Environmental modeling of uranium interstitial compositions of non-stoichiometric oxides: experimental and theoretical analysis

Study of uranium interstitial compositions of non-stoichiometric oxides UO_2+x (x ∈ 0.1–0.02) in gas and condense phases has been presented, using various soft-ionization mass spectrometric methods such as ESI-, APCI-, and MALDI-MS at a wide dynamic temperature gradient (∈ 25–300 °C). Linearly polarized vibrational spectroscopy has been utilized in order to assign unambiguously, the vibrational frequencies of uranium non-stoichiometric oxides. Experimental design has involved xUO_2.66·yUO_2.33, xUO_2.66·yUO_2.33/SiO₂, xUO_2.66·yUO_2.33/SiO₂ (NaOH) and SiO₂/x′NaOH·y′UO₂(NO₃)₂·6H₂O, multicomponent systems (x = 1, y ∈ 0.1–1.0 and x′ = 1, y′ ∈ 0.1–0.6) as well as phase transitions UO₂(NO₃)₂·6H₂O → {U₄O₉(UO_2.25)} → U₃O₇(UO_2.33) → U₃O₈(UO_2.66) → {UO₃}, thus ensuring a maximal representativeness to real environmental conditions, where diverse chemical, geochemical and biochemical reactions, including complexation and sorption onto minerals have occurred. Experimental factors such as UV-irradiation, pH, temperature, concentration levels, solvent types and ion strength have been taken into consideration, too. As far as uranium speciation represents a challenging analytical task in terms of chemical identification diverse coordination species, mechanistic aspects relating incorporation of oxygen into UO _2+x form the shown full methods validation significantly impacts the field of environmental radioanalytical chemistry. UO₂ is the most commonly used fuel in nuclear reactors around the globe; however, a large non-stoichiometric range ∈ UO_1.65–UO_2.25 has occurred due to radiolysis of water on UO₂ surface yielding to H₂O₂, OH^·, and more. Each of those compositions has different oxygen diffusion. And in this respect enormous effort has been concentrated to study the potential impact of hazardous radionuclide on the environment, encompassing from the reprocessing to the disposal stages of the fuel waste, including the waste itself, the processes in the waste containers, the clay around the containers, and geological processes. In a broader sense, thereby, this study contributes to field of environmental analysis highlighting the great ability of various soft-ionization MS methods, particularly, MALDI-MS one, for direct assay of complex multicomponent heterogeneous mixtures at fmol–attomol concentration ranges, along with it the great instrumental features allowing, not only meaningful quantitative, but also structural information of the analytes, thus making the method indispensable for environmental speciation of radionuclides, generally.     

Radon in indoor air of primary schools: determinant factors,their variability and effective dose

Radon is a radioactive gas, abundant in granitic areas, such as in the city of Porto at the north-east of Portugal. This gas is a recognized carcinogenic agent, being appointed by the World Health Organization as the leading cause of lung cancer after smoking. The aim of this preliminary survey was to determine indoor radon concentrations in public primary schools, to analyse the main factors influencing their indoor concentration levels and to estimate the effective dose in students and teachers in primary schools. Radon concentrations were measured in 45 classrooms from 13 public primary schools located in Porto, using CR-39 passive radon detectors for about 2-month period. In all schools, radon concentrations ranged from 56 to 889 Bq/m³ (mean = 197 Bq/m³). The results showed that the limit of 100 Bq/m³ established by WHO IAQ guidelines was exceeded in 92 % of the measurements, as well as 8 % of the measurements exceeded the limit of 400 Bq/m³ established by the national legislation. Moreover, the mean annual effective dose was calculated as 1.25 mSv/y (ranging between 0.58 and 3.07 mSv/y), which is below the action level (3–10 mSv). The considerable variability of radon concentration observed between and within floors indicates a need to monitor concentrations in several rooms for each floor. A single radon detector for each room can be used, provided that the measurement error is considerably lower than variability of radon concentration between rooms. The results of the present survey will provide useful baseline data for adopting safety measures and dealing effectively with radiation emergencies. In particular, radon remediation techniques should be used in buildings located in the highest radon risk areas of Portugal. The results obtained in the current study concerning radon levels and their variations will be useful to optimize the design of future research surveys.     

Simulations of the flow in the Mahakam river–lake–delta system,Indonesia

Large rivers often present a river–lake–delta system, with a wide range of temporal and spatial scales of the flow due to the combined effects of human activities and various natural factors, e.g., river discharge, tides, climatic variability, droughts, floods. Numerical models that allow for simulating the flow in these river–lake–delta systems are essential to study them and predict their evolution under the impact of various forcings. This is because they provide information that cannot be easily measured with sufficient temporal and spatial detail. In this study, we combine one-dimensional sectional-averaged (1D) and two-dimensional depth-averaged (2D) models, in the framework of the finite element model SLIM, to simulate the flow in the Mahakam river–lake–delta system (Indonesia). The 1D model representing the Mahakam River and four tributaries is coupled to the 2D unstructured mesh model implemented on the Mahakam Delta, the adjacent Makassar Strait, and three lakes in the central part of the river catchment. Using observations of water elevation at five stations, the bottom friction for river and tributaries, lakes, delta, and adjacent coastal zone is calibrated. Next, the model is validated using another period of observations of water elevation, flow velocity, and water discharge at various stations. Several criteria are implemented to assess the quality of the simulations, and a good agreement between simulations and observations is achieved in both calibration and validation stages. Different aspects of the flow, i.e., the division of water at two bifurcations in the delta, the effects of the lakes on the flow in the lower part of the system, the area of tidal propagation, are also quantified and discussed.     

Storm-induced transfer of particulate trace metals to the deep-sea in the Gulf of Lion (NW Mediterranean Sea)

In order to calculate budgets of particulate matter and sediment-bound contaminants leaving the continental shelf of the Gulf of Lion (GoL), settling particles were collected in March 2011 during a major storm, using sediment traps. The collecting devices were deployed in the Cap de Creus submarine canyon, which represents the main export route. Particulate matter samples were analyzed to obtain mass fluxes and contents in organic carbon, Al, Cr, Co, Ni, Cu, Zn, Cd, Pb and La, Nd and Sm. The natural or anthropogenic origin of trace metals was assessed using enrichment factors (EFs). Results are that Zn, Cu and Pb appeared to be of anthropogenic origin, whereas Ni, Co and Cr appeared to be strictly natural. The anthropogenic contribution of all elements (except Cd) was refined by acid-leaching (HCl 1 N) techniques, confirming that Zn, Cu and Pb are the elements that are the most enriched. However, although those elements are highly labile (59–77 %), they do not reflect severe enrichment (EFs <4). Most particles originate from the Rhone River. This has been confirmed by two different tracing procedures using rare earth elements ratios and concentrations of acid-leaching residual trace metals. Our results hence indicate that even in this western extremity of the GoL, storm events mainly export Rhone-derived particles via the Cap de Creus submarine canyons to the deep-sea environments. This export of material is significant as it represents about a third of the annual PTM input from the Rhone River.     

Quantifying the effect of wind on internal wave resonance in Lake Villarrica,Chile

Lake Villarrica, located in south central Chile, has a maximum depth of 167 m and a maximum fetch of about 20 km. The lake is monomictic, with a seasonal thermocline located at a depth of approximately 20 m. Field data show the presence of basin-scale internal waves that are forced by daily winds and affected by Coriolis acceleration. A modal linear and non-linear analysis of internal waves has been used, assuming a two-layer system. The numerical simulations show good agreement with the internal wave field observations. The obtained modes were used to study the energy dissipation within the system, which is necessary to control the amplitude growth. Field data and numerical simulations identify (1) the occurrence of a horizontal mode 1 Kelvin wave, with a period of about a day that coincides with the frequency of daily winds, suggesting that this mode of the Kelvin waves is in a resonant state (subject to damping and controlled by frictional effects in the field) and (2) the presence of higher-frequency internal waves, which are excited by non-linear interactions between basin-scale internal waves. The non-linear simulation indicates that only 10 % of the dissipation rate of the Kelvin wave is because of bottom friction, while the rest 90 % represents the energy that is radiated from the Kelvin wave to other modes. Also, this study shows that modes with periods between 5 and 8 h are excited by non-linear interactions between the fundamental Kelvin wave and horizontal Poincaré-type waves. A laboratory study of the resonant interaction between a periodic forcing and the internal wave field response has also been performed, confirming the resonance for the horizontal mode 1 Kelvin wave.     

Exposure and Health Effects of Cadmium

The results of a study of photocatalytic degradation of phenol using aqueous oxygenated TiO₂ (anatase) suspensions in a batch Pyrex photoreactor are reported. The influence on the photodegradation rate of various parameters as pH, phenol and TiO₂ content, oxygen partial pressure, anions present in the dispersions was investigated. A complete oxidation of phenol was observed. Intermediate compounds, catechol and quinone, were detected. It was observed that the photodegradation also proceeded with sunlight radiation. A mechanistic and kinetic model, which accounts for the results obtained, is given. Likely reasons for inactivity of the rutile modification for this reaction are also given.     

Human resilience and environmental degradation: The eco-cultural link in the Sahel

The relationship between human resilience and environmental degradation was studied in the Sahel. The strongest predictors of human resilience were rate of environmental degradation, avoidance, problem solving and locus of control. Compared to pastoralists, agriculturalists were more stressed and marginalized. Women in all groups scored higher on marginalization and stress than men.     

New aspect in seagrass acclimation: leaf mechanical properties vary spatially and seasonally in the temperate species Cymodocea nodosa Ucria (Ascherson)

Seagrasses may acclimate to environmental heterogeneity through phenotypic plasticity. In contrast to leaf morphology, which has been a central point in seagrass acclimation studies, plasticity in leaf biomechanics and fibre content is poorly understood, despite being crucial in plant ecological performance, especially regarding physical forces. We hypothesised that mechanical traits (e.g. breaking force, strength, toughness, and stiffness) and fibre content of seagrass leaves vary as morphology does under differential environments. Cymodocea nodosa was seasonally monitored at three locations around Cádiz Bay (southern Spain) with hydrodynamic regime as the most noticeable difference between them. Leaves showed plasticity in both morphology and mechanical traits, with wave-exposed individuals presenting short but extensible and tough leaves. Leaf fibre content was invariant along the year and with little spatial variability. Cross-sectional area rather than material properties or fibre content differentiates leaf mechanical resistance. Seagrass capacity to thrive under a range of mechanical forces may be dictated by their plasticity in morpho-biomechanical traits, a key element for the hydrodynamical performance and, hence, for species colonisation and distribution.