Toxicity of the sawdust used for phosphorus recovery in a eutrophic reservoir: experiments with Lactuca sativa and Allium cepa.

Eutrophication is one of the environmental problems arising from the increase of essential nutrient concentrations, mainly phosphorus and nitrogen. In contrast to excess phosphorus, the depletion of phosphate rock deposits used for the production of fertilizers compromises the food supply. Therefore, the development of technologies that propose the recovery of the phosphorus contained in eutrophic environments for its later use for agricultural fertilization purposes is very important to ensure global food security. This work aimed to evaluate the toxic potential of the sawdust (biosorbent previously used for phosphorus adsorption) in order to enable its application in agriculture. For this, toxicity experiments with Lactuca sativa (lettuce) and Allium cepa (onion) seeds were performed. The phytotoxic potential was assessed by means of the seed germination index and physiological parameters such as radicle and hypocotyl growth. Cytotoxicity, genotoxicity, and mutagenicity tests were also performed on onion seeds. From statistical tests, it was possible to affirm that the sawdust did not promote inhibition of seed germination and radicle and hypocotyl growth. No genotoxicity, cytotoxicity and, mutagenicity were observed, which allowed to state that the sawdust is not toxic to the onion species, which reinforces the possibility of application of the biosorbent for soil fertilization purposes. Therefore, the use of sawdust for phosphorus biosorption with the subsequent agricultural application is promising and quite important from a global food security point of view.

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.

Equilibrium and kinetic studies of the adsorption of antibiotics from aqueous solutions onto powdered zeolites.

The performances of two FAU-type zeolites with different SiO2/Al2O3 ratios were evaluated for the removal of antibiotics of three different classes, namely azithromycin, ofloxacin, and sulfamethoxazole, from aqueous solutions. Commercial zeolites were used, without any previous treatment. Use of a small adsorbent dosage resulted in fast antibiotic adsorption that followed pseudo-second order kinetics. The removals of azithromycin and sulfamethoxazole were highly pH-dependent, with low removal percentages observed under acid (pH 2.5-4.5) and basic (pH 8.5-10.5) conditions, respectively. The Freundlich isotherm model provided the best fits to the adsorption data. The adsorption mechanisms appeared to involve both electrostatic and H-bonding interactions. Using an antibiotics mixture, percentage removals of azithromycin and ofloxacin onto the zeolites of up to 79% were obtained. Both materials presented good adsorption (>50%) of azithromycin and ofloxacin from a real sample of effluent wastewater. The results showed that zeolites with FAU structure can be used as effective adsorbents for the removal of antibiotics with different physicochemical properties, including molecules with large volumes, such as azithromycin.

Spatio-temporal evaluation of emerging contaminants and their partitioning along a Brazilian watershed.

The occurrence, partitioning, and spatio-temporal distribution of seven pharmaceuticals for human use, three steroid hormones and one personal care product were determined in surface water, suspended particulate matter (SPM), and sediment of Piraí Creek and Jundiaí River (Jundiaí River Basin, São Paulo, Brazil). The maximum average detected concentrations of the compounds in the Piraí River samples were < 30 ng L-1, except for caffeine (222 ng L-1). In Jundiaí River samples, most of the compounds were frequently detected, wherein caffeine had the highest concentration, with maximum average concentrations of 14,050 ng L-1, followed by atenolol (431 ng L-1), ibuprofen (268 ng L-1) and diclofenac (214 ng L-1). Atenolol, propranolol, estrone, and triclosan were the contaminants most frequently detected in sediment and SPM samples. Triclosan had the highest average proportion of SPM as opposed to in the aqueous phase (> 75%). Contaminants with acid functional groups showed, in general, a lower tendency to bind to particulate matter and sediments. In addition, hydrophobicity had an important effect on their environmental partitioning. The spatial distribution of contaminants along the Jundiaí River was mainly affected by the higher concentration of contaminants in water samples collected downstream from a sewage treatment plant (STP). The results obtained here clearly showed the importance of the analysis of some contaminants in the whole water, meaning both dissolved and particulate compartments in the water, and that the partitioning is ruled by a set of parameters associated to the physicochemical characteristics of contaminants and the matrix properties of the studied, which need be considered in an integrated approach to understand the fate of emerging chemical contaminants in aquatic environments.

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.

Electrical conductivity and emerging contaminant as markers of surface freshwater contamination by wastewater.

The use of chemical markers of undoubted anthropogenic sources for surface freshwater contamination by wastewaters was evaluated employing correlations observed between measured physico-chemical parameters as the electrical conductivity and the concentration of different emerging organic compounds. During the period from April/2011 to April/2012 spatial-temporal variations and contamination patterns of two rivers (Piraí and Jundiaí rivers), São Paulo state, Brazil were evaluated. Seven physico-chemical parameters and concentrations of different classes of emerging contaminants were determined in samples collected in seven field campaigns. The high linear correlation coefficients obtained for the compounds diclofenac (r=0.9085), propanolol (r=0.8994), ibuprofen (r=0.8720) and atenolol (r=0.7811) with electrical conductivity, also corroborated by principal component analysis (PCA), point to the potential use of these compounds as markers of investigated surface water contamination by wastewaters. Due to specific inputs, these environmental markers showed very good effectiveness for the identification and differentiation of water body contamination by discharges of treated and untreated urban sewage.

The application of biochemical responses to assess environmental quality of tropical estuaries: field surveys.

A battery of biomarkers of exposure (EROD, DBF, GST and GPx) and effect (lipid peroxidation and DNA damage - strand breaks) were analyzed in gill tissues from caged and native oysters Crassostrea rhizophorae exposed to two tropical estuarine systems in SW Brazil: Santos (S1, S2, S3, S4) and Paranaguá (P1 - control, P2, P3, P4). The exposure lasted 28 days. Native oysters were sampled in the same areas where caged systems were exposed. Significant induction of biomarkers of exposure to organic compounds and oxidative stress (p < 0.05) were observed in all transplanted individuals from Santos resulting in DNA damage and lipid peroxidation. Biological adverse effects were more evident in oysters transplanted in the Santos Estuarine System, a recognized contaminated area, than in the Paranaguá Estuarine System, surrounded by urban areas and Environmental Protected Areas. Native specimens from both estuaries showed adaption to the impacts of several contamination sources affecting the ecosystem. The use of transplanted C. rhizophorae proved to be a suitable tool for assessing and monitoring the environmental quality in mangrove ecosystems. This integrated approach employing multi-biomarker responses under field conditions could be incorporated as a descriptor of health status in tropical estuarine systems.

Dynamics of fipronil in Oleo Lagoon in Jataí Ecological Station, São Paulo-Brazil.

Fipronil is a phenylpyrazole pesticide widely used to protect sugar-cane crops from insect pests. After reaching the environment, this insecticide may have several fates. This research aimed to propose a kinetic model to describe the fate of commercial fipronil Regent 800WG in the sediment-water interface of the Oleo Lagoon in the Mogi-Guaçu river floodplain, situated within the Jataí Ecological Station, by means of a microcosm scale experiment. Results showed that a small fraction of the pesticide is quickly dragged to the sediment while most of it remains in the water column. Biodegradation proves to be an important fipronil degradation route, especially when microorganisms capable of using fipronil as sole carbon source increase their population, as a function of exposure time. Biodegradation rates were higher in the sediment than in the water column.