Electron accepting capacity of dissolved organic matter as determined by reaction with metallic zinc

Information about the chemical electron accepting capacity (EAC) of dissolved organic matter (DOM) is scarce owing to a lack of applicable methods. We quantified the electron transfer from metallic Zn to natural DOM in batch experiments at DOC concentrations of 10–100 mg-C L^− 1 and related it to spectroscopic information obtained from UV-, synchronous fluorescence, and FTIR- spectroscopy. The electron donating capacity of DOM and pre-reduced DOM was investigated using Fe(CN)₆³⁻ as electron acceptor. Presence of DOM resulted in release of dissolved Zn, consumption of protons, and slower release of hydrogen compared to reaction of metallic Zn with water at pH 6.5. Comparison with reaction stoichiometry confirmed that DOM accepted electrons from metallic Zn. The release of dissolved Zn was dependent on pH, DOC concentration, ionic strength, and organic matter properties. The reaction appeared to be completed within about 24 h and was characterized by pseudo first order kinetics with rate constants of 0.5 to 0.8 h^− 1. EAC per mass unit of carbon ranged from 0.22 mmol g^− 1 C to 12.6 mmol g^− 1 C. Depending on the DOM, a calculated 28–127% of the electrons transferred from metallic Zn to DOM could be subsequently donated to Fe(CN)₆³⁻. EAC decreased with DOC concentration, and increased with aromaticity, carboxyl, and phenolic content of the DOM. The results indicate that an operationally defined EAC of natural DOM can be quantified by reaction with metallic Zn and that DOM properties control the electron transfer. Shortcomings of the method are the coagulation and precipitation of DOM during the experiment and the production of hydrogen and dissolved Zn by reaction of metallic Zn with water, which may influence the determined EAC.     

Conservation of Mediterranean seascapes: analyses of existing protection schemes

Marine protected areas (MPAs) are aimed at managing and protecting marine environments. Their design, however, often disregards both a thorough knowledge of the distribution of habitats and assemblages and the use of proper experimental evaluations of the efficacy of MPAs by comparing protected vs. unprotected zones. About 200 MPAs have been recently instituted in the Mediterranean area, but the evidence of their efficacy is scant. The MPA of Torre Guaceto (Southern Adriatic Sea, Italy) is one of the rare cases of effective protection enforcement. The reserve was instituted more than 10 years ago, a period currently considered as sufficient to show responses by organisms to protection. The MPA is divided into a C zone, the general reserve, where many activities are permitted, a B zone, the partial reserve where restrictions increase and two A zones, the integral reserve where access is prohibited. The goals of the paper were to map the distribution of benthic assemblages to assess if they were properly represented in the differently protected zones, and to test the efficacy of protection by quantifying possible differences between the assemblages in two control areas and in the two A zones, where human impact is completely excluded. The analysis of habitat and assemblage distribution within the MPA showed that the zones with total protection do not include most valuable environmental types. Most of the considered variables (i.e. cover of substratum, number of taxa, and average abundance of the most common taxa) were not significantly different in and out of the A zones, at each time of sampling. Results, however, suggested a possible effect of protection in modifying patterns of abundance of sponges under Cystoseira canopy (more abundant in the fully protected zone). In the subtidal habitat, differences were found in the structure of the whole assemblage and in the abundance of encrusting coralline red algae (more abundant outside the fully protected area). Notwithstanding the correct general methodology employed in the study, a lack of statistical power could have a role in preventing the detection of ecologically relevant effects of protection. In some instances, data pooling allowed a discrimination between cases where there was clearly no effect of protection and cases where there might be. On this basis, the optimization of this experimental design should be considered in further studies. In any case, if the goals of MPAs have not been clearly stated, efficacy of protection might prove very difficult to test even with the use of sound experimental designs.     

Records of environmental and climatic changes during the late Holocene from Svalbard: palaeolimnology of Kongressvatnet

A multi-core, multidisciplinary palaeolimnological study of the partially varved sediment of a deep, meromictic, arctic lake, Kongressvatnet (Svalbard, Western Spitsbergen), provides a record of environmental and climatic changes during last ca. 1800 years. The chronology of sedimentation was established using several dating techniques (¹³⁷Cs, ²¹⁰Pb, varve counts, palaeomagnetic correlation). A multiproxy record of palaeolimnological variability was compiled based on sedimentation rates, magnetic properties, varve thickness, organic matter, geochemistry, pigments from algal and photosynthetic bacteria, mineralogy and biological assemblages (diatoms, Cladocera). The major features recognised in our master core K99-3 include a shift in sediment source and supply (magnetic measurements, geochemistry) probably caused by glaciological changes in the catchment around 38–32 cm core depth (AD 700–820). Additional environmental changes are inferred at 20–18, 8–4.5 and 3–2 cm (AD ca. 1160–1255; 1715–1880; 1940–1963, respectively). During the past ca. 120 years a prominent sedimentological change from brownish-grey, partly laminated silt-clay (varves) to black organic-rich deposits was observed. From AD 1350 to AD1880 the sediment is comprised of a continuous sequence of varves, whereas the earlier sediments are mostly homogeneous with only a few short intercalated laminated sections between AD 860 and 1350. Sedimentation and accumulation rates increased during the last 30 years (modern warming). Pigment concentrations are very low in the lower ca. 32 cm of the core (AD 820) probably because of the high turbidity high energy environment. The high sulphur content in the uppermost 32 cm of sediment has given rise to two horizontally stratified populations of sulphur anaerobic photosynthetic bacteria, as inferred from their specific carotenoids. These bacteria populations are much more abundant during the Little Ice Age (LIA) than during warmer periods (e.g., during the Medieval Warm Period and 20th century). Diatoms are lacking from the core base up to 18 cm (ca. AD 1255); at this level, species indicative of mesotrophic water are present, whereas from 17 cm to the top of the core, oligotrophic taxa such as Staurosira construens/S. pinnata complex dominate, indicating extended ice coverage and more oligotrophic waters during the LIA. The concentration of Cladocera subfossil remains (dominated by Chydorus) are relatively high in the deepest sections (54–32 cm), whereas the upper 32 cm are characterized by a very low concentration of remains, possibly because of the strongly anoxic conditions, and in this upper sediment section rotifer resting eggs become prevalent. We interpret these changes as responses to climate forcing through its impact on glacial melt water, lake ice cover duration and mainly redox conditions in deep water. The observed changes suggest that at least some of our recorded changes may parallel the Greenland Ice core, although our study added more details about the inferred climatic changes. Further aspects are discussed, such as catchment processes, glacial activity, duration of the Medieval Warm Period, the Little Ice Age, local human activity, and limnology.     

Rapid and reliable seismic source characterization in earthquake early warning systems: current methodologies,results, and new perspectives

In the present paper, we provided a review of the main principles and methodologies on which the current earthquake early warning systems are grounded and will also provide a perspective view for next future developments and improvements. First, we introduce the standard methodologies for the source characterization in earthquake early warning, with a special focus on the real-time earthquake magnitude determination. We discuss the suitability of existent methodologies and empirical regression laws for very large events. We then present the different approaches for the rapid prediction of the ground shaking and of the potential damaged zone, both based on traditional seismic data and on the use of continuous GPS data. Finally, the last part of the paper provides the perspective view toward a next generation of early warning systems, linking new research achievements about the earthquake rupture nucleation and the development of new methods/technologies aimed at a fast and high-resolution, real-time modeling of the ongoing source process and accurate prediction of the quake shaking at the regional and local scale.     

Mechanisms of bubble coalescence in silicic magmas

Bubble coalescence is an important process that strongly affects magmatic degassing. Without coalescence, bubbles remain isolated from one another in the melt, severely limiting gas release. Despite this fact, very little has been done to identify coalescence mechanisms from textures of magmatic rocks or to quantify the dynamics of bubble coalescence in melts. In this paper, we present a systematic study of bubble-coalescence mechanisms and dynamics in natural and experimentally produced bubbly rhyolite magma. We have used a combination of natural observations aided by high-resolution X-ray computed tomography, petrological experiments, and physical models to identify different types of bubble?Cbubble interaction that lead to coalescence on the timescales of magma ascent and eruption. Our observations and calculations suggest that bubbles most efficiently coalesce when inter-bubble melt walls thin by stretching rather than by melt drainage from between converging bubble walls. Orders of magnitude are more rapid than melt drainage, bubble wall stretching produces walls thin enough that inter-bubble pressure gradients may cause the melt wall to dimple, further enhancing coalescence. To put these results into volcanogical context, we have identified magma ascent conditions where each coalescence mechanism should act, and discuss the physical conditions for preserving coalescence structures in natural pumice. The timescales we propose could improve volcanic eruption models, which currently do not account for bubble coalescence. Although we do not address the effect of shear strain on bubble coalescence, the processes discussed here may operate in several different eruption regimes, including vesiculation of lava domes, post-fragmentation frothing of vulcanian bombs, and bubbling of pyroclasts in conduits.     

Shallow velocity model of the Northern Flank of Stromboli Volcano, deduced by high frequency surface wave dispersion

The wavefield produced by the Stromboli volcano explosion quakes shows a significant amount of surface waves. Rayleigh waves recorded by a linear array have been investigated to infer the shear-wave velocity model of the Stromboli northern flank. The group velocity dispersion curve was obtained using the multiple filter technique, while the phase velocity dispersion curve was calculated both by phase-matched filtering and performing a p– stack on the observed waveforms. Through the inversion of these curves we were able to recover the shear-wave structure to a depth of about 190 m.     

Naturally occurring radionuclides and their geochemical interactions at a geothermal site in the North German Basin

The activities of the most common, naturally occurring radionuclides ²³⁸U, ²²⁶Ra, ²¹⁰Pb, ²²⁸Ra, ²²⁸Th, and ⁴⁰K were measured by gamma-ray spectrometry in samples from reservoir rocks, geothermal fluids, and mineral precipitates at the geothermal research site Groß Schönebeck (North German Basin). Results demonstrated that the specific activity of the reservoir rock is within the range of the mean concentration in the upper earth crust of <800 Bq/kg for ⁴⁰K and <60 Bq/kg for radionuclides of the ²³⁸U and ²³²Th series, respectively. The geothermal fluid showed elevated activity concentrations (up to 100 Bq/l) for ²²⁶Ra, ²¹⁰Pb, and ²²⁸Ra, as compared to concentrations found in natural groundwater. Their concentration in filter residues even increased up to 100 Bq/g. These residues contain predominantly two different mineral phases: a Sr-rich barite (Sr, BaSO₄) and laurionite (PbOHCl), which both precipitate upon cooling from the geothermal fluid. Thereby they presumably enrich the radionuclides of Ra (by substitution of Ba) and Pb. Analysis of these precipitates further showed an increased ²²⁶Ra/²²⁸Ra ratio from around 1–1.7 during the initial months of fluid production indicating a change in fluid composition over time which can be explained by different contributions of stimulated reservoir rock areas to the overall produced fluid.