the factors controlling both fluid compositions and alteration patterns.     

Dehydration melting of tonalites. Part I. Beginning of melting

 The beginning of dehydration melting in the tonalite system (biotite-plagioclase-quartz) is investigated in the pressure range of 2–12 kbar. A special method consisting of surrounding a crystal of natural plagioclase (An₄₅) with a biotite-quartz mixture, and observing reactions at the plagioclase margin was employed for precise determination of the solidus for dehydration melting. The beginning of dehydration melting was worked out at 5 kbar for a range of compositions of biotite varying from iron-free phlogopite to iron-rich Ann₇₀, with and without titanium, fluorine and extra aluminium in the biotite. The dehydration melting of phlogopite + plagioclase (An₄₅) + quartz begins between 750 and 770°C at pressures of 2 and 5 kbar, at approximately 740°C at 8 kbar and between 700 and 730°C at 10 kbar. At 12 kbar, the first melts are observed at temperatures as low as 700°C. The data indicate an almost vertical dehydration melting solidus curve at low pressures which bends backward to lower temperatures at higher pressures (> 5 kbar). The new phases observed at pressures ≤ 10 kbar are melt + enstatite + clinopyroxene + potassium feldspar ± amphibole. In addition to these, zoisite was also observed at 12 kbar. With increasing temperature, phlogopite becomes enriched in aluminium and deficient in potassium. Substitution of octahedral magnesium by aluminium and titanium in the phlogopite, as well as substitution of hydroxyl by fluorine, have little effect on the beginning of dehydration melting temperatures in this system. The dehydration melting of biotite (Ann₅₀) + plagioclase (An₄₅) + quartz begins 50°C below that of phlogopite bearing starting composition. Solid reaction products are orthopyroxene + clinopyroxene + potassium feldspar ± amphibole. Epidote was also observed above 8 kbar, and garnet at 12 kbar (750°C). The experiments on the iron-bearing system performed at ≤ 5 kbar were buffered with NiNiO. The f _{O 2} in high pressure runs lies close to CoCoO. With the substitution of octahedral magnesium and iron by aluminium and titanium, and replacement of hydroxyl by fluorine in biotite, the beginning of dehydration melting temperatures in this system increase up to 780°C at 5 kbar, which is 70°C above the beginning of dehydration melting of the assemblage containing biotite (Ann₅₀) of ideal composition. The dehydration melting at 5 kbar in the more iron-rich Ann₇₀-bearing starting composition begins at 730°C, and in the Ann₂₅-bearing assemblage at 710°C. This indicates that quartz-biotite-plagioclase assemblages with intermediate compositions of biotite (Ann₂₅ and Ann₅₀) melt at lower temperatures as compared to those containing Fe-richer or Mg-richer biotites. This study shows that the dehydration melting of tonalites may begin at considerably lower temperatures than previously thought, especially at high pressures (>5 kbar). Received: 27 December 1995 / Accepted: 7 May 1996     

Evolution of anthropogenic and biomass burning emissions of air pollutants at global and regional scales during the 1980�C2010 period

Several different inventories of global and regional anthropogenic and biomass burning emissions are assessed for the 1980?C2010 period. The species considered in this study are carbon monoxide, nitrogen oxides, sulfur dioxide and black carbon. The inventories considered include the ACCMIP historical emissions developed in support of the simulations for the IPCC AR5 assessment. Emissions for 2005 and 2010 from the Representative Concentration Pathways (RCPs) are also included. Large discrepancies between the global and regional emissions are identified, which shows that there is still no consensus on the best estimates for surface emissions of atmospheric compounds. At the global scale, anthropogenic emissions of CO, NO_x and SO₂ show the best agreement for most years, although agreement does not necessarily mean that uncertainty is low. The agreement is low for BC emissions, particularly in the period prior to 2000. The best consensus is for NO_x emissions for all periods and all regions, except for China, where emissions in 1980 and 1990 need to be better defined. Emissions of CO need better quantification in the USA and India for all periods; in Central Europe, the evolution of emissions during the past two decades needs to be better determined. The agreement between the different SO₂ emissions datasets is rather good for the USA, but better quantification is needed elsewhere, particularly for Central Europe, India and China. The comparisons performed in this study show that the use of RCP8.5 for the extension of the ACCMIP inventory beyond 2000 is reasonable, until more global or regional estimates become available. Concerning biomass burning emissions, most inventories agree within 50?C80%, depending on the year and season. The large differences between biomass burning inventories are due to differences in the estimates of burned areas from the different available products, as well as in the amount of biomass burned.     

The effect of submarine groundwater discharge on nutrient and salinity regimes in a coastal lagoon off Perth, Western Australia

Submarine groundwater discharge (SGD) into a coastal lagoon off Perth, Western Australia, contains nitrate and silicate in concentrations two orders of magnitude higher than those of the receiving waters. This discharge delivers enough nitrate to replace that dissolved in the lagoon water mass about every eight days and enough silicate to replace the lagoon silicate in about 48 days. The delivery rate of nitrate nitrogen by SGD is equal to about 48% of that required for observed growth rates of lagoon macrophytes. Surface salinity is lower close to the shore as a result of SGD. During calm conditions a salinity front was observed in the lagoon, with a nearshore pool of nutrient-enriched water floating above the more saline ocean water.     

Spatial variability in growth and reproduction of the Pacific oyster Crassostrea gigas (Thunberg, 1793) along the west European coast

The Pacific oyster Crassostrea gigas was introduced in Europe for commercial purposes in the mid 1960s. It was initially thought that low winter temperatures would restrain this species' reproduction and settlement; however, its present distribution in areas where no introduction has taken place suggests that natural invasion and expansion has occurred. Along the European coast, wild populations of Pacific oysters are already found from northern Germany to southern Portugal. Whether C. gigas will continue to further expand through northern waters will depend on its physiological performance. In this study, the performance of wild oyster populations has been studied in terms of growth and reproduction at three stations: La Rochelle (France; 46°N), Yerseke (Oosterschelde estuary, The Netherlands, 51°N), and Texel (Wadden Sea estuary, The Netherlands, 53°N). The French population had the lowest somatic-shell mass ratio and an increase in maximum shell length, somatic and gonadal mass was observed from France to the Netherlands. In addition, mean oocyte diameter decreased significantly from south to north. The combination of increasing gonadal mass and decreasing oocyte volume suggests an increasing reproductive output in terms of egg numbers from France to The Netherlands. Differences in temperature between locations will at least be partly responsible for the observed patterns; however, other environmental factors (such as food availability, predation pressure, sediment type and/or seston concentration) cannot be excluded. Since smaller eggs (oocytes) are thought to have a longer development time, the environmental conditions along the Dutch coast may result in increased larval dispersal and possibly in further population expansion.     

Growth and reproduction of the bivalve Spisula subtruncata (da Costa) in Dutch coastal waters

The bivalve Spisula subtruncata is usually abundant in shallow coastal waters along the Dutch coast. However, its biomass has been decreasing since 1995. In order to assess whether reproductive failure may be the cause of the observed decline over the last decades, the energy investment in reproduction of a population of S. subtruncata from central Dutch coastal waters was studied. The population studied consisted of individuals of up to four years old. Shell length reached maximum values of around 32 mm and individual total body, somatic and gonadal ash-free dry mass reached maximum values of about 278 mg AFDM, 252 mg AFDM and 76 mg AFDM, respectively. A clear seasonal cycle in somatic and gonadal mass was observed. Somatic and gonadal mass indices increased in early spring and reached maximum values during summer, followed by a decrease to minimum values at the beginning of the following year. Spawning was in June–July and settlement of spat seems to have occurred in July–August. Mean oocyte diameter was 57.43 ± 0.03 μm, corresponding to a volume of 98972 μm³. These results suggested that reproductive failure was not the cause of the current population decline. Most likely, unsuccessful settlement of spat and/or severe predation during the first months of life were responsible for the observed patterns.     

On Flare-CME Characteristics from Sun to Earth Combining Remote-Sensing Image Data with <Emphasis Type="Italic">In Situ</Emphasis> Measurements Supported by Modeling

We analyze the well-observed flare and coronal mass ejection (CME) from 1 October 2011 (SOL2011-10-01T09:18) covering the complete chain of effects – from Sun to Earth – to better understand the dynamic evolution of the CME and its embedded magnetic field. We study in detail the solar surface and atmosphere associated with the flare and CME using the Solar Dynamics Observatory (SDO) and ground-based instruments. We also track the CME signature off-limb with combined extreme ultraviolet (EUV) and white-light data from the Solar Terrestrial Relations Observatory (STEREO). By applying the graduated cylindrical shell (GCS) reconstruction method and total mass to stereoscopic STEREO-SOHO (Solar and Heliospheric Observatory) coronagraph data, we track the temporal and spatial evolution of the CME in the interplanetary space and derive its geometry and 3D mass. We combine the GCS and Lundquist model results to derive the axial flux and helicity of the magnetic cloud (MC) from in situ measurements from Wind. This is compared to nonlinear force-free (NLFF) model results, as well as to the reconnected magnetic flux derived from the flare ribbons (flare reconnection flux) and the magnetic flux encompassed by the associated dimming (dimming flux). We find that magnetic reconnection processes were already ongoing before the start of the impulsive flare phase, adding magnetic flux to the flux rope before its final eruption. The dimming flux increases by more than 25% after the end of the flare, indicating that magnetic flux is still added to the flux rope after eruption. Hence, the derived flare reconnection flux is most probably a lower limit for estimating the magnetic flux within the flux rope. We find that the magnetic helicity and axial magnetic flux are lower in the interplanetary space by ～?50% and 75%, respectively, possibly indicating an erosion process. A CME mass increase of 10% is observed over a range of \({\sim}\,4\,\mbox{--}\,20~\mathrm{R}_{\odot }\). The temporal evolution of the CME-associated core-dimming regions supports the scenario that fast outflows might supply additional mass to the rear part of the CME.     

Glacier change in Garibaldi Provincial Park, southern Coast Mountains, British Columbia, since the Little Ice Age

Fluctuations of glaciers during the 20th century in Garibaldi Provincial Park, in the southern Coast Mountains of British Columbia, were reconstructed from historical documents, aerial photographs, and fieldwork. Over 505 km², or 26%, of the park, was covered by glacier ice at the beginning of the 18th century. Ice cover decreased to 297 km² by 1987–1988 and to 245 km² (49% of the early 18th century value) by 2005. Glacier recession was greatest between the 1920s and 1950s, with typical frontal retreat rates of 30 m/a. Many glaciers advanced between the 1960s and 1970s, but all glaciers retreated over the last 20 years. Times of glacier recession coincide with warm and relatively dry periods, whereas advances occurred during relatively cold periods. Rapid recession between 1925 and 1946, and since 1977, coincided with the positive phase of the Pacific Decadal Oscillation (PDO), whereas glaciers advanced during its negative phase (1890–1924 and 1947–1976). The record of 20th century glacier fluctuations in Garibaldi Park is similar to that in southern Europe, South America, and New Zealand, suggesting a common, global climatic cause. We conclude that global temperature change in the 20th century explains much of the behaviour of glaciers in Garibaldi Park and elsewhere.     

Ocean currents determine functional connectivity in an Antarctic deep‐sea shrimp

The coherency among larval stages of marine taxa, ocean currents and population connectivity is still subject to discussion. A common view is that organisms with pelagic larval stages have higher dispersal abilities and therefore show a relatively homogeneous population genetic structure. Contrary to this, local genetic differentiation is assumed for many benthic direct developers. Specific larval or adult migratory behavior and hydrographic effects may significantly influence distribution patterns, rather than passive drifting abilities alone. The Southern Ocean is an ideal environment to test for the effects of ocean currents on population connectivity as it is characterized by several well‐defined and strong isolating current systems. In this study we studied the genetic structure of the decapod deep‐sea shrimp Nematocarcinus lanceopes, which has planktotrophic larval stages. We analysed 194 individuals from different sample localities around the Antarctic continent using nine microsatellite markers. Consistent with a previous study based on mitochondrial DNA markers, primarily weak genetic patterns among N. lanceopes populations around the continent were found. Using ocean resistance modeling approaches we were able to show that subtle genetic differences among populations are more likely explained by ocean currents rather than by geographic distance for the Atlantic Sector of the Southern Ocean.