Performance comparison of commercial TiO2: separation and reuse for bacterial photo-inactivation and emerging pollutants photo-degradation

This research aims to compare the disinfection and degradation effectiveness in water of a commercial suspension of nano-TiO₂ (TiO₂Levenger) with the standard TiO₂Degussa P25. Photo-inactivation and photo-degradation experiments were conducted with UVA-vis light. Concerning the disinfection, the effects of TiO₂ dose (0–2 g/l), water matrix, bacterium type (Gram-positive or Gram-negative), and bacterial regrowth after the photo-treatments were studied for each catalyst. The experimental results show that Enterococcus sp. (Gram-positive) was more resistant to the photo-treatments than Escherichia coli (Gram-negative) for both catalyst; however, postirradiation trends showed similar behavior for both bacteria, favoring regrowth for short-treated cells and decay for longer-treated ones. Caffeine was selected as a model substance of pharmaceuticals and personal care products. In terms of caffeine removal, the effects of TiO₂ dose (0–2 g/l) and water matrix were analyzed. Besides, the comparison between mechanical coagulation-flocculation-decantation and simple decantation of TiO₂ was carried out. The results show that simple decantation allowed the recovery of 97.5% of TiO₂ Degussa P25 and TiO₂ Levenger within 1 day of simple decantation, while applying the proposed mechanical coagulation-flocculation decantation 99.7% of recovery of both catalysts was achieved in 2 hours. Finally, the subsequent reuse of both catalysts was proved with little loss of efficiency in terms of photo-disinfection during the four cycles. Nevertheless, the standard TiO₂ Degussa P25 photo-degradation efficiency of caffeine decreases considerably as compared to commercial suspension of TiO₂ Levenger concerning the reutilization.

     

Assesment of Trace Elements and Organic Pollutants from a Marine Oil Complex into the Coral Reef System of Cayo Arcas, Mexico

Possible contaminants produced by the Petroleos Mexicanos (PEMEX) marine oil complex in the vicinity of the Cayo Arcas (Mexico) coral reef ecosystem were evaluated by analyzing sediments and sea water for hydrocarbons and metal elements. We found that the concentrations of aliphatic hydrocarbons in the sea water were generally low, with the highest values detected near the oil station; the concentration of polycyclic aromatic hydrocarbons (PAHs) was generally below the detection limit. The hydrocarbons found in the sediments seem to have a pyrogenic origin, and were probably produced by marine traffic in the study area. The total PAH concentration did not exceed the NOAA criteria, although levels of some individual PAHs did. The only metal detected in the sea water at high concentrations was nickel. The Ni/V ratio in the sediments indicates the contribution of crude oil to the system. The high content of Ni and Zn was attributed to the ballast waters from the oil tankers that load at the station's monobuoys. The presence of fine sediments that commonly originate from terrestrial ecosystems supported this assumption.     

Method for the determination of selected organochlorine pesticides and polychlorinated biphenyls in human serum based on a gel permeation chromatographic clean-up

A gel permeation chromatographic (GPC) clean-up based method was developed for determination of selected organochlorine pesticides and polychlorinated biphenyls in human serum. The method permits automation of the sample extract clean-up stage and is designed to work with small amounts of sample. Different working variables were studied in its development, including injection volume, flow rate, and fat amount as the most representative coextract. The method provides solvent and time savings. Initial extraction was performed using 96-well solid-phase disk extraction plates, and quantification was performed by gas chromatography with electron capture detection and mass spectrometry. Recoveries of PCB congeners 28, 52, 101, 118, 138, 153, and 180 and organochlorine pesticides HCB, β-HCH, γ-HCH, heptachlor epoxide, p,p′-DDE, and p,p′-DDT at two spiking levels ranged from 55% to 115% with relative standard deviations ranging from 2.0% to 14.6%. Limits of quantification ranged from 0.06 to 0.16 ng mL⁻¹ for PCBs and from 0.12 to 0.36 ng mL⁻¹ for organochlorine pesticides. Finally, the method was applied to the analysis of 38 serum samples and the results were compared with those of another procedure validated at the laboratory.     

Impacts of future land use/land cover on wildfire occurrence in the Madrid region (Spain)

This paper assesses the relative importance of socioeconomic factors linked to fire occurrence through the simulation of future land use/land cover (LULC) change scenarios in the Madrid region (Spain). This region is a clear example of the socioeconomic changes that have been occurring over recent decades in the European Mediterranean as well as their impact on LULC and fire occurrence. Using the LULC changes observed between 1990 and 2006 as a reference, future scenarios were run up to 2025 with the conversion of land use and its effects model. Simultaneously, the relationship between LULC arrangement (interfaces) and historical fire occurrence was calculated using logistic regression analysis and used to quantify changes in future fire occurrence due to projected changes in LULC interfaces. The results revealed that it is possible to explain the probability of fire occurrence using only variables obtained from LULC maps, although the explanatory power of the model is low. In this context, border areas between some LULC types are of particular interest (i.e., urban/forest, grassland/forest and agricultural/forest interfaces). Results indicated that expected LULC changes in Euro-Mediterranean regions, particularly given the foreseeable increase in the wildland–urban interface, will substantially increase fire occurrence (up to 155 %). This underlines the importance of future LULC scenarios when planning fire prevention measures.     

The use of olive-mill waste compost to promote the plant vegetation cover in a trace-element-contaminated soil

The applicability of a mature compost as a soil amendment to promote the growth of native species for the phytorestoration of a mine-affected soil from a semi-arid area (SE Spain), contaminated with trace elements (As, Cd, Cu, Mn, Pb and Zn), was evaluated in a 2-year field experiment. The effects of an inorganic fertiliser were also determined for comparison. Bituminaria bituminosa was the selected native plant since it is a leguminous species adapted to the particular local pedoclimatic conditions. Compost addition increased total organic-C concentrations in soil with respect to the control and fertiliser treatments, maintained elevated available P concentrations throughout the duration of the experiment and stimulated soil microbial biomass, while trace elements extractability in the soil was rather low due to the calcareous nature of the soil and almost unaltered in the different treatments. Tissue concentrations of P and K in B. bituminosa increased after the addition of compost, associated with growth stimulation. Leaf Cu concentration was also increased by the amendments, although overall the trace elements concentrations can be considered non-toxic. In addition, the spontaneous colonisation of the plots by a total of 29 species of 15 different families at the end of the experiment produced a greater vegetation cover, especially in plots amended with compost. Therefore, the use of compost as a soil amendment appears to be useful for the promotion of a vegetation cover and the phytostabilisation of moderately contaminated soils under semi-arid conditions.     

Natural forest expansion on reclaimed coal mines in Northern Spain: the role of native shrubs as suitable microsites

The characterization of suitable microsites for tree seedling establishment and growth is one of the most important tasks to achieve the restoration of native forest using natural processes in disturbed sites. For that, we assessed the natural Quercus petraea forest expansion in a 20-year-old reclaimed open-cast mine under sub-Mediterranean climate in northern Spain, monitoring seedling survival, growth, and recruitment during 5 years in three contrasting environments (undisturbed forest, mine edge, and mine center). Seedling density and proportion of dead branches decreased greatly from undisturbed forest towards the center of the mine. There was a positive effect of shrubs on Q. petraea seedling establishment in both mine environments, which increase as the environment undergoes more stress (from the mine edge to the center of the mine), and it was produced by different shrub structural features in each mine environment. Seedling survival reduction through time in three environments did not lead to a density reduction because there was a yearly recruitment of new seedlings. Seedling survival, annual growth, and height through time were greater in mine sites than in the undisturbed forest. The successful colonization patterns and positive neighbor effect of shrubs on natural seedlings establishment found in this study during the first years support the use of shrubs as ecosystem engineers to increase heterogeneity in micro-environmental conditions on reclaimed mine sites, which improves late-successional Quercus species establishment.     

Ecological risk assessment of organic waste amendments using the species sensitivity distribution from a soil organisms test battery

Safe amendment rates (the predicted no-effect concentration or PNEC) of seven organic wastes were estimated from the species sensitivity distribution of a battery of soil biota tests and compared with different realistic amendment scenarios (different predicted environmental concentrations or PEC). None of the wastes was expected to exert noxious effects on soil biota if applied according either to the usual maximum amendment rates in Europe or phosphorus demands of crops (below 2 tonnes DM ha⁻¹). However, some of the wastes might be problematic if applied according to nitrogen demands of crops (above 2 tonnes DM ha⁻¹). Ammonium content and organic matter stability of the studied wastes are the most influential determinants of the maximum amendment rates derived in this study, but not pollutant burden. This finding indicates the need to stabilize wastes prior to their reuse in soils in order to avoid short-term impacts on soil communities.     

Comparison of solid-phase and eluate assays to gauge the ecotoxicological risk of organic wastes on soil organisms

Development of methodologies to assess the safety of reusing polluted organic wastes in soil is a priority in Europe. In this study, and coupled with chemical analysis, seven organic wastes were subjected to different aquatic and soil bioassays. Tests were carried out with solid-phase waste and three different waste eluates (water, methanol, and dichloromethane).Solid-phase assays were indicated as the most suitable for waste testing not only in terms of relevance for real situations, but also because toxicity in eluates was generally not representative of the chronic effects in solid-phase.No general correlations were found between toxicity and waste pollutant burden, neither in solid-phase nor in eluate assays, showing the inability of chemical methods to predict the ecotoxicological risks of wastes. On the contrary, several physicochemical parameters reflecting the degree of low organic matter stability in wastes were the main contributors to the acute toxicity seen in collembolans and daphnids.     

Sorption of 2,4-d on natural and organic amended soils of different characteristics

The effect of one organic amendment consisting of an urban waste compost (UWC) was assessed on the sorption properties of the herbicide 2,4-D on four soils of different physicochemical characteristics. The soils chosen were a Typic Haphorthod (ST), a Typic Endoaquept (SR), an Entic Pelloxerert (TO), and a Typic Eutrochrept (AL). Adsorption experiments were performed on the original soils, and on mixtures of these soils with UWC at a rate of 6.25% (w/w). These mixtures were used just after preparation, and after aging for 8 and 25 weeks. 2,4-D adsorption was the highest on ST soil, whereas the lowest adsorption was for SR soil. This behavior is related to the high amount of organic matter (OM) and amorphous iron and aluminum oxides content on soil ST, whereas soil SR had the lowest OM content and specific surface area of the soils of this study. Addition of exogenous OM to soils caused an increase in the 2,4-D adsorption by three of the soils treated with UWC, with the only exception being ST soil, due to an observed decrease in its specific surface area. The adsorbed amounts of the herbicide on aged organic fertilized soils diminished in three of the amended soils, but was still greater than on unammended soils. In contrast, the ST soil showed the largest adsorption for unammended soil.