Eriophorum angustifolium and Lolium perenne metabolic adaptations to metals- and metalloids-induced anomalies in the vicinity of a chemical industrial complex

As plants constitute the foundation of the food chain, concerns have been raised about the possibility of toxic concentrations of metals and metalloids being transported from plants to the higher food chain strata. In this perspective, the use of important phytotoxicity endpoints may be of utmost significance in assessing the hazardous nature of metals and metalloids and also in developing ecological soil screening levels. The current study aimed to investigate the role of glutathione (GSH) and its associated enzymes in the metabolic adaptation of two grass species namely Eriophorum angustifolium Honck. and Lolium perenne L. to metals and metalloids stress in the vicinity of a chemical industrial complex (Estarreja, Portugal). Soil and plant samples were collected from contaminated (C) and non-contaminated (reference, R) sites, respectively, near and away from the Estarreja Chemical Complex, Portugal. Soils (from 0 to 10 and 10 to 20 cm depths) were analyzed for pH, organic carbon, and metals and metalloids concentrations. Plant samples were processed fresh for physiological and biochemical estimations, while oven-dried plant samples were used for metals and metalloids determinations following standard methodologies. Both soils and plants from the industrial area exhibited differential concentrations of major metals and metalloids including As, Cu, Hg, Pb, and Zn. In particular, L. perenne shoot displayed significantly higher and lower concentrations of Pb and As, respectively at contaminated site (vs. E. angustifolium). Irrespective of sites, L. perenne shoot exhibited significantly higher total GSH pool, oxidized glutathione (GSSG) and oxidized protein (vs. E. angustifolium). Additionally, severe damages to photosynthetic pigments, proteins, cellular membrane integrity (in terms of electrolyte leakage), and lipid peroxidation were also perceptible in L. perenne shoot. Contrarily, irrespective of the sites, activities of catalase and GSH-regenerating enzyme, GSH reductase, and GSH-metabolizing enzymes such as GSH peroxidase and GSH sulfotransferase were significantly higher in shoot of E. angustifolium. Despite the higher total GSH content, L. perenne is vulnerable to multi-metals-induced stress in comparison to E. angustifolium as depicted by increased GSH- and protein oxidation, low reactive oxygen radical-processing potential (exhibited in terms of low catalase activity) and poor GSH pool utilization efficiency (in terms of lower GSH-associated enzymes activities). The outcome of the present study may be significant for understanding vital GSH-mediated metals and metalloids tolerance mechanisms in plants as well as their unsuitability for animal consumption due to higher metals and metalloids burdens.     

A multi-approach monitoring of particulate matter, metals and PAHs in an urban street canyon

For the first time until now, the results from a prediction model (Atmospheric Dispersion Modelling System (ADMS)-Road) of pollutant dispersion in a street canyon were compared to the results obtained from biomonitors. In particular, the instrumental monitoring of particulate matter (PM10) and the biomonitoring of 14 polycyclic aromatic hydrocarbons (PAHs) and 11 metals by Quercus ilex leaves and Hypnum cupressiforme moss bags, acting as long- and short-term accumulators, respectively, were carried out. For both PAHs and metals, similar bioaccumulation trends were observed, with higher concentrations in biomonitors exposed at the leeward canyon side, affected by primary air vortex. The major pollutant accumulation at the leeward side was also predicted by the ADMS-Road model, on the basis of the prevailing wind direction that determines different exposure of the street canyon sides to pollutants emitted by vehicular traffic. A clear vertical (3, 6 and 9 m) distribution gradient of pollutants was not observed, so that both the model and biomonitoring results suggested that local air turbulences in the street canyon could contribute to uniform pollutant distribution at different heights.     

Analyzing the cost effectiveness of Santiago, Chile's policy of using urban forests to improve air quality

Santiago, Chile has the distinction of having among the worst urban air pollution problems in Latin America. As part of an atmospheric pollution reduction plan, the Santiago Regional Metropolitan government defined an environmental policy goal of using urban forests to remove particulate matter less than 10 microm (PM(10)) in the Gran Santiago area. We used cost effectiveness, or the process of establishing costs and selecting least cost alternatives for obtaining a defined policy goal of PM(10) removal, to analyze this policy goal. For this study, we quantified PM(10) removal by Santiago's urban forests based on socioeconomic strata and using field and real-time pollution and climate data via a dry deposition urban forest effects model. Municipal urban forest management costs were estimated using management cost surveys and Chilean Ministry of Planning and Cooperation documents. Results indicate that managing municipal urban forests (trees, shrubs, and grass whose management is under the jurisdiction of Santiago's 36 municipalities) to remove PM(10) was a cost-effective policy for abating PM(10) based on criteria set by the World Bank. In addition, we compared the cost effectiveness of managing municipal urban forests and street trees to other control policies (e.g. alternative fuels) to abate PM(10) in Santiago and determined that municipal urban forest management efficiency was similar to these other air quality improvement measures.     

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.     

Electric Swing Adsorption for CO2 removal from flue gases

One of the most important sources of CO₂ emissions are the fossil-fuel fired plants for production of electricity. Removal of CO₂ from flue gas streams for further sequestration has been proposed by the International Panel on Climate Change experts as one of the most reliable solutions to mitigate anthropogenic greenhouse emissions. When natural gas is employed as fuel, the molar fraction of CO₂ in the flue gas is lower than 5% causing serious problems for capture. The purpose of this work is to present experimental validation of an Electric Swing Adsorption (ESA) technology that may be employed for carbon capture for low molar fractions of CO₂ in the flue gas streams. To improve energy utilization, an activated carbon honeycomb monolith with low electrical resistivity was employed as selective adsorbent. A mathematical model for this honeycomb is proposed as well as different ESA cycles for CO₂ capture.     

Effect of modified Fenton treatment on the thermal behavior of contaminated harbor sediments

This study presents the results of experimental Fenton-like treatments conducted on marine sediment slurries (2g sediment vs. 20 ml liquid). The sediment was collected in a harbor situated in a high density industrial area, characterized by a great hydrocarbon C>12 and PAHs contamination. The investigated parameters were: the H(2)O(2) dose, the reagent's pH and the effect of a phosphate salt and ferrous iron addition. To evaluate sediment's characteristics COD, particle size, thermogravimetric and differential thermal analyses were performed under N(2) and O(2) atmosphere while dissolved organic carbon and COD analyses were performed on the filtrate. Results indicate that the treatment was able to change the organic matter to a less hydrophobic state, to destroy part of the organic carbon (up to 78% decrease of the 200-400 degrees C labile organic matter), to lower the COD of the sediment (60% COD removal maximum) and to increase the cumulated distribution undersize. In addition as the treated sediment showed easier-to-handle characteristics, reduced caking and lower aggregation capacity, the modified Fenton treatment could also be considered a pre-treatment of a successive thermal treatment.     

Assessment of the effects of soil PAH accumulation by a battery of ecotoxicological tests

Surface soils were collected at remote, urban and industrial sites in the Southern of Italy in order to evaluate PAH concentrations and assess the toxic effects by a battery of ecotoxicological tests. The tests were performed on whole soils and on both organic and aqueous extracts. Further goal of this study was to integrate the results coming from each test and matrix in a synthetic toxicity index. The highest summation sigmaPAH concentrations were measured at the industrial soil, although this one did not show an high ecotoxicological risk. Among the performed tests, the phytotoxicity tests showed the highest sensitivity. For whole soil, the worst case always has been represented by test through bacteria. Our results could represent the first step toward the selection of a proper battery to characterize the soil ecotoxicological risk.     

Significance of urinary arsenic speciation in assessment of seafood ingestion as the main source of organic and inorganic arsenic in a population resident near a coastal area

In order to characterize the different sources of exposure to arsenic (As), urinary excretion of total As, the sum of inorganic As+MMA+DMA determined by the hydride generation-atomic absorption spectrophotometry technique, and the species As(3), As(5), monomethylarsonic acid (MMA), dimethylarsinic acid (DMA) and arsenobetaine were determined in 49 workers at a steel foundry, with presumed occupational exposure to As, and 50 subjects from the general population, all males. No evidence of occupational exposure to As resulted from environmental monitoring performed in the foundry, although the analysis of minerals used as raw materials showed the presence of As, particularly in fossils and fine ores. The urinary concentrations of As(3), MMA, DMA, the sum of inorganic As+MMA+DMA and total As were not different in the two groups, while arsenobetaine appeared significantly higher in the controls than in the workers. The different species of urinary As were all significantly correlated. Urinary excretion of As(3) was associated with the consumption of mineral water and with residence in an industrial zone, while MMA, DMA, arsenobetaine, the sum of inorganic As+MMA+DMA and total As urinary excretion were associated with the consumption of crustaceans and/or shellfish 3 days or less before urine collection. Multiple regression analysis confirmed these results. In conclusion, in populations with a high consumption of seafood, living in areas characterized by coastal/marine As pollution, only speciation of As can identify a prevalent role of environmental sources, like the consumption of seafood contaminated by As, in determining urinary As excretion, and exclude an occupational origin of the exposure.     

Photodegradation of the steroid hormones 17beta-estradiol (E2) and 17alpha-ethinylestradiol (EE2) in dilute aqueous solution

The photochemical transformation of natural estrogenic steroid 17beta-estradiol (E2) and the synthetic oral contraceptive 17alpha-ethinylestradiol (EE2) has been studied in dilute non buffered aqueous solution (pH 5.5-6.0) upon monochromatic (254 nm) and polychromatic (lambda>290 nm) irradiation. Upon irradiation at 254 nm, the quantum yields of E2 and EE2 photolysis were similar and evaluated to be 0.067+/-0.007 and 0.062+/-0.007, respectively. Upon polychromatic excitation, and by using phenol as chemical actinometer, the photolysis efficiencies have been determined to be 0.07+/-0.01 and 0.08+/-0.01 for E2 and EE2, respectively. For both estrogens, photodegradation by-products were identified with GC/MS and LC/MS. In a first step, a model compound--5,6,7,8-tetrahydro-2-naphthol (THN)--, which represents the photoactive phenolic group, was used to obtain basic photoproduct structural informations. Numerous primary and secondary products were observed, corresponding to hydroxylated phenolic- or quinone-type compounds.