Triclocarban: UV photolysis,wastewater disinfection,and ecotoxicity assessment using molecular biomarkers

Triclocarban (TCC) is an antibacterial agent found in pharmaceuticals and personal care products (PPCP). It is potentially bioaccumulative and an endocrine disruptor, being classified as a contaminant of emerging concern (CEC). In normal uses, approximately 96% of the used TCC can be washed down the drain going into the sewer system and eventually enter in the aquatic environment. UV photolysis can be used to photodegrade TCC and ecotoxicity assays could indicate the photodegradation efficiency, since the enormous structural diversity of photoproducts and their low concentrations do not always allow to identify and quantify them. In this work, the TCC was efficiently degraded by UVC direct photolysis and the ecotoxicity of the UV-treated mixtures was investigated. Bioassays indicates that Daphnia similis (48 h EC₅₀ = 0.044 μM) was more sensitive to TCC than Pseudokirchneriella subcapitata (72 h IC₅₀ = 1.01 μM). TCC and its photoproducts caused significant effects on Eisenia andrei biochemical responses (catalase and glutathione-S-transferase); 48 h was a critical exposure time, since GST reached the highest activity values. UVC reduced the TCC toxic effect after 120 min. Furthermore, TCC was photodegraded in domestic wastewater which was simultaneously disinfected for total coliform bacterial (TCB) (360 min) and Escherichia coli (60 min).

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Graphical abstract TCC degradation and ecotoxicological assessment

     

Evaluation of the sensitivity spectrum of a video tracking system with zebrafish (<Emphasis Type="Italic">Danio rerio</Emphasis>) exposed to five different toxicants

The aim of this study was to develop a biological early warning system for the detection of aquatic toxicity and test it with five toxicants with distinct chemical nature. This was done in order to verify the spectrum of sensitivities of the proposed system, as well as the potential identification capability of the tested contaminants, using only the analysis of zebrafish’s behavior. Six experimental conditions were tested: negative control and five toxicants (bleach, lindane, tributyltin, mercury, and formaldehyde). The exposure time was 45 min, and the concentrations used corresponded to 9% of LC₅₀’s-96 h for the tested compounds, to ensure ecologically relevant results. A total of 108 fish were used, with each individual experimental condition being tested 18 times. A statistical model of diagnosis was used, combining self-organizing map and correspondence analysis. The values of sensitivity, specificity, accuracy, false positive, false negative, positive predictive value (PPV), and negative predictive value (NPV) were calculated. The objectives of the work were accomplished and the system showed a good overall diagnostic performance with 79% in accuracy, 77% in sensitivity, and 88% in specificity. The lowest result of the predictive values was 78% (lindane and mercury), in the case of the NPV, and 86% (bleach and lindane), in the case of the PPV. The best result of the predictive values was 100% (bleach and tributyltin), for the NPV, and 89% (tributyltin), for the PPV. Regarding the five tested toxicants, the system was able to correctly identify the agent responsible for the contamination in 40% of the positive diagnoses.     

Dental enamel as biomarker for environmental contaminants in relevant industrialized estuary areas in São Paulo,Brazil

Heavy metal contamination is a long-standing and very well-known public health problem, and its exposure can cause damage to several organs of human body, especially on the central nervous system of young children and teenagers. The aim of this article is to evaluate lead, cadmium, and manganese contamination in 125 children from 6 to 13 years old living in contaminated areas during the period from 2006 to 2009 (São Vicente, Cubatão Downtown, Bertioga and Cubatão Pilões/Água Fria). This estuary area is the most important example of environmental degradation by chemicals from industrial sources. This is a cross-sectional study through clinical examinations and dental enamel tests. All mothers from these children lived in the area since before the pregnancy. Lead, cadmium, and manganese levels (μg/g) were measured on dental enamel samples through graphite furnace atomic absorption spectrometry, searching for the occurrence of heavy metals. The mean lead concentrations were 139.48 μg/g in Cubatão Pilões/Água Fria, 170.45 μg/g in Cubatão Downtown, 213.52 μg/g in São Vicente, and 151.89 μg/g in Bertioga. The mean cadmium concentrations were 10.83 μg/g in Cubatão Pilões/Água Fria, 12.58 μg/g in Cubatão Downtown, 10.92 μg/g in São Vicente, and 14.57 μg/g in Bertioga. The mean manganese concentrations were 23.49 μg/g in Cubatão Pilões/Água Fria, 30.90 μg/g in Cubatão Downtown, 41.46 μg/g in São Vicente, and 42.00 μg/g in Bertioga. Dental surface enamel may be used as an efficient biomarker of past environmental exposure to lead, manganese, and cadmium which are associated to well-known sources of heavy metal contamination. The results suggest that the evaluated children were exposed to sources of lead, cadmium, and manganese since before their conceptions. Although Bertioga initially was chosen as a control area of this study, it was also was verified to have heavy metal contamination on examined children.     

Genotoxicity in adult residents in mineral coal region—a cross-sectional study

The present study assessed the DNA damage in environmentally exposed volunteers living in seven municipalities in an industrial coal region, through the use of the comet assay with blood cells and the micronucleus test with buccal cells. Blood and buccal smears were collected from 320 male volunteers living in seven cities inserted in a coal region. They were ages of 18 and 50 years and also completed a questionnaire intended to identify factors associated with DNA damage through a Poisson regression analysis. The comet assay detected significant differences in DNA damage in volunteers from different municipalities, and neighboring cities (Pedras Altas, Aceguá, and Hulha Negra) had a higher level of DNA damage in relation to control city. Some of the risk factors associated with identified DNA lesions included residence time and life habits. On the other hand, the micronucleus test did not identify differences between the cities studied, but the regression analysis identified risk factors such as age and life habits (consumption of mate tea and low carbohydrates diet). We conclude that there are differences in the DNA damage of volunteers from different cities of the carboniferous region, but the presence of micronuclei in the oral mucosa does not differ between the same cities. Furthermore, we alert that some related factors may increase the risk of genotoxicity, such as residence location and time, and living and food habits. Finally, we suggest the need for continuous biomonitoring of the population, as well as for investing in health promotion in these vulnerable populations.

     

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.

     

Organochlorine compounds in bovine milk from the state of Mato Grosso do Sul – Brazil

Organochlorines are highly hydrophobic, synthetic organic pollutants that accumulate in the environment and in food webs. The primary route of human exposure to organochlorines is through food-mainly fat-rich food of animal origin such as meat, fish, and dairy products. Here we determined the presence and concentration of organochlorine residues in pasteurized milk from Mato Grosso do Sul, Brazil, to monitor consumer exposure to these contaminants. Organochlorine pesticides in milk samples were analyzed using solid phase extraction in octadecyl silica-prepacked columns and identified by gas chromatography using an electron capture detector. Of the 100 composite samples analyzed, more than 90% contained residues of organochlorine pesticides: aldrin was present in 44% of the samples, followed by ∑DDT (36%), mirex (34%), endosulfan (32%), chlordane (17%), dicofol (14%), heptachlor (11%) and dieldrin (11%). Compared to the values established by law, the concentration of the compounds in some samples was above the reference values. Given the importance that milk and its products have in the human diet, it is essential to know whether the levels of pesticide residues are kept well below the recommended levels to minimize the risk to human health.     

Earthworm ecotoxicological assessments of pesticides used to treat seeds under tropical conditions

Ecotoxicological laboratory tests (lower-tier tests) are fundamental tools for assessing the toxicity of pesticides to soil organisms. In this study, using these tests under tropical conditions, we quantified the impact of the insecticides imidacloprid, fipronil, and thiametoxam, and the fungicides captan and carboxin + thiram, all of which are used in the chemical treatment of crop seeds, on the survival, reproduction, and behavior of Eisenia andrei (Oligochaeta). With the exception of imidacloprid, none of the pesticides tested caused mortality in E. andrei in artificial soils. The LC₅₀ of imidacloprid was estimated as 25.53 mg active ingredient kg^?1 of dry soil. Earthworm reproduction rates were reduced by imidacloprid (EC₅₀ = 4.07 mg kg^?1), fipronil (EC₂₀ = 23.16 mg kg^?1), carboxin + thiram (EC₅₀ = 56.38 mg kg^?1), captan (EC₅₀ = 334.84 mg kg^?1), and thiametoxam (EC₅₀ = 791.99 mg kg^?1). Avoidance behavior was observed in the presence of imidacloprid (AC₅₀ = 0.11 mg kg^?1), captan (AC₅₀ = 33.54 mg kg^?1), carboxin + thiram (AC₅₀ = 60.32 mg kg^?1), and thiametoxam (AC₅₀ = >20 mg kg^?1). Earthworms showed a preference for soils with the insecticide fipronil. Imidacloprid was the most toxic of the substances tested for E. andrei. The avoidance test was the most sensitive test for most pesticides studied, but results varied between pesticides. These results offer new insights on the toxicity of pesticides used to treat seeds in tropical regions. However, they should be complemented with higher-tier tests in order to reduce the uncertainties in risk assessment.     

Enhanced resistance of yeast mutants deficient in low-affinity iron and zinc transporters to stannous-induced toxicity

Tin or stannous (Sn²⁺) compounds are used as catalysts, stabilizers in plastic industries, wood preservatives, agricultural biocides and nuclear medicine. In order to verify the Sn²⁺ up-take and toxicity in yeast cells we utilized a multi-elemental analysis known as particle-induced X-ray emission (PIXE) along with cell survival assays and quantitative real-time PCR. The detection of Sn²⁺ by PIXE was possible only in yeast cells in stationary phase of growth (STAT cells) that survive at 25 mM Sn²⁺ concentration. Yeast cells in exponential phase of growth (LOG cells) tolerate only micro-molar Sn²⁺ concentrations that result in intracellular concentration below of the method detection limit. Our PIXE analysis showed that STAT XV185-14c yeast cells demonstrate a significant loss of intracellular elements such as Mg, Zn, S, Fe and an increase in P levels after 1 h exposure to SnCl₂. The survival assay showed enhanced tolerance of LOG yeast cells lacking the low-affinity iron and zinc transporters to stannous treatment, suggesting the possible involvement in Sn²⁺ uptake. Moreover, our qRT-PCR data showed that Sn²⁺ treatment could generate reactive oxygen species as it induces activation of many stress-response genes, including SOD1, YAP1, and APN1.     

Isolation of mesotrione-degrading bacteria from aquatic environments in Brazil

Mesotrione is a benzoylcyclohexane-1,3-dione herbicide that inhibits 4-hydroxyphenyl pyruvate dioxygenase in target plants. Although it has been used since 2000, only a limited number of degrading microorganisms have been reported. Mesotrione-degrading bacteria were selected among strains isolated from Brazilian aquatic environments, located near corn fields treated with this herbicide. Pantoea ananatis was found to rapidly and completely degrade mesotrione. Mesotrione did not serve as a sole C, N, or S source for growth of P. ananatis, and mesotrione catabolism required glucose supplementation to minimal media. LC-MS/MS analyses indicated that mesotrione degradation produced intermediates other than 2-amino-4-methylsulfonyl benzoic acid or 4-methylsulfonyl-2-nitrobenzoic acid, two metabolites previously identified in a mesotrione-degrading Bacillus strain. Since P. ananatis rapidly degraded mesotrione, this strain might be useful for bioremediation purposes.     

Effect of variations in the redox potential of Gleysol on barium mobility and absorption in rice plants

Two assays were designed to obtain information about the influence of redox potential variations on barium mobility and bioavailability in soil. One assay was undertaken in leaching columns, and the other was conducted in pots cultivated with rice (Oryza sativa) using soil samples collected from the surface of Gleysol in both assays. Three doses of barium (100,300 mg kg⁻¹ and 3000 mg kg⁻¹-soil dry weight) and two redox potential values (oxidizing and reducing) were evaluated. During the incubation period, the redox potential (Eh) was monitored in columns and pots until values of −250 mV were reached. After the incubation period, geochemical partitioning was conducted on the barium using the European Communities Bureau of Reference (BCR) method. Rainfall of 200 mm d⁻¹ was simulated in the columns and in the planting of rice seedlings in the pots. The results of the geochemical partitioning demonstrated that the condition of reduction favors increased barium concentrations in the more labile chemical forms and decreased levels in the chemical forms related to oxides. The highest barium concentrations in leached extracts (3.36 mg L⁻¹) were observed at the highest dose and condition of reduction at approximately five times above the drinking water standard. The high concentrations of barium in the soil did not affect plant dry matter production. The highest levels and accumulation of barium in roots, leaves, and grains of rice were found at the highest dose and condition of reduction. These results demonstrate that reduction leads to solubilization of barium sulfate, thereby favoring greater mobility and bioavailability of this element.