Source apportionment and health impact assessment of atmospheric particulate matter in the city of São Carlos, Brazil.

In this study, positive matrix factorization method was used for source apportionment of PM10 in the city of São Carlos from 2015 to 2018. The annual mean concentrations of PM10, 15 PAHs, 4 oxy-PAHs, 6 nitro-PAHs, 21 saccharides, and 17 ions in these samples were in the ranges 18.1 ± 6.99 to 25.0 ± 11.3 µg m-3 for PM10, 9.80 × 10-1 ± 2.06 to 2.03 ± 8.54 × 10-1 ng m-3 for ΣPAHs, 83.9 ± 35.7 to 683 ± 521 pg m-3 for Σoxy-PAHs, 1.79 × 10-2 ± 1.23 × 10-1 to 7.12 ± 4.90 ng m-3 for Σnitro-PAHs, 83.3 ± 44.7 to 142 ± 85.9 ng m-3 for Σsaccharides, and 3.80 ± 1.54 to 5.66 ± 4.52 µg m-3 for Σions. For most species, the concentrations were higher in the dry season than in the rainy. This was related not only to the low rainfall and relative humidity characteristic of the dry season but also to an increase in fire spots recorded in the region between April and September every year from 2015 to 2018. A 4-factor solution provided the best description of the dataset, with the four identified sources of PM10 being soil resuspension (28%), biogenic emissions (27%), biomass burning (27%), and vehicle exhaust together with secondary PM (18%). Although the PM10 concentrations were not above the limit established by local legislation, the epidemiological study showed that by reducing PM2.5 concentrations to the level recommended by the WHO, approximately 35 premature deaths per 100,000 population could be avoided annually. The results revealed that biomass burning continues to be one of the main anthropic sources of emissions to the atmosphere in the region, so it needs to be incorporated into the existing guidelines and policies to reduce the concentration of particulate matter to within the limits recommended by the WHO, in order to avoid premature deaths.

Development of a simple method to quantify fipronil and its intermediates in soil.

A simple and reproducible method was developed and validated for simultaneous quantification of the pesticide fipronil and its intermediates fipronil desulfinyl, fipronil sulfone and fipronil sulfide, in soil. The analytes were extracted by ultrasonic bath and the ratio of solvents (hexane/acetone), number and time of cycles were optimized by Box-Behnken design with a triplicate central point. The optimal extraction conditions were achieved through a response surface analysis. The clean-up step was conducted by cartridges of solid phase extraction (SPE) containing silica (Florisil®) and aluminum oxide. Gas chromatography with electron capture detection (GC-ECD) was employed for separating fipronil and its intermediates with a suitable resolution and runtime of 20 minutes. The best quantification was achieved with 1 : 1 (v/v) acetone/hexane and 2 ultrasound cycles of 15 minutes each. The recovery values were between 81 to 108%, with relative standard deviation (RSD) lower than 6%, with no effect of the used matrix. Analytical curves presented regression coefficients values above 0.9908 for a concentration range from 0.005 to 0.6 µg g-1. Limits of detection (LOD) from 0.002 to 0.006 µg g-1 and limits of quantification (LOQ) from 0.006 to 0.020 µg g-1 were reached for all analytes. This method can be used to monitor and quantify fipronil and its intermediates in soil.

Multivariate analyses of the effect of an urban wastewater treatment plant on spatial and temporal variation of water quality and nutrient distribution of a tropical mid-order river.

Freshwater resources are increasingly scarce due to human activities, and the understanding of water quality variations at different spatial and temporal scales is necessary for adequate management. Here, we analyze the hypotheses that (1) the presence of a wastewater treatment plant (WWTP) and (2) a polluted tributary that drains downstream from the WWTP change the spatial patterns of physicochemical variables (pH, turbidity, dissolved oxygen, and electrical conductivity) and nutrient concentrations (reactive soluble phosphorus, total phosphorus, nitrogen series, total nitrogen, and total dissolved carbon) along a mid-order river in SE Brazil and that these effects depend on rainfall regime. Six study sites were sampled along almost 4 years to evaluate the impacts of human activities, including sites upstream (1-3) and downstream (5-6) from the WWTP. The impacts were observed presenting an increasing trend from the source (site 1) towards Água Quente stream (site 4, the polluted tributary), with signs of attenuation at site 5 (downstream from both WWTP and site 4) and the river mouth (site 6). Input of nutrients by rural and urban runoff was observed mainly at sites 2 and 3, respectively. At sites 4 and 5, the inputs of both untreated and treated wastewaters increased nutrient concentrations and changed physicochemical variables, with significant impacts to Monjolinho River. Seasonal variations in the measured values were also observed, in agreement with the pluviometric indexes of the region. Univariate analyses suggested no effect of the WWTP for most variables, with continued impacts at sites downstream, but non-parametric multivariate analysis indicated that these sites were recovering to chemical characteristics similar to upstream sites, apparently due to autodepuration. Therefore, multivariate methods that allow rigorous tests of multifactor hypotheses can greatly contribute to determine effects of both point and non-point sources in river systems, thus contributing to freshwater monitoring and management.

Ultrasound-assisted extraction method for the simultaneous determination of emerging contaminants in freshwater sediments.

Sediments are the fate of several emerging organic contaminants, such as pharmaceuticals, personal care products and hormones, and therefore an important subject in environmental monitoring studies. In the present work, a simple and sensitive method was developed, validated and applied for the simultaneous extraction of atenolol, caffeine, carbamazepine, diclofenac, ibuprofen, naproxen, propranolol, triclosan, estrone, 17-ß-estradiol and 17-α-ethinylestradiol using ultrasound-assisted extraction from freshwater sediment samples followed by solid-phase extraction clean-up and liquid chromatography with tandem mass spectrometry detection. The solvent type and extraction pH were evaluated to obtain the highest recoveries of the compounds. The best method shows absolute recoveries between 54.0 and 94.4% at 50 ng/g concentration. The method exhibits good precision with relative standard deviation ranging from 1.0-16%. The detection and quantification limits ranged from 0.006-0.067 and 0.016-0.336 ng/g, respectively. The developed method was successfully applied to freshwater sediment samples collected from different sites in Jundiaí River basin of São Paulo State, Brazil. The compounds atenolol, caffeine, propranolol and triclosan were detected in all the sampling sites with concentrations of 13.8, 41.0, 28.5 and 176 ng/g, respectively.