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.     

Iron, cadmium, and chromium in seagrass (Thalassia testudinum) from a coastal nature reserve in karstic Yucatán

The management of protected areas in karstic regions is a challenge because flooded cave systems form there and provide underground hydrological conducts that may link different zones. As a consequence, affectations to the protected areas can possibly occur as a consequence of human activities in remote areas and may therefore pass undetected. Thus, the monitoring of possible contaminants in these regions is becoming imperative. In this work, we analyze the concentration of essential (iron) and non-essential metals (cadmium and chromium) in the seagrass Thalassia testudinum that grows in Yalahau Lagoon, located in a near-to-pristine protected area of the Yucatán Peninsula, close to the rapidly developing touristic belt of the Mexican Caribbean. Salinity and silicate patterns show that Yalahau is an evaporation lagoon, where groundwater discharge is important. High iron (>400 μg/g), cadmium (>4 μg/g), and chromium (≈1 μg/g) concentrations were found in the area of highest groundwater input of the lagoon. High levels (5.1 μg/g) were also found near the town dump. In the rest of the sampling sites, metal concentrations remained near to background levels as estimated from other works. Temporal changes of concentrations in the seagrass tissues show also a local input and an input from the groundwater that could provoke an environmental problem in the Yalahau Lagoon in the near future.     

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.     

Compositional data analysis of smoke emissions from debris piles with low-density polyethylene

ABSTRACT

Data describing the composition of smoke are inherently multivariate and always non-negative parts of a whole. The data are relative and the information is contained in the ratios between parts of the composition. A prior analysis of smoke emissions produced from the burning of manzanita wood mixed with low-density polyethylene plastic applied traditional statistical methods to the compositional data and found no effect. The current paper applies compositional data techniques to these smoke emissions to determine if the prior analysis was accurate. Analysis of variance of the isometric log-ratios showed that LDPE significantly affected the CO₂ emission ratio for 8 of the 191 trace gases; this analysis showed none of the gases identified in the previous analysis were affected by LDPE. LDPE did not affect the CO₂ emission ratios for the alkanes, alkenes, alkynes, aldehydes, cycloalkanes, cycloalkenes, diolefins, ketones, MAHs, and PAHs. Compositional data analysis should be used to analyze smoke emissions data. Burning contaminant-free LDPE should produce emissions like wood.     

Combining Intended Demand and Yes/No Responses in the Estimation of Contingent Valuation Models

The contingent valuation method (CVM) has limitations arising from the lack of a direct link between estimated willingness to pay and consumer behavior regarding the use of the good being evaluated. To estimate the total value of a resource under a capacity constraint, information on intended use is introduced as an integral part of the CVM. This combined approach allows use and non-use values to be distinguished for a sample of users and non-users. The econometric specification is applied to estimate the benefits of reducing water pollution on beaches located near an important metropolitan area of South America.     

Study of metal fractionation in river sediments. A comparison between kinetic and sequential extraction procedures

The extraction kinetic of trace metals (Cd, Cu, Pb, and Zn) in river sediments by four extraction agents was studied. As extractants ammonium acetate, acetic acid, hydroxylamine and EDTA solutions were assayed. These reagents can leach the metals more or less selectively from several metal compartments of sediments. The metal leaching kinetic model permits classification of the metal species in labile and moderately-labile ones. The combination of two or more non specific reagents permits a high characterisation of metal distribution and leachability. The results obtained with this model in four river sediments were compared with data obtained by the SM&T sequential extraction procedure, in order to characterise the chemical nature of leached metal.     

Kinetics of photodegradation and ozonation of pentachlorophenol

The oxidation of 2,3,4,5,6-pentachlorophenol (PCP) has been carried out by a photodecomposition process using a polychromatic UV irradiation, and by an ozonation process. In the photodegradation process, the pH accelerated the decomposition rate and the approximate first-order rate constants were evaluated, with values between 0.16+/-0.005 min(-1) at pH=3 and 0.26+/-0.007 min(-1) at pH=9. A more rigorous kinetic study led to the determination of the quantum yields of the reaction, with values of 200+/-7x10(-3) mol/Eins for pH=3 and 22+/-1.1x10(-3) mol/Eins for pH=9. In the ozonation process, the rate constants for the reaction between ozone and PCP were determined by means of a competition kinetics, with values in the range from 0.67x10(5) to 314x10(5) l/mols. The specific rate constants for the un-dissociated and dissociated forms of PCP were also calculated. Finally, in both processes, the intermediate reaction products were identified, the most important being tetrachlorocatechol, tetrachlorohydroquinone and tetra-p-chlorobenzoquinone. Free chloride ion released, which was favored at high pHs, was also followed in both processes.     

Post-breeding migration in male great bustards: low tolerance of the heaviest Palaearctic bird to summer heat

Radio tracking of 142 males captured at 44 leks in Spain showed that partial migration of great bustard males in summer is a widespread behaviour in many Iberian populations, in contrast to their previously assumed sedentariness. A variable number of males migrated immediately after mating to summering areas with lower temperatures and human population densities and more trees and rainfall levels than the breeding sites. Birds selected there fields with trees and sunflower crops which provided shade during the hottest midday hours and protective cover against predators. Males breeding in areas with higher July temperatures had a higher tendency to migrate, and males from hotter, southern regions migrated longer distances than those from milder, northern regions and showed a preferred northward direction. These results confirmed various predictions from the weather sensitivity hypothesis, suggesting that summer migration of great bustard males represents primarily an adaptation to escape the summer heat of most breeding areas in central and southern Iberia. The hypothesis that males migrated to benefit from higher food availability at the summering areas could not be rejected by our results. Finally, migrating males also gained more tranquillity during the post-breeding moult due to the lower human population density at the summering areas. Summer migration of Iberian great bustard males may thus be interpreted as a form of behavioural thermoregulation which has not been described for other Palaearctic populations of this species or for other bird species breeding in temperate latitudes.     

Effect of delayed first feeding on larval performance of the spider crab Maja brachydactyla assessed by digestive enzyme activities and biometric parameters

The effect of food deprivation on larval performance of the spider crab Maja brachydactyla was studied in terms of survival, moulting capacity, size, weight and enzymatic activities. Five feeding treatments that differed in the initial age of first feeding larvae (fed from hatching, 2, 4 and 6 days post-hatching and unfed) were tested for 20 days. Newly hatched larvae kept without food supply lasted for 10 days and did not moult; with 50% survival observed at 6 days post-hatching. Larvae (zoea I stage) were only able to tolerate 2 days of food deprivation after the onset of exogenous feeding without their performance being compromised. Multivariate analyses suggest that digestive enzyme activities may be good indicators of the nutritional condition of larvae.