Warmer early instrumental measurements versus colder reconstructed temperatures: shooting at a moving target

Comparison of tree-ring-based warm-season temperature reconstructions and their instrumental target data reveals substantial divergence between (warmer) early instrumental measurements and (colder) proxy estimates. Here we detail this systematic misfit for the Northern Hemisphere before 1900 and the European Alps before 1850. Five hypotheses related to both proxy and target uncertainties are presented towards explaining this phenomenon. These include: (1) tree-ring detrending methods, (2) biological persistence in the proxy time-series, (3) uncertainties and instabilities in the growth response to given climatic parameters, (4) reduced instrumental station availability back in time, and (5) instrumental data homogeneity. We suggest that uncertainties in the choice of instrumental targets at the hemispheric scale, and instrumental data inhomogeneities at the Alpine and possibly also the hemispheric-scale are the most important factors in explaining this offset. Assessment of homogeneity at larger scales remains challenging. Attention is drawn to possible warm biases in early thermometer shelters and the relevance of proxy/target discrepancies for understanding and quantifying the amplitude of both recent anthropogenic and past natural forced climate fluctuations.     

Depth and morphology of reflectors from the non-linear inversion of arrival-time and waveform semblance data. Part I: method and applications to synthetic data

We propose a two-dimensional, non-linear method for the inversion of reflected/converted traveltimes and waveform semblance designed to obtain the location and morphology of seismic reflectors in a lateral heterogeneous medium and in any source-to-receiver acquisition lay-out. This method uses a scheme of non-linear optimization for the determination of the interface parameters where the calculation of the traveltimes is carried out using a finite-difference solver of the Eikonal equation, assuming an a priori known background velocity model. For the search for the optimal interface model, we used a multiscale approach and the genetic algorithm global optimization technique. During the initial stages of inversion, we used the arrival times of the reflection phase to retrieve the interface model that is defined by a small number of parameters. In the successive steps, the inversion is based on the optimization of the semblance value determined along the calculated traveltime curves. Errors in the final model parameters and the criteria for the choice of the best-fit model are also estimated from the shape of the semblance function in the model parameter space. The method is tested and validated on a synthetic dataset that simulates the acquisition of reflection data in a complex volcanic structure. This study shows that the proposed inversion approach is a valid tool for geophysical investigations in complex geological environments, in order to obtain the morphology and positions of embedded discontinuities.     

Thorough wetting and drainage of a peat lysimeter in a climate change scenario

A peat deposit (Zennare basin, Venice coastland, Italy) was monitored in previous field studies to investigate the hydrological response of organic soil to meteorological dynamics. Field tests and modelling predictions highlighted the risk of the complete loss of this peat layer during the next 50 years, due to oxidation enhanced by the increased frequency of warmer periods. Unfortunately, despite the considerable impacts that are expected to affect peat bogs (in this area and worldwide), only a few experimental studies have been carried out to assess the hydrologic response of peat to severe water scarcity. Because of that, an undisturbed 0.7 m³ peat monolith was collected, transferred to the laboratory and instrumented. The total weight (representative of the water content dynamics of the peat monolith as a whole), and two vertical profiles of matric potentials and water content were monitored in controlled water-scarce conditions. After an extended air-drying period, the monolith was used as an undisturbed peat lysimeter and a complete cycle of wetting and drainage was performed. Supplementary measurements of matric potential ψ and water content θ were collected by testing peat subsamples on a suction table apparatus. A set of water retention curves was determined in a range of matric potentials broader (ψ down to −7 m) than the current natural conditions in the field (minimum ψ = −1 m). While water content at saturation showed values similar to those in the original natural conditions (θ ≅ 0.8), a remarkable loss of water holding capacity (even for low potentials) has been highlighted, especially in deep layers that are now permanently below the water table. The retention curves changed shape and values, with a more pronounced hysteresis visible in an increasing distance between wetting and drying data. Hydraulic non-equilibrium between the water content and water potential could be a possible cause and it is worth modelling in future studies. The parameters of the van Genuchten retention curves were obtained for the wetting and the drying phases.     

Keratose-dominated sponge grounds from temperate mesophotic ecosystems (NW Mediterranean Sea)

Differently from the North Atlantic Ocean, only few examples of sponge grounds are known from the Mediterranean Sea, mainly thriving in the deep sea. In this study, a novel temperate mesophotic ecosystem dominated by massive keratose sponges is reported from the Ligurian deep continental shelf. An extensive Remotely Operated Vehicle (ROV) survey allowed to study the structure and large-scale distribution of this biocoenosis. The sponge grounds here described are highly fragmented, being formed by a large number of dense, discrete aggregations of Sarcotragus foetidus (up to 7.7 specimens/m²) and other sponges, including Spongia lamella and Axinella polypoides. They mainly occur on flat, patchy and highly silted hardgrounds between 40 and 70 m depth. These sponge-dominated ecosystems have an exceptionally wide spatial distribution, estimated to cover up to nearly 200 hectares, with the largest sponge grounds occurring along the westernmost part of the Ligurian coast, probably in relation to more suitable oceanographic conditions. The dominant sponge species reach considerable heights (up to 65 cm), greatly increasing the habitat three-dimensionality and acting as poles of attraction for a diverse sessile and vagile fauna. In addition, the high abundance of the keratose sponge grounds at mesophotic depths might represent a larval source for shallow-water populations that in the last decades have been stricken by several mass mortality events.     

MgAl2O4 spinels from Allende and NWA 763 carbonaceous chondrites: Structural refinement,cooling history,and trace element contents

MgAl₂O₄ spinels from Allende and NWA 763 carbonaceous chondrites were studied by X‐ray single crystal diffraction, SEM, electron microprobe, LA‐ICP‐MS, and Raman spectroscopy. Those from Allende are almost pure, but, in one case, we found a strong FeO_tot zonation. Spinels from NWA 763 show Mg‐Fe²⁺ substitutions. Almost pure MgAl₂O₄ spinels from both meteorites underwent slow cooling and reached their intracrystalline closure temperature (T_c) in the range 460–520 °C. The NWA 763 spinel with higher FeO content shows a T_c of about 720 °C. X‐ray single crystal diffraction and Raman spectroscopy suggest a slow cooling and an ordered structure with trivalent cations in M site and divalent in T site. Among the trace elements, Ti and Co are enriched with respect to the terrestrial analogs, while Mn, Ni, and Sn show intermediate values between different terrestrial occurrences. Vanadium cannot be used as a tracer of extraterrestrial origin as for Cr‐spinels, because its content is similar in extraterrestrial and terrestrial spinels. In the zoned crystal from Allende, Co show a strong zonation similar to that of FeO.     

A multidisciplinary study of the Cape Peloro brackish area (Messina, Italy): characterisation of trophic conditions, microbial abundances and activities

In the framework of the VECTOR DIVCOST Project, a 2-year investigation was started in 2006, with the aim of testing the sensibility of microbial parameters to environmental changes and of assessing whether they can provide information about functional changes in the carbon cycle. The investigation was performed in the surface waters of two small brackish ponds (Ganzirri and Faro), located in the Cape Peloro transitional area (Sicily, Italy). The seasonal changes in both the microbial compartment [bacterioplankton, vibrios, exoenzymatic hydrolysis of proteins and polysaccharides, bacterial secondary production (HBP) and community respiration] and the trophic state of suspended matter [total suspended matter (TSM), particulate organic carbon (POC), particulate organic nitrogen (PON), C/N] were analysed in relation to the hydrological characteristics [temperature, salinity, oxygen, fluorescence, NH₄, NO₂, NO₃, PO₄]. Despite marked differences in the nutritional input and the diversification in both carbon budget and trophic level, the two ponds show similar trends in many of the investigated factors, hardly influenced by seasonal variations. Temporally coupled trends were observed for some parameters (enzyme activities, vibrios abundances, respiratory activity), whereas others (POC, PON, heterotrophic bacterial production, bacterioplankton) showed a seasonal shift between the two lakes. The different behaviour found for the some biotic parameters suggests that their response to environmental conditions may be modulated differently between the two lakes, which, despite their spatial proximity and reciprocal connection, do not always show contemporaneous functional processes.     

Effects of desferrioxamine-B on the release of arsenic from volcanic rocks

Microorganisms play an important role in As mobilization into groundwater by directly influencing As speciation or indirectly inducing solubilisation from As-bearing phases, such as Fe, Mn and Al oxides. Iron oxide dissolution could also be induced by siderophores, small-molecule compounds produced by microorganisms to favour Fe uptake. Well waters exceeding the potable water limit of 10 μg As L⁻¹ (0.133 μM) have been widely reported in geothermal areas. Mechanisms responsible for these high As concentrations have not yet been thoroughly elucidated and the complexity of As mobilization in volcanic aquifers is still open to multiple interpretations. The present study was based on batch release experiments aimed at verifying and quantifying the effect of siderophores on As mobilization from volcanic rocks (lava, tuff, peperino and fallout deposit) at different pH and ligand concentration. In the experiments the siderophore trihydroxamate desferroxamine B (Dfob) was used and its effect on As release from volcanic rocks was manifest after the first days. The most favourable pH for As release was pH 6 while concentrations above 250 μM Dfob considerably enhanced As and Fe concentrations in solution. The As release from rocks was between 2.0–10% at pH 6 and 2.4–8.8% at pH 8. The As/Fe ratio in solution changed with time suggesting different release mechanisms and higher mobility of As compared to Fe during the first phase of the experiment. The presence of siderophore increased Fe dissolution rates up to 10 orders of magnitude. The As release correlated with Al, Mn, Fe, Si, V, Ga and Sb and the release of all these elements increased with increasing Dfob concentration. In alkaline environments also Cu, Zn and Pb were mobilized. The presence of siderophores represents a possible trigger for As mobilization from iron binding minerals to the water phase, with interesting implications for groundwater quality, plant uptake and bacterial communities.     

The effect of organic compounds in the oxidation kinetics of Cr(III) by H2O2

The oxidation of Cr(III) has been studied in NaCl solutions in the presence of two siderophore models, acetohydroxamic acid (Aha) and benzohydroxamic acid (Bha), the natural siderophore Desferal (DFOB) and the synthetic aminocarboxilate (ethylenedinitrilo)-tetra-acetic acid (EDTA) as a function of pH (8-9), ionic strength (0.01-2 M) and temperature (10-50 °C), at different Cr(III)-organic compound ratios. The addition of Aha and Bha caused the rates to increase at low ligand/Cr(III) ratios and decrease at high ratios. The variation of the pseudo first order rate constant (k₁) as a function of the ligand concentration has been attributed to the formation of three Cr(III)-organo species (1:1, 1:2, 1:3), which can form in the presence of monohydroxamic acids. A kinetic model has been developed that gives a value of 600 (min⁻¹) for the pseudo first order rate constant k_1CrAha²⁺ and values approaching zero for and k_1CrAha3. These kinetic results demonstrate that these monohydroxamic acids are able to bind with Cr(III) under experimental conditions that may occur in natural waters and can increase the oxidation rates of Cr(III) with H₂O₂ by a factor of 3.5 at an Aha/Cr(III) ratio of about 50-100.The monohydroxamic acids also affect the rates on aged products of Cr(III), suggesting that these ligands are able to affect the oxidation rates by releasing reactive Cr(III). DFOB and EDTA do not have a great effect on the oxidation of Cr(III) with H₂O₂. This is thought to be due to the much longer times they need to form complexes with Cr(III) compared to Aha and Bha. The rates for the formation of DFOB and EDTA complexes with Cr(III) are not competitive with the rates of the formation of aged Cr(III). After allowing Cr(III) and DFOB to react for 5 days to form the complex, reaction rates of Cr(III) with H₂O₂ appear to be lowered probably because of steric hindrance of the chelated Cr(III).