Inverse modeling of multicomponent reactive transport through single and dual porosity media

Compacted bentonite is foreseen as buffer material for high-level radioactive waste in deep geological repositories because it provides hydraulic isolation, chemical stability, and radionuclide sorption. A wide range of laboratory tests were performed within the framework of FEBEX (Full-scale Engineered Barrier EXperiment) project to characterize buffer properties and develop numerical models for FEBEX bentonite. Here we present inverse single and dual-continuum multicomponent reactive transport models of a long-term permeation test performed on a 2.5 cm long sample of FEBEX bentonite. Initial saline bentonite porewater was flushed with 5.5 pore volumes of fresh granitic water. Water flux and chemical composition of effluent waters were monitored during almost 4 years. The model accounts for solute advection and diffusion and geochemical reactions such as aqueous complexation, acid-base, cation exchange, protonation/deprotonation by surface complexation and dissolution/precipitation of calcite, chalcedony and gypsum. All of these processes are assumed at local equilibrium. Similar to previous studies of bentonite porewater chemistry on batch systems which attest the relevance of protonation/deprotonation on buffering pH, our results confirm that protonation/deprotonation is a key process in maintaining a stable pH under dynamic transport conditions. Breakthrough curves of reactive species are more sensitive to initial porewater concentration than to effective diffusion coefficient. Optimum estimates of initial porewater chemistry of saturated compacted FEBEX bentonite are obtained by solving the inverse problem of multicomponent reactive transport. While the single-continuum model reproduces the trends of measured data for most chemical species, it fails to match properly the long tails of most breakthrough curves. Such limitation is overcome by resorting to a dual-continuum reactive transport model.     

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.     

Proposal for the integration of decentralised composting of the organic fraction of municipal solid waste into the waste management system of Cuba

Municipal solid waste (MSW) generation and management in Cuba was studied with a view to integrating composting of the organic fractions of MSW into the system. Composting is already included as part of the environmental strategy of the country as an appropriate waste management solution. However, no programme for area-wide implementation yet exists. The evaluation of studies carried out by some Cuban and international organisations showed that organic matter comprises approximately 60-70% of the MSW, with households being the main source. If all organic waste fractions were considered, the theoretical amount of organic waste produced would be approximately 1 Mio. Mg/a, leading to the production of approximately 0.5 Mio. Mg/a of compost. Composting could, therefore, be a suitable solution for treating the organic waste fractions of the MSW. Composting would best be carried out in decentralised systems, since transportation is a problem in Cuba. Furthermore, low technology and low budget composting options should be considered due to the problematic local economic situation. The location for such decentralised composting units would optimally be located at urban agricultural farms, which can be found all over Cuba. These farms are a unique model for sustainable farming in the world, and have a high demand for organic fertiliser. In this paper, options for the collection and impurity-separation in urban areas are discussed, and a stepwise introduction of source-separation, starting with hotel and restaurant waste, is suggested. For rural areas, the implementation of home composting is recommended.     

Blends of HDPE wastes: study of the properties

In this work we have analysed the properties of blends of recycled high-density polyethylene (HDPE) filled with talc. We have used two kinds of polymer matrices. The first one came entirely from ground injection moulded parts whereas the second was bimodal, incorporating 80% of the previous HDPE and 20% of recycled HDPE coming from bottles. We have also used two kinds of commercial talc characterized by a medium particle size of 2 microm and 10 microm, respectively. The amount of talc added to both matrices weighed of 10% and 20%. With regards to the mechanical properties of the analysed composites, greater values of Young's modulus and break stresses were found using a smaller particle size and higher talc content. On the other hand, the combination of the two HDPEs with very different viscosities produced a notable increase in the strain at break and in the absorbed energy; both measured at high and low strain rates. Despite the differences in viscosities between the two HDPEs, we did not observe separation of phases during either the processing or testing. Under impact loading, the higher energy absorption in the composites was observed when the finest talc grade with a 10% content weight was added to the bimodal matrix.     

Influence of Technological Process on Biodegradation of PVA/Waxy Starch Blends in an Aerobic and Anaerobic Environment

Improving biodegradability of PVA/starch blends is a reality already documented by a number of works. Admittedly, mechanical properties of products (for example, tensile strength) are somewhat worse, but suitable composition optimizing or chemical modifying of starch may eliminate the problem to a large degree. This work is an attempt to find another potential effect influencing biodegradability, that of technological procedure for producing films from these blends on an extruder. The procedure with a so-called pre-extrusion step (two-stage) and dry-blend (single-stage) produced blends of slightest differences in achieved biodegradability (virtually within limits of experimental error) in aerobic (76 vs. 79%) as well as anaerobic breakdown (48 vs. 52%). Conversely, morphological analysis exhibited superior homogeneity of films prepared by the two-stage process; their tensile strength was also higher.     

The role of internal and external information in foraging decisions of Melipona workers (Hymenoptera: Meliponinae)

Social insect foragers have to make foraging decisions based on information that may come from two different sources: information learned and memorised through their own experience (“internal” information) and information communicated by nest mates or directly obtained from their environment (“external” information). The role of these sources of information in decision-making by foragers was studied observationally and experimentally in stingless bees of the genus Melipona. Once a Melipona forager had started its food-collecting career, its decisions to initiate, continue or stop its daily collecting activity were mainly based upon previous experience (activity on previous days, the time at which foraging was initiated the day(s) before, and, during the day, the success of the last foraging flights) and mediated through direct interaction with the food source (load size harvested and time to collect a load). External information provided by returning foragers advanced the start of foraging of experienced bees. Most inexperienced bees initiated their foraging day after successful foragers had returned to the hive. The start of foraging by other inexperienced bees was stimulated by high waste-removal activity of nest mates. By experimentally controlling the entries of foragers (hence external information input) it was shown that very low levels of external information input had large effect on the departure of experienced foragers. After the return of a single successful forager, or five foragers together, the rate of forager exits increased dramatically for 15 min. Only the first and second entry events had large effect; later entries influenced forager exit patterns only slightly. The results show that Melipona foragers make decisions based upon their own experience and that communication stimulates these foragers if it concerns the previously visited source. We discuss the organisation of individual foraging in Melipona and Apis mellifera and are led to the conclusion that these species behave very similarly and that an information-integration model (derived from Fig. 1) could be a starting point for future research on social insect foraging. Received: 16 April 1997 / Accepted after revision: 30 August 1997     

Semi-parametric statistical approaches for space-time process prediction

The problem of estimation and prediction of a spatial-temporal stochastic process, observed at regular times and irregularly in space, is considered. A mixed formulation involving a non- parametric component, accounting for a deterministic trend and the effect of exogenous variables, and a parametric component representing the purely spatio-temporal random variation is proposed. Correspondingly, a two-step procedure, first addressing the estimation of the non- parametric component, and then the estimation of the parametric component is developed from the residual series obtained, with spatial-temporal prediction being performed in terms of suitable spatial interpolation of the temporal variation structure. The proposed model formula-tion, together with the estimation and prediction procedure, are applied using a Gaussian ARMA structure for temporal modelling to space-time forecasting from real data of air pollution concentration levels in the region surrounding a power station in northwest Spain.     

Essential (Cu) and nonessential (Cd and Pb) metals in ichthyofauna from the coasts of Sinaloa state (SE Gulf of California)

With the aim of giving an overview on concentration and distribution of Cd, Cu, and Pb in fish from the coasts of Sinaloa state (SE Gulf of California), specimens with different feeding habits were collected in five locations. Sampling occurred between June 2003 and March 2004. Metal analyses on fish tissues were made by graphite furnace (Cd, Pb) and flame (Cu) atomic absorption spectrophotometry. Metal concentrations in tissues of carnivorous fish were grouped together and compared with corresponding concentrations in non-carnivorous fish; Cu and Pb levels were significantly (p?<?0.05) higher in liver of non-carnivorous species. Though no samples exceeded the maximum level set in international legislation for fish, from the perspective of the public health and considering the legal limits of fishery products for human consumption, Cu concentrations were exceeded (in tissues different from muscle) in four carnivorous and five non-carnivorous species according to the Australian legislation. In the case of Cd, two carnivorous species (Pomadasys leuciscus and Caulolatilus princeps) and one non-carnivorous species (Mugil cephalus), showed concentrations over the maximum level of 2 μg g^???1 dry weight considered in the Mexican legislation. Considering average amounts of fish consumption in Mexico, daily mineral intake (DMI) values for Cu and percentage weekly intake (PWI) of Cd and Pb were estimated; none of the analyzed metals in edible portion of analyzed fish could be detrimental to humans.     

Estimation of pollutant partition in sandy soils with different water contents

The objectives of this work were: (1) to identify an isotherm model to relate the contaminant contents in the gas phase with those in the solid and non-aqueous liquid phases; (2) to develop a methodology for the estimation of the contaminant distribution in the different phases of the soil; and (3) to evaluate the influence of soil water content on the contaminant distribution in soil. For sandy soils with negligible contents of clay and natural organic matter, contaminated with benzene, toluene, ethylbenzene, xylene, trichloroethylene (TCE), and perchloroethylene (PCE), it was concluded that: (1) Freundlich’s model showed to be adequate to relate the contaminant contents in the gas phase with those in the solid and non-aqueous liquid phases; (2) the distribution of the contaminants in the different phases present in the soil could be estimated with differences lower than 10% for 83% of the cases; and (3) an increase of the soil water content led to a decrease of the amount of contaminant in the solid and non-aqueous liquid phases, increasing the amount in the other phases.     

Total metal levels in crayfish Astacus leptodactylus (Eschscholtz, 1823), and surface sediments in Lake Terkos, Turkey

The aim of this study was to determine the total metal accumulation (aluminium, copper, manganese, lead, cadmium and iron) in different organs and eggs of Astacus leptodactylus (Eschscholtz, 1823) and sediments total metal contents (aluminium, copper, manganese, lead, cadmium, iron, zinc, chromium, nickel) in Lake Terkos. Water and sediment samples were collected from two stations at two different depths (1 and 2 m) of Lake Terkos in May 2008. Crayfish samples were collected by trammel net at the same region. Primary hydrographic conditions, such as temperature (13.6–19.4°C), salinity (0.27–0.34‰), dissolved oxygen (7.04–12.30 mg l^???1) and pH (7.42–8.51), were recorded for each sampling point. Moreover, the total organic carbon (1.65–5.44%) and the total calcium carbonate contents (19.44–41.16%) of sediment samples were determined. According to the Turkish Food Codex (J Zool 26:283–288, 2002), the maximum allowable Pb and Cd levels in crayfish are 0.5 mg/kg wet weight. Accordingly, the Pb and Cd levels determined in A. leptodactylus samples are below this limit. However, when compared with the acceptable metal limits defined by WHO, Australian National Health and Medical Research Council and Ministry of Agriculture in United Kingdom (UK), it is clear that the Cu level is at the limit and the Cd results exceed the limit. When the metal contents in sediment samples from Lake Terkos are examined, it is seen that the Al, Fe, Mn, Ni and Cu contents are lower while Zn, Cr, Cd and Pb contents are higher than the crustal average values. The high values draw attention to the land-based domestic and industrial inputs. Lake Terkos sediments have high enrichment factors (EF) of Zn, Cr, Cd and Pb metals which corroborate this result. The low EFs of Fe, Ni and Cu are due to the natural (terrigeneous) inputs. Additionally, there is no Al, Fe, Ni and Cu metal enrichment in these lake sediments because of the low contamination factor (CF) values. However, it is moderately contaminated by Zn, Cr and Pb, and heavily contaminated by Cd.