Cementation of kerogen-rich marls by alkaline fluids released during weathering of thermally metamorphosed marly sediments. Part I: Isotopic (C,O) study of the Khushaym Matruk natural analogue (central Jordan)

The Khushaym Matruk site in central Jordan may represent a natural analogue depicting the interaction of alkaline solutions with a clayey sedimentary formation or with clay-rich confining barriers at the interface with concrete structures in waste disposal sites. In this locality, past spontaneous combustion of organic matter in a clayey biomicritic formation produced a ca. 60 m-thick layer of cement-marble containing some of the high-temperature phases usually found in industrial cements (e.g., spurrite, brucite, and Ca-aluminate). A vertical cross-section of the underlying sediments was used in order to study the interaction between cement-marbles and neighbouring clayey limestones under weathering conditions. A thermodynamic approach of the alteration parageneses (calcite–jennite–afwillite–brucite and CSH phases) in the cement-marbles constrains the interacting solutions to have had pH-values between 10.5 and 12. Over 3 m, the sediments located beneath the metamorphic unit were compacted and underwent carbonation. They display large C and O isotopic variations with respect to “pristine” sediments from the bottom of the section. Low δ¹³C-values down to −31.4‰/PDB show the contribution of CO₂ derived from the oxidization of organic matter and from the atmosphere to the intense carbonation process affecting that particular sedimentary level. The size of the C isotopic anomalies, their geometrical extent and their coincidence with the variations of other markers like the Zn content, the structure of organic matter, the mineralogical composition, all argue that the carbonation process was induced by the percolation of high pH solutions which derived from the alteration of cement-marbles. The temperature of the carbonation process remains conjectural and some post-formation O isotopic reequilibration likely affected the newly-formed carbonate. Carbonation induced a considerable porosity reduction, both in fractures and matrixes. The Khushaym Matruk site may have some bearing to the early life of a repository site, when water saturation of the geological formations hosting the concrete structures is incomplete, enabling simultaneous diffusion of alkaline waters and gaseous CO₂ in the near field.     

Cementation of kerogen-rich marls by alkaline fluids released during weathering of thermally metamorphosed marly sediments. Part II: Organic matter evolution,magnetic susceptibility and metals (Ti,Cr, Fe) at the Khushaym Matruk natural analogue (Central Jordan)

Spontaneous combustion, less than 1 Ma ago, affected a 60-m thick sediment pile of biomicrite at the Khushaym Matruck site (Jordan). The present study shows that three retrograde alteration stages occurred: weathering, thermal stress and oxidative alkaline perturbation. μ-FT-i.r. spectra of isolated kerogens and oxygen index of whole rocks indicate that oxidation of organic matter occurred down to ∼10 m beneath the metamorphosed zone at Khushaym Matruck. The occurrence of the oxidative weathering bacterially mediated, as suggested by the mass chromatograms of saturated hydrocarbons, can explain high Rock-Eval T_max values and low petroliferous potential measured along the sedimentary pile. On the other hand, the thermal extent of combustion events was limited to the first 2 m from the contact. The mean reflectance of 0.20–0.24% and porosity of ca. 50% of the grey clayey biomicrites indicate that organic matter was very immature and sediments were unconsolidated at the time of the combustion event. Using mineralogy, microscopic analyses of vegetable debris and magnetic susceptibility, a suite of characteristic points corresponding to the thermal imprint can be assessed: (i) x = 0m, T ∼ 1000 °C, (ii) x = 1 m, T ∼ 350 °C, (iii) x = 2 m, T ∼ 150 °C and (iv) x > ∼ 8 m, T ∼ 30 °C. Paleocirculation of meteoric groundwater in the ‘cement-marbles’ generated high-pH fluids that have circulated via fractures and through the matrix porosity of the underlying biomicrites but have also induced alkaline hydrolysis and oxidative attack of the organic matter. The polysaccharide/lignin ratio derived from μ-FT-i.r. analyses shows that the delignification of vegetable debris and degradation of polysaccharides progressively decline in the indurated zone, which indicates a decrease in the pH of migrating solutions. The latter also severely oxidized organic matter at 2.10 and 3.05 m as revealed by the oxygen index and induced the generation of bitumen. The spatial correlation between the oxidation levels of organic matter and the metal contents (Fe, Ti and Cr) suggests that redox reactions were responsible for the immobilization of metals in the indurated biomicrites. The intensity of these reactions is attributed to changes in the fluid flow regime within the sedimentary column.     

Reconstitution des apports en éléments traces métalliques et bilan de leur migration dans un Luvisol sableux soumis à 100 ans d'irrigation massive par des eaux usées brutes

Raw wastewaters were massively spread on sandy luvisols near Paris from 1899 to 2002, leading to high trace metals (TM) pollution of soils. Mass balance calculations were performed on a soil profile to assess vertical migration of TM. The contamination was estimated by subtracting the natural pedo-geochemical background of the horizons. TM inputs were estimated using Cr as an invariant. It is shown that Pb and Cr remained in the surface horizon, while Ni, Cd, Cu and Zn migrated downward, being more or less trapped depending on the physicochemical properties of the horizons. To cite this article: C. Dère et al., C. R. Geoscience 338 (2006).     

From the green color of eskolaite to the red color of ruby: an X-ray absorption spectroscopy study

The best known cause for colors in insulating minerals is due to transition metal ions as impurities. As an example, Cr³⁺ is responsible for the red color of ruby (α-Al₂O₃:Cr³⁺) and the green color of eskolaite (α-Cr₂O₃). Using X-ray absorption measurements, we connect the colors of the Cr _x Al_2−x O₃ series with the structural and electronic local environment around Cr. UV–VIS electronic parameters, such as the crystal field and the Racah parameter B, are related to those deduced from the analysis of the isotropic and XMCD spectra at the Cr L_2,3-edges in Cr_0.07Al_1.93O₃ and eskolaite. The Cr–O bond lengths are extracted by EXAFS at the Cr K-edge in the whole Cr _x Al_2−x O₃ (0.07≤x< 2) solid solution series. The variation of the mean Cr–O distance between Cr_0.07Al_1.93O₃ and α-Cr₂O₃ is evaluated to be 0.01₅ Å (≈1%). The variation of the crystal field in the Cr _x Al_2−x O₃ series is discussed in relation with the variation of the averaged Cr–O distances.     

Contribution of Secondary VOC to the Composition of Aqueous Atmospheric Particles: A Modeling Approach

Measurements show that 20–60% of the carbon mass present in fine atmospheric particulate matter consists of water soluble organic compounds (WSOC). However, only 5–20% of this WSOC has been identified, mainly as dicarboxylic acids. Because of their high solubility in water, multifunctional secondary compounds derived from the gas-phase oxidation of volatile organic compounds (VOC) are suspected to be key contributors to the WSOC. To test this assumption, an estimate of aqueous uptake of secondary VOC was included in a highly detailed gas-phase mechanism which treats explicitly the formation of the secondary VOC from a set of representative primary species. Simulations were conducted for 2 scenarios, representing typical rural and urban areas. It was observed that the uptake of secondary VOC can lead to WSOC mass concentrations in the range of a few C m^–3, in fairly good agreement with typical WSOC mass concentrations measured. Speciation of WSOC was found to be mainly as tri- or higher multifunctional hydroxy-carbonyl species and hydroxy-hydroperoxide-carbonyl species, in urban and rural environments, respectively. However, it was also found that taking into account only the absorption of secondary VOC does not bring the carboxylic acids mass concentration in agreement with measurements. An attempt was made to explain this discrepancy by introducing chemistry occurring within deliquescent aerosols.     

Complete metamorphic cycle and long-lived anatexis in the c. 2.1 Ga Mistinibi Complex,Canada

Secular changes in the architecture, thermal state, and metamorphic style of global orogens are thought to have occurred since the Archean; however, despite widespread research, the driving mechanisms for such changes remain unclear. The Paleoproterozoic may prove to be a key era for investigating secular changes in global orogens, as it marks the earliest stage of an eon that saw the onset of modern-style global tectonics. The 2.1 Ga granulite-facies Mistinibi-Raude Domain (MRD), located in the Southeastern Churchill Province, Canada, offers a rare exposure of Paleoproterozoic high metamorphic grade supracrustal sequences (Mistinibi Complex, MC). Rocks from this domain were subjected to petrochronological investigations to establish P–T–t–X evolutions and to provide first order thermal state, burial and exhumation rates, and metamorphic gradients for the transient Paleoproterozoic times. To obtain comprehensive insight into the P–T–t–X evolution of the MRD, we used multi-method geochronology—Lu–Hf on garnet and U–Pb on zircon and monazite—integrated with detailed petrography, trace element chemistry, and phase equilibria modelling. Despite the extensive use of zircon and monazite as geochronometers, their behaviour in anatectic conditions is complex, leading to substantial ambiguity in interpreting the timing of prograde metamorphism. Our results indicate a clockwise metamorphic path involving significant melt extraction from the metasedimentary rocks, followed by cooling from >815°C to ~770°C at ~0.8 GPa. The timing of prograde burial and cooling from supra- to subsolidus conditions is constrained through garnet, monazite, and zircon petrochronology at 2,150–2,120 Ma and at 2,070–2,080 Ma, respectively. These results highlight long-lived residence of the rocks at mid-crustal supra-solidus conditions (55–70 Ma), with preserved prograde and retrograde supra-solidus monazite and zircon. The rocks record extremely slow burial rates (0.25–0.30 km/Ma) along a high metamorphic gradient (900–1,000°C/GPa), which appears symptomatic of Paleoproterozoic orogens. The MC did not record any significant metamorphism after 2,067 Ma, despite having collided with terranes that record high-grade metamorphism during the major 1.9–1.8 Ga Trans-Hudson orogeny. The MC would therefore represent a remnant of a local early Paleoproterozoic metamorphic infrastructure, later preserved as superstructure in the large hot Trans-Hudson orogen.     

Modelling evaporation processes in soils from the Huasco salt flat basin,Chile

The need to understand and simulate hydrological phenomena and their interactions, and the impact of anthropogenic and climate changes on natural environments have promoted the study of evaporation from bare soils in arid climates. In closed Altiplano basins, such as those encountered in arid and hyper arid basins in northern Chile, evaporation from shallow groundwater is the main source of aquifer depletion, and thus, its study is crucial for water resources management. The objective of this work is to understand the mechanisms of evaporation in saline soils with shallow water tables, in order to better quantify evaporation fluxes and improve our understanding of the water balance in these regions. To achieve this objective, a model that couples fluid flow with heat transfer was developed and calibrated using column experiments with saline soils from the Huasco salt flat basin, Chile. The model enables determination of both liquid and water vapour fluxes, as well as the location of the evaporation front. Experimental results showed that salt transport inside the soil profile modified the water retention curve, highlighting the importance of including salt transport when modelling the evaporation processes in these soils. Indeed, model simulations only agreed with the experimental data when the effect of salt transport on water retention curves was taken into account. Model results also showed that the evaporation front is closer to the soil surface as the water table depth reduces. Therefore, the model allows determining the groundwater level depth that results in disconnection of liquid fluxes in the vadose zone. A sensitivity analysis allowed understanding the effect of water‐flux enhancements mechanisms on soil evaporation. The results presented in this study are important as they allow quantifying the evaporation that occurs in bare soils from Altiplano basins, which is typically the main water discharge in these closed basins. Copyright © 2016 John Wiley & Sons, Ltd.     

Reindeer management during the colonization of Sami lands: A long-term perspective of vulnerability and adaptation strategies

Reindeer husbandry's strong connection to the land, together with the ongoing climate-change debate, has generated growing interest in its socio-ecological resilience and vulnerability. The ability of indigenous societies and their activities to respond to change is widely recognized to be dependent on several factors, such as socioeconomic forces and aspects of governance, all of which have long historical backgrounds. However, although historians constantly address questions about human societies, there have been very few historical studies on their resilience, vulnerability and adaptation strategies. Here, using historical sources, we analyze the vulnerability of reindeer husbandry (and the Sami societies that depended on it) in Sweden during the 19th century. We demonstrate that although reindeer management was a much more diverse enterprise at that time than it is now, the major adaptation strategy and constraining forces were similar to those of today. The foremost adaptation strategy was, and still is, the flexible use of pasture area, and the clearest constraints during the 19th century were the loss of authority over the land and the imposed regulation of reindeer management-both of which were strongly connected to the process of colonization.

Terminology

Throughout this paper we use the terms reindeer management and reindeer pastoralism interchangeably. Sami reindeer pastoralism has been described as a complex system with two different aspects of management: herding and husbandry. Husbandry has been defined as the accumulations of profit whereas herding has been defined as the control of the animals in the terrain (Paine, 1970, p. 53). In a Swedish context husbandry questions concerning slaughter and castration of reindeer were discussed within the household and herding matters were resolved jointly within the traditional working community Siida. The Siida consisted of households working together on traditional pasturelands and these constellations were grouped together into administrative reindeer pasture districts (Sami villages) ( [Ingold, 1978], [Fellman, 1910] and [Beach, 1981]).     

Scale-dependent habitat use by a large free-ranging predator,the Mediterranean fin whale

Since the heterogeneity of oceanographic conditions drives abundance, distribution, and availability of prey, it is essential to understand how foraging predators interact with their dynamic environment at various spatial and temporal scales. We examined the spatio-temporal relationships between oceanographic features and abundance of fin whales (Balaenoptera physalus), the largest free-ranging predator in the Western Mediterranean Sea (WM), through two independent approaches. First, spatial modeling was used to estimate whale density, using waiting distance (the distance between detections) for fin whales along ferry routes across the WM, in relation to remotely sensed oceanographic parameters. At a large scale (basin and year), fin whales exhibited fidelity to the northern WM with a summer-aggregated and winter-dispersed pattern. At mesoscale (20–100 km), whales were found in colder, saltier (from an on-board system) and dynamic areas defined by steep altimetric and temperature gradients. Second, using an independent fin whale satellite tracking dataset, we showed that tracked whales were effectively preferentially located in favorable habitats, i.e. in areas of high predicted densities as identified by our previous model using oceanographic data contemporaneous to the tracking period. We suggest that the large-scale fidelity corresponds to temporally and spatially predictable habitat of whale favorite prey, the northern krill (Meganyctiphanes norvegica), while mesoscale relationships are likely to identify areas of high prey concentration and availability.