Spatial-temporal occurrence of contaminants of emerging concern in urban rivers in southern Brazil.

The widespread use and misuse of antibiotics and pesticides has been linked with several risks to the environment and human health. In the present report, the results of the monitoring of 64 pharmaceuticals and 134 pesticides occurrence in an urban river in Southern Brazil are presented and discussed. Sampling campaigns have covered the period 2016-2018. The identification and determination of the analytes were achieved by high-resolution mass spectrometry. The data were analyzed using chemometric tools to obtain spatial-temporal models. Toxicological evaluation was achieved using acute toxicity (zebrafish standardized protocol), and determination of risk quotient. Within the 198 analytes included in the targeted analysis method for surface water, 33 were identified in an urban river during 2 years of monitoring, being 20 pharmaceuticals and 13 pesticides. Using high-resolution mass spectrometry, a suspect screening approach was established in an un-target analysis. The evaluation was carried out using a data bank built from consumption data of drugs and pesticides, in the metropolitan region of Porto Alegre - RS and their respective metabolites. The suspect screening analysis done with a data bank with more than 1450 compounds results in 27 suspect findings. The target analysis results showed a continuous prevalence of non-steroidal anti-inflammatories, analgesics, antipyretics, beta-blockers, corticoids, and antibiotics. Regarding the pesticides, the main classes were fungicides, especially those from triazol and strobilurin classes.

Ecotoxicological evaluation of fruit extracts from yerba mate progenies (Ilex paraguariensis a St-Hil.): a natural biopesticide.

This study evaluated the biocidal activity of aqueous fruit extracts from Ilex paraguariensis progenies at different ripening stages in two ecotoxicity assays using Pomacea canaliculata juveniles and Danio rerio larvae. Mutagenicity was verified by the Salmonella/microsome assay (TA 98 and TA 100) in the presence and absence of hepatic metabolism in vitro. The results showed that the snails were more sensitive than the larvae to the P.1 progeny extracts in all three evaluated ripening stages. P.3 progeny extracts were the most toxic to Danio rerio larvae after 96 hours of exposure. The toxicity results indicate that the progenies' selection influenced the metabolic contents present in the fruits in all ripening stages over time, indicating high molluscicidal activity for the P.1 progeny. In the Salmonella/microsome assays, the semi-ripe and ripe extracts from progenies P.1 and P.3 showed mainly base pair substitution mutation in assays with metabolism, but at higher doses than the toxic concentrations detected for Danio rerio or Pomacea canaliculata. Therefore, the toxicological investigation of the progenies' extracts can be interesting, given the selection of plant materials influenced the response of the bioassays.

Evaluation of effect of hazardous contaminants in areas for the abstraction of drinking water.

The lower portion of Taquari River is influenced by compounds from anthropic activities causing concern about the drinking water supplied to cities in the region. The study objective was to investigate the presence of contaminants at drinking water abstraction sites, defining the mutagenic effects of these stressors as an ecosystem quality parameter and its possible effects on human health. Geographic Information System techniques were used to investigate sources of contamination and it was found that agricultural activities predominated with a few medium and high potential pollutant agricultural activities, besides a soil area that was contaminated and undergoing an intervention process. Mutagenic effects were evaluated by Salmonella/microsome assay using TA98, TA97a, TA100, YG1041 and YG1042 strains in the presence and absence of metabolic activation (S9). Mutagenesis found in organic sediment extracts and surface water samples showed the prevalence of direct-acting mutagens at the drinking water abstraction sites. Taquari (Ta032, the sampling points were named according to the initial letters of the river (Ta), followed by the number of kilometers from the mouth) showed the highest mutagenic potency in sediment, while Ta063, at Bom Retiro do Sul, presented it in the water sample. In the Triunfo region (Ta011) there were significant responses in sediment and in water samples. The samples at General Câmara (Ta006) showed the least presence of contaminants. The Allium cepa test applied to sediments in natura showed significant micronucleus induction in Ta032 in accordance with the Salmonella/microssome assay. The test performed on Danio rerio embryos (FET) in the in natura water samples did not present significant responses. Chemical analyses of polycyclic aromatic hydrocarbons and metals already identified as chemical markers in the area indicated a small contribution to the mutagenic potency, calling attention to the fact that other direct-acting pollutants may be present at the drinking water abstraction sites.

Is fish embryo test (FET) according to OECD 236 sensible enough for delivering quality data for effluent risk assessment?

Over the past few years, the fish embryo test (FET) has become widely accepted as an animal-friendly protocol for ecotoxicological research. As Organisation for Economic Co-operation and Development (OECD) 236, the FET has been widely applied for simple mixture exposures under the Registration, Evaluation, Authorisation, and Restriction of Chemicals regulation of the European Union; and now its use is spreading worldwide as a supposedly reliable whole-effluent test (i.e., the testing of complex mixture exposures). However, comparative peer-reviewed data regarding the FET's efficiency for whole-effluent tests are virtually nonexistent. The primary objective of the present study was to make the first comparative test between the FET according to OECD 236 and other standard and slightly modified standard fish protocols used worldwide for whole-effluent tests. For that, we used an untreated hospital effluent considered to be highly toxic but disposed of in municipal sewerage. The base methods were OECD 203 (juvenile), US Environmental Protection Agency method 2000.0 (larvae), and OECD 236 (embryo). We also evaluated the addition of 3 virtually costless sublethal metrics (immobility, nonhatching, and pericardial edema) that could enhance the sensitivity of OECD 236. We observed acute toxicity in all 8 methodologies tested, with a clear escalation in sensitivity (larvae > juvenile ≥ embryo). Larvae were the most sensitive life stage for whole-effluent tests. The addition of sublethal metrics to OECD 236 enhanced its previous sensitivity in over 30%. Thus we conclude that OECD 236 acts below its potential and that the embryonic stage (as used in the FET) may not be the most sensitive life stage for whole-effluent tests. Environ Toxicol Chem 2018;37:2925-2932. © 2018 SETAC.

Determination of pharmaceutical compounds in hospital wastewater and their elimination by advanced oxidation processes.

This study investigates the mineralization efficiency, i.e. removal of total organic carbon (TOC) in hospital wastewater by direct ozonation, ozonation with UV radiation (O3/UV), homogeneous catalytic ozonation (O3/Fe2+) and homogeneous photocatalytic ozonation (O3/Fe2+/UV). The influence of pH and reaction time was evaluated. For the best process, toxicity and degradation efficiency of the selected pharmaceutical compounds (PhCs) were determined. The results showed that the PhCs detected in the hospital wastewater were completely degraded when the mineralization efficiency reached 54.7% for O3/UV with 120 minutes of reaction time using a rate of 1.57 g O3 h-1. This process also achieved a higher chemical oxygen demand removal efficiency (64.05%), an increased aromaticity reduction efficiency (81%) and a toxicity reduction.

Comparison of different advanced oxidation processes for the removal of amoxicillin in aqueous solution.

Amoxicillin (AMX) is a widely used penicillin-type antibiotic whose presence in the environment has been investigated. In this work, the degradation of the AMX in aqueous solutions by ozonation, ozonation with UV radiation (O3/UV), homogeneous catalytic ozonation (O3/Fe2+) and homogeneous photocatalytic ozonation (O3/Fe2+/UV) was investigated. The performance results have been compared in terms of removal of amoxicillin and total organic carbon (mineralization efficiency). In all processes, complete amoxicillin degradation was obtained after 5 min. However, low mineralization was achieved. For the best available process, the potential toxicity of AMX intermediates formed after ozonation was examined using a Fish Embryo Toxicity test. Results reveal that O3 in alkaline solution and O3/Fe2+/UV provide the highest mineralization rates. Ecotoxicity showed that no acute toxicity was observed during the exposure period of 96 h.

Assessment of the toxicity of wastewater from the metalworking industry treated using a conventional physico-chemical process.

This article presents results from a toxicity reduction evaluation program intended to describe wastewater from the metalworking industry that was treated using a conventional physico-chemical process. The toxicity of the wastewater for the microcrustacean Daphnia magna was predominantly expressive. Alkaline cyanide wastewater generated from electroplating accounted for the largest number of samples with expressive toxicity. When the raw wastewater concentrations in the batches were repeated, inexpressive toxicity variations were observed more frequently among the coagulated-flocculated samples. At the coagulation-flocculation step, 22.2 % of the treatments had reduced acute toxicity, 30.6 % showed increased toxicity, and 47.2 % remained unchanged. The conductivity and total dissolved solids contents of the wastewater indicated the presence of salts with charges that were inappropriate for the survival of daphnid. The wastewaters treated by neutralization and coagulation-flocculation had average metallic compound contents that were greater than the reference toxic concentrations reported in other studies, suggesting that metals likely contributed to the toxic effects of the wastewater on freshwater microcrustaceans. Thus, alternative coagulants and flocculants should be assessed, and feasible doses should be determined to improve wastewater treatment. In addition, advanced treatment processes should be assessed for their abilities to remove dissolved toxic salts and ions.

Photocatalytic degradation of rosuvastatin: analytical studies and toxicity evaluations.

Photocatalytic degradation of rosuvastatin, which is a drug that has been used to reduce blood cholesterol levels, was studied in this work employing ZnO as catalyst. The experiments were carried out in a temperature-controlled batch reactor that was irradiated with UV light. Preliminary the effects of the photocatalyst loading, the initial pH and the initial rosuvastatin concentration were evaluated. The experimental results showed that rosuvastatin degradation is primarily a photocatalytic process, with pseudo-first order kinetics. The byproducts that were generated during the oxidative process were identified using nano-ultra performance liquid chromatography tandem mass spectrometry (nano-UPLC-MS/MS) and acute toxicity tests using Daphnia magna were done to evaluate the toxicity of the untreated rosuvastatin solution and the reactor effluent.

Treatment of solutions containing nonylphenol ethoxylate by photoelectrooxidation.

In this work the photoelectrooxidation (PEO) was applied in the treatment of a solution containing nonylphenol ethoxylate surfactant (NP4EO). The use of different lamps (125 and 250 W), current density (5 and 10 mA cm(-2)) and treatment time (0, 60, 120, 180 and 240 min) were investigated. The samples were characterized by UV/Vis, total organic carbon (TOC), gas chromatography associated to mass spectroscopy (GC/MS) and ecotoxicity. The reaction kinetics were calculated and the light flux and pH were measured. The results of analysis by UV/Vis show that there is degradation of nonylphenol ethoxylated in the treatment time of 240 min for all configurations, and the configurations that used a 250 W lamp and a current density of 10 mA cm(-2) obtained better results, with a reduction of 83% in TOC, indicating a high mineralization of the surfactant. It was further found in the GC/MS that the configurations that used the 125 W lamp promoted a smaller incident light flux on the solution, and, regardless of the applied current density, it was generated the reaction intermediate nonylphenol, more toxic than the parent compound. The opposite can be observed when a 250 W lamp was used, which produced a higher incident light flux. Based on the degradation products detected, a simplified mechanism for degradation of nonylphenol ethoxylate was proposed. Although a treatment time of 240 min with photoelectrooxidation with different configurations was not effective in the complete mineralization of the compound, a promising process was developed with the treatment using a lamp of 250 W and a current density of 10 mA cm(-2), which generated a solution with less toxicity than the original one.

Evaluation of genotoxicity and toxicity of water and sediment samples from a Brazilian stream influenced by tannery industries.

This paper reports results of genotoxicity and toxicity studies of water and sediment samples collected from the Estância Velha stream of southern Brazil, a stream transporting both domestic sewage and effluents from regional factories working in the leather industry. Three sites were selected: in the stream headwaters (Site 1), located downstream of an urban area (Site 2), and near the basin outfall (Site 3). Results obtained with Allium cepa showed no evidence of chromosomal mutation, either in water or in sediment, during winter or summer seasons, but samples collected below Site 1 showed high toxicity. Physical and chemical analyses showed high concentrations of pollutants at these sites. Ecotoxicity tests with Daphnia magna and Ceriodaphnia dubia measured toxicity in water from Sites 2 and 3 in summer 2004. A toxic effect on Hyalella azteca was only found in sediment from Site 3 during winter 2003 and summer 2004. The results suggest that the synergy among different compounds in domestic and industrial sewage discharges can make it difficult to maintain system stability.

Assessment of the freshwater annual fish Cynopoecilus melanotaenia as a toxicity test organism using three reference substances.

This study presents a preliminary evaluation of the use of the Brazilian fish Cynopoecilus melanotaenia as a test organism in toxicity tests. The cryptobiotic stage presented by the eggs of fish C. melanotaenia can overcome the difficulty of continuously keeping cultures and recruiting healthy animals in sufficient numbers to be used in toxicity tests. In order to determine the applicability of this species as a test organism, three different reference substances were evaluated in 96-h acute toxicity tests: Copper sulfate (CuSO4 x 5H2O), sodium dodecil sulfate (C12H25NaO4S), and sodium chloride (NaCl). Sensitivity ranged as follows: copper sulfate (0.05-0.13 mg/L), sodium dodecil sulfate (10.7-19.0 mg/L), and sodium chloride (1.44-1.96 g/L). We conclude that C. melanotaenia shows potential as a test organism in toxicity tests; however, further research should be conducted with other substances and should be compared with the research on other species before we can reach more conclusive results.