Measurements of PM<Subscript>10</Subscript> ions and trace gases with the online system MARGA at the research station Melpitz in Germany – A five-year study

An hourly quantification of inorganic water-soluble PM₁₀ ions and corresponding trace gases was performed using the Monitor for AeRosols and Gases in ambient Air (MARGA) at the TROPOS research site in Melpitz, Germany. The data availability amounts to over 80% for the five-year measurement period from 2010 to 2014. Comparisons were performed for the evaluation of the MARGA, resulting in coefficients of determinations (slopes) of 0.91 (0.90) for the measurements against the SO₂ gas monitor, 0.84 (0.88), 0.79 (1.39), 0.85 (1.20) for the ACSM NO₃ ^?, SO₄ ^2? and NH₄ ⁺ measurements, respectively, and 0.85 (0.65), 0.88 (0.68), 0.91 (0.83), 0.86 (0.82) for the filter measurements of Cl^?, NO₃ ^?, SO₄ ^2? and NH₄ ⁺, respectively. A HONO comparison with a batch denuder shows large scatter (R² = 0.41). The MARGA HNO₃ is underestimated compared to a batch and coated denuder with shorter inlets (slopes of 0.16 and 0.08, respectively). Less NH₃ was observed in coated denuders for high ambient concentrations. Long-time measurements show clear daily and seasonal variabilities. Potential Source Contribution Function (PSCF) analysis indicates the emission area of particulate ions Cl^?, NO₃ ^?, SO₄ ^2?, NH₄ ⁺, K⁺ and gaseous SO₂ to lie in eastern European countries, predominantly in wintertime. Coarse mode sea salt particles are transported from the North Sea to Melpitz. The particles at Melpitz are nearly neutralised with a mean molar ratio of 0.90 for the five-year study. A slight increase of the neutralization ratio over the last three years indicates a stronger decrease of the anthropogenically emitted NO₃ ^? and SO₄ ^2? compared to NH₄ ⁺.     

High resolution analysis of uranium and thorium concentration as well as U-series isotope distributions in a Neanderthal tooth from Payre (Ardèche, France) using laser ablation ICP-MS

We have mapped U (²³⁸U) and Th (²³²Th) elemental concentrations as well as U-series isotope distributions in a Neanderthal tooth from the Middle Palaeolithic site of Payre using laser ablation ICP-MS. The U-concentrations in an enamel section varied between 1 and 1500 ppb. The U-concentration maps show that U-migration through the external enamel surface is minute, the bulk of the uranium having migrated internally via the dentine into the enamel. The uranium migration and uptake is critically dependent on the mineralogical structure of the enamel. Increased U-concentrations are observed along lineaments, some of which are associated with cracks, and others may be related to intra-prismatic zones or structural weaknesses reaching from the dentine into the enamel. The uranium concentrations in the dentine vary between about 25,000 and 45,000 ppb. Our systematic mapping of U-concentration and U-series isotopes provides insight into the time domain of U-accumulation. Most of the uranium was accumulated in an early stage of burial, with some much later overprints. None of the uranium concentration and U-series profiles across the root of the tooth complied with a single stage diffusion-adsorption (D-A) model that is used for quality control in U-series dating of bones and teeth. Nevertheless, in the domains that yielded the oldest apparent U-series age estimates, U-leaching could be excluded. This means that the oldest apparent U-series ages of around 200 ka represent a minimum age for this Neanderthal specimen. This is in good agreement with independent age assessments (200-230 ka) for the archaeological layer, in which it was found.The Th elemental concentrations in the dental tissues were generally low (between about 1 and 20 ppb), and show little relationship with the nature of the tissue.     

Corrosion-induced gas generation in a nuclear waste repository: Reactive geochemistry and multiphase flow effects

Corrosion of steel canisters, stored in a repository for spent fuel and high-level nuclear wastes, leads to the generation and accumulation of H₂ gas in the backfilled emplacement tunnels, which may significantly affect long-term repository safety. Previous studies have used H₂ generation rates based on the volume of the waste or canister material and the stoichiometry of the corrosion reaction. However, Fe corrosion and H₂ generation rates vary with time, depending on factors such as amount of Fe, water availability, water contact area and aqueous and solid chemistry. To account for these factors and feedback mechanisms, a chemistry model was developed related to Fe corrosion, coupled with two-phase (liquid and gas) flow phenomena that are driven by gas-pressure buildup associated with H₂ generation and water consumption. Results indicate that by dynamically calculating H₂ generation rates based on a simple model of corrosion chemistry, and by coupling this corrosion reaction with two-phase flow processes, the degree and extent of gas-pressure buildup could be much smaller compared to a model that neglects the coupling between flow and reactive transport mechanisms. By considering the feedback of corrosion chemistry, the gas pressure increases initially at the canister, but later decreases and eventually returns to a stabilized pressure that is slightly higher than the background pressure. The current study focuses on corrosion under anaerobic conditions for which the coupled hydrogeochemical model was used to examine the role of selected physical parameters on H₂ gas generation and corresponding pressure buildup in a nuclear waste repository. The developed model can be applied to evaluate the effect of water and mineral chemistry of the buffer and host rock on the corrosion reaction for future site-specific studies.     

A New method for identifying possible causal relationships between CO2, total solar irradiance and global temperature change

The study compares two formulas for calculating the daily evapotranspiration ET₀ for a reference crop. The first formula was proposed by Allen et al. (AL), while the second one was proposed by Katerji and Perrier with the addition of the carbon dioxide (CO₂) effect on evapotranspiration (KP). The study analyses the impact of the calculation by the two formulas on the irrigation requirement (IR). Both formulas are based on the Penman-Monteith equation but adopt different approaches for parameterising the canopy resistance r _c . In the AL formula, r _c is assumed constant and not sensitive to climate change, whereas in the KP formula, r _c is first parameterised as a function of climatic variables, then ET₀ is corrected for the air CO₂ concentration. The two formulas were compared in two periods. The first period involves data from two sites in the Mediterranean region within a measured climate change period (1981–2006) when all the input climatic variables were measured. The second period (2070–2100) involves data from a future climate change period at one site when the input climatic variables were forecasted for two future climate scenarios (A2 and B2). The annual cumulated values of ET₀ calculated by the AL formula are systematically lower than those determined by the KP formula. The differences between the ET₀ estimation with the AL and KP formulas have a strong impact on the determination of the IR for the reference crop. In fact, for the two periods, the annual values of IR when ET₀ is calculated by the AL formula are systematically lower than those calculated by the KP formula. For the actual measured climate change period, this reduction varied from 26 to 28 %, while for the future climate change period, it varied based on the scenario from 16 % (A2) to 20 % (B2).     

Calculations of the seasonal loadings of North Sea sediments with persistent aromatic organochlorines

The content and distribution of ΣPCB (as the sum of 24 individual components), HCB and p,p′-DDE was determined in sediments taken from the North Sea during two seasons. The mass-balance of aromatic organochlorine compounds in the upper 2 cm of sediments is calculated and dicussed in relation to pollutant dispersal.     

Study of inorganic ligand-chromium(III)-surface ternary complexes by ESR spectroscopy

Cr(III) sorbed at the solid/water interface of latex and hectorite was studied by ESR spectroscopy in the presence of different inorganic ligands. The ESR spectra of the surface obtained in the presence of selenite, phosphate and fluoride can be explained in terms of ternary surface complex formation. This is contrasted by the behaviour of sulfate and selenate ions which were found to have no effect on the ligand field of Cr(III), either in the adsorbed state or in solution.     

Geophysical characterization of the lithological control on the kinematic pattern in a large clayey landslide (Avignonet,French Alps)

Lithology variation is known to have a major control on landslide kinematics, but this effect may remain unnoticed due to low spatial coverage during investigation. The large clayey Avignonet landslide (French Alps) has been widely studied for more than 35 years. Displacement measurements at 38 geodetic stations over the landslide showed that the slide surface velocity dramatically increases below an elevation of about 700 m and that the more active zones are located at the bottom and the south of the landslide. Most of the geotechnical investigation was carried out in the southern part of the landslide where housing development occurred on lacustrine clay layers. In this study, new electrical prospecting all across the unstable area revealed the unexpected presence of a thick resistive layer covering the more elevated area and overlying the laminated clays, which is interpreted as the lower part of moraine deposits. The downslope lithological boundary of this layer was found at around 700 m asl. This boundary coincides with the observed changes in slide velocity and in surface roughness values computed from a LiDAR DTM acquired in 2006. This thick permeable upper layer constitutes a water reservoir, which is likely to influence the hydromechanical mechanism of the landslide. The study suggests a major control of vertical lithological variations on the landslide kinematics, which is highlighted by the relation between slide velocity and electrical resistivity.