Sorption of copper, zinc and lead on soil mineral phases

Soil mineral phases play a significant role in controlling heavy metal mobility in soils. The effective study of their relation needs the integrated use of several analytical methods. In this study, analytical electron microscopy analyses were combined with sequential chemical extractions on soils spiked with Cu, Zn and Pb. Our aims were to study the metal sorption capacity of soil mineral phases and the effect of presence of iron oxide and carbonate on this property of soil minerals. Copper and Pb were found to be characterized by higher and stronger sorption on the studied samples than Zn. Only the former two metals showed significant differences in their immobilized metal amounts on the studied samples and soil mineral particles. Highest metal amounts were sorbed on the swelling clay mineral particles (smectites and vermiculites), but iron-oxide phases may also have similar lead sorption capacity. Alkaline conditions due to the carbonate content of soils resulted both in increased sorption on the mineral particles for Cu and in enhanced role of precipitation for all the studied metals. On the other hand, the intimate association of phyllosilicates and iron resulted in significant increase in metal sorption capacity of the given particle. The results of sequential extractions could be successfully completed by the analytical electron microscopy analyses for studying the sorption capacity of discrete mineral particles. Their integrated use helps us in better understanding the heavy metal-mineral interactions in soils.     

Biochemical effects of clomazone herbicide on piava (Leporinus obtusidens)

This study aims to verify the effects of the clomazone concentration used in rice fields on acetylcholinesterase (AChE), thiobarbituric acid reactive substances (TBARS), protein carbonyl and catalase activity in tissues of piava (Leporinus obtusidens). LC(50)-96h was 5.0 mg L(-1) and the fish were exposed to 1/10 of LC(50)-96 h: 0.5 mg L(-1) of clomazone for 96 and 192h. The same parameters were also assayed after a recovery period of 192 h in clean water. AChE activity was reduced only in the brain and heart of fish exposed for 96 h. AChE activity was decreased in the brain, muscle and heart tissues after 192 h of exposure. After 192 h of recovery period, AChE activity remained diminished in brain and muscle and showed a decrease in eye. However, after 192 h of recovery, AChE activity in heart was recovered. Fish showed increased TBARS levels in brain at all experimental periods. TBARS levels decreased in liver and muscle tissues after 192 h of exposure. The increase in muscle TBARS persisted in fish transferred to clean water. Protein carbonyl in the liver was increased in all periods studied including the recovery period. Catalase activity was reduced during all periods. The present study demonstrates the occurrence of disorders in AChE, TBARS, protein carbonyl and catalase activity in piava. The results also show changes in fish after exposure to an environmentally relevant concentration of clomazone. Most effects observed persisted after the recovery period. Thus, these parameters may be used to monitor clomazone toxicity in fish.     

Increased thyroid volume, prevalence of thyroid antibodies and impaired fasting glucose in young adults from organochlorine cocktail polluted area: outcome of transgenerational transmission?

In 137 females (F) and 94 males (M) aged 21-35 years from organochlorines (OCs) polluted area (POLL) increased thyroid volume (ThV), prevalence of antibodies to thyroperoxidase (TPOab), thyrotropin receptor (TRab) and of impaired fasting glucose (IFG) was found compared to 116 F and 107 M from background pollution area (BCGR). In F and M from POLL also strikingly increased level of PCBs, DDE and HCB was found. Such findings were compared to the generation of their parents aged 41-55 years consisting of 320F/213M from POLL and 406F/231M from BCGR. However, in spite of strikingly lower level of those OCs in young adults from POLL, they showed about the same prevalence of adverse health signs as the old generation. From such reason 44 young F and 40 young M with lowest PCBs level from POLL were selected to obtain nearly the same PCB level as found in all young F and M from BCGR. In such PCB adjusted groups the prevalence of TPOab, TRab, IFG and increased ThV was still significantly higher than that in all young subjects from BCGR. At the same time, also the level of DDE and HCB in such PCBs adjusted groups was considerably lower. It was concluded that such adverse effects in young adults from POLL possibly did not result from their actual OCs levels, but very likely from their exposure to high OCs levels of their mothers during their prenatal and perinatal life. Thus, the data may be compatible with present views on transgenerational transmission of endocrine disruptors action.     

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.     

Assessment of the phytoextraction potential of high biomass crop plants

A hydroponic screening method was used to identify high biomass crop plants with the ability to accumulate metals. Highest values of shoot accumulation were found in maize cv. Ranchero, rapeseed cv. Karat, and cardoon cv. Peralta for Pb (18 753 mg kg(-1)), Zn (10 916 mg kg(-1)), and Cd (242 mg kg(-1)), respectively. Subsequently, we tested the potential of these three cultivars for the phytoextraction of a metal spiked compost, finding out that, in cardoon and maize plants, increasing Zn and Cd concentrations led to lower values of root and shoot DW. By contrast, rapeseed shoot growth was not significantly affected by Cd concentration. Finally, a metal polluted soil was used to check these cultivars' phytoextraction capacity. Although the soil was phytotoxic enough to prevent the growth of cardoon and rapeseed plants, maize plants phytoextracted 3.7 mg Zn pot(-1). We concluded that the phytoextraction performance of cultivars varies depending on the screening method used.     

Antibacterial behavior of silver-modified clinoptilolite-heulandite rich tuff on coliform microorganisms from wastewater in a column system

The water disinfecting behavior of silver-modified clinoptilolite–heulandite rich tuff (ZSAg) as an antibacterial agent against coliform microorganisms from water in a continuous mode was investigated. Silver recovery from the disinfected effluents by the sodium-modified clinoptilolite–heulandite rich tuff (ZSNa) was also considered. Escherichia coli (ATCC 8739) and total coliform microorganisms, as indicators of microbiological contamination of water, were chosen to achieve the disinfection of synthetic wastewater or municipal wastewater. Ammonium (NH₄⁺) and chloride (Cl⁻) ions were added to the synthetic wastewater as an interfering chemical species on the disinfection processes. The antibacterial activity of the ZSAg as a bactericide was measured by the coliform concentration as evaluated by the APHA method. The amount of silver in the disinfected effluents was determined using atomic absorption spectroscopy. The inactivation of the ZSAg was calculated from the breakthrough curves based on the model reported by Gupta et al. It was found that when the silver concentration in the effluent is less than 0.6 μg/mL, the bacterial survival percentage increased and the volume of disinfected water diminished. The total silver amounts found in the effluent at the end of the disinfection processes varied depending on the water treated (synthetic or municipal wastewater). The presence of NH₄⁺ ions in synthetic wastewater influent notably improved the disinfected water volume (zero NVC/100 mL), in comparison to the disinfection of the same influent without NH₄⁺ ions. A contrary water disinfection behavior was observed in the presence of Cl⁻ ions. The silver recovery does not depend on the mass of the sodium zeolitic bed according with the wastewater to be treated (synthetic or municipal wastewater) and the presence of NH₄⁺ or Cl⁻ ions in the influent also influenced the silver recovery from wastewater. The ZSNa did not have antibacterial activity. Therefore the amount of bactericide agent (silver-modified natural zeolite), coliform microorganisms from water (E. coli or consort of coliform microorganisms) as well as the water quality (synthetic wastewater or municipal wastewater) influenced both the disinfection process and the silver recovery in a column system.     

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.     

Particulate matter levels in a South American megacity: the metropolitan area of Lima-Callao,Peru

The temporal and spatial trends in the variability of PM₁₀ and PM_2.5 from 2010 to 2015 in the metropolitan area of Lima-Callao, Peru, are studied and interpreted in this work. The mean annual concentrations of PM₁₀ and PM_2.5 have ranges (averages) of 133–45 μg m^?3 (84 μg m^?3) and 35–16 μg m^?3 (26 μg m^?3) for the monitoring sites under study. In general, the highest annual concentrations are observed in the eastern part of the city, which is a result of the pattern of persistent local winds entering from the coast in a south-southwest direction. Seasonal fluctuations in the particulate matter (PM) concentrations are observed; these can be explained by subsidence thermal inversion. There is also a daytime pattern that corresponds to the peak traffic of a total of 9 million trips a day. The PM_2.5 value is approximately 40% of the PM₁₀ value. This proportion can be explained by PM₁₀ re-suspension due to weather conditions. The long-term trends based on the Theil-Sen estimator reveal decreasing PM₁₀ concentrations on the order of ?4.3 and ?5.3% year^?1 at two stations. For the other stations, no significant trend is observed. The metropolitan area of Lima-Callao is ranked 12th and 16th in terms of PM₁₀ and PM_2.5, respectively, out of 39 megacities. The annual World Health Organization thresholds and national air quality standards are exceeded. A large fraction of the Lima population is exposed to PM concentrations that exceed protection thresholds. Hence, the development of pollution control and reduction measures is paramount.     

A Novel Formulation for Designing a Monitoring Strategy: Application to the Design of a River Quality Monitoring System

In this work, we propose a technique to automatically optimize the monitoring of any distributed indicator (concentration of a substance along a river, blood pressure of a patient over time, etc.) for which a reliable estimate is previously available. From a mathematical point of view, the problem is based on obtaining a reliable estimate of the chosen indicator (e.g., by numerical simulation), and then solving a multi-objective optimization problem (with mixed real and integer variables) whose solution must provide an efficient and satisfactory monitoring strategy. As an illustrative case, we show the steps to follow in order to implement that strategy when designing a system for monitoring water quality in a river. Finally, we present and analyze the results when applying the proposed technique to study a real case in the Neuse River (North Carolina, USA).