Dissolution–precipitation processes governing the carbonation and silicification of the serpentinite sole of the New Caledonia ophiolite

The weathering of mantle peridotite tectonically exposed to the atmosphere leads commonly to natural carbonation processes. Extensive cryptocrystalline magnesite veins and stock-work are widespread in the serpentinite sole of the New Caledonia ophiolite. Silica is systematically associated with magnesite. It is commonly admitted that Mg and Si are released during the laterization of overlying peridotites. Thus, the occurrence of these veins is generally attributed to a per descensum mechanism that involves the infiltration of meteoric waters enriched in dissolved atmospheric CO₂. In this study, we investigate serpentinite carbonation processes, and related silicification, based on a detailed petrographic and crystal chemical study of serpentinites. The relationships between serpentine and alteration products are described using an original method for the analysis of micro-X-ray fluorescence images performed at the centimeter scale. Our investigations highlight a carbonation mechanism, together with precipitation of amorphous silica and sepiolite, based on a dissolution–precipitation process. In contrast with the per descensum Mg/Si-enrichment model that is mainly concentrated in rock fractures, dissolution–precipitation process is much more pervasive. Thus, although the texture of rocks remains relatively preserved, this process extends more widely into the rock and may represent a major part of total carbonation of the ophiolite.     

The age of the Roter Kamm impact crater,Namibia: Constraints from 40Ar-39Ar,K-Ar,Rb-Sr,fission track,and 10Be-26Al studies

Abstract The well-preserved 2.5 km diameter Roter Kamm impact crater is located in the Namib desert in Namibia. The impact has occurred in Precambrian granitic and granodioritic orthogneisses of the 1200–900 Ma old Namaqualand Metamorphic Complex which were partly covered by Gariep metasediments; the granites are invaded by quartz veins and quartz-feldspar-pegmatites. Previous geological field evidence suggested a crater age of about 5–10 Ma. In order to constrain this age, we selected a set of basement rocks (granites, granodiorites) exposed at the crater rim and studied the Rb-Sr, K-Ar, ⁴⁰Ar-³⁹Ar, and ¹⁰Be-²⁶Al isotopic systems as well as apatite fission track ages of these samples. The Rb-Sr isotopic systematics confirm the derivation of these samples from the Namaqualand basement (age about 1.29 Ga), which underwent Damaran orogenesis at about 650 Ma. No basement rocks with Rb-Sr ages younger than about 410 Ma were identified. The K-Ar ages of pseudotachylite and melt breccia samples show that these samples are dominated by incompletely degassed fragments of basement rocks, with some retaining their original metamorphic ages of about 470 Ma. The apatite fission track ages range from 20–28 Ma, which may be interpreted as an extension of the 25 Ma Burdigalian peneplanation event, or as incomplete resetting of the apatite fission tracks during the impact event. The ¹⁰Be and ²⁶Al exposure age of a quartz sample isolated from a quartz-pegmatite was found to be 150 ka; it is likely that the exposure of the sample began after material covering it had been removed by erosion 150 ka ago. Two glassy fractions extracted from a rim granite were dated by ⁴⁰Ar-³⁹Ar analysis. One sample gives practically a plateau age of 3.7 ± 0.3 Ma, while the other gives a minimum age of 3.6 Ma. The best available age estimate for the Roter Kamm crater is therefore 3.7 ± 0.3 Ma.     

High-pressure behaviour along the jadeite NaAlSi2O6–aegirine NaFeSi2O6 solid solution up to 10 GPa

The volume variation as a function of pressure along the jadeite–aegirine solid solution was determined at room temperature up to pressures between 6.5 and 9.7 GPa by single-crystal X-ray diffraction. The unit-cell volumes collected at room pressure for the different compositions indicate a slight deviation from linearity along the join. The pressure–volume data have been fitted using a third-order Birch-Murnaghan equation of state (BM3-EoS). The bulk modulus, K _T0, varies from 134.0(7) GPa for pure jadeite to 116.1(5) GPa for pure aegirine. Its evolution with composition along the join is not linear and can be described by the following second order polynomial:

Excess of bottom-released methane in an Arctic shelf sea polynya in winter

Latent heat polynyas are regions generating strong ice formation, convection and extensive water mass formation. Here we report on the effects of these processes on resuspension of sediments and subsequent methane release from the seafloor and on the resulting excess methane concentration in surface water on a polar shelf during winter. The study is based on measurements of concentration and δ¹³C values of methane, water temperature, salinity, light transmission and sea ice data collected in March 2003 in Storfjorden, southern Svalbard. In winter, strong and persistent northeasterly winds create polynyas in eastern Storfjorden and cause ice formation. The resulting brine-enriched water cascades from the Storfjordbanken into the central depression thereby enhancing the turbulence near the seafloor. A distinct benthic nepheloid layer was observed reflecting the resuspension of sediments by the cascading dense bottom water. High concentrations of ¹³C-depleted methane suggest submarine discharge of methane with the resuspended sediments. As the source of the submarine methane, we propose recent bacterial methanogenesis near the sediment surface because of extremely high accumulation rates of organic carbon in Storfjorden. Convective mixing transports newly released methane from the bottom to the sea surface. This eventually results in an excess concentration in surface water with respect to the atmospheric equilibrium, and a sea-air flux of methane during periods of open water. When a new ice cover is formed, methane becomes trapped in the water column and subsequently oxidized. Thus, the residual methane is strongly enriched in ¹³C in relation to the δ¹³_CCH4${\delta }^{13}{\mathrm{C}}_{{\mathrm{CH}}_4}$ signature of atmospheric methane. Our results show that latent heat polynyas may induce a direct pathway for biogases like methane from sediments to the atmosphere through coupling of biogeochemical and oceanographic processes. Extrapolating these processes to all Arctic ocean polynyas, we estimate a transfer of CH₄ between 0.005 and 0.02 Tg yr⁻¹. This is not a large contribution but the fluxes from the polynyas are 20–200 times larger than the ocean average and the methane evasion process in polynyas is certainly one that can be altered under climate change.     

Burying receivers for improved time‐lapse seismic repeatability: CO2CRC Otway field experiment

4D seismic is widely used to remotely monitor fluid movement in subsurface reservoirs. This technique is especially effective offshore where high survey repeatability can be achieved. It comes as no surprise that the first 4D seismic that successfully monitored the CO₂ sequestration process was recorded offshore in the Sleipner field, North Sea. In the case of land projects, poor repeatability of the land seismic data due to low S/N ratio often obscures the time‐lapse seismic signal. Hence for a successful on shore monitoring program improving seismic repeatability is essential. Stage 2 of the CO2CRC Otway project involves an injection of a small amount (around 15,000 tonnes) of CO₂/CH₄ gas mixture into a saline aquifer at a depth of approximately 1.5 km. Previous studies at this site showed that seismic repeatability is relatively low due to variations in weather conditions, near surface geology and farming activities. In order to improve time‐lapse seismic monitoring capabilities, a permanent receiver array can be utilised to improve signal to noise ratio and hence repeatability. A small‐scale trial of such an array was conducted at the Otway site in June 2012. A set of 25 geophones was installed in 3 m deep boreholes in parallel to the same number of surface geophones. In addition, four geophones were placed into boreholes of 1–12 m depth. In order to assess the gain in the signal‐to‐noise ratio and repeatability, both active and passive seismic surveys were carried out. The surveys were conducted in relatively poor weather conditions, with rain, strong wind and thunderstorms. With such an amplified background noise level, we found that the noise level for buried geophones is on average 20 dB lower compared to the surface geophones. The levels of repeatability for borehole geophones estimated around direct wave, reflected wave and ground roll are twice as high as for the surface geophones. Both borehole and surface geophones produce the best repeatability in the 30–90 Hz frequency range. The influence of burying depth on S/N ratio and repeatability shows that significant improvement in repeatability can be reached at a depth of 3 m. The level of repeatability remains relatively constant between 3 and 12 m depths.     

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.     

Hydrochemical variation in the springs water between Jerusalem–Ramallah Mountains and Jericho Fault,Palestine

The spatial and temporal changes of the composition of the groundwater from the springs along the Wadi Qilt stream running from the Jerusalem–Ramallah Mountains towards the Jericho Plain is studied during the hydrological year 2006/2007. The residence time and the intensity of recharge play an important role in controlling the chemical composition of spring water which mainly depends on distance from the main recharge area. A very important factor is the oxidation of organics derived from sewage and garbage resulting in variable dissolved CO₂ and associated HCO₃ ⁻ concentration. High CO₂ yields lower pH values and thus under-saturation with respect to calcite and dolomite. Low CO₂ concentrations result in over-saturation. Only at the beginning and at the end of the rainy season calcite saturation is achieved. The degradation of dissolved organic matter is a major source for increasing water hardness. Besides dissolution of carbonates dissolved species such as nitrate, chloride, and sulfate are leached from soil and aquifer rocks together with only small amounts of Mg. Mg not only originates from carbonates but also from Mg–Cl waters are leached from aquifer rocks. Leaching of Mg–Cl brines is particularly high at the beginning of the winter season and lowest at its end. Two zones of recharge are distinguishable. Zone 1 represented by Ein Fara and Ein Qilt is fed directly through the infiltration of meteoric water and surface runoff from the mountains along the eastern mountain slopes with little groundwater residence time and high flow rate. The second zone is near the western border of Jericho at the foothills, which is mainly fed by the under-groundwater flow from the eastern slopes with low surface infiltration rate. This zone shows higher groundwater residence time and slower flow rate than zone 1. Groundwater residence time and the flow rate within the aquifer systems are controlled by the geological structure of the aquifer, the amount of active recharge to the aquifer, and the recharge mechanism. The results of this study may be useful in increasing the efficiency of freshwater exploitation in the region. Some precautions, however, should be taken in future plans of artificial recharge of the aquifers or surface-water harvesting in the Wadi. Because of evaporation and associated groundwater deterioration, the runoff water should be artificially infiltrated in zones of Wadis with high storage capacity of aquifers. Natural infiltration along the Wadis lead to evaporation losses and less quality of groundwater.     

Alpine Evidence for Atmospheric Circulation Patterns in Europe during the Last Glacial Maximum

The configuration of Alpine accumulation areas during the last glacial maximum (LGM) has been reconstructed using glacial–geological mapping. The results indicate that the LGM ice surface consisted of at least three major ice domes, all located south of the principal weather divide of the Alps. This implies that the buildup of the main Alpine ice cover during oxygen isotope stage (OIS) 2 was related to precipitation by dominant southerly atmospheric circulation, in contrast to today's prevalent westerly airflow. Such a reorganization of the atmospheric circulation is consistent with a southward displacement of the Oceanic Polar Front in the North Atlantic and of the associated storm track to the south of the Alps. These results, combined with additional paleoclimate records from western and southern Europe, allow an interpretation of the asynchronous evolution of the different European ice caps during the last glaciation. δ¹⁸O stages (OIS) 4 and 3 were characterized by location of the Polar Front north of 46°N (Gulf of Biscay). This affected prevailing westerly circulation and, thus, ice buildup in western Scandinavia, the Pyrénées, Vosges, and northern Alps. At the LGM, however, the Polar Front lay at 44°N, causing dominating southerly circulation and reduced precipitation in central and northern Europe.