Biogeochemical processes involving dissolved CO2 and CH4 at Albano, Averno, and Monticchio meromictic volcanic lakes (Central–Southern Italy)

This paper focuses on the chemical and isotopic features of dissolved gases (CH₄ and CO₂) from four meromictic lakes hosted in volcanic systems of Central–Southern Italy: Lake Albano (Alban Hills), Lake Averno (Phlegrean Fields), and Monticchio Grande and Piccolo lakes (Mt. Vulture). Deep waters in these lakes are characterized by the presence of a significant reservoir of extra-atmospheric dissolved gases mainly consisting of CH₄ and CO₂. The δ¹³C-CH₄ and δD-CH₄ values of dissolved gas samples from the maximum depths of the investigated lakes (from ?66.8 to ?55.6?‰ V-PDB and from ?279 to ?195?‰ V-SMOW, respectively) suggest that CH₄ is mainly produced by microbial activity. The δ¹³C-CO₂ values of Lake Grande, Lake Piccolo, and Lake Albano (ranging from ?5.8 to ?0.4?‰ V-PDB) indicate a significant CO₂ contribution from sublacustrine vents originating from (1) mantle degassing and (2) thermometamorphic reactions involving limestone, i.e., the same CO₂ source feeding the regional thermal and cold CO₂-rich fluid emissions. In contrast, the relatively low δ¹³C-CO₂ values (from ?13.4 to ?8.2?‰ V-PDB) of Lake Averno indicate a prevalent organic CO₂. Chemical and isotopic compositions of dissolved CO₂ and CH₄ at different depths are mainly depending on (1) CO₂ inputs from external sources (hydrothermal and/or anthropogenic); (2) CO₂–CH₄ isotopic exchange; and (3) methanogenic and methanotrophic activity. In the epilimnion, vertical water mixing, free oxygen availability, and photosynthesis cause the dramatic decrease of both CO₂ and CH₄ concentrations. In the hypolimnion, where the δ¹³C-CO₂ values progressively increase with depth and the δ¹³C-CH₄ values show an opposite trend, biogenic CO₂ production from CH₄ using different electron donor species, such as sulfate, tend to counteract the methanogenesis process whose efficiency achieves its climax at the water–bottom sediment interface. Theoretical values, calculated on the basis of δ¹³C-CO₂ values, and measured δ¹³C_TDIC values are not consistent, indicating that CO₂ and the main carbon-bearing ion species (HCO₃ ^?) are not in isotopic equilibrium, likely due to the fast kinetics of biochemical processes involving both CO₂ and CH₄. This study demonstrates that the vertical patterns of the CO₂/CH₄ ratio and of δ¹³C-CO₂ and δ¹³C-CH₄ are to be regarded as promising tools to detect perturbations, related to different causes, such as changes in the CO₂ input from sublacustrine springs, that may affect aerobic and anaerobic layers of meromictic volcanic lakes.     

Biogeochemistry of mineral-organic associations across a long-term mineralogical soil gradient (0.3-4100 kyr), Hawaiian Islands

Organic matter (OM) in mineral-organic associations (MOAs) represents a large fraction of carbon in terrestrial ecosystems which is considered stable against biodegradation. To assess the role of MOAs in carbon cycling, there is a need to better understand (i) the time-dependent biogeochemical evolution of MOAs in soil, (ii) the effect of the mineral composition on the physico-chemical properties of attached OM, and (iii) the resulting consequences for the stabilization of OM. We studied the development of MOAs across a mineralogical soil gradient (0.3-4100 kyr) at the Hawaiian Islands that derived from basaltic tephra under comparable climatic and hydrological regimes. Mineral-organic associations were characterized using biomarker analyses of OM with chemolytic methods (lignin phenols, non-cellulosic carbohydrates) and wet chemical extractions, surface area/porosity measurements (N₂ at 77 K and CO₂ at 273 K), X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), and differential scanning calorimetry (DSC). The results show that in the initial weathering stage (0.3 kyr), MOAs are mainly composed of primary, low-surface area minerals (olivine, pyroxene, feldspar) with small amounts of attached OM and lignin phenols but a large contribution of microbial-derived carbohydrates. As high-surface area, poorly crystalline (PC) minerals increase in abundance during the second weathering stage (20-400 kyr), the content of mineral-associated OM increased sharply, up to 290 mg C/g MOA, with lignin phenols being favored over carbohydrates in the association with minerals. In the third and final weathering stage (1400-4100 kyr), metastable PC phases transformed into well crystalline secondary Fe and Al (hydr)oxides and kaolin minerals that were associated with less OM overall, and depleted in both lignin and carbohydrate as a fraction of total OM. XPS, the N₂ pore volume data and OM-mineral volumetric ratios suggest that, in contrast to the endmember sites where OM accumulated at the surfaces of larger mineral grains, topsoil MOAs of the 20-400-kyr sites are composed of a homogeneous admixture of small-sized PC minerals and OM, which originated from both adsorption and precipitation processes. The chemical composition of OM in surface-horizon MOAs, however, was largely controlled by the uniform source vegetation irrespective of the substrate age whereas in subsoil horizons, aromatic and carboxylic C correlated positively with oxalate-extractable Al and Si and CuCl₂-extractable Al concentrations representing PC aluminosilicates and Al-organic complexes (r² > 0.85). Additionally, XPS depth profiles suggest a zonal structure of sorbed OM with aromatic carbons being enriched in the proximity of mineral surfaces and amide carbons (peptides/proteins) being located in outer regions of MOAs. Albeit the mineralogical and compositional changes of OM, the rigidity of mineral-associated OM as analyzed by DSC changed little over time. A significantly reduced side chain mobility of sorbed OM was, however, observed in subsoil MOAs, which likely arose from stronger mineral-organic bindings. In conclusion, our study shows that the properties of soil MOAs change substantially over time with different mineral assemblages favoring the association of different types of OM, which is further accentuated by a vertical gradient of OM composition on mineral surfaces. Factors supporting the stabilization of sorbed OM were (i) the surface area and reactivity of minerals (primary or secondary crystalline minerals versus PC secondary minerals), (ii) the association of OM with micropores of PC minerals (via ‘sterically’ enhanced adsorption), (iii) the effective embedding of OM in ‘well mixed’ arrays with PC minerals and monomeric/polymeric metal species, (iv) the inherent stability of acidic aromatic OM components, and (iv) an impaired segmental mobility of sorbed OM, which might increase its stability against desorption and microbial utilization.     

Development and testing of a physically based,three-dimensional model of surface and subsurface hydrology

We present a numerical, catchment-scale model that solves flow equations of surface and subsurface flow in a three-dimensional domain. Surface flow is described by the two-dimensional parabolic approximation of the St. Venant equation, using Manning’s equation of motion; subsurface flow is described by the three-dimensional Richards’ equation for the unsaturated zone and by three-dimensional Darcy’s law for the saturated zone, using an integrated finite difference formulation. The hydrological component is a dynamic link library implemented within a comprehensive model which simulates surface energy, radiation budget, snow melt, potential evapotranspiration, plant development and plant water uptake. We tested the model by comparing distributed and integrated three-dimensional simulated and observed perched water depth (PWD), stream flow data, and soil water contents for a small catchment. Additional tests were performed for the snow melting algorithm as well as the different hydrological processes involved. The model successfully described the water balance and its components as evidenced by good agreement between measured and modelled data.     

Ecological classification of macrophytes and phytobenthos for rivers in Germany according to the water framework directive

A new assessment system for macrophytes and phytobenthos in German rivers meeting the requirements of the Water Framework Directive (WFD) of the European Community is described. Biocoenotic types based on biological, chemical and hydromorphological data from over 200 river sites covering the main ecoregions, hydromorphological stream types and degradation forms have been defined. For developing a classification system the quality element macrophytes and phytobenthos was divided into three components: macrophytes, benthic diatoms and remaining phytobenthos. For macrophytes seven types including one subtype, for benthic diatoms 14 types including three subtypes and for the remaining phytobenthos five river types were identified. The benthic vegetation at reference condition was described for most of the river types. Degradation is characterised as deviation in benthic vegetation species composition and abundance from the reference biocoenosis. For classification in five ecological status classes, several metrics were developed and used in combination with existing indices. For some of the described river types additional investigations are necessary before a classification system can be developed.     

The fate of foramol (“temperate-type”) carbonate platforms

On rimmed shelves of Bahamian-type, characterized by chlorozoan associations and typical of tropical seas, carbonate production keeps pace with normal sea-level rise except when rapid rise or drastic environmental changes occurs. On the other hand, open temperate carbonate shelves are characterized by low carbonate production of the foramol association (molluscs, benthic foraminifera, bryozoans, coralline algae, etc.) and generally show seaward relict sediments, because carbonate production cannot keep pace with normal rate of sea-level change.

Several examples of recent drowning foramol carbonate platforms (e.g., large areas of the Mediterranean Sea, eastern-northeastern Yucatan Shelf) as well as analogous ancient drowned foramol-type carbonate platforms (e.g., early to middle Miocene of the Southern Apennines; Miami Terrace) may support the idea that the drowning of many ancient carbonate platforms has been favoured by their biogenic (foramol sensu lato) constitution. Because of their typically low rate of growth, foramol carbonate platforms are fated to be drowned even if the sea-level rise is one with which the normal growth of chlorozoan platforms can keep pace. Similar conditions may also occur in tropical areas where variations in environmental conditions, such as the presence of cold waters, changes in salinity and increased nutrients, preclude the development of chlorozoan associations.     

Geodynamic significance of the Raspas Metamorphic Complex (SW Ecuador): geochemical and isotopic constraints

The Raspas Metamorphic Complex of southwestern Ecuador is regarded as the southernmost remnant of oceanic and continental terranes accreted in the latest Jurassic–Early Cretaceous. It consists of variably metamorphosed rock types. (1) Mafic and ultramafic rocks metamorphosed under high-pressure (HP) conditions (eclogite facies) show oceanic plateau affinities with flat REE chondrite-normalized patterns, Nd_{150 Ma} ranging from +4.6 to 9.8 and initial Pb isotopic ratios intermediate between MORB and OIB. (2) Sedimentary rocks metamorphosed under eclogitic conditions exhibit LREE enriched patterns, strong negative Eu anomalies, Rb, Nb, U, Th, Pb enrichments, low Nd_{150 Ma} values (from −6.4 to −9.5), and high initial ⁸⁷Sr/⁸⁶Sr and ^206,207,208Pb/²⁰⁴Pb isotopic ratios suggesting they were originally sediments derived from the erosion of an old continental crust. (3) Epidote-bearing amphibolites show N-MORB affinities with LREE depleted patterns, LILE, Zr, Hf and Th depletion, high Nd_{150 Ma} (>+10) and low initial Pb isotopic ratios.The present-day well defined internal structure of the Raspas Metamorphic Complex seems to be inconsistent with the formerly proposed interpretation of a “tectonic mélange”. The association of oceanic plateau rocks and continent-derived sediments both metamorphosed in HP conditions suggests that the thin edge of the oceanic plateau first entered the subduction zone and dragged sediments downward of the accretionary wedge along the Wadatti–Benioff zone. Subsequently, when its thickest part arrived into the subduction zone, the oceanic plateau jammed the subduction processes, due to its high buoyancy.In Ecuador and Colombia, the latest Jurassic–Early Cretaceous suture involves HP oceanic plateau rocks and N-MORB rocks metamorphosed under lower grades, suggesting a composite or polyphase nature for the latest Jurassic–Early Cretaceous accretionary event.     

Compton dragged gamma-ray bursts: the spectrum

Recently several studies have jointly analysed data from different cosmological probes with the motivation of estimating cosmological parameters. Here we generalize this procedure to allow freedom in the relative weights of various probes. This is done by including in the joint χ ² function a set of 'hyper-parameters', which are dealt with using Bayesian considerations. The resulting algorithm, which assumes uniform priors on the log of the hyper-parameters, is very simple: instead of minimizing     (where     is per data set j ) we propose to minimize     (where N _j is the number of data points per data set j ). We illustrate the method by estimating the Hubble constant H ₀ from different sets of recent cosmic microwave background (CMB) experiments (including Saskatoon, Python V, MSAM1, TOCO and Boomerang ). The approach can be generalized for combinations of cosmic probes, and for other priors on the hyper-parameters.     

Optimal experimental design for reservoir property estimates in geothermal exploration

During geothermal reservoir development, drilling deep boreholes turns out to be extremely expensive and risky. Thus, it is of great importance to work out the details of suitable borehole locations in advance. Here, given a set of existing boreholes, we demonstrate how a sophisticated numerical technique called optimal experimental design helps to find a location of an additional exploratory borehole that reduces risk and, ultimately, saves cost. More precisely, the approach minimizes the uncertainty when deducing the effective permeability of a buried reservoir layer from a temperature profile measured in this exploratory borehole. In this paper, we (1) outline the mathematical formulation in terms of an optimization problem, (2) describe the numerical implementation involving various software components, and (3) apply the method to a 3D numerical simulation model representing a real geothermal reservoir in northern Italy. Our results show that optimal experimental design is conceptually and computationally feasible for industrial-scale applications. For the particular reservoir and the estimation of permeability from temperature, the optimal location of the additional borehole coincides with regions of high flow rates and large deviations from the mean temperature of the reservoir layer in question. Finally, the presentation shows that, methodologically, the optimization method can be generalized from estimating permeability to finding any other reservoir properties.     

Pre‐Variscan metagabbro from NW Sardinia,Italy: evidence of an enriched asthenospheric mantle source for continental alkali basalts

Small metagabbro bodies are enclosed in the metasedimentary sequence of NW Sardinia. The metagabbros represent the last magmatic episode before the continent–continent collision that built up the Variscan chain of north Sardinia. The metagabbros are composed of variable proportions of plagioclase and pyroxene igneous relics and metamorphic minerals. Major and trace element data, specifically high TiO₂ and P₂O₅ and low K and Rb contents, as well as light rare‐earth elements, Nb and Ta enrichment, suggest an alkaline affinity for the gabbro and emplacement in a within‐plate tectonic setting. The gabbro was derived from an ocean island alkali basalt‐like asthenospheric mantle source enriched with incompatible elements and uncontaminated by crustal or subducted materials. Non‐modal modelling indicates a 5–7% partial melting of the asthenospheric mantle. Copyright © 2003 John Wiley & Sons, Ltd.