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.     

Differential reproductive strategies of two bivalves in the Dutch Wadden Sea

Cerastoderma edule and Mya arenaria are two common bivalve species in European waters. Longevity and maximum size are much greater in the latter species. Because comparison of species life-history strategies states that a long life span (i.e. high annual survival) generally goes with lower fecundity, we hypothesise that reproductive output would be lower in M. arenaria than in C. edule. In the present paper, we studied the reproductive strategies of these two species in an intertidal and a subtidal area of the western Dutch Wadden Sea, by following seasonal changes in absolute and relative weights of somatic and gonadal tissues in these bivalves. Starting of spawning was similar in the two species, around May, except for intertidal M. arenaria, which initiated spawning in August. Individual energy investment in reproduction was similar for the two species but, unlike M. arenaria, C. edule spawned completely, releasing all energy of gonadal mass in the form of gametes. Mya arenaria used the gonad not only for reproduction but also for storage. In the intertidal area, we found a trade-off between longevity and reproduction, i.e. maximum reproductive output (expressed as a proportion of body mass) was higher in C. edule than in M. arenaria. However, since body size is larger and life span longer in M. arenaria than in C. edule, mean lifetime reproductive output per individual must be higher in the first than in the latter. Based on the differences in reproductive strategies of these two species, we hypothesise that the negative effects of warming climate on bivalve population dynamics in the Wadden Sea will be stronger in C. edule than in M. arenaria.     

Inter‐laboratory Characterisation of Apatite Reference Materials for Chlorine Isotope Analysis

Here we report on a set of six apatite reference materials (chlorapatites MGMH#133648, TUBAF#38 and fluorapatites MGMH#128441A, TUBAF#37, 40, 50) which we have characterised for their chlorine isotope ratios; these RMs span a range of Cl mass fractions within the apatite Ca₁₀(PO₄)₆(F,Cl,OH)₂ solid solution series. Numerous apatite specimens, obtained from mineralogical collections, were initially screened for ³⁷Cl/³⁵Cl homogeneity using SIMS followed by δ³⁷Cl characterisation by gas source mass spectrometry using both dual‐inlet and continuous‐flow modes. We also report major and key trace element compositions as determined by EPMA. The repeatability of our SIMS results was better than ± 0.10‰ (1s) for the five samples with > 0.5 % m/m Cl and ± 0.19‰ (1s) for the low Cl abundance material (0.27% m/m). We also observed a small, but significant crystal orientation effect of 0.38‰ between the mean ³⁷Cl/³⁵Cl ratios measured on three oriented apatite fragments. Furthermore, the results of GS‐IRMS analyses show small but systematic offset of δ³⁷Cl_SMOC values between the three laboratories. Nonetheless, all studied samples have comparable chlorine isotope compositions, with mean 10³δ³⁷Cl_SMOC values between +0.09 and +0.42 and in all cases with 1s ≤ ± 0.25.     

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.     

Carry-over effects of the membrane interface probe

The membrane interface probe (MIP) is widely used to characterize the subsurface distribution of volatile organic compounds (VOCs). One problem that arises during MIP application is that disproportionately high MIP signals are obtained after passing source zones which contain mobile or residual phases. This serious problem occurs because of a carry-over effect, in particular caused by compound-specific retention times in the conventional unheated transfer line, commonly used during such an investigation. The objective of this study was to perform a qualitative methodical field evaluation of the carry-over effect of a conventional MIP system with a conventional unheated transfer line. This was achieved by coupling a mobile mass spectrometer to the MIP device. Results obtained were then further compared with those achieved using a laser induced fluorescence (LIF) system. Because of this coupling, time- and depth-dependent signals for different substances became known. Field evaluation data obtained showed complex superpositions of compounds with MIP system results. As a result of this superposition, MIP signals from the saturated zone beneath the source zone (zone with free and/or residual phase) are blurred and are therefore not representative of particular depths. However, utilizing multidirectional probing alongside conventional MIP probing (forwards and backwards), it was possible to detect the upper and lower phase boundary of the source zone. These MIP results correlated excellently with the LIF results. An important conclusion that can be drawn from the field investigation is that coupling a mobile mass spectrometer to the MIP system enables advanced MIP signal interpretation to be successfully achieved.     

The coast between Cabo de Santa Maria (Portugal) and Rabat (Morocco): a mega-size headland-bay shoreline under control of the North Atlantic swell?

Equilibrium headland-bay beach systems have been mathematically described by logarithmic, parabolic and hyperbolic curve functions. The largest system of this type reported to date has a shoreline length of about 62 km. In the present study, an apparent headland-bay system is presented which has a shoreline length of about 500 km. It was discovered on satellite images, and is located between Cabo de Santa Maria in Portugal and the coastal city of Rabat in Morocco. It appears to be controlled by long-period North Atlantic swells diffracting around Cabo São Vicente at the south-western tip of Portugal, in combination with SW–SE wind wave climates impinging on the northern shoreline of Cádiz Bay. The coast shows two marked departures from the equilibrium shoreline along its central section north and south of the Strait of Gibraltar, which are easily explained. Thus, the promontories to the north of the strait still exist because there has not been sufficient time to erode these back to the equilibrium shoreline since postglacial sea-level recovery. The coastal indentation to the south is explained by an insufficient sediment supply from terrestrial sources to facilitate the required beach accretion. Perfectly adjusted planimetric headland-bay shoreline shapes represent situations where wave orthogonals approach the coast at right angles everywhere, i.e. there is no longer any alongshore sediment transport. Equilibrium shorelines form independently of the grain size of the beach sediment, whereas morphodynamic beach states are indirectly affected by the shoreline shapes because the latter are modulated by wave period and breaker height which also control the morphodynamic response of the beach in combination with the local grain size.     

I Zwicky 1: Decomposition and dynamics of the nearby QSO host

We address current theories of research on morphology, environment and evolution of active galaxies in the form of a detailed case study of the nearby QSO host I Zw 1. This study is based on sub-kpc resolution ¹²CO(1-0) observations with the BIMA mm-interferometer and on near-infrared imaging with ISAAC at the VLT. The ¹²CO(1-0) maps reveal a circumnuclear molecular gas ring with a radius of 0.9 kpc. The imaging data in the J-band are analyzed with respect to a disk-bulge decomposition. Together with a model of the gas rotation curve, the radial profile of the dynamical J-band mass-to-light ratio (M/L) is discussed. The J-band images give new evidence for an interaction between I Zw 1 and its nearby companion. First results from a sequence of N-body simulations for an extensive test of the parameter space of the interaction are presented. This revised version was published online in August 2006 with corrections to the Cover Date.