Long-term geochemical evolution of the near field repository: insights from reactive transport modelling and experimental evidences

The KBS-3 underground nuclear waste repository concept designed by the Swedish Nuclear Fuel and Waste Management Co. (SKB) includes a bentonite buffer barrier surrounding the copper canisters and the iron insert where spent nuclear fuel will be placed. Bentonite is also part of the backfill material used to seal the access and deposition tunnels of the repository. The bentonite barrier has three main safety functions: to ensure the physical stability of the canister, to retard the intrusion of groundwater to the canisters, and in case of canister failure, to retard the migration of radionuclides to the geosphere. Laboratory experiments (< 10 years long) have provided evidence of the control exerted by accessory minerals and clay surfaces on the pore water chemistry. The evolution of the pore water chemistry will be a primordial factor on the long-term stability of the bentonite barrier, which is a key issue in the safety assessments of the KBS-3 concept.In this work we aim to study the long-term geochemical evolution of bentonite and its pore water in the evolving geochemical environment due to climate change. In order to do this, reactive transport simulations are used to predict the interaction between groundwater and bentonite which is simulated following two different pathways: (1) groundwater flow through the backfill in the deposition tunnels, eventually reaching the top of the deposition hole, and (2) direct connection between groundwater and bentonite rings through fractures in the granite crosscutting the deposition hole. The influence of changes in climate has been tested using three different waters interacting with the bentonite: present-day groundwater, water derived from ice melting, and deep-seated brine. Two commercial bentonites have been considered as buffer material, MX-80 and Deponit CA-N, and one natural clay (Friedland type) for the backfill. They show differences in the composition of the exchangeable cations and in the accessory mineral content. Results from the simulations indicate that pore water chemistry is controlled by the equilibrium with the accessory minerals, especially carbonates. pH is buffered by precipitation/dissolution of calcite and dolomite, when present. The equilibrium of these minerals is deeply influenced by gypsum dissolution and cation exchange reactions in the smectite interlayer. If carbonate minerals are initially absent in bentonite, pH is then controlled by surface acidity reactions in the hydroxyl groups at the edge sites of the clay fraction, although its buffering capacity is not as strong as the equilibrium with carbonate minerals. The redox capacity of the bentonite pore water system is mainly controlled by Fe(II)-bearing minerals (pyrite and siderite). Changes in the groundwater composition lead to variations in the cation exchange occupancy, and dissolution–precipitation of carbonate minerals and gypsum. The most significant changes in the evolution of the system are predicted when ice-melting water, which is highly diluted and alkaline, enters into the system. In this case, the dissolution of carbonate minerals is enhanced, increasing pH in the bentonite pore water. Moreover, a rapid change in the population of exchange sites in the smectite is expected due to the replacement of Na for Ca.     

Screening risk areas for sediment and phosphorus losses to improve placement of mitigation measures

Identification of vulnerable arable areas to phosphorus (P) losses is needed to effectively implement mitigation measures. Indicators for source (soil test P, STP), potential mobilization by erosion (soil dispersion), and transport (unit-stream power length-slope, LS) risks were used to screen the vulnerability to suspended solids (SS) and P losses in two contrasting catchments regarding topography, soil textural distribution, and STP. Soils in the first catchment ranged from loamy sand to clay loam, while clay soils were dominant in the second catchment. Long-term SS and total P losses were higher in the second catchment in spite of significantly lower topsoil STP. A higher proportion of areas in the second catchment were identified with higher risk due to the significantly higher risk of overland flow generation (LS) and a significantly higher mobilization risk in the soil dispersion laboratory tests. A simple screening method was presented to improve the placement of mitigation measures.     

Enhanced activated persulfate oxidation of ciprofloxacin using a low-grade titanium ore under sunlight: influence of the irradiation source on its transformation products

Environmental Science and Pollution Research - In this work, the activated persulfate oxidation of ciprofloxacin (CIP) using a low-grade titanium ore under sunlight or simulated sunlight were...     

Immobilization of Horseradish Peroxidase on Macroporous Glycidyl-Based Copolymers with Different Surface Characteristics for the Removal of Phenol

Journal of Polymers and the Environment - Novel macroporous copolymers of glycidyl methacrylate and ethylene glycol dimethacrylate&nbsp;with mean pore size diameters ranging from 150 to...     

Organochlorine and butyltin residues in walleye pollock (Theragra chalcogramma) from Bering Sea, Gulf of Alaska and Japan Sea

Persistent organochlorine (OC) and toxic butyltin compounds (BTs) were determined in walleye pollock (Theragra chalcogramma) collected from Gulf of Alaska, Bering Sea and Japan Sea, during 1991 and 1992. Polychlorinated biphenyls (PCBs) and dichlorodiphenyltrichloroethane (DDTs) and its metabolites were the most abundant compounds ranging up to 3200 and 2500 ng/g on lipid weight, respectively, followed by chlordane compounds (CHLs), hexachlorocyclohexane isomers (HCHs) and hexachlorobenzene (HCB) in the liver of walleye pollock. Concentrations of HCHs and HCB in walleye pollock from these remote areas were higher than those in fishes from the western North Pacific and Japanese coastal waters, indicating atmospheric transport of these compounds to higher latitude regions such as Bering Sea and Gulf of Alaska and/or local input around northern Japan Sea. The concentrations of other OCs were generally comparable to those in fishes from North Pacific Ocean and Japanese waters but significantly lower than in cod-like fishes from North Atlantic and European countries. Among sampling locations, walleye pollock from Japan Sea showed higher concentrations of DDTs and HCHs compared to fishes from Bering Sea and Gulf of Alaska, suggesting greater input of these compounds around Japan Sea. Slower declining trend of DDTs and CHLs and an increasing pattern of PCBs concentrations were found in walleye pollock from Bering Sea during 1982-1992. This may imply a continuous input of these compounds by long-range transport and/or long-term persistency in these cold regions. Compared to the fishes from Japan Sea, walleye pollock from Bering Sea and Gulf of Alaska showed higher proportions of alpha-HCH and p,p'-DDE in the composition of HCH isomers and DDT compounds, respectively. This suggests selective transportability of these compounds during long-range transport to higher latitude remote areas. Concentrations of tributyltin (TBT) in the muscle of walleye pollock ranged from 1.1 to 5.5 ng/g on wet weight. Concentrations of TBT in deep-sea walleye pollock from Gulf of Alaska and Bering Sea were lower than those in Japan Sea.     

Chiral pharmaceuticals in the environment

Many pharmaceutical pollutants are chiral, existing in the environment as a single enantiomer or as mixtures of the two enantiomers. In spite of their similar physical and chemical properties, the different spatial configurations lead the enantiomers to have different interactions with enzymes, receptors or other chiral molecules, which can give diverse biological response. Consequently, biodegradation process and ecotoxicity tend to be enantioselective. Despite numerous ongoing research regarding analysis and monitorization of pharmaceutical ingredients in the environment, the fate and effects of single enantiomers of chiral pharmaceuticals (CP) in the environment are still largely unknown. There are only few chiral analytical methods to accurately measure the enantiomeric fraction (EF) in environmental matrices and during biodegradation processes. Furthermore, the ecotoxicity studies usually consider the enantiomeric pair as unique compound. We reviewed the current knowledge about CP in the environment, as well as the chiral analytical methods to determine the EF in environmental matrices. The degradation and removal processes of CP of important therapeutic classes, usually detected in the environment, and their toxicity to aquatic organisms were also reviewed. On the other hand, this review demonstrate that despite the great importance of the stereochemistry in pharmaceutical science, pharmacology and organic chemistry, this is normally neglected in environmental studies. Therefore, CP in the environment need much more attention from the scientific community, and more research within this subject is required.     

Temporal separation of two fin whale call types across the eastern North Pacific

Fin whales (Balaenoptera physalus) produce a variety of low-frequency, short-duration, frequency-modulated calls. The differences in temporal patterns between two fin whale call types are described from long-term passive acoustic data collected intermittently between 2005 and 2011 at three locations across the eastern North Pacific: the Bering Sea, off Southern California, and in Canal de Ballenas in the northern Gulf of California. Fin whale calls were detected at all sites year-round, during all periods with recordings. At all three locations, 40-Hz calls peaked in June, preceding a peak in 20-Hz calls by 3–5 months. Monitoring both call types may provide a more accurate insight into the seasonal presence of fin whales across the eastern North Pacific than can be obtained from a single call type. The 40-Hz call may be associated with a foraging function, and temporal separation between 40- and 20-Hz calls may indicate the separation between predominately feeding behavior and other social interactions.     

Climate change and human health in Latin America: drivers, effects, and policies

Many people would be increasingly affected by living under critical conditions in Latin America if, as expected, global warming aggravates disease and pest transmission processes. Heat waves and air pollution would increase heat-related diseases and illness episodes in large cities. Fire smoke has been associated with irritation of the throat, lung and eyes, and respiratory problems. Climate extreme increases associated with climate change would cause physical damage, population displacement, and adverse effects on food production, freshwater availability and quality. It would also increase the risks of infectious and vector-borne diseases. Climate change impacts the geographical range, seasonality, and the incidence rate of vector-borne diseases, such as malaria. Climate-related ecological changes may expand cholera transmission, particularly among populations in low-laying tropical coastal areas. El Niño conditions may affect the incidence of infectious diseases, such as malaria. Ocean warming would increase temperature-sensitive toxins produced by phytoplankton, which could cause more frequent contamination of seafood. A clearer understanding on the current role of climate change in disease patterns will be able to improve forecasts of potential future impacts of projected climate change and support action to reduce such impacts.