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.     

A novel approach to predict aquatic toxicity from molecular structure

The main aim of the study was to develop quantitative structure-activity relationship (QSAR) models for the prediction of aquatic toxicity using atom-based non-stochastic and stochastic linear indices. The used dataset consist of 392 benzene derivatives, separated into training and test sets, for which toxicity data to the ciliate Tetrahymena pyriformis were available. Using multiple linear regression, two statistically significant QSAR models were obtained with non-stochastic (R2=0.791 and s=0.344) and stochastic (R2=0.799 and s=0.343) linear indices. A leave-one-out (LOO) cross-validation procedure was carried out achieving values of q2=0.781 (scv=0.348) and q2=0.786 (scv=0.350), respectively. In addition, a validation through an external test set was performed, which yields significant values of Rpred2 of 0.762 and 0.797. A brief study of the influence of the statistical outliers in QSAR's model development was also carried out. Finally, our method was compared with other approaches implemented in the Dragon software achieving better results. The non-stochastic and stochastic linear indices appear to provide an interesting alternative to costly and time-consuming experiments for determining toxicity.     

Wild boar (Sus scrofa) as a bioindicator of organochlorine compound contamination in terrestrial ecosystems of West Pomerania Province, NW Poland

The aim of this study was to detect the presence and determine the residue levels of DDT, lindane, endrin and polychlorinated biphenyls (PCBs) in the liver of wild boars from the area of West Pomerania, NW Poland; to determine the activity of glutathione S-transferase (GST) as a biomarker of biological response and to assess the toxicological risk for consumers of the wild boar offal. The presence of pesticide residues and PCBs was found in all examined liver samples. The highest concentration was observed for endrin, and then, the descending order was PCBs >DDTs >lindane >dl-PCBs. The mean hepatic concentrations of endrin, PCBs, DDTs and lindane were 117.28, 78.59, 67.95 and 7.24 ng/g lipid weight, respectively. Among the dioxin-like PCB congeners, 118 and 156 were dominant in liver samples. The mean toxic equivalent (TEQ) level calculated for dl-PCBs was 2.10?±?1.11 pg WHO-PCB-TEQ/g. There was a statistically significant (p?<?0.05) negative correlation between the concentration of lindane, DDTs and PCBs (as a sum of indicator congeners) in the liver and in the activity of GST. However, GST activities showed no significant correlation with any of the dl-PCBs. In five boar liver samples, the levels of certain organochlorine compounds exceeded the maximum residue levels (MRLs). In one sample, the MRLs were exceeded simultaneously for PCBs, endrin and DDTs and in another one—for endrin and DDTs. In the remaining three samples, only PCB levels were exceeded.     

Assessing the ecological effects of human impacts on coral reefs in Bocas del Toro,Panama

Environmental and biological reef monitoring was conducted in Almirante Bay (Bahía Almirante) in Bocas del Toro, Panama, to assess impacts from anthropogenic developments. An integrated monitoring investigated how seasonal temperature stress, turbidity, eutrophication and physical impacts threatened reef health and biodiversity throughout the region. Environmental parameters such as total suspended solids [TSS], carbon isotopes (δ¹³C), C/N ratios, chlorophyll a, irradiance, secchi depth, size fractions of the sediments and isotope composition of dissolved inorganic carbon [DIC] of the water were measured throughout the years 2010 and 2011 and were analysed in order to identify different impact sources. Compared to data from Collin et al. (Smithsonian Contributions to the Marine Sciences 38:324–334, 2009) chlorophyll a has doubled at sites close to the city and the port Almirante (from 0.46–0.49 to 0.78–0.97 μg l^?1) and suspension load increased, visible by a decrease in secchi depth values. Visibility decreased from 9-13 m down to 4 m at the bay inlet Boca del Drago, which is strongly exposed to river run off and dredging for the shipping traffic. Eutrophication and turbidity levels seemed to be the determining factor for the loss of hard coral diversity, most significant at chlorophyll a levels higher than 0.5 μg l^?1 and TSS levels higher than 4.7 mg l^?1. Hard coral cover within the bay has also declined, at some sites down to <10 % with extremely low diversities (7 hard coral species). The hard coral species Porites furcata dominated the reefs in highly impacted areas and showed a strong recovery after bleaching and a higher tolerance to turbidity and eutrophication compared to other hard coral species in the bay. Serious overfishing was detected in the region by a lack of adult and carnivorous fish species, such as grunts, snappers and groupers. Study sites less impacted by anthropogenic activities and/or those with local protection showed a higher hard coral cover and fish abundance; however, an overall loss of hard coral diversity was observed.     

Characterization of As and trace metals embedded in PM10 particles in Puebla City, México

Forty-eight air-filter samples (PM₁₀) were analysed to identify the concentration level of partially leached metals (PLMs; As, Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb and V) from Puebla City, México. Samples were collected during 2008 from four monitoring sites: (1) Tecnológico (TEC), (2) Ninfas (NIN), (3) Hermanos Serdán (HS) and (4) Agua Santa (AS). The results indicate that in TEC, As (avg. 424 ng m^?3), V (avg. 19.2 ng m^?3), Fe (avg. 1,202 ng m^?3), Cu (avg. 86.6 ng m^?3), Cr (41.9 ng m^?3) and Ni (18.6 ng m^?3) are on the higher side than other populated regions around the world. The enrichment of PLMs is due to the industrial complexes generating huge dust particles involving various operations. The results are supported by the correlation of metals (Mn, Cd and Co) with Fe indicating its anthropogenic origin and likewise, As with Cd, Co, Fe, Mn, Pb and V. The separate cluster of As, Fe and Mn clearly signifies that it is due to continuous eruption of fumaroles from the active volcano Popocatépetl in the region.     

Macro- and microelement distribution in organs of Glyceria maxima and biomonitoring applications

The content of nutrients (N, P, K, Ca and Mg) and of trace metals (Fe, Cu, Mn, Zn, Pb, Cd, Co and Ni) in water, bottom sediments and various organs of Glyceria maxima from 19 study sites selected in the Jeziorka River was determined. In general, the concentrations of nutrients recorded in the plant material decreased in the following order: leaf>root>rhizome>stem, while the concentrations of the trace elements showed the following accumulation scheme: root>rhizome>leaf>stem. The bioaccumulation and transfer factors for nutrients were significantly higher than for trace metals. G. maxima from agricultural fields was characterised by the highest P and K concentrations in leaves, and plants from forested land contained high Zn and Ni amounts. However, the manna grass from small localities showed high accumulation of Ca, Mg and Mn. Positive significant correlations between Fe, Cu, Zn, Cd, Co and Ni concentrations in water or sediments and their concentrations in plant indicate that G. maxima may be employed as a biomonitor of trace element contamination. Moreover, a high degree of similarity was noted between self-organizing feature map (SOFM)-grouped sites of comparable quantities of elements in the water and sediments and sites where G. maxima had a corresponding content of the same elements in its leaves. Therefore, SOFM could be recommended in analysing ecological conditions of the environment from the perspective of nutrients and trace element content in different plant species and their surroundings.     

Organochlorine pesticide residue levels in blood serum of inhabitants from Veracruz, Mexico

The objective of the present study was to monitor the levels of organochlorine pesticides HCB; α-, β-, γ-HCH; pp'DDE; op'DDT; and pp'DDT in blood serum of Veracruz, Mexico inhabitants. Organochlorine pesticides were analyzed in 150 blood serum samples that constituted that which remained after clinical analyses, using gas chromatography-electron-capture detection (GC-ECD). The results were expressed as milligrams per kilogram on fat basis and micrograms per liter on wet weight. Only the following pesticides were detected: p,p'-DDE was the major organochlorine component, detected in 100% of samples at mean 15.8 mg/kg and 8.4 μg/L; p,p'-DDT was presented in 41.3.% of monitored samples at mean 3.1 mg/kg and 1.4 μg/L; β-HCH was found in 48.6% of the samples at mean 4.9 mg/kg and 2.7 μg/L; op'DDT was determined to be in only 3.3% of monitored samples at mean 2.7 mg/kg and 1.4 μg/L. The pooled samples divided according to sex showed significant differences of β-HCH and pp'DDE concentrations in females. The samples grouped according to age presented the third tertile as more contaminated in both sexes, indicating age as a positively associated factor with serum organochlorine pesticide levels in Veracruz inhabitants.