Probing molecular-level transformations of dissolved organic matter: insights on photochemical degradation and protozoan modification of DOM from electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry

Molecular-level characterization of natural organic matter (NOM) has been elusive due to the inherent complexity of natural organic mixtures and to the fact that individual components are often polar and macromolecular. Electrospray ionization (ESI) is a “soft” ionization technique that ionizes polar compounds from aqueous solution prior to injection into a mass spectrometer. The highest resolution and mass accuracy of compounds within NOM have been achieved when ESI is combined with an ultrahigh-resolution mass spectrometer such as the Fourier transform ion cyclotron resonance mass spectrometer (FT-ICR MS). With this technique, individual molecules within a variety of natural organic mixtures can be detected and their elemental composition can be determined. At low mass-to-charge (m/z) ratio, the resolution is high enough to assign exact molecular formulas allowing specific components of these mixtures to be identified. In addition to molecular identification, we can now use ESI FT-ICR MS to examine molecular-level changes in different organic mixtures as a function of relevant geo-processes, such as microbial alterations and photochemistry. Here we present the results from the application of ESI FT-ICR MS to two geochemical questions: (1) the effect of photoirradiation on the molecular composition of fulvic acids and (2) the role of protozoan grazers in the modification of DOM in aquatic systems.     

Fluid Geochemistry as Indicator of Tectonically-Related,Deep Water Circulations in the Sardinian Rift-Campidano Graben (Italy): New Insights from Environmental Isotopes

The EC funded Geochemical Seismic Zonation program (EEC GSZ Project 1996–1998) chose Sardinia as a low-seismicity site, in which the relationships between fluid geochemistry and seismo-tectonics had to be investigated and results compared with outcomes from other selected high-seismicity sites. A first article, examining the role of fault segmentation and seismic quiescence on the geochemical composition of groundwaters and gases, has already been presented (Angelone et al. 2005). This article deals with environmental isotopes which, together with selected hydrochemical data, give hints on tectonically-related fluid circulations. Four water-dominated hydrothermal systems were considered, all located along regional fault systems and discharging groundwaters belonging to the Na–HCO₃ and Na–Cl facies. In the considered systems, groundwater circulation takes place, principally, in the Palaeozoic Crystalline Basement (PCB), with the exception of the Logudoro system, where hydrological circuits develop in the Mesozoic Carbonate Platform (MCP). The high CO₂ contents, the non-attainment of fluid-rock equilibrium and the large lithological variability prevent the construction of a unique hydrogeological–geochemical conceptual model. In this case, stable isotopes provide a useful tool to describe the origin of fluids and their subterranean movements. Stable isotopes of water, integrated with hydrochemical data, indicate that fluids are derived from three main end members. The dominant component is a relatively recent local meteoric water; the second one is marine water; and the third one is a fossil freshwater, depleted in heavy isotopes with respect to modern rains. The latter end member entered the aquifer system in the past, when climatic conditions were greatly different from today. At least two circulation systems can be recognised, namely a shallow cold system and a deep hydrothermal system, as well as two distinct hydrological processes: (1) gravity-controlled descent of cold water towards greater depths and (2) convection linked to a thermal gradient, causing deep fluids to rise up from the hydrothermal reservoir towards the surface. The highly variable δ¹³C_TDIC values suggest the presence of two distinct CO₂ sources, namely, a biogenic one and a thermogenic one. The relation between the isotopic compositions of CO₂ and He indicates an increased mantle signature in uprising CO₂-rich fluids.     

Acoustic-gravity waves in the thermosphere of Venus

Properties of acoustic-gravity waves in the upper atmosphere of Venus are studied using a two-fluid model which includes the effects of wave-induced diffusion in a diffusively separated atmosphere. In conjunction with neutral mass spectrometer data from the Pioneer Venus orbiter, the theory should provide information on the distribution of wave sources in the Venus upper atmosphere. Observed wave structure in species density measurements should generally have periods ?30–35 min, small N₂, CO, and O amplitudes, and highly variable phase shifts relative to CO₂. A near resonance may exist between downward phase-propagating internal gravity and diffusion waves near the 165-km level at periods near 29 min. As a result, if very large He wave amplitudes are observed near this level, it will indicate that the wave source is below the 150- to 175-km level and that the exospheric temperature is close to 350°K. Wave energy dissipation may be an important mechanism for heating of the nightside Venus thermosphere. Large-density oscillations in stratospheric cloud layer constituents are also possible and may be detectable by the Pioneer Venus large probe neutral mass spectrometer.     

Velocity fields associated with the magnetic component of solar faculae

The StokesV asymmetries observed in solar faculae can be interpreted by invoking the presence of magnetic and velocity fields variations along the line-of-sight. By means of a perturbative approach, we develop the theoretical dependence on magnetic and velocity fields of the StokesV profile around its zero-crossing point. We find that the empirical curves of growth for theV zero-crossing point and the slope, as well as the curve of growth for the integral (previously derived by Sánchez Almeidaet al., 1989, through the same approach), are reproduced quite well with a single atmosphere which assumes such simultaneous variations.The depth dependence of the fields that give the best fit in our model presents several striking properties which cannot be released without totally compromising the goodness of the fit. Namely, the magnetic field strength increases towards the observer while the downflowing velocity field decreases. Both variations must occur co-spatially, in the same atmospheric layers. This fact seems to contradict theoretical models for the fanning out parts of magnetic concentrations which foresee a sharp separation between a static magnetic layer and a deep zone with velocity fields. We discuss a possible solution of such contradiction in terms of a finite optical thickness of the boundary layer between zones with and without magnetic field in faculae.Paper presented at the 11th European Regional Astronomical Meetings of the IAU on New Windows to the Universe, held 3–8 July, 1989, Tenerife, Canary Islands, Spain.     

Fracture analysis in the south-western Corinth rift (Greece) and implications on fault hydraulic behavior

This paper reviews the data concerning the fracture network and the hydraulic characteristics of faults in an active zone of the Gulf of Corinth. Pressure gap measured through fault planes shows that in this area the active normal faults (Aigion, Helike) act, at least temporarily and locally, as transversal seal. The analysis of the carbonate cements in the fractures on both the hangingwall and the footwall of the faults also suggests that they have acted as local seals during the whole fault zone evolution. However, the pressure and the characteristics of the water samples measured in the wells indicate that meteoric water circulates from the highest part of the relief to the coast, which means it goes through the fault zones. Field quantitative analysis and core studies from the AIG-10 well have been performed to define both regional and fault-related fracture networks. Then laboratory thin section observations have been done to recognize the different fault rocks characterizing the fault zone components. These two kinds of approach give information on the permeability characteristics of the fault zone. To synthesize the data, a schematic conceptual 3D fluid flow modeling has been performed taking into account fault zone permeability architecture, sedimentation, fluid flow, fault vertical offset and meteoric water influx, as well as compaction water flow. This modeling allows us to fit all the data with a model where the fault segments act as a seal whereas the relays between these segments allow for the regional flow from the Peloponnese topographic highs to the coast.     

Characterization and migration of atmospheric REE in soils and surface waters

Rainwater and snow collected from three different sites in France (Vosges Mountains, French Alps and Strasbourg) show more or less similar shapes of their REE distribution patterns. Rainwater from Strasbourg is the most REE enriched sample, whereas precipitations from the two mountainous, less polluted catchments are less REE enriched and have concentrations close to seawater. They are all strongly LREE depleted.Different water samples from an Alpine watershed comprising snow, interstitial, puddle and streamwater show similar REE distributions with LREE enrichment (rainwater normalized) but MREE and HREE depletion. In this environment, where water transfer from the soil to the river is very quick due to the low thickness of the soils, it appears that REE in streamwater mainly originate from atmospheric inputs. Different is the behaviour of the REE in the spring- and streamwaters from the Vosges Mountains. These waters of long residence time in the deep soil horizons react with soil and bedrock REE carrying minerals and show especially significant negative Eu anomalies compared to atmospheric inputs. Their Sr and Nd isotopic data suggest that most of the Sr and Nd originate from apatite leaching or dissolution. Soil solutions and soil leachates from the upper soil horizons due to alteration processes strongly depleted in REE carrying minerals, have REE distribution patterns close to those of lichens and throughfall. Throughfall is slightly more enriched especially in light REE than filtered rainwater probably due to leaching of atmospheric particles deposited on the foliage and also to leaf excretion.Data suggest that Sr and Nd isotopes of the soil solutions in the upper soil horizons originate from two different sources: 1) An atmospheric source with fertilizer, dust and seawater components and 2) A source mainly determined by mineral dissolution in the soil. These two different sources are also recognizable in the Sr and Nd isotopic composition of the tree’s throughfall solution. The atmospheric contributions of Sr and Nd to throughfall and soil solution are of 20 to 70 and 20%, respectively. In springwater, however, the atmospheric Sr and REE contribution is not detectable.     

Sediment yield and storage variations in the Négron River catchment (south western Parisian Basin,France) during the Holocene period

In the Négron River catchment area (162 km²), surface‐sediment stores are composed of periglacial calcareous ‘grèze’ (5 × 10⁶ t) and loess (21 × 10⁶ t), and Holocene alluvium (12·6 × 10⁶ t), peat (0·6 × 10⁶ t) and colluvium (18·5 × 10⁶ t). Seventy‐five per cent of the Holocene sediments is stored along the thalwegs. Present net sediment yield, calculated from solid discharge at the Négron outlet, is low (0·6 t km^?2 a^?1) due to the dominance of carbonate rocks in the catchment. Mean sediment yield during the Holocene period is 7·0 t km^?2 a^?1 from alluvium stores and 7·6 t km^?2 a^?1 from colluvium stores. Thus, the gross sediment yield during the Holocene period is about 18·7 t km^?2 a^?1 and the sediment delivery ratio 3 per cent. The yield considerably varies from one sub‐basin to another (3·9 to 24·5 t km^?2 a^?1) according to lithology: about 25 per cent and 50 per cent of initial stores of periglacial grèze and loess respectively were reworked during the Holocene period. Sediment yield has increased by a factor of 6 in the last 1000 years, due to the development of agriculture. The very high rate of sediment storage on the slope during that period (88 per cent of the yield) can be accounted for by the formation of cultivation steps (‘rideaux’). It is predicted that the current destruction of these steps will result in a sediment wave reaching the valley floors in the coming decades. Subboreal and Subatlantic sediments and pollen assemblages in the Taligny marsh, where one‐third of the alluvium is stored, show the predominant influence of human activity during these periods in the Négron catchment. Copyright © 2002 John Wiley & Sons, Ltd.     

Thermomechanical properties of deep argillaceous formations

A difficulty in the interpretation of mechanical and thermo-mechanical tests on specimens drawn from large argillaceous formations is the strong inhomogeneity of void ratio, clay minerals and carbonates content.

In this paper a relationship is developed to link strength and the maximum preconsolidation stress to the initial void ratio and carbonate content. Compressibility is also correlated to carbonates.

Thermal strains in drained and undrained conditions for a Spanish, a belgian and an Italian natural clay are compared. In the elastic state strains are comparable, while in the plastic range thermal strains are highest for the Belgian clay, lower in the Spanish cemented clay and lowest in the Italian clay, very stiff and cemented.