Identification of new ozonation disinfection byproducts of 17β-estradiol and estrone in water

Estrogens are a class of micro-pollutants found in water at low concentrations (in the ng L⁻¹ range), but often sufficient to exert estrogenic effects due to their high estrogenic potency. Disinfection of waters containing estrogens through oxidative processes has been shown to lead to the formation of disinfection byproducts, which may also be estrogenic. The present work investigates the formation of disinfection byproducts of 17β-estradiol (E2) and estrone (E1) in the treatment of water with ozone. Experiments have been carried out at two different concentrations of the estrogens in ground water (100 ng L⁻¹ and 100 μg L⁻¹) and at varying ozone dosages (0-30 mg L⁻¹). Detection of the estrogens and their disinfection byproducts in the water samples has been performed by means of ultra performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS) with a triple quadrupole (QqQ) and a quadrupole-time of flight (QqTOF) instrument. Both E2 and E1 have been found to form two main byproducts, with molecular mass (MM) 288 and 278 in the case of E2, and 286 and 276 in the case of E1, following presumably the same reaction pathways. The E2 byproduct with MM 288 has been identified as 10epsilon-17beta-dihydroxy-1,4-estradieno-3-one (DEO), in agreement with previously published results. The molecular structures and the formation pathways of the other three newly identified byproducts have been suggested. These byproducts have been found to be formed at both high and low concentrations of the estrogens and to be persistent even after application of high ozone dosages.     

Exergy analysis as a tool for the integration of very complex energy systems: The case of carbonation/calcination CO2 systems in existing coal power plants

A common characteristic of carbon capture and storage systems is the important energy consumption associated with the CO₂ capture process. This important drawback can be solved with the analysis, synthesis and optimization of this type of energy systems. The second law of thermodynamics has proved to be an essential tool in power and chemical plant optimization. The exergy analysis method has demonstrated good results in the synthesis of complex systems and efficiency improvements in energy applications.In this paper, a synthesis of pinch analysis and second law analysis is used to show the optimum window design of the integration of a calcium looping cycle into an existing coal power plant for CO₂ capture. Results demonstrate that exergy analysis is an essential aid to reduce energy penalties in CO₂ capture energy systems. In particular, for the case of carbonation/calcination CO₂ systems integrated in existing coal power plants, almost 40% of the additional exergy consumption is available in the form of heat. Accordingly, the efficiency of the capture cycle depends strongly on the possibility of using this heat to produce extra steam (live, reheat and medium pressure) to generate extra power at steam turbine. The synthesis of pinch and second law analysis could reduce the additional coal consumption due to CO₂ capture 2.5 times, from 217 to 85 MW.     

Zinc distribution in soils amended with different kinds of sewage sludge

Sewage sludge (SS) can be applied to cropland to supply and recycle nutrients and organic carbon. Potentially toxic elements in the sludge, however, are of environmental concern. This study evaluates the changes in chemical speciation of Zn in three representative pristine soils of the Pampas Region, Argentina, measured with sequential extraction over a one-year period. Pure SS or SS containing 30% (DM) of its own incineration ash (AS) was applied to the soils at an application rate of 150Mgha(-1). Zn was sequentially fractionated into exchangeable, organically bound, inorganic and residual fractions. The application of the SS and AS amendments significantly increased Zn concentration in all soil fractions at each sampling date. At day 1, Zn was mainly found in the residual fraction. A year after the application of the amendments, redistribution towards the inorganic fraction was observed (41-76% of total Zn content). Zn found in exchangeable and inorganic fractions depended on soil pH rather than on the type of soil used. A negative and significant correlation was found between exchangeable Zn concentrations and soil pH (r=0.94), and a positive and significant correlation between inorganic Zn concentrations and soil pH (r=0.92). For each amended soil and sampling date, no significant differences were observed between SS or AS treatments for the exchangeable fraction. Moreover, the use of AS did not cause significant differences in Zn concentration in the other soil fractions compared to SS. Based on these results, land spreading of AS may be similar to SS diaposal in terms of Zn mobility.     

Estimating the environmental impact of micro-pollutants in the low Ebro River (Spain): an approach based on screening toxicity with Vibrio fischeri

The aim of this study was to assess the likely impacts on the ecosystems due to agricultural, human, and industrial activities carried out in an ecologically important area of the Ebro River (Spain). For it, a screening site specific ecological risk assessment was conducted. Considering the presence of high levels of potentially toxic substances, such as metals and chlorinated organic compounds, aqueous and organic extracts were used to assess toxicity in sediments by using the photo-luminescent bacteria Vibrio fischeri (Microtox) as screening response variable. Sediment samples collected during 2005-2006 in the last course of the Ebro River and its Delta have been analyzed. Toxic responses have shown strong relationships to the levels of pollutants in the area. Moreover, various sites presented some toxicity level, probably because of other factors associated with reducing environments into the sediments. Results indicate that Microtox bioassay is an appropriate tool to perform risk assessment studies at screening level.     

Contamination by organochlorine compounds in the edible tissue of four sturgeon species from the Caspian Sea (Iran)

This study focused on accumulation of organochlorine compounds (OCs), including dichloro-diphenyl-trichloroethanes (DDTs), hexachlorobenzene (HCB), hexachlorocyclohexanes (HCHs), and polychlorinated biphenyls (PCBs) accumulation in the muscle of four sturgeon (Persian sturgeon, Acipenser persicus; Stellate sturgeon, Acipenser stellatus; Ship sturgeon, Acipenser nudiventris and Beluga sturgeon, Huso huso) from the southern Caspian Sea. The DDT group was prominent in all of the sturgeon muscle tested constituting almost half or more of the total organochlorine content. Contaminant concentration generally followed this order: DDTs>PCBs>HCHs>HCB. The OCs concentrations in Beluga sturgeon (H. huso) were the highest and over four times higher than in the next highest species (A. nudiventris). From an ecotoxicological point of view, the concentrations of OCs in experimental fishes do not reflect a comparatively clean and pollution-free environment; however, results from this study shown that the inflow of organic pollutants into the Caspian Sea has been reduced when compared with prior studies. Levels of measured OCs in sturgeon were relatively low, but the level of some OCs in some of the specimens tested exceeded the guidelines for food; therefore, the maximum allowable daily consumption rate for sturgeon from this watershed may be limited by DDTs and PCBs content for high risk populations.     

Mass balance to assess the efficiency of a mechanical-biological treatment

Using mechanical-biological treatment of residual municipal solid waste, it is possible to significantly lower landfill volume and gas and leachate emissions. Moreover, the landfill characteristics are improved. The performance of the Mende (France) mechanical-biological treatment plant is assessed via mass balances coupled with manual sorting according to the MODECOMtrade mark methodology and biochemical methane potential after 90 days of incubation. The site includes mechanical sorting operations, a rotary sequential bioreactor, controlled aerobic stabilisation corridors, maturation platforms, and a sanitary landfill site for waste disposal in separated cells. Results showed that several steps could be improved: after a first sieving step, about 12% of the potentially biodegradable matter is landfilled directly without any treatment; mechanical disintegration of papers and cardboards in the rotary sequential bioreactor is insufficient and leads to a high proportion of papers and cardboards being landfilled without further treatment. Two fine fractions go through stabilisation and maturation steps. At the end of the maturation step, about 54% of the potentially biodegradable matter is degraded. The biochemical methane potential after 90 days of incubation is reduced by 81% for one of the two fine fractions and reduced by 88% for the other one. Considering the whole plant, there is a reduction of nearly 20% DM of the entering residual municipal solid waste.     

Biochemical responses of the marine mussel Mytilus galloprovincialis to petrochemical environmental contamination along the North-western coast of Portugal

Following the development of urban and industrial centres petrochemical products have become a widespread class of contaminants. The aim of this study was to investigate the effects of petrochemical contamination in wild populations of mussels (Mytilus galloprovincialis) along the NW Atlantic coast of Portugal by applying antioxidant and energetic metabolism parameters as biomarkers. For that, mussels were collected at five sampling sites presenting different petrochemical contamination levels. To evaluate the mussels' antioxidant status, enzymatic activities of catalase, superoxide dismutase, glutathione peroxidase, glutathione reductase, glutathione S-transferases, as well as glutathione redox status were evaluated in gills and digestive glands of mussels collected from the selected sites. Lipid peroxidation was determined in the same tissues to quantify cellular oxidative damage. Furthermore, to investigate how energetic processes may respond to these contaminants, the activity of NADP(+)-dependent isocitrate dehydrogenase was determined in mussels' digestive glands, and octopine dehydrogenase was determined in mussels' posterior adductor muscle. Furthermore, the concentrations of aliphatic hydrocarbons, unresolved complex mixture and polycyclic aromatic hydrocarbons (PAHs) were quantified in mussels' tissue, and abiotic parameters were quantified in water samples collected at each site. Several biomarkers showed statistically significant differences among sampling sites. The redundancy analysis (RDA) used to perform the integrated analysis of the data showed a clear separation of the sampling sites in three different assemblages, which are in agreement with the PAHs levels found in mussels tissues. In addition, the RDA indicated that some of the selected biomarkers may be influenced by abiotic parameters (e.g. salinity, pH, nitrates and ammonia). The approach selected for this study seems to be suitable for monitoring petrochemical contamination.     

Arsenic speciation of atmospheric particulate matter (PM10) in an industrialised urban site in southwestern Spain

An arsenic speciation study has been performed in PM10 samples collected on a fortnight basis in the city of Huelva (SW Spain) during 2001 and 2002. The arsenic species were extracted from the PM10 filters using a NH2OH x HCl solution and sonication, and determined by HPLC-HG-AFS. The mean bulk As concentration of the samples analyzed during 2001 and 2002 slightly exceed the mean annual 6 ng m(-3) target value proposed by the European Commission for 2013, arsenate [As(V)] being responsible for the high level of arsenic. The speciation analyses showed that As(V) was the main arsenic species found, followed by arsenite [As(III)] (mean 6.5 and 7.8 ng m(-3) for As(V), mean 1.2 and 2.1 ng m(-3) for As(III), in 2001 and 2002, respectively). The high levels of arsenic species found in PM10 in Huelva have a predominant industrial origin, such as the one from a nearby copper smelter, and do not present a seasonal pattern. The highest daily levels of arsenic species correspond to synoptic conditions in which the winds with S and SW components transport the contaminants from the main emission source. The frequent African dust outbreaks over Huelva may result in an increment of mass levels of PM10, but do not represent a significant input of arsenic in comparison to the anthropogenic source. The rural background levels of arsenic around Huelva are rather high, in comparison to other rural or urban areas in Spain, showing a relatively high atmosphere residence time of arsenic. This work shows the importance of arsenic speciation in studies of aerosol chemistry, due to the presence of arsenic species [As(III) and As(V)] with distinct toxicity.     

Relations between PM10 composition and cell toxicity: a multivariate and graphical approach

Previous studies have used particle mass and size as metrics to link airborne particles with deleterious health effects. Recent evidence suggests that particle composition can play an important role in PM-toxicity; however, little is known about the specific participation of components (individually or acting in groups) present in such a complex mixture that accounts for toxicity. This work explores relationships among PM(10) components in order to identify their covariant structure and how they vary in three sites in Mexico City. Relationships between PM(10) with cell toxicity and geographical location were also explored. PM(10) was analyzed for elemental composition, organic and elemental carbon, endotoxins and the induction of inhibition of cell proliferation, IL-6, TNFalpha and p53. PM(10) variables were evaluated with principal component analysis and one-way ANOVA. The inhibition of cell proliferation, IL-6 and TNFalpha were evaluated with factorial ANOVA and p53 with the Welch test. The results indicate that there is heterogeneity in particle mass, composition and toxicity in samples collected at different sites. Multivariate analysis identified three major groups: (1) S/K/Ca/Ti/Mn/Fe/Zn/Pb; (2) Cl/Cr/Ni/Cu; and (3) endotoxins, organic and elemental carbon. Groups 1 and 3 showed significant differences among sites. Factorial ANOVA modeling indicated that cell proliferation was affected by PM concentration; TNFalpha and IL-6 by the interaction of concentration and site, and p53 was different by site. Radial plots suggest the existence of complex interactions between components, resulting in characteristic patterns of toxicity by site. We conclude that interactions of PM(10) components determine specific cellular outcomes.