Seasonal and air mass trajectory effects on dissolved organic matter of bulk deposition at a coastal town in south-western Europe

Rainwater contains a complex mixture of organic compounds which may influence climate, terrestrial and maritime ecosystems and thus human health. In this work, the characteristics of DOM of bulk deposition at a coastal town on the southwest of Europe were assessed by UV–visible and three-dimensional excitation–emission matrix fluorescence spectroscopies and by dissolved organic carbon (DOC) content. The seasonal and air mass trajectory effects on dissolved organic matter (DOM) of bulk deposition were evaluated. The absorbance at 250 nm (UV_250nm) and integrated fluorescence showed to be positively correlated with each other, and they were also positively correlated to the DOC in bulk deposition, which suggest that a constant fraction of DOM is likely to fluoresce. There was more chromophoric dissolved organic matter (CDOM) present in summer and autumn seasons than in winter and spring. Bulk deposition associated with terrestrial air masses contained a higher CDOM content than bulk deposition related to marine air masses, thus highlighting the contribution of terrestrial/anthropogenic sources.     

Pilot monitoring study of ibuprofen in surface waters of north of Portugal

Ibuprofen is amongst the most worldwide consumed pharmaceuticals. The present work presents the first data in the occurrence of ibuprofen in Portuguese surface waters, focusing in the north area of the country, which is one of the most densely populated areas of Portugal. Analysis of ibuprofen is based on pre-concentration of the analyte with solid phase extraction and subsequent determination with liquid chromatography coupled to fluorescence detection. A total of 42 water samples, including surface waters, landfill leachates, Wastewater Treatment Plant (WWTP), and hospital effluents, were analyzed in order to evaluate the occurrence of ibuprofen in the north of Portugal. In general, the highest concentrations were found in the river mouths and in the estuarine zone. The maximum concentrations found were 48,720 ng?L^?1 in the landfill leachate, 3,868 ng?L^?1 in hospital effluent, 616 ng?L^?1 in WWTP effluent, and 723 ng?L^?1 in surface waters (Lima river). Environmental risk assessment was evaluated and at the measured concentrations only landfill leachates reveal potential ecotoxicological risk for aquatic organisms. Owing to a high consumption rate of ibuprofen among Portuguese population, as prescribed and non-prescribed medicine, the importance of hospitals, WWTPs, and landfills as sources of entrance of pharmaceuticals in the environment was pointed out. Landfill leachates showed the highest contribution for ibuprofen mass loading into surface waters. On the basis of our findings, more studies are needed as an attempt to assess more vulnerable areas.     

Distribution of steroid- and dioxin-like activities between sediments, POCIS and SPMD in a French river subject to mixed pressures

The contamination of aquatic systems by endocrine disrupting chemicals (EDCs) is now a widely established fact. Nevertheless, there is still a scarcity of knowledge concerning the source, transport, fate and bioavailability of such active compounds. In the present study we assessed the distribution of estrogenic, (anti-)androgenic, pregnane X receptor-like (PXR) and dioxin-like activities between sediment and water compartments using a polar organic compound integrative sampler (POCIS) and a semi-permeable membrane device (SPMD) passive sampler in a river where sediment has been previously described as highly and multi-contaminated. We first confirmed the contamination pattern of this river sediment between 2004, 2009 and 2010 samples, suggesting that this river is subject to a constant high contamination level. However, we showed a different distribution pattern of these activities between compartments: estrogenic activity was mainly detected in POCIS extracts and to a lesser extent in sediment and SPMD extracts; anti-androgenic activities were mainly detected in SPMD and sediment extracts while no activity was detected in POCIS extracts; PXR-like activity was detected in all three investigated compartments, with POCIS > SPMD > sediment; dioxin-like activity was mainly found in the sediment and the SPMD extracts. Overall, partitioning of the biological activities was in accordance with physicochemical properties (e.g., log K _ow) of typical known active chemicals in each bioassay. Furthermore, in order to establish whether the chemicals involved in these activities were similar between the compartments, we fractionated sediment, POCIS and SPMD extracts using a multi-step fractionation procedure. This highlighted differences in the nature of active chemicals between compartments. Altogether, our results support the need to consider different compartments in order to enhance exposure assessment.     

Photocatalytic degradation of contaminants of concern with composite NF-TiO2 films under visible and solar light

This study reports the synthesis and characterization of composite nitrogen and fluorine co-doped titanium dioxide (NF-TiO₂) for the removal of contaminants of concern in wastewater under visible and solar light. Monodisperse anatase TiO₂ nanoparticles of different sizes and Evonik P25 were assembled to immobilized NF-TiO₂ by direct incorporation into the sol–gel or by the layer-by-layer technique. The composite films were characterized with X-ray diffraction, high-resolution transmission electron microscopy, environmental scanning electron microscopy, and porosimetry analysis. The photocatalytic degradation of atrazine, carbamazepine, and caffeine was evaluated in a synthetic water solution and in an effluent from a hybrid biological concentrator reactor (BCR). Minor aggregation and improved distribution of monodisperse titania particles was obtained with NF-TiO₂-monodisperse (10 and 50 nm) from the layer-by-layer technique than with NF-TiO₂?+?monodisperse TiO₂ (300 nm) directly incorporated into the sol. The photocatalysts synthesized with the layer-by-layer method achieved significantly higher degradation rates in contrast with NF-TiO₂-monodisperse titania (300 nm) and slightly faster values when compared with NF-TiO₂-P25. Using NF-TiO₂ layer-by-layer with monodisperse TiO₂ (50 nm) under solar light irradiation, the respective degradation rates in synthetic water and BCR effluent were 14.6 and 9.5?×?10^?3?min^?1 for caffeine, 12.5 and 9.0?×?10^?3?min^?1 for carbamazepine, and 10.9 and 5.8?×?10^?3?min^?1 for atrazine. These results suggest that the layer-by-layer technique is a promising method for the synthesis of composite TiO₂-based films compared to the direct addition of nanoparticles into the sol.     

Investigation of the inorganic and organic phosphorus forms in animal manure

The most viable way to beneficially use animal manure on most farms is land application. Over the past few decades, repeated manure application has shown adverse effects on environmental quality due to phosphorus (P) runoff with rainwater, leading to eutrophication of aquatic ecosystems. Improved understanding of manure P chemistry may reduce this risk. In this research, 42 manure samples from seven animal species (beef and dairy cattle, swine, chicken, turkey, dairy goat, horse, and sheep) were sequentially fractionated with water, NaHCO?, NaOH, and HCl. Inorganic (P(i)), organic (P(o)), enzymatic hydrolyzable (P(e); monoester-, DNA-, and phytate-like P), and nonhydrolyzable P were measured in each fraction. Total dry ash P (P(t)) was measured in all manures. Total fractionated P (P(ft)) and total P(i) (P(it)) showed a strong linear relationship with P(t). However, the ratios between P(ft)/P(t) and P(it)/P(t) varied from 59 to 117% and from 28 to 96%, respectively. Water and NaHCO? extracted most of the P(i) in manure from ruminant+horse, whereas in nonruminant species a large fraction of manure P was extracted in the HCl fraction. Manure P(e) summed over all fractions (P(et)) accounted for 41 to 69% of total P(0) and 4 to 29% of P(t). The hydrolyzable pool in the majority of the manures was dominated by phytate- and DNA-like P in water, monoester- and DNA-like P in NaHCO?, and monoester- and phytate-like P in NaOH and HCl fractions. In conclusion, if one assumes that the P(et) and P(it) from the fractionation can become bioavailable, then from 34 to 100% of P(t) in animal manure would be bioavailable. This suggests the need for frequent monitoring of manure P for better manure management practices.     

Precision placement of separated dairy sludge improves early phosphorus nutrition and growth in corn ( L.)

Efficient use of manure nutrients by crops is necessary to minimize losses to the environment. This field study examined the possibility of replacing side-banded mineral P with precision-placed high-P sludge (6.2-11.0% dry matter) obtained after settling dairy manure slurry. The sludge was injected at about 30 kg P ha (36.0-51.2 m ha) into the soil at corn row spacing, and the corn was planted 5, 10, and 15 cm beside the injection furrow. Controls included no added P and side-banded commercial P fertilizer. The treatments were tested on corn with low and high root colonization by arbuscular mycorrhizae (AM). The study showed that sludge did not impede AM root colonization, corn germination, or seedling growth. Corn plants with both high and low levels of AM colonization responded to the sludge from the three-leaf stage and showed the greatest benefit at the six-leaf stage. Corn responded more to sludge placed at 5 than at 15 cm from the corn rows, whereas the response at the 10-cm spacing was intermediate. There was little difference in seedling growth or final harvest parameters between the side-banded fertilizer P and the 5-cm sludge treatment. The results show a new way to use manure nutrients, namely precision-placement sludge for corn. This may obviate the need for chemical fertilizers for improving farm nutrient balances. Other anticipated benefits are less energy use for hauling and injection of the sludge fraction and reduced risk of nutrient loss by runoff and volatilization (ammonia) and nuisance odors due to injection.     

Factors controlling phosphate interaction with iron oxides

Factors such as pH, solution ion composition, and the presence of natural organic matter (NOM) play a crucial role in the effectiveness of phosphorous adsorption by iron oxides. The interplay between these factors shows a complicated pattern and can sometimes lead to controversial results. With the help of mechanistic modeling and adsorption experiments, the net macroscopic effect of single and combined factors can be better understood and predicted. In the present work, the relative importance of the above-mentioned factors in the adsorption of phosphate was analyzed using modeling and comparison between the model prediction and experimental data. The results show that, under normal soil conditions, pH, concentration of Ca, and the presence of NOM are the most important factors that control adsorption of phosphate to iron oxides. The presence of Ca not only enhances the amount of phosphate adsorbed but also changes the pH dependency of the adsorption. An increase of dissolved organic carbon from 0.5 to 50 mg L can lead to a >50% decrease in the amount of phosphate adsorbed. Silicic acid may decrease phosphate adsorption, but this effect is only important at a very low phosphate concentration, in particular at high pH.     

Investigation of an Escherichia coli environmental benchmark for waterborne pathogens in agricultural watersheds in Canada

Canada's National Agri-Environmental Standards Initiative sought to develop an environmental benchmark for low-level waterborne pathogen occurrence in agricultural watersheds. A field study collected 902 water samples from 27 sites in four intensive agricultural watersheds across Canada from 2005 to 2007. Four of the sites were selected as reference sites away from livestock and human fecal pollution sources in each watershed. Water samples were analyzed for Campylobacter spp., Salmonella spp., Escherichia coli O157:H7, Cryptosporidium spp., Giardia spp., and the water quality indicator E. coli. The annual mean number of pathogen species was higher at agricultural sites (1.54 ± 0.07 species per water sample) than at reference sites (0.75 ± 0.14 species per water sample). The annual mean concentration of E. coli was also higher at agricultural sites (491 ± 96 colony-forming units [cfu] 100 mL(-1)) than at reference sites (53 ± 18 cfu 100 mL(-1)). The feasibility of adopting existing E. coli water quality guideline values as an environmental benchmark was assessed, but waterborne pathogens were detected at agricultural sites in 80% of water samples with low E. coli concentrations (<100 cfu 100 mL(-1)). Instead, an approach was developed based on using the natural background occurrence of pathogens at reference sites in agricultural watersheds to derive provisional environmental benchmarks for pathogens at agricultural sites. The environmental benchmarks that were derived were found to represent E. coli values lower than geometric mean values typically found in recreational water quality guidelines. Additional research is needed to investigate environmental benchmarks for waterborne pathogens within the context of the "One World, One Health" perspective for protecting human, domestic animal, and wildlife health.     

Addressing climate change: Determinants of consumers' willingness to act and to support policy measures

Consumers influence climate change through their consumption patterns and their support or dismissal of climate mitigation policy measures. Both climate-friendly actions and policy support comprise a broad range of options, which vary in manifold ways and, therefore, might be influenced by different factors. The aims of the study were, therefore, two-fold: first, we intended to find a meaningful way to classify different ways of addressing climate change. Second, we aimed to examine which determinants influence people's willingness to engage in these behaviors. We conducted a large-scale mail survey in Switzerland in which respondents rated, among other items, their willingness to act or support a range of possible actions and mitigations measures. A principal component analysis indicated that a distinction in terms of a behavior's directness as well as a differentiation according to perceived costs seem to be appropriate to classify climate-friendly actions. Multiple regression analyses showed that perceived costs and perceived climate benefit turned out to be the strongest predictors for willingness to act or to support climate policy measures. The strong influence of perceived climate benefit might reflect a strategy of reducing cognitive dissonance. As high-cost behaviors are more difficult to adopt, consumers may reduce dissonance by dismissing high-cost behaviors as not effective in terms of climate mitigation. Political affiliation proved to be another strong determinant of willingness to act or support. Participants on the right wing were less willing to show indirect climate-friendly behaviors, change their mobility behaviors, and to support any type of climate mitigation policy measures. Climate-friendly low-cost behaviors, however, were not influenced by political affiliation.