Solar CPC pilot plant photocatalytic degradation of bisphenol A in waters and wastewaters using suspended and supported-TiO2. Influence of photogenerated species

Photocatalytic degradation of bisphenol A (BPA) in waters and wastewaters in the presence of titanium dioxide (TiO₂) was performed under different conditions. Suspensions of the TiO₂ were used to compare the degradation efficiency of BPA (20 mg L^?1) in batch and compound parabolic collector (CPC) reactors. A TiO₂ catalyst supported on glass spheres was prepared (sol–gel method) and used in a CPC solar pilot plant for the photodegradation of BPA (100 μg L^?1). The influence of OH·, O₂ ^·?, and h ⁺ on the BPA degradation were evaluated. The radicals OH· and O₂ ^·? were proved to be the main species involved on BPA photodegradation. Total organic carbon (TOC) and carboxylic acids were determined to evaluate the BPA mineralization during the photodegradation process. Some toxicological effects of BPA and its photoproducts on Eisenia andrei earthworms were evaluated. The results show that the optimal concentration of suspended TiO₂ to degrade BPA in batch or CPC reactors was 0.1 g L^?1. According to biological tests, the BPA LC₅₀ in 24 h for E. andrei was of 1.7?×?10^?2 mg cm^?2. The photocatalytic degradation of BPA mediated by TiO₂ supported on glass spheres suffered strong influence of the water matrix. On real municipal wastewater treatment plant (MWWTP) secondary effluent, 30 % of BPA remains in solution; nevertheless, the method has the enormous advantage since it eliminates the need of catalyst removal step, reducing the cost of treatment.     

Optimization of Microwave-Assisted and Conventional Heating Comparative Synthesis of Poly(lactic acid) by Direct Melt Polycondensation from Agroindustrial Banana (Musa AAA Cavendish) and Pineapple (Ananas comosus) Fermented Wastes

In Costa Rica, a lot of pineapple (Ananas comosus) and banana (Musa AAA) agroindustrial residues are generated each year. These residues can be used to obtain l-lactic acid by fermentation, ultrafiltration and electrodialysis. Poly(l-lactic acid) (PLLA) is a biodegradable and renewable polyester with many industrial and biomedical applications. There is a growing interest to improve the energetic efficiency of the synthesis of PLLA, because the main issue to produce this polymer is the high productive cost compared with petrochemical traditional commodities. In this research, the synthesis of PLLA through two different techniques was compared: microwave-assisted and conventional heating. On microwave synthesis the best results were obtained using lower temperatures and lower reaction times than the conventional heated synthesis. The reaction time was reduced from 15 h by conventional heating to 4.5 h using microwave-assisted synthesis.     

The Effect of Chain Extender on Poly(3-hydroxybutyrate-co-3-hydroxyvalerate): Thermal Degradation,Crystallization, and Rheological Behaviours

Poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV), a semi-polycrystalline biopolymer from the polyhydroxyalkanonate family has in recent years become a commercial bioplastic with mechanical properties comparable to isotactic polypropylene and enhanced O₂, CO₂ and H₂O barrier properties. However, its brittleness and sensitivity to thermal and hydrolysis degradations restrict its applications. To overcome the problems associated with degradation during processing blending of PHBV and an epoxy-functionalized chain extender (Joncryl^® ADR-4368 S) was conducted in a twin screw extruder. The effect of concentration of the chain extender on thermal, crystallization and rheological behaviours of PHBV was investigated. Thermal gravimetric analysis results indicated improvement in the resistance to thermal decomposition of PHBV by introducing the chain extender. This was accompanied with calculation of thermal degradation activation energy (E_a) using the Flyn–Walls–Ozawa method which confirmed increase of E_a with the increase in content of the chain extender. The rheological behaviour and crystallization of modified PHBV was characterized by rotational rheometry and differential scanning calorimetry techniques, respectively. The results show that addition of chain extender enhanced viscosity of PHBV and also reduce the rate of crystallization.     

Sorption and desorption of carbamazepine, naproxen and triclosan in a soil irrigated with raw wastewater: estimation of the sorption parameters by considering the initial mass of the compounds in the soil

The amphipod Hyalella azteca was exposed for 28 d to different combinations of Zn contaminated sediment and food. Sediment exposure (+clean food) resulted in increased Zn body burdens, increased mortality and decreased body mass when the molar concentrations of simultaneously extracted Zn were greater than the molar concentration of Acid Volatile Sulfide (SEM_Zn-AVS > 0), suggesting that dissolved Zn was a dominant route of exposure. No adverse effect was noted in the foodexposure (+clean sediment), suggesting selective feeding or regulation. Combined exposure (sediment + food) significantly increased adverse effects in comparison with sediment exposure, indicating contribution of dietary Zn to toxicity and bioaccumulation. The observed enhanced toxicity also supports the assumption on the presence of an avoidance/selective feeding reaction of the amphipods in the single sediment or food exposures. During 14 d post-exposure in clean medium, the organisms from the same combined exposure history received two feeding regimes, i.e. clean food and Zn spiked food. Elevated Zn bioaccumulation and reduced reproduction were noted in amphipods that were offered Zn spiked food compared to the respective organisms that were fed clean food. This was explained by the failure of avoidance/selective feeding behavior in the absence of an alternative food source (sediment), forcing the amphipods to take up Zn while feeding. Increasing Zn body burdens rejected the assumption that Zn uptake from food was regulated by H. azteca. Our results show that the selective feeding behavior should be accounted for when assessing ecological effects of Zn or other contaminants, especially when contaminated food is a potential exposure route.     

Regression method of the hydrophobicity ruler approach for determining octanol/water partition coefficients of very hydrophobic compounds

A regression method was developed for the hydrophobicity ruler approach, which is an indirect method for determining the octanol/water partition coefficients of very hydrophobic compounds. Two constants introduced into the mathematical model were obtained by regression of the absorption data sampled before the partition equilibrium. A water miscible organic solvent was used to increase the solubility of the very hydrophobic compounds in the aqueous solution so that the hydrophobicity scale was reduced and the equilibration was accelerated. Polydimethylsiloxane/methanol aqueous solution and a series of 21 polychlorinated biphenyls (PCBs) were used to demonstrate the regression method. The PCB compounds with known experimental logK(o/w) values served as reference compounds, while the PCB compounds without known logK(o/w) values were determined. The distribution coefficients (logK(p/s)), uptake and elimination rate constants were obtained from the two regression constants for each compound (reference or unknown). The correlation of the logK(p/s) values of the reference PCB compounds with their logK(o/w) values was linear (logK(o/w)=2.69logK(p/s)+0.76, R(2)=0.97). The logK(o/w) values were compared with literature values and suggested that some values from the literature far off the calibration line could be inaccurate. The critical experimental factors, the merits of the regression method were discussed.     

Distribution pattern, reproductive biology, and fishery of the wedge sole Dicologlossa cuneata in the Gulf of Cadiz, south-west Spain

The wedge sole Dicologlossa cuneata (Moreau, 1881) is a coastal species that lives along the inner shelf waters of the Gulf of Cadiz down to a depth of 115 m. Its fishery, the size composition of the exploited population, and its reproduction have been studied on the basis of data acquired from commercial statistics from 1984 to 1994 and from sampling carried out during 1993 and 1994. The relative abundance of the species and its geographic and bathymetric distribution have been examined by analysis of four trawl surveys carried out from 1992 to 1994. D. cuneata is captured mainly by the trawl fleet, and to a lesser extent by gillnet gears. Wedge sole fishery has a marked seasonality. Size-frequency distributions from commercial samples and from bottom-trawl surveys are very similar, ranging from 12 to 26 cm total body length (TL). D. cuneata is a “repeat-spawner”. Peak spawning is from January to May. Females attain sexual maturity at 18 cm TL, while sexually mature males have been observed at 15 cm TL. The flexibility of the spawning strategy of D. cuneata throughout its distribution range is discussed. The scarcity of small specimens in the monthly samples and sequential spawning throughout the year prevented the estimation of growth parameters by means of length-frequency analysis. D. cuneata is present in greatest abundances in the sandy–muddy bottoms of the Guadalquivir River mouth at 15 to 30 m depth. Its optimum habitat coincides with the principal commercial fishing grounds. The possibility of reproductive vertical migration is discussed, but more precise data are needed before a viable hypothesis can be made. Received: 1 July 1997 / Accepted: 27 November 1997     

Towards the definition of budget models for the evolution of deltas

Global climatic change is likely to take place and could eventually affect Mediterranean deltas and other lowlying coastal regions. This would have serious implications for the natural resources of these deltaic areas, as well as for human settlements and related economic activities. To achieve sound decision making, to prevent damages and to avoid risky investments, it is necessary to understand the integral functioning of deltaic areas and to determine their vulnerability and response to large-scale change phenomena. Optimal use of the available knowledge will require that existing and new field measurements are combined and that integrated (physical/ecological) conceptual models of deltaic behaviour are developed with socio-economics scenarios as boundary conditions. This paper illustrates the methodological effort towards organizing a modeling framework to conduct budget computations at various scales with reference to the most significant ‘physiogrpahic units’ and to the most significant deltaic processes. The final objective is to handle the problem of evaluating possible changes under different scenarios.     

In-situ application of colloidal activated carbon for PFAS-contaminated soil and groundwater: A Swedish case study

Soil and groundwater contamination by per- and polyfluoroalkyl substances (PFAS) has been a significant concern to human health and environmental quality. Remediation of contaminated sites is crucial to prevent plume expansion but can prove challenging due to the persistent nature of PFAS combined with their high aqueous mobility. In this case study, we investigated the potential of colloidal activated carbon (CAC) for soil stabilization at the pilot scale, aiming to entrap PFAS and prevent their leaching from soil into groundwater. Monitoring of the site revealed the presence of two potential sources of PFAS contamination at concentrations up to 23 μg L⁻¹ for ∑₁₁PFAS in groundwater. After CAC application, initial results indicated a 76% reduction of ∑₁₁PFAS and high removal rates for long-chain PFAS, such as perfluorooctane sulfonic acid and perfluorooctanoic acid. A spike in concentrations was noticed 6 months after injection of CAC, showing a rebound of the plume and a reduction of treatment effectiveness. Based on long-term monitoring data, the treatment effectiveness for ∑₁₁PFAS dropped to 52%. The rebound of concentrations was attributed to the plume bypass of the barrier due to the presence of high conductivity zones, which likely occurred because of seasonal changes in groundwater flow directions or the CAC application at the site. This demonstrates the need for a detailed and accurate hydrogeological understanding of contaminated sites before designing and applying stabilization techniques, especially at sites with high geologic and hydrologic complexity. The results herein can serve as a guideline for treating similar sites and help avoid potential pitfalls of remedial efforts.