Occurrence,elimination, and risk of anticoagulant rodenticides and drugs during wastewater treatment

Anticoagulants are biocides widely used as pest control agents in agriculture, urban infrastructures, and domestic applications for the control of rodents. Other anticoagulants such as warfarin and acenocoumarol are also used as drugs against thrombosis. After use, anticoagulants are discharged to sewage grids and enter wastewater treatment plants (WWTPs). Our hypothesis is that WWTP effluents can be a source of anticoagulants to receiving waters and that these can affect aquatic organisms and other nontarget species. Therefore, the objective of the present study was to determine the occurrence of 11 anticoagulants in WWTPs receiving urban and agricultural wastewaters. Warfarin was the most ubiquitous compound detected in influent waters and was partially eliminated during the activated sludge treatment, and low nanograms per liter concentration were found in the effluents. Other detected compounds were coumatetralyl, ferulenol, acenocoumarol, flocoumafen, brodifacoum, bromadiolone, and difenacoum at concentrations of 0.86–87.0 ng L^?1. Considering water volumes of each WWTP, daily emissions were estimated to be 0.02 to 21.8 g day^?1, and thus, WWTPs contribute to the loads of anticoagulants to receiving waters. However, low aquatic toxicity was observed using Daphnia magna as a model aquatic organism.     

TXRF analysis of soils and sediments to assess environmental contamination

Total reflection x-ray fluorescence spectroscopy (TXRF) is proposed for the elemental chemical analysis of crustal environmental samples, such as sediments and soils. A comparative study of TXRF with respect to flame atomic absorption spectroscopy and inductively coupled plasma optical emission spectroscopy was performed. Microwave acid digestion and suspension preparation methods are evaluated. A good agreement was found among the results obtained with different spectroscopic techniques and sample preparation methods for Cr, Mn, Fe, Ni, Cu, and Zn. We demonstrated that TXRF is suitable for the assessment of environmental contamination phenomena, even if the errors for Pb, As, V, and Ba are ingent.     

Concentration of trace elements in feathers of three Antarctic penguins: Geographical and interspecific differences

Antarctica is often considered as one of the last pristine regions, but it could be affected by pollution at global and local scale. Concentrations of Al, Cr, Mn, Fe, Ni, Cu, Zn, As, Se, Cd and Pb were determinated by ICP-MS in feathers (n = 207 individuals) of gentoo, chinstrap and Adélie penguin collected in 8 locations throughout the Antarctic Peninsula (2006-2007). The highest levels of several elements were found in samples from King George Island (8.08, 20.29 and 1.76 μg g⁻¹ dw for Cr, Cu and Pb, respectively) and Deception Island (203.13, 3.26 and 164.26 μg g⁻¹ dw for Al, Mn and Fe, respectively), where probably human activities and large-scale transport of pollutants contribute to increase metal levels. Concentrations of Cr, Mn, Cu, Se or Pb, which are similar to others found in different regions of the world, show that some areas in Antarctica are not utterly pristine.     

Application of QuEChERS method and gas chromatography-mass spectrometry for the analysis of cypermethrin residue in milk

Analytical methods for the isolation and determination of cypermethrin in milk, based on the solid-phase microextraction (SPME) and QuEChERS methods (Quick, Easy, Cheap, Effective, Rugged, and Safe) are presented. The SPME technique was not appropriate to analyse cypermethrin in milk, even establishing the best extraction conditions, polydimethylsiloxane fiber, 60 min time extraction, 60 °C temperature extraction, addition of salt (NaCl) and stirring rate. The extraction efficiency was low probably because of the matrix constituents. The QuEChERS method involves the extraction of the analyte with acetonitrile and simultaneous liquid-liquid partitioning formed by adding anhydrous MgSO(4) plus NaCl, followed by the removal of residual water and cleanup using a procedure called dispersive solid-phase extraction, in which anhydrous MgSO(4) plus PSA and C18 are mixed with 1 mL of acetonitrile extract. The detection and quantification limits were 0.01 and 0.04 mg kg(-1), respectively, and the percentage recovery obtained ranged from 92 to 105% with relative standard deviations below 7%.     

DMSO EVOL™ as novel non-toxic solvent for polyethersulfone membrane preparation

Environmental Science and Pollution Research - The possibility of replacing traditional toxic solvents normally employed during the preparation of polymeric membranes with greener alternatives...     

Relationship between leaf antioxidants and ozone injury in Nicotiana tabacum ‘Bel-W3’ under environmental conditions in São Paulo,SE – Brazil

Previous studies have reported that the extent of leaf injury in Nicotiana tabacum “Bel-W3” exposed to environmental conditions in the city of São Paulo is influenced by weather conditions. This influence may occur by means of antioxidant responses. Thus, this study aimed to evaluate whether daily antioxidant responses to environmental variations interfere on the progression of leaf injury on plants of this cultivar during their exposure in a state park of São Paulo and to determine a linear combination of variables, among antioxidants and environmental factors, which mostly explain this visible response. Plants were exposed at the mentioned site for 14 days in four different experiments. During each experiment, three plants were daily sampled to determine the accumulated percentage of leaf area affected by necrosis and antioxidant responses (concentrations of total ascorbic acid (AA) and activity of superoxide dismutase (SOD) and peroxidases (POD)). Ozone concentrations and weather conditions were also daily measured. Pearson correlations and multivariate analyses assessed the relationship between biological and environmental variables. Leaf injury appeared between the 3rd and 6th days of exposure and increased over the exposure periods. The daily concentrations of AA tended to decrease with time of exposure in all experiments, but the activity of SOD and POD oscillated during plant exposure. Positive correlations were observed between AA or SOD and O₃ concentrations, as well as negative correlations between AA and air temperature. The increasing percentage of leaf necrosis across the whole period was explained by decreasing levels of AA 2 days before injury estimation and by higher O₃ concentrations 5 days before (R² = 0.36; p < 0.001). The use of N. tabacum Bel-W3 as a bioindicator can be restricted by leaf antioxidant responses to both atmospheric contamination and weather conditions.     

Influence of natural events on the concentration and composition of atmospheric particulate matter

A ten-month field study aimed to determine the contribution of natural events (i.e. sea-salt and mineral dust events) to urban PM concentration was carried out at six sampling sites in Central Italy (Lazio region). Four indicators have been used to identify natural events during the period of the study. The first one is constituted by the ratio between number of particles in the coarse to the accumulation mode. It is simple, cheap, and the information are given in quasi-real time, but the nature of the event (sea-salt or mineral dust) is not detectable. The second indicator relies on the chemical analysis of the collected PM by X-ray fluorescence (XRF) and allows a robust identification of sea-salt and crustal components. The third one is based on diagnostic ratios of elemental fractions: Mg_extractable/Ti_residue for sea-salt and Ti_residue/Sb_residue for mineral dust. It requires skilled staff but it is most accurate and sensible. The last indicator, constructed on the basis of natural radioactivity data, is not diagnostic for the nature of the event but it is able to estimate the increase in PM concentration with respect to the expected concentration in the absence of natural events.The relevance of natural events and the variations in PM concentration and composition during the study are discussed. The joined use of the four indicators allowed the identification of about 20 natural PM episodes. In general, sea-salt aerosol events did not cause exceedance of the daily EU limit value for PM₁₀. Saharan dust events, instead, were in most cases responsible for the exceedance of the limit value at all stations.     

Occurrence and congener specific profiles of polybrominated diphenyl ethers and their hydroxylated and methoxylated derivatives in breast milk from Catalonia

The presence of polybrominated diphenyl ethers (PBDEs) from mono to hepta brominated and 11 hydroxylated (OH-) and methoxylated (MeO-) PBDEs was examined in 37 breast milk samples collected from 11 mothers living in Barcelona. An extraction method based on accelerated solvent extraction followed by gas chromatography coupled to high resolution mass spectrometry was used to inequivocally identify all target compounds at the low pg g(-1) lw level. Data obtained were examined for absolute and relative concentrations and specific PBDE, OH- and MeO-PBDE congener patterns. Sigma PBDE concentration ranged between 1,161 and 1,372,797 pg g(-1) lw and BDEs 47, 99, 100, 153 and 183 accounted for more than 80% of the total PBDEs. All tri and tetra OH- and MeO-PBDEs compounds were detected at levels between 6 and 14,984 pg g(-1)lw. The median ratio OH/PBDE and MeO-PBDEs/PBDEs was from 2.9% to 1.6%, respectively, suggesting either that PBDE metabolism to OH- and MeO- derivatives is not an important degradation route in humans or either OH- and MeO-PBDEs are rapidly excreted. No significant correlation was observed between PBDEs and OH- and MeO-PBDE, although OH- and OMe-PBDEs co-occurred in mothers' milk (R(2)=0.5349). According to the daily intake of PBDEs and OH- and MeO-PBDEs, which was between 0.47 and 363 ng d(-1) (excluding a smoking donor), potential health risks associated with these compounds are assessed.     

Sediments as a sink for UV filters and benzotriazoles: the case study of Upper Iguaçu watershed,Curitiba (Brazil)

Ingredients in home and personal care products, including UV filters and benzotriazoles, are high production volume chemicals extensively used in our daily life, despite several studies revealed their potential eco-toxicity and endocrine-disrupting capacity. Due to some features, such as high lipophilicity, low degradability, and persistence of many of these compounds, sediments can be considered a sink for them in the aquatic environment. In the present study, nine organic UV filters and three benzotriazoles were investigated for the first time in sediments from four urban rivers in Brazil. The contaminants were analyzed by liquid chromatography-tandem mass spectrometry (LC-MS/MS). The results revealed that octocrylene (OC), etylhexyl-methoxycinnamate (EHMC), benzophenone-3 (oxybenzone, BP3), and benzotriazole (BZT) were the predominant compounds adsorbed on the sediments, with concentrations ranging from 5.6 to 322.2 ng g⁻¹ dry weight. The results reported in this work constitute the first data on the accumulation of polar benzotriazoles and lipophilic organic UV filters in sediments from Brazil.