Multi-isotope (Ba,C, O) partitioning during experimental carbonatization of a hyper-alkaline solution

Carbonates formed from hyperalkaline aqueous solutions at the Earth?s surface are known to bear the most extreme disequilibrium isotope signatures reported so far in nature. We present here the results for stable carbon (C), oxygen (O), and barium (Ba) isotope fractionation during the precipitation of witherite (BaCO₃) induced by the chemical absorption of atmospheric carbon dioxide (CO₂) into an aqueous hyper-alkaline solution (at 4° and 21?°C; 1?atm total pressure). Independent from temperature, the barium carbonate formation was associated with a substantial enrichment of the lighter C and O isotopes in the solid compared to the atmosphere (C, O), close to previous results found in experiments and nature. A new approach is introduced to explain oxygen isotope fractionation upon hydroxylation of CO₂. With Ba isotope enrichment factors between ?0.45 and ?0.53‰ (^138/134ε) or ?0.34 and ?0.40‰ (^137/134ε), respectively, the synthesized BaCO₃ displays the highest kinetic enrichment of the light Ba isotope in the carbonate solid reported so far.     

Response of the North Atlantic subpolar gyre to persistent North Atlantic oscillation like forcing

The response of the North Atlantic subpolar gyre (SPG) to a persistent positive (or negative) phase of the North Atlantic oscillation (NAO) is investigated using an ocean general circulation model forced with idealized atmospheric reanalysis fields. The integrations are analyzed with reference to a base-line integration for which the model is forced with idealized fields representing a neutral state of the NAO. In the positive NAO case, the results suggest that the well-known cooling and strengthening of the SPG are, after about 10 years, replaced by a warming and subsequent weakening of the SPG. The latter changes are caused by the advection of warm water from the subtropical gyre (STG) region, driven by a spin-up of the Atlantic meridional overturning circulation (AMOC) and the effect of an anomalous wind stress curl in the northeastern North Atlantic, which counteracts the local buoyancy forcing of the SPG. In the negative NAO case, however, the SPG response does not involve a sign reversal, but rather shows a gradual weakening throughout the integration. The asymmetric SPG-response to the sign of persistent NAO-like forcing and the different time scales involved demonstrate strong non-linearity in the North Atlantic Ocean circulation response to atmospheric forcing. The latter finding indicates that analysis based on the arithmetic difference between the two NAO-states, e.g. NAO+ minus NAO?, may hide important aspects of the ocean response to atmospheric forcing.     

Identifying Environmental and Natural Resource Management Conflict Potential Using Participatory Mapping

Methods have been proposed for identifying land use conflict potential using participatory mapping data and models. In a case study from Finland, we extend conflict mapping research by evaluating the capacity for participatory mapping to identify conflict for land uses that include mining, tourism development, commercial forestry, recreation, and nature protection. We evaluated two conflict models using reference sites where conflict was expected and assessed whether conflict potential was influenced by participant social group (resident, visitor, holiday home owner). The conflict models correctly identified the locations of current and proposed mining projects and major tourism locations (ski areas) in the region, while conflict for commercial forestry and reindeer herding was spatially distributed. Preferences for land use by social group were more similar than different across the study region. Identification of conflict potential using participatory mapping can provide a useful planning diagnostic but would benefit from additional research for validation.     

Microstructures of structure I and II gas hydrates from the Gulf of Mexico

Gas hydrate samples from various locations in the Gulf of Mexico (GOM) differ considerably in their microstructure. Distinct microstructure characteristics coincide with discrete crystallographic structures, gas compositions and calculated thermodynamic stabilities.     

Climate projections over CORDEX Africa domain using the fifth-generation Canadian Regional Climate Model (CRCM5)

Following the CORDEX experimental protocol, climate simulations and climate-change projections for Africa were made with the new fifth-generation Canadian Regional Climate Model (CRCM5). The model was driven by two Global Climate Models (GCMs), one developed by the Max-Planck-Institut für Meteorologie and the other by the Canadian Centre for Climate Modelling and Analysis, for the period 1950–2100 under the RCP4.5 emission scenario. The performance of the CRCM5 simulations for current climate is discussed first and compared also with a reanalysis-driven CRCM5 simulation. It is shown that errors in lateral boundary conditions and sea-surface temperature from the GCMs have deleterious consequences on the skill of the CRCM5 at reproducing specific regional climate features such as the West African Monsoon and the annual cycle of precipitation. For other aspects of the African climate however the regional model is able to add value compared to the simulations of the driving GCMs. Climate-change projections for periods until the end of this century are also analysed. All models project a warming throughout the twenty-first century, although the details of the climate changes differ notably between model projections, especially for precipitation changes. It is shown that the climate changes projected by CRCM5 often differ noticeably from those of the driving GCMs.     

Age of Jurassic continental tholeiites of French Guyana, Surinam and Guinea: Implications for the initial opening of the Central Atlantic Ocean

A detailed ⁴⁰Ar/³⁹Ar study, of mineral separates from the Jurassic Atlantic Continental Tholeiites (JACT) of Guyana (French Guyana and Surinam, South America), and Guinea (West Africa) related to the initial opening of the Central Atlantic, has been carried out. In French Guyana, plateau ages of 196.0 ± 5.7 Ma and 196.1 ± 7.5 Ma were obtained on single, small amphibole grains from NNW—SSE trending dykes. In Guinea, single biotite grains from intrusive formations from the Kakoulima and Fouta Djalon areas yielded plateau ages of 200.4 ± 0.2 Ma and 194.8 ± 0.5 Ma, concordant with high temperature apparent ages on other biotites. The bulk plagioclase samples display disturbed age spectra due to alteration and excess argon. However, intermediate temperature, weighted mean plagioclase ages are similar in both regions of Guyana and Guinea, ranging from 200.2 ± 2.4 Ma to 188.7 ± 1.9 Ma, partly in agreement with the amphibole and biotite data.

These data, combined with previous ⁴⁰Ar/³⁹Ar and U/Pb results from the northern part of the Central Atlantic margins, indicate intense magmatic activity distributed over a large area from Iberia to Liberia (ca. 4500 km long) for a short period of time (204-195 Ma, perhaps less for the bulk of the magmatism) during the initial break-up of Pangea continent. These data do not support an initiation of the magmatism from a radial volcano-tectonic system centred in the south of the region, as suggested by May [1], and the initial break-up seems to affect the whole Central Atlantic during a period of 9 Ma.     

Raman study of radiation-damaged zircon under hydrostatic compression

Pressure-induced changes of Raman band parameters of four natural, gem-quality zircon samples with different degrees of self-irradiation damage, and synthetic ZrSiO₄ without radiation damage, have been studied under hydrostatic compression in a diamond anvil cell up to ~10 GPa. Radiation-damaged zircon shows similar up-shifts of internal SiO₄ stretching modes at elevated pressures as non-damaged ZrSiO₄. Only minor changes of band-widths were observed in all cases. This makes it possible to estimate the degree of radiation damage from the width of the ν₃(SiO₄) band of zircon inclusions in situ, almost independent from potential “fossilized pressures” or compressive strain acting on the inclusions. An application is the non-destructive analysis of gemstones such as corundum or spinel: broadened Raman bands are a reliable indicator of self-irradiation damage in zircon inclusions, whose presence allows one to exclude artificial color enhancement by high-temperature treatment of the specimen.     

Sorption of Np(V) and Np(IV) onto kaolinite: Effects of pH,ionic strength,carbonate and humic acid

The sorption of Np(V) and Np(IV) onto kaolinite has been studied in the absence and presence of humic acid (HA) in a series of batch equilibrium experiments under different experimental conditions: [Np]₀: 1.0 × 10^-6 or 1.0 × 10^-5 M, [HA]₀: 0 or 50 mg/L, I: 0.01 or 0.1 M NaClO₄, solid to liquid ratio: 4 g/L, pH: 6–11, anaerobic or aerobic conditions, without or with carbonate. The results showed that the Np(V) sorption onto kaolinite is affected by solution pH, ionic strength, Np concentration, presence of carbonate and HA. In the absence of carbonate, the Np(V) uptake increased with pH up to ∼96% at pH 11. HA further increased the Np(V) sorption between pH 6 and 9 but decreased the Np(V) sorption between pH 9 and 11. In the presence of carbonate, the Np(V) sorption increased with pH and reached a maximum of 54% between pH 8.5 and 9. At higher pH values, the Np(V) sorption decreased due to the presence of dissolved neptunyl carbonate species with a higher negative charge that were not sorbed onto the kaolinite surface which is negatively charged in this pH range. HA again decreased the Np(V) uptake in the near-neutral to alkaline pH range due to formation of aqueous neptunyl humate complexes. The decrease of the initial Np(V) concentration from 1.0 × 10⁻⁵ M to 1.0 × 10⁻⁶ M led to a shift of the Np(V) adsorption edge to lower pH values. A higher ionic strength increased the Np(V) uptake onto kaolinite in the presence of carbonate but had no effect on Np(V) uptake in the absence of carbonate.     

Closed-system marine burial diagenesis: isotopic data from the Austin Chalk and its components

ABSTRACT
The carbon and oxygen isotopic composition of the Austin Chalk was examined in cores representing a range of depths from surface to 3000 m in order to document the effects of burial diagenesis on carbon and oxygen isotopic composition. Low magnesium calcite oysters were separated (from 500 um wide areas) and analysed to estimate the starting composition of Cretaceous marine sediment. These gave an average value of -2·5%δ¹⁸O; + 2·0%δ¹³C (PDB). The compositions of micrite, intergranular cement, and fracture cement were analysed, and their deviation from this original marine composition was evaluated to document the progression of chalk diagenesis. Interestingly, micrite exhibits only minor variation in composition from marine values despite present burial depth ranges in excess of 3000 m. The average deviation from δ18O marine is less than 1·5. Furthermore, intergranular cement and particularly fracture cements, which occur only in the deepest cores and which clearly post-date micrite lithification, are generally indistinguishable from micrite in composition. Isotopic compositions exhibit no correlation with depth of burial despite abundant petrographic evidence of deep burial diagenesis. This uniformity in composition is interpreted as reflecting a closed, rock-dominated diagenetic system in which the compositions of precipitated carbonate cements were controlled by the composition of dissolving carbonates during lithification. As such, the composition of burial cement is not representative of the rock-water temperatures during precipitation.
Thus, in the context of isotopic analyses from other carbonate systems, unless the degree of openness of the diagenetic system is known, oxygen isotopic signatures of cements cannot directly be converted to the rock-water temperatures at which they were precipitated unless the composition of the ambient porefluid is also known.