RESUMO
Diuron and Irgarol are common antifouling biocides used in paints to prevent the attachment and growth of fouling organisms on ship hulls and other submerged structures. Concerns about their toxicity to non-target aquatic organisms have led to various restrictions on their use in antifouling paints worldwide. Previous studies have shown the widespread presence of these substances in port areas along the Brazilian coast, with a concentration primarily in the southern part of the country. In this study, we conducted six sampling campaigns over the course of 1 year to assess the presence and associated risks of Diuron and Irgarol in water collected from areas under the influence of the Maranhão Port Complex in the Brazilian Northeast. Our results revealed the absence of Irgarol in the study area, irrespective of the sampling season and site. In contrast, the mean concentrations of Diuron varied between 2.0 ng L-1 and 34.1 ng L-1 and were detected at least once at each sampling site. We conducted a risk assessment of Diuron levels in this area using the risk quotient (RQ) method. Our findings indicated that Diuron levels at all sampling sites during at least one campaign yielded an RQ greater than 1, with a maximum of 22.7, classifying the risk as "high" based on the proposed risk classification. This study underscores the continued concern regarding the presence of antifouling biocides in significant ports and marinas in Brazilian ports, despite international bans.
Assuntos
Incrustação Biológica , Desinfetantes , Poluentes Químicos da Água , Diurona/análise , Desinfetantes/análise , Brasil , Estuários , Poluentes Químicos da Água/análise , Monitoramento Ambiental/métodos , Triazinas/análiseRESUMO
Organotin-based (OTs: TBT and TPT) antifouling paints have been banned worldwide, but recent inputs have been detected in tropical coastal areas. However, there is a lack of studies evaluating the toxicity of both legacy and their substitute antifouling booster biocides (e.g., Irgarol and diuron) on neotropical species. Therefore, the acute toxicity of four antifouling biocides (TBT, TPT, Irgarol, and diuron) was investigated using the marine planktonic organisms Acartia tonsa and Mysidopsis juniae, the estuarine tanaid Monokalliapseudes schubarti (water exposure), and the burrowing amphipod Tiburonella viscana (spiked sediment exposure). Results confirmed the high toxicity of the OTs, especially to planktonic species, being about two orders of magnitude higher than Irgarol and diuron. Toxic effects of antifouling compounds were observed at levels currently found in tropical coastal zones, representing a threat to planktonic and benthic invertebrates. Furthermore, deterministic PNECmarine sediment values suggest that environmental hazards in tropical regions may be higher due to the higher sensitivity of tropical organisms. Since regulations on antifouling biocides are still restricted to a few countries, more ecotoxicological studies are needed to derivate environmental quality standards based on realistic scenarios. The present study brings essential contributions regarding the ecological risks of these substances in tropical and subtropical zones.
Assuntos
Anfípodes , Incrustação Biológica , Desinfetantes , Poluentes Químicos da Água , Animais , Diurona/toxicidade , Diurona/análise , Plâncton , Desinfetantes/toxicidade , Desinfetantes/análise , Incrustação Biológica/prevenção & controle , Poluentes Químicos da Água/toxicidade , Poluentes Químicos da Água/análise , Organismos Aquáticos , Monitoramento Ambiental , Triazinas/análiseRESUMO
This review summarized booster biocides studies from Latin America and the Caribbean during the last two decades. Studies were focused on six countries, with most of them in Brazil. In water and sediment, diuron and Irgarol were the most abundant and frequent biocides, probably due to their former intense use. Antifouling paint particles were also reported and had mainly DCOIT, which is currently the most used booster biocide. Toxicity of individual booster biocides was tested in laboratory, and most effects were related to chlorothalonil, DCOIT, dichlofluanid, and Irgarol, including, but not limited to DNA damage, fertility decrease, and mortality at different trophic levels. This review highlighted the need for further studies on environmental occurrence of booster biocides in Latin America and Caribbean associated to ecotoxicological studies. Such information is essential to determine the potential ecological risks and to create directives regarding safe limits of booster biocides in aquatic systems.
Assuntos
Incrustação Biológica , Desinfetantes , Poluentes Químicos da Água , América Latina , Desinfetantes/toxicidade , Desinfetantes/análise , Incrustação Biológica/prevenção & controle , Poluentes Químicos da Água/toxicidade , Poluentes Químicos da Água/análise , Região do Caribe , Pintura , Diurona/análise , Triazinas/análise , Monitoramento AmbientalRESUMO
Natural pH values in coastal waters vary largely among locations, ecosystems, and time periods; still, there is an ongoing acidification trend. In this scenario, more acidic pH values can alter bioavailability of organic contaminants, to organisms. Despite this, interactive effects between pH and chemical substances are not usually considered in Ecological Risk Assessment protocols. This study investigated the effects of pH on the toxicity of a hydrophobic organic compound on a benthic community using a microcosm experiment setup to assess the response of nematode assemblages exposed to environmentally relevant concentrations of Irgarol at two natural pH conditions. Estuarine nematode assemblages were exposed to two concentrations of Irgarol at pH 7.0 and 8.0 for periods of 7 and 35 days. Lower diversity of nematode genera was observed at the highest tested Irgarol concentration (1281 ± 65 ng.g-1). The results showed that the effects of Irgarol contamination were independent of pH variation, indicating no influence of acidification within this range on the toxicity of Irgarol to benthic meiofauna. However, the results showed that estuarine nematode assemblages are impacted by long-term exposure to low (but naturally occurring) pHs. This indicates that estuarine organisms may be under naturally high physiological pressure and that permanent changes in the ecosystem's environmental factors, such as future coastal ocean acidification, may drive organisms closer to the edges of their tolerance windows.
Assuntos
Nematoides , Poluentes Químicos da Água , Animais , Ecossistema , Monitoramento Ambiental , Concentração de Íons de Hidrogênio , Água do Mar , Triazinas/análise , Poluentes Químicos da Água/análise , Poluentes Químicos da Água/toxicidadeRESUMO
Melamine is a compound commonly used in the manufacturing of plastic and flame retardant products, but due to its solubility on water and high nitrogen content, it is also used to adulterate milk to mask adulteration by dilution in protein content tests. This work proposes a quick method using excitation-emission matrix (EEM) fluorescence spectroscopy and second-order calibration methods (PARAFAC and U-PLS/RBL) for the identification and quantification of melamine in milk. The proposed method uses a single clean-up step with acetic acid, resulting in a quick, low-cost, and environmentally friendly procedure, in agreement with green chemistry principles. Both PARAFAC and U-PLS/RBL were capable of detecting melamine in milk above 120.6 and 146.5 ppm respectively, adequate for adulterations above 2% in volume, with RMSEPs of 68.6 and 81.9 ppm, respectively.
Assuntos
Leite , Triazinas , Animais , Calibragem , Contaminação de Alimentos/análise , Leite/química , Espectrometria de Fluorescência , Triazinas/análiseRESUMO
Although booster biocides (Irgarol, diuron, chlorothalonil, dichlofluanid, and DCOIT) have been detected in sediments along the Brazilian coastal areas, the risk associated to their occurrence and levels is still unknown. Thus, the ecological risk of booster biocides to sediment-dwelling organisms from the Brazilian coast was assessed using a risk characterization approach through the Risk Quotient (Measured environmental concentration (MEC)/Predicted no effect concentrations (PNECs)). Sedimentary PNECs for Irgarol, diuron, chlorothalonil and DCOIT were derived based on published ecotoxicological data from both freshwater and marine studies, while a NORMAN methodology was used to derived it for dichlofluanid. Results showed that DCOIT, diuron, Irgarol, chlorothalonil, and dichlofluanid can pose high risk on 47%, 35%, 15%, 1% and 1%, respectively, of the 113 Brazilian sites appraised. Considering the trend of expansion of navigation/maritime activities, DCOIT may worsen its impact over the coastal areas of Brazil, especially ports, but also ship/boatyards, marinas, and maritime traffic zones. The present study is an important contribution to support advance on policy formulation concerning booster biocides worldwide, particularly considering the lack of regulation on the use of antifouling biocides in Brazil.
Assuntos
Desinfetantes , Poluentes Químicos da Água , Brasil , Desinfetantes/análise , Desinfetantes/toxicidade , Diurona/análise , Diurona/toxicidade , Monitoramento Ambiental , Sedimentos Geológicos , Medição de Risco , Triazinas/análise , Triazinas/toxicidade , Poluentes Químicos da Água/análiseRESUMO
Biopurification systems are useful in the management of pesticide residues and provide an option to dispose wastewaters of agricultural origin derived from pesticide application practices. The analysis of pesticide residues in the biopurification system biomixture is necessary to determine whether the removal of the target compounds occurs with reliable results. In this study, the pesticide extraction methodology was optimized and validated in a biomixture composed of coconut fiber, compost and soil, to determine a total of 43 molecules, distributed among triazines (10), triazoles (13) and organophosphates (20) using liquid chromatography coupled to a triple quadrupole mass spectrometer. For the validation, the parameters of linearity, matrix effect, limit of determination (LOD), specificity, selectivity, precision, trueness and robustness in the proposed biomixture were evaluated. The analyses of those parameters revealed satisfactory results of the method for most of the compounds, with the exception of diclorvos and ciromazine, for which the development of an alternative method is recommended. Once the extraction methodology was validated, the removal of eight molecules was assayed in a biopurification system used for the simultaneous treatment of a mixture of pesticide commercial formulations. Although most of the compounds were at least partially removed, none of them was eliminated at levels below the LOD. The removal pattern of ametryn, atrazine, chlorpyrifos, malathion and terbutryn was comparable to those obtained in other efficient biomixtures, and the highly recalcitrant triadimenol was eliminated; nonetheless, tebuconazole and diazinon were not significantly removed.
Assuntos
Biodegradação Ambiental , Resíduos de Praguicidas/análise , Triazinas/análise , Triazóis/análise , Poluentes Químicos da Água/análise , Cromatografia Líquida/métodos , Limite de Detecção , Modelos Lineares , Resíduos de Praguicidas/química , Resíduos de Praguicidas/isolamento & purificação , Reprodutibilidade dos Testes , Espectrometria de Massas em Tandem/métodos , Triazinas/química , Triazinas/isolamento & purificação , Triazóis/química , Triazóis/isolamento & purificação , Poluentes Químicos da Água/química , Poluentes Químicos da Água/isolamento & purificaçãoRESUMO
This research aimed at implementing and validating a method for analysis of pesticide residues in crops. QuEChERS extraction method with PSA purification was used following analyzes by gas chromatography with tandem mass spectrometry in Selected Reaction Monitoring mode. A short run method was successfully developed for the determination of 41 pesticides, confirmed by two precursor-products for each analyte. The calibration curve for each analyte was linear at concentration range from 1 to 500 µg kg-1 with correlation coefficients higher than 0.99, low limits of detection (0.03 - 10.22 µg kg-1) and satisfactory precision. The developed method was used to investigate apples; mangos; strawberries; cucumbers and tomatoes from the Rio de Janeiro Food Distribution Center (CEASA).Most of the targeted pesticides (78%) were below detection limits. Apple and strawberry presented the highest pesticide contamination levels, many of which are not authorized by tthe Brazilian national regulatory agency (ANVISA).
Assuntos
Produtos Agrícolas/química , Cromatografia Gasosa-Espectrometria de Massas/métodos , Resíduos de Praguicidas/análise , Piretrinas/análise , Extração em Fase Sólida/métodos , Espectrometria de Massas em Tandem/métodos , Triazinas/análise , Brasil , Cucumis sativus/química , Contaminação de Alimentos/análise , Fragaria/química , Solanum lycopersicum/química , Malus/química , Mangifera/químicaRESUMO
Considering the increase in agricultural production in Tocantins and in the use of pesticides for such production, this work investigates the levels of pesticide residues in different environmental compartments (soil, sediment, and water samples) of the Formoso River in the state of Tocantins, Brazil. The presence of pesticides of the triazine, triazole, and benzimidazole classes was analyzed by UHPLC-MS/MS from April 2018 to February 2019. There were four quarterly collections in the dry and rainy periods. The active principles were not found in sediment samples. In soil samples, only the active ingredients tebuconazole and propiconazole were found in the third collection campaign. The active ingredients amethryn, atrazine, carbendazim, epoxiconazole, metconazole, propiconazole, simazine, tebuconazole, and tetraconazole were found in water samples from Formoso River at concentrations of up to 0.286 µg L-1 (atrazine). Although the substances are in low concentrations, we cannot assume that this toxicity is low considering that the risk of a certain pesticide depends on levels and exposure time. Therefore, the action of substances external to the natural environment always threatens biodiversity.
Assuntos
Benzimidazóis/análise , Praguicidas/análise , Triazinas/análise , Triazóis/análise , Poluentes Químicos da Água/análise , Brasil , Cromatografia Líquida de Alta Pressão , Monitoramento Ambiental , Sedimentos Geológicos/análise , Resíduos de Praguicidas/análise , Rios/química , Poluentes do Solo/análise , Espectrometria de Massas em TandemRESUMO
A method for the simultaneous determination of three commonly used coccidiostats in chicken liver was developed, comprising a multi-residue QuEChERS (quick, easy, cheap, effective, rugged and safe) extraction step, and a liquid chromatography-ultra violet-fluorescence (HPLC-UV/FL) analysis. The QuEChERS extraction was optimized using an experimental design approach that includes a screening step to obtain the critical variables, an optimization step using multiple response surface analysis and the calculation of a desirability parameter. The optimized method was validated with fortified samples, reaching an average recovery of 91% and an overall precision of 5.5% (mean of three analytes at three levels). Limits of detection calculated on fortified samples were 20 µg kg-1 for lasalocid, 15 µg kg-1 for nicarbazin and 120 µg kg-1 for diclazuril. These values resulted at least one order of magnitude lower than the maximum allowed residue limit (MRL) of the studied coccidiostats for chicken liver.