Microbial mineralization and assimilation of black carbon: Dependency on degree of thermal alteration

Black carbon is degraded slowly in the environment and its formation can therefore be an effective sink for atmospheric CO₂. This study examined whether charcoal is assimilated by microorganisms or not and estimated the rate of mineralization depending on the degree of thermal alteration of the black carbon. Charcoals were produced at three different temperatures from homogeneously ¹⁴C labelled plant material and incubated in soil, and ¹⁴C in the evolved CO₂ and the microbial biomass was measured. Unlike parallel plant samples, CO₂ evolution from the charcoals showed no lag phase, but a period of faster CO₂ evolution for the first 5–8 days followed by a period of slow evolution. The mineralization of charcoal appeared to decrease with increasing temperature at which it was produced. This was also the case after the initial period of fast CO₂ evolution. With the techniques used, it was not possible to observe any microbial assimilation of charcoal, either because it did not occur, or because the methods used were not sufficiently sensitive. However, the lack of a lag phase in the CO₂ evolution from the charcoals is in line with earlier evidence that charcoal is initially oxidized at the surfaces by abiotic processes.     

Groundwater flow and contaminant transport modelling at an air weapons range

Numerical modelling was done at the Cold Lake Air Weapons Range, Canada, to test whether the dissolved RDX and nitrate detected in groundwater come from the same sources, and to predict whether contamination poses a threat to the surface water receptors near the site. Military live fire training activities may indeed pose a risk of contamination to groundwater resources, however field investigations on military bases are quite recent, and little information is available on the long-term behaviour of munition residues related contaminants. Very limited information was available about the contaminant source zones, which were assigned based on our knowledge of current training activities. The RDX plume was well represented with the model, but the heterogeneous distribution of nitrate concentrations was more difficult to reproduce. It was nonetheless determined that both contaminants originate from the same areas. According to the model, both contaminants should reach the nearby river, but concentrations in the river should remain very low if the source zone concentration does not change. Finally, the model allowed the recommendation of a new location for the main bombing target, which would offer added protection to the river and the lake into which it flows.     

The age of the martian meteorite Northwest Africa 1195 and the differentiation history of the shergottites

Samarium-neodymium isotopic analyses of unleached and acid-leached mineral fractions from the recently identified olivine-bearing shergottite Northwest Africa 1195 yield a crystallization age of 347 ± 13 Ma and an value of +40.1 ± 0.9. Maskelynite fractions do not lie on the Sm-Nd isochron and appear to contain a martian surface component with low ¹⁴⁷Sm/¹⁴⁴Nd and ¹⁴³Nd/¹⁴⁴Nd ratios that was added during shock. The Rb-Sr system is disturbed and does not yield an isochron. Terrestrial Sr appears to have affected all of the mineral fractions, although a maximum initial ⁸⁷Sr/⁸⁶Sr ratio of 0.7016 is estimated by passing a 347 Ma reference line through the maskelynite fraction that is least affected by contamination. The high initial value and the low initial ⁸⁷Sr/⁸⁶Sr ratio, combined with the geologically young crystallization age, indicate that Northwest Africa 1195 is derived from a source region characterized by a long-term incompatible-element depletion.The age and initial Sr and Nd isotopic compositions of Northwest Africa 1195 are very similar to those of Queen Alexandra Range 94201, indicating these samples were derived from source regions with similar Sr-Nd isotopic systematics. These similarities suggest that these two meteorites share a close petrogenetic relationship and might have been erupted from a common volcano. The meteorites Yamato 980459, Dar al Gani 476, Sayh al Uhaymir 005/008, and Dhofar 019 also have relatively old ages between 474 and 575 Ma and trace element and/or isotopic systematics that are indicative of derivation from incompatible-element-depleted sources. This suggests that the oldest group of meteorites is more closely related to one another than they are to the younger meteorites that are derived from less incompatible-element-depleted sources. Closed-system fractional crystallization of this suite of meteorites is modeled with the MELTS algorithm using the bulk composition of Yamato 980459 as a parent. These models reproduce many of the major element and mineralogical variations observed in the suite. In addition, the rare earth element systematics of these meteorites are reproduced by fractional crystallization using the proportions of phases and extents of crystallization that are calculated by MELTS. Other shergottites that demonstrate enrichments in incompatible-elements and have evolved Sr and Nd isotopic systematics have some geochemical systematics that are similar to those observed in the depleted group. Most notably, although they exhibit a very limited range of incompatible trace element and isotopic compositions, they have highly variable major element compositions. This is also consistent with evolution from a common mantle source region by variable amounts of fractional crystallization. If this scenario is correct, it suggests that the combined effects of source composition and fractional crystallization are likely to account for the major element, trace element, and isotopic diversity of all shergottites.     

Magnesium isotope systematics of the lithologically varied Moselle river basin, France

Magnesium and strontium isotope signatures were determined during different seasons for the main rivers of the Moselle basin, northeastern France. This small basin is remarkable for its well-constrained and varied lithology on a small distance scale, and this is reflected in river water Sr isotope compositions. Upstream, where the Moselle River drains silicate rocks of the Vosges mountains, waters are characterized by relatively high ⁸⁷Sr/⁸⁶Sr ratios (0.7128-0.7174). In contrast, downstream of the city of Epinal where the Moselle River flows through carbonates and evaporites of the Lorraine plateau, ⁸⁷Sr/⁸⁶Sr ratios are lower, down to 0.70824.Magnesium in river waters draining silicates is systematically depleted in heavy isotopes (δ²⁶Mg values range from −1.2 to −0.7‰) relative to the value presently estimated for the continental crust and a local diorite (−0.5‰). In comparison, δ²⁶Mg values measured in soil samples are higher (∼0.0‰). This suggests that Mg isotope fractionation occurs during mineral leaching and/or formation of secondary clay minerals. On the Lorraine plateau, tributaries draining marls, carbonates and evaporites are characterized by low Ca/Mg (1.5-3.2) and low Ca/Sr (80-400) when compared to local carbonate rocks (Ca/Mg = 29-59; Ca/Sr = 370-2200), similar to other rivers draining carbonates. The most likely cause of the Mg and Sr excesses in these rivers is early thermodynamic saturation of groundwater with calcite relative to magnesite and strontianite as groundwater chemistry progressively evolves in the aquifer. δ²⁶Mg of the dissolved phases of tributaries draining mainly carbonates and evaporites are relatively low and constant throughout the year (from −1.4‰ to −1.6‰ and from −1.2‰ to −1.4‰, respectively), within the range defined for the underlying rocks. Downstream of Epinal, the compositions of the Moselle River samples in a δ²⁶Mg vs. ⁸⁷Sr/⁸⁶Sr diagram can be explained by mixing curves between silicate, carbonate and evaporite waters, with a significant contribution from the Vosgian silicate lithologies (>70%). Temporal co-variation between δ²⁶Mg and ⁸⁷Sr/⁸⁶Sr for the Moselle River throughout year is also observed, and is consistent with a higher contribution from the Vosges mountains in winter, in terms of runoff and dissolved element flux. Overall, this study shows that Mg isotopes measured in waters, rocks and soils, coupled with other tracers such as Sr isotopes, could be used to better constrain riverine Mg sources, particularly if analytical uncertainties in Mg isotope measurements can be improved in order to perform more precise quantifications.     

Origins of high pH mineral waters from ultramafic rocks, Central Portugal

This paper reviews the geochemical, isotopic (²H, ¹⁸O, ¹³C, ³H and ¹⁴C) and numerical modelling approaches to evaluate possible geological sources of the high pH (11.5)/Na–Cl/Ca–OH mineral waters from the Cabeço de Vide region (Central-Portugal). Water–rock interaction studies have greatly contributed to a conceptual hydrogeological circulation model of the Cabeço de Vide mineral waters, which was corroborated by numerical modelling approaches. The local shallow groundwaters belong to the Mg–HCO₃ type, and are derived by interaction with the local serpentinized rocks. At depth, these type waters evolve into the high pH/Na–Cl/Ca–OH mineral waters of Cabeço de Vide spas, issuing from the intrusive contact between mafic/ultramafic rocks and an older carbonate sequence. The Cabeço de Vide mineral waters are supersaturated with respect to serpentine indicating that they may cause serpentinization. Magnesium silicate phases (brucite and serpentine) seem to control Mg concentrations in Cabeço de Vide mineral waters. Similar δ²H and δ¹⁸O suggest a common meteoric origin and that the Mg–HCO₃ type waters have evolved towards Cabeço de Vide mineral waters. The reaction path simulations show that the progressive evolution of the Ca–HCO₃ to Mg–HCO₃ waters can be attributed to the interaction of meteoric waters with serpentinites. The sequential dissolution at CO₂ (g) closed system conditions leads to the precipitation of calcite, magnesite, amorphous silica, chrysotile and brucite, indicating that the waters would be responsible for the serpentinization of fresh ultramafic rocks (dunites) present at depth. The apparent age of Cabeço de Vide mineral waters was determined as 2790 ± 40 a BP, on the basis of ¹⁴C and ¹³C values, which is in agreement with the ³H concentrations being below the detection limit.     

Quantitative sinkhole hazard assessment. A case study from the Ebro Valley evaporite alluvial karst (NE Spain)

Quantitative sinkhole hazard assessments in karst areas allow calculation of the potential sinkhole risk and the performance of cost-benefit analyses. These estimations are of practical interest for planning, engineering, and insurance purposes. The sinkhole hazard assessments should include two components: the probability of occurrence of sinkholes (sinkholes/km² year) and the severity of the sinkholes, which mainly refers to the subsidence mechanisms (progressive passive bending or catastrophic collapse) and the size of the sinkholes at the time of formation; a critical engineering design parameter. This requires the compilation of an exhaustive database on recent sinkholes, including information on the: (1) location, (2) chronology (precise date or age range), (3) size, and (4) subsidence mechanisms and rate. This work presents a hazard assessment from an alluvial evaporite karst area (0.81 km²) located in the periphery of the city of Zaragoza (Ebro River valley, NE Spain). Five sinkholes and four locations with features attributable to karstic subsidence where identified in an initial investigation phase providing a preliminary probability of occurrence of 0.14 sinkholes/km² year (11.34% in annual probability). A trenching program conducted in a subsequent investigation phase allowed us to rule out the four probable sinkholes, reducing the probability of occurrence to 0.079 sinkholes/km² year (6.4% in annual probability). The information on the severity indicates that collapse sinkholes 10–15 m in diameter may occur in the area. A detailed study of the deposits and deformational structures exposed by trenching in one of the sinkholes allowed us to infer a modern collapse sinkhole approximately 12 m in diameter and with a vertical throw of 8 m. This collapse structure is superimposed on a subsidence sinkhole around 80 m across that records at least 1.7 m of synsedimentary subsidence. Trenching, in combination with dating techniques, is proposed as a useful methodology to elucidate the origin of depressions with uncertain diagnosis and to gather practical information with predictive utility about particular sinkholes in alluvial karst settings: precise location, subsidence mechanisms and magnitude, and timing and rate of the subsidence episodes.     

EPR investigation of the methyl radical,the hydrogen atom and carbon oxide radicals in Maxixe-type beryl

The EPR spectra of Maxixe-type beryl contain a large number of overlapping signals. The angular dependence of the 1:3:3:1 signal typical for the CH₃ radical shows that this radical is located at the center of the channel cavity with its symmetry axis parallel to the crystal c-axis and is rotating around this axis. Its EPR spectrum is axially symmetric with g _// = 2.00263, g _⊥ = 2.00249 and A_// = 2.288 mT, A_⊥ = 2.256 mT. These anisotropies have the opposite signs of those found for surface-adsorbed methyl radicals. Hydrogen atoms are located at position 2a at the center of the beryl cavity and the EPR parameters of the narrow doublet signal are A ₀ = 1,407 MHz and g = 2.00230. Another doublet signal, which is broader and has axial symmetry with g _// = 2.00265, g _⊥ = 2.00625 and A_// = 0.895 mT, A_⊥ = 0.885 mT, could come from a HCO₃ radical. One narrow and easily saturated signal with g _// = 2.00227 and g _⊥ = 2.00386 is interpreted to arise from a carbon monoxide radical in the beryl channel, oriented with its axis parallel to the crystal c-axis. Additional weak doublet lines, which have similar g values as the carbon monoxide radical, are created by nearby hydrogens. A powder spectrum with g _// = 2.0017 and g _⊥ = 2.0004 appears upon UV irradiation of the single crystal and is easily saturated. This spectrum is interpreted to arise from a carbon dioxide radical, which rotates around its symmetry axis.     

La pénétration de l'air froid dans une vallée alpine

Résumé Les observations de deux stations situées à l'entrée de la vallée du Rhône et à l'intérieur de celle-ci permettent de déterminer dans une certaine mesure comment l'air froid pénètre dans cette longue vallée des Alpes suisses. L'accès se fait beaucoup plus souvent par-dessus les montagnes de l'Ouest ou du Nord que par le chenal de la vallée seulement.

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Summary The observations of two stations at the entrance and in the interior of the Rhône valley allow to a certain degree to determine how cold air penetrates this long extended valley of the Swiss Alps. The influx of air takes much more frequently place over the mountains in the West and North than through the trough of the valley.

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Zusammenfassung Die Beobachtungen von zwei Stationen, die am Eingang und im Inneren des Rhonetals gelegen sind, erlauben einigermaßen festzustellen, wie die Kaltluft in dieses langgestreckte Tal der Schweizeralpen eindringt. Dabei erfolgt der Luftzustrom viel häufiger über die Berge im W und N als ausschließlich durch die Talrinne.

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Avec 1 Figure     

Diurnal changes in the bio-optical properties of the phytoplankton in the Alborán Sea (Mediterranean Sea)

The changes in the phytoplankton absorption properties during a diurnal cycle were investigated at one station located in the north-western area of the Alborán Sea. The experiment was performed in spring when the water column was strongly stratified. This hydrological situation permitted the establishment of a deep chlorophyll a (chl a) fluorescence maximum (DFM) which was located on average close to the lower limit of the mixed layer and the nutricline. The relative abundance of pico-phytoplankton (estimated as its contribution to the total chl a) was higher in the surface, however, micro-phytoplankton dominated the community at the DFM level. Chl a specific absorption coefficient (a*(λ)) also varied with optical depth, with a* (the spectrally average specific absorption coefficient) decreasing by 30% at the DFM depth with respect to the surface. A significant negative correlation between the contribution of the micro-phytoplankton to the total chl a and a* was obtained indicating that a* reduction was due to changes in the packaging effect. Below the euphotic layer, a* increased three-fold with respect to the DFM, which agrees with the expected accumulation of accessory pigments relative to chl a as an acclimation response to the low available irradiance. The most conspicuous change during the diurnal cycle was produced in the euphotic layer where the chl a concentration decreased significantly in the afternoon (from a mean concentration of 1.1 μg L⁻¹ to 0.7 μg L⁻¹) and increased at dusk when it averaged 1.4 μg L⁻¹. In addition, a* and the blue-to-red absorption band ratio increased in the afternoon. These results suggest that a*(λ) diurnal variability was due to increase in photo-protective and accessory pigments relative to chl a. The variation ranges of a*(λ) at 675 and 440 nm (the absorption peaks in the red and blue spectral bands, respectively) in the euphotic layer were 0.01–0.04 and 0.02–0.10 m² mg⁻¹ chl a, respectively. Approximately 30% out of this variability can be attributed to the diurnal cycle. This factor should therefore be taken into account in refining primary production models based on phytoplankton light absorption.