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.     

Municipal waste management in Sicily: practices and challenges

There are numerous problems yet to be solved in waste management and although efforts towards waste recovery and recycling have been made, landfills are still the most common method used in the EU and many other industrialised countries. Thermal disposal, particularly incineration, is a tested and viable alternative. In 2004, only 11% of the annual waste production of Italy was incinerated. Sicily, with over five million inhabitants, is the second largest region in Italy where waste management is now a critical problem. The use of landfills can no longer be considered a satisfactory environmental solution; therefore, new methods have to be chosen and waste-to-energy plants could provide an answer. This paper gives details of municipal solid waste management in Sicily following a new Waste Management Plan. Four waste-to-energy plants will generate electricity through a steam cycle; the feedstock will become the residue after material recovery, which is calculated as 20-40% weight of the collected municipal solid waste.     

Attribution of Carbon Dioxide Fluxes to Crop Types in a Heterogeneous Agricultural Landscape of Argentina

The increasing proportion of agricultural lands worldwide makes it necessary to intensify the research concerning the carbon exchange at agricultural sites. In order to determine the Net Ecosystem Exchange (NEE) in an agricultural landscape in the province of Buenos Aires, Argentina, we carried out eddy covariance measurements with a flux tower, which was placed between two agricultural fields. Therefore, the measured CO₂ flux represents the accumulated flux from both areas, i.e., from different crop types. We here present an analysis method which attributes the flux to the two crop types. For this analysis, we applied the Hsieh footprint model to identify the contributing source area to the flux measurement. We then applied a multiple regression analysis to calculate the NEE in the growing season 2011/2012 for each field separately. The pronounced differences in the time courses of the CO₂ fluxes in the two fields can be explained by the different sowing times and different growth stages of both cultivations. The time courses furthermore show that the CO₂ uptake of the plants was strongly affected by the drought which lasted from December 2011 to January 2012. For the growth cycle of maize (216 days), the NEE was ?240 g C m^?2 and for the growth cycle of soybean (154 days) ?231 g C m^?2. In order to obtain the NEE of a complete agricultural cycle (from harvest to harvest), we also considered the NEE of autumn and winter 2011. Uncertainties of the spatially partitioned NEE are quantified and discussed.     

Assessing reliable indicators to sewage pollution in coastal soft-bottom communities

Physicochemical characteristics of sediment and benthic communities were studied in the proximity of seven sewage outfalls with differences in flow and wastewater treatment in the Western Mediterranean Sea. Redox potential was the only abiotic parameter which showed a pattern related with distance to outfalls, whereas granulometry, percentage of organic matter, metal concentrations or pH did not show changes related with outfall presence. Benthic community analysis proved to be the most suitable monitoring tool. The results showed that the highest impacted stations corresponded with those closest to outfall with the highest flow and only pre-treatment, whilst a decrease of this tendency was detected in the locations where secondary treatment takes place. Meta-analysis showed a decrease of amphipods and tanaids abundance as well as redox potential, as the indicators with the clearest response to sewage presence.     

A methodology to identify representative configurations of sensors for monitoring soil moisture

Soil moisture is the key link among hydroecological compartments, responding dynamically to sequences of atmospheric processes and management conditions and modulating physical, chemical, and biological processes in the soil. Currently, there are a variety of monitoring techniques to measure, directly or indirectly, the soil moisture. However, some practical issues remain open like the definition a priori of the number, location and depth of the monitoring points, and the impact of failing or poor performance soil moisture sensors. Here, we present a set of techniques, namely Δθ time series, wavelet filtering, and time stability, to identify representative points and monitoring depths through an analysis of hourly soil moisture time series for different configuration of the monitoring network. We used real data from a monitoring network consisting of seven monitoring points, each one with four EC-5 probes (Decagon Devices Inc., Pullman, WA) at 20, 40, 60, and 100?cm. The use of simple time series of Δθ allowed us to assess the spatiotemporal influence of the monitoring points, while the wavelet periodograms allowed us to get insight about the response of the monitoring points at different time scales. Both methods are easy to implement or adapt to specific conditions, being coherent to the results derived from time stability analysis. For our case study, we concluded that we could reallocate 16 sensors (out of 28) without a significant loss of information. However, the final decision strongly relies on a deep knowledge of the site features and the objectives of the monitoring network.     

The spatial statistics formalism applied to mapping electromagnetic radiation in urban areas

Determining the electromagnetic radiation levels in urban areas is a complicated task. Various approaches have been taken, including numerical simulations using different models of propagation, sampling campaigns to measure field values with which to validate theoretical models, and the formalism of spatial statistics. In the work, we present here that this latter technique was used to construct maps of electric field and its associated uncertainty from experimental data. For this purpose, a field meter and a broadband probe sensitive in the 100-kHz–3-GHz frequency range were used to take 1,020 measurements around buildings and along the perimeter of the area. The distance between sampling points was 5 m. The results were stored in a geographic information system to facilitate data handling and analysis, in particular, the application of the formalism of spatial statistical to the analysis of the distribution of the field levels over the study area. The spatial structure was analyzed using the variographic technique, with the field levels at non-sampled points being interpolated by kriging. The results indicated that, in the urban area analyzed in the present work, the linear density of sampling points could be reduced to a distance which coincides with the length of the blocks of buildings without the statistical parameters varying significantly and with the field level maps being reproduced qualitatively and quantitatively.     

Fractionation of heavy metals and assessment of contamination of the sediments of Lake Titicaca

Chemical weathering is one of the major geochemical processes that control the mobilization of heavy metals. The present study provides the first report on heavy metal fractionation in sediments (8–156 m) of Lake Titicaca (3,820 m a.s.l.), which is shared by the Republic of Peru and the Plurinational State of Bolivia. Both contents of total Cu, Fe, Ni, Co, Mn, Cd, Pb, and Zn and also the fractionation of these heavy metals associated with four different fractions have been determined following the BCR scheme. The principal component analysis suggests that Co, Ni, and Cd can be attributed to natural sources related to the mineralized geological formations. Moreover, the sources of Cu, Fe, and Mn are effluents and wastes generated from mining activities, while Pb and Zn also suggest that their common source is associated to mining activities. According to the Risk Assessment Code, there is a moderate to high risk related to Zn, Pb, Cd, Mn, Co, and Ni mobilization and/or remobilization from the bottom sediment to the water column. Furthermore, the Geoaccumulation Index and the Enrichment Factor reveal that Zn, Pb, and Cd are enriched in the sediments. The results suggest that the effluents from various traditional mining waste sites in both countries are the main source of heavy metal contamination in the sediments of Lake Titicaca.     

DDT, DDE, and 1-hydroxypyrene levels in children (in blood and urine samples) from Chiapas and Oaxaca, Mexico

The aim of this study was to evaluate the DDT, DDE, and 1-hydroxypyrene exposure levels of children living in communities located in southeastern Mexico. The study communities were Lacanja and Victoria in Chiapas state and Ventanilla in Oaxaca state. Children living in Lacanja had total blood DDT levels (mean?±?SD, 29,039.6?±?11,261.4 ng/g lipid) that were significantly higher than those of children in Victoria (10,220.5?±?7,893.1 ng/g lipid) and Ventanilla (11,659.7?±?6,683.7 ng/g lipid). With respect to the 1-hydroxypyrene levels in urine samples, the levels in Lacanja (4.8?±?4.1 μg/L or 4.5?±?3.9 μmol/mol creatinine) and Victoria (4.6?±?3.8 μg/L or 3.9?±?3.0 μmol/mol Cr) were significantly higher than levels found in Ventanilla (3.6?±?1.4 μg/L or 2.5?±?0.5 μmol/mol Cr). In conclusion, our data indicate high levels of exposure in children living in the communities studied in this work. The evidence found in this study could be further used as a trigger to revisit local policies on environmental exposures.