Pesticide fate in tropical wetlands of Brazil: an aquatic microcosm study under semi-field conditions

A contamination of off-site aquatic environments with pesticides has been observed in the tropics, yet only sparse information exists about pesticide fate in such ecosystems. The objective of our semi-field study was to elucidate the fate of alachlor, atrazine, chlorpyrifos, endosulfan, metolachlor, profenofos, simazine, and trifluralin in the aqueous environment of the Pantanal wetland (MT, Brazil). To this aim, water and water/sediment microcosms of two sizes (0.78 and 202 l) were installed in the outskirts of this freshwater lagoon environment and pesticide dissipation was monitored for up to 50 d after application. The physical-chemical water conditions that developed in the microcosms were reproducible among field replicates for both system sizes. Pesticide dissipation was substantially enhanced for most pesticides in small microcosms relative to the large ones (reduced DT(50) by a factor of up to 5.3). The presence of sediment in microcosms led to increased persistence of chlorpyrifos, endosulfan, and trifluralin in the test systems, while for polar pesticides (alachlor, atrazine, metolachlor, profenofos, and simazine) a lesser persistence was observed. Atrazine, simazine, metolachlor, and alachlor were identified as the most persistent pesticides in large water microcosms (DT(50) > or = 47 d); in large water/sediment systems endosulfan beta, atrazine, metolachlor, and simazine showed the slowest dissipation (DT(50) > or = 44 d). A medium-term accumulation in the sediment of tropical ecosystems can be expected for chlorpyrifos and endosulfan isomers (11-35% of applied amount still extractable at 50 d after application). We conclude that the persistence of the studied pesticides in aquatic ecosystems of the tropics is not substantially lower than during summer in temperate regions.     

A safety culture maturity model for petrochemical companies in Brazil

A framework to measure safety culture maturity in the Brazilian oil and gas companies was formulated based on the model of Hudson (2001). Following a review of the safety culture literature, a questionnaire was designed to measure five aspects of organisational safety indicative of five levels of cultural maturity. The questionnaire was completed by the safety managers of 23 petrochemical companies based in Camacari, Bahia, Brazil and they were interviewed one month later. The reliability of the questionnaire was tested by asking the same questions in an interview and comparing the results (alternate forms reliability). The correlation coefficients between the questionnaire and interview scores on each dimension ranged from r = 0.7 to 0.9, demonstrating good reliability of the measures used. The research findings demonstrated that the 23 companies studied showed characteristics of different levels of safety culture maturity. Most scores were at the level of proactive. The model of Hudson (2001) and the revised framework and questionnaire were found to be practical to use, making it possible to identify levels of safety culture maturity in the context of the Brazilian petrochemical industry.     

Adsorption Kinetics of Dyes in Single and Binary Systems Using Cyanoguanidine-Crosslinked Chitosan of Different Deacetylation Degrees

The crosslinking of chitosan with cyanoguanidine shows some advantages, such as the improved the stability in acid solutions and the decrease of adsorbent cost. In this work, cyanoguanidine-crosslinked chitosan and pure chitosan were prepared to apply in the adsorption of Food Yellow 4 (FY4) and Food Blue 2 (FB2), in single and binary systems. Effects of pH and deacetylation degree (DD) of chitosan in adsorption were evaluated. The adsorbents were characterized by Fourier transform infrared spectroscopy and scanning electron microscopy. The kinetic data were analyzed by pseudo-first order, pseudo-second order and Avrami models. The conditions of pH 3 and DD 95% were the more suitable to reach the highest adsorption capacities in all experimental assays. Under these conditions, the adsorption capacities for FY4 were approximately of 392 and 200 mg g^?1 and, for FB2 were approximately of 370 and 184 mg g^?1, respectively, in the single and binary systems. The Avrami model was suitable to represent the kinetic curves in all conditions, and the highest adsorption capacities were found for FY4 in binary aqueous system, being for the pure chitosan of 229 mg g^?1 and crosslinked chitosan of 218 mg g^?1. The Langmuir and extended Langmuir models presented a good fit to the equilibrium data in both systems. It was found that, the chitosan crosslinked with cyanoguanidine improved the chemical stability of chitosan as adsorbent.     

Development,validation and matrix effect of a QuEChERS method for the analysis of organochlorine pesticides in fish tissue

This study aims to develop and validate a method to determine OCPs in fish tissues, minimizing the consumption of sample and reagents, by using a modified QuEChERS along with ultrasound, d-SPE and gas chromatography with an electron capture detector (GC-ECD), refraining the pooling. Different factorial designs were employed to optimize the sample preparation phase. The validation method presented a recovery of around 77.3% and 110.8%, with RSD lower than 13% and the detection limits were between 0.24 and 2.88 μgkg^?1, revealing good sensitiveness and accuracy. The method was satisfactorily applied to the analysis of tissues from different species of fish and OCPs residues were detected. The proposed method was shown effective to determine OCPs low concentrations in fish tissues, using small sample mass (0.5 g), making the sample analyses viable without the need for grouping (pool).     

The use of multivariate statistical methods for optimization of the surface water quality network monitoring in the Paraopeba river basin,Brazil

This study sought to evaluate and propose adjustments to the water quality monitoring network of surface freshwaters in the Paraopeba river basin (Minas Gerais, Brazil), using multivariate statistical methods. A total of 13,560 valid data were analyzed for 19 water quality parameters at 30 monitoring sites, over a period of 5 years (2008–2013). The cluster analysis grouped the monitoring sites in eight groups based on similarities of water quality characteristics. This analysis made it possible to detect the most relevant monitoring stations in the river basin. The principal components analysis associated with non-parametric tests and the analysis of violation of the standards prescribed by law, allowed for identifying the most relevant parameters which must be maintained in the network (thermotolerant coliforms, total manganese, and total phosphorus). The discharge of domestic sewage and industrial wastewater, that from mining activities and diffuse pollution from agriculture and pasture areas are the main sources of pollution responsible for the surface water quality deterioration in this basin. The BP073 monitoring site presents the most degraded water quality in the Paropeba river basin. The monitoring sites BP094 and BP092 are located geographically close and they measure similar water quality, so a possible assessment of the need to maintain only one of the two in the monitoring network is suggested. Therefore, multivariate analyses were efficient to assess the adequacy of the water quality monitoring network of the Paraopeba river basin, and it can be used in other watersheds.     

Using multivariate techniques as a strategy to guide optimization projects for the surface water quality network monitoring in the Velhas river basin,Brazil

Surface water quality monitoring networks are usually deployed and rarely re-evaluated with regard to their effectiveness. In this sense, this work sought to evaluate and to guide optimization projects for the water quality monitoring network of the Velhas river basin, using multivariate statistical methods. The cluster, principal components, and factorial analyses, associated with non-parametric tests and the analysis of violation to the standards set recommended by legislation, identified the most relevant water quality parameters and monitoring sites, and evaluated the sampling frequency. Thermotolerant coliforms, total arsenic, and total phosphorus were considered the most relevant parameters for characterization of water quality in the river basin. The monitoring sites BV156, BV141, BV142, BV150, BV137, and BV153 were considered priorities for maintenance of the network. The multivariate statistical analysis showed the importance of a monthly sampling frequency, specifically the parameters considered most important.     

Does fungicide application in vineyards induce resistance to medical azoles in Aspergillus species?

This study assessed if the use of sterol demethylase inhibitor fungicides in vineyard production can induce resistance to azoles in Aspergillus strains and if it can induce selection of resistant species. We also tried to identify the Aspergillus species most prevalent in the vineyards. Two vineyards from northern Portugal were selected from “Vinhos Verdes” and “Douro” regions. The vineyards were divided into plots that were treated or not with penconazole (PEN). In each vineyard, air, soil, and plant samples were collected at three different times. The strains of Aspergillus spp. were isolated and identified by morphological and molecular techniques. We identified 46 Aspergillus section Nigri, eight Aspergillus fumigatus, seven Aspergillus lentulus, four Aspergillus wentii, two Aspergillus flavus, two Aspergillus terreus, one Aspergillus calidoustus, one Aspergillus westerdijkiae, one Aspergillus tamarii, and one Eurotium amstelodami. Aspergillus strains were evaluated for their susceptibility to medical azoles used in human therapy (itraconazole, posaconazole, and voriconazole) and to agricultural azoles (PEN) used in the prevention and treatment of plant diseases. The isolates showed moderate susceptibility to voriconazole. We did not observe any decrease of susceptibility to the medical azoles tested throughout the testing period in any of the treated plots, although some of the resistant species were isolated from there.     

Mercury concentration in fish from Piracicaba River (Minas Gerais, Brazil)

Mercury emissions from some upstream gold mining areas and recent findings of high natural Hg levels in sediments motivated studies on the Hg cycle in the Minas Gerais state. The study presents the total mercury amount found in Geophagus brasiliensis' muscular tissue (wet weight) and sediments from Piracicaba River. Mercury was analyzed using acid digestion followed by determination of total mercury by cold vapour atomic absorption spectrophotometry. This study was also complemented with the analysis of the limnological parameters (water temperature, conductivity, total dissolved solids, suspended particles, pH, dissolved oxygen, maximum depth, photic index and total carbon). The mercury concentration in sediments samples was higher than the mercury concentration in muscular tissue of fish. The lowest Hg level measured in fish was 0.0147 microg g( - 1), while the highest was 0.101 microg g( - 1). In the sediment samples, the lowest and highest levels were 0.02 microg g( - 1) and 0.16 microg g( - 1), respectively. The Hg concentrations in fish and sediment were both under the maximum limit permitted by the World Health Organization.     

3,4-Dimethylpyrazol phosphate effect on nitrous oxide, nitric oxide, ammonia, and carbon dioxide emissions from grasslands

Intensively managed grasslands are potentially a large source of NH3, N2O, and NO emissions because of the large input of nitrogen (N) in fertilizers. Addition of nitrification inhibitors (NI) to fertilizers maintains soil N in ammonium form. Consequently, N2O and NO losses are less likely to occur and the potential for N utilization is increased, and NH3 volatilization may be increased. In the present study, we evaluated the effectiveness of the nitrification inhibitor 3,4-dimethylpyrazol phosphate (DMPP) on NH3, N2O, NO, and CO2 emissions following the application of 97 kg N ha(-1) as ammonium sulfate nitrate (ASN) and 97 kg NH4+ -N ha(-1) as cattle slurry to a mixed clover-ryegrass sward in the Basque Country (northern Spain). After slurry application, 16.0 and 0.7% of the NH4+ -N applied was lost in the form of N2O and NO, respectively. The application of DMPP induced a decrease of 29 and 25% in N2O and NO emissions, respectively. After ASN application 4.6 and 2.8% of the N applied was lost as N2O and NO, respectively. The application of DMPP with ASN (as ENTEC 26; COMPO, Münster, Germany) unexpectedly did not significantly reduce N2O emissions, but induced a decrease of 44% in NO emissions. The amount of NH4+ -N lost in the form of NH3 following slurry and slurry + DMPP applications was 7.8 and 11.0%, respectively, the increase induced by DMPP not being statistically significant. Levels of CO2 emissions were unaffected in all cases by the use of DMPP. We conclude that DMPP is an efficient nitrification inhibitor to be used to reduce N2O and NO emissions from grasslands.     

Monitoring heavy metal concentrations in leachates from a forest soil subjected to repeated applications of sewage sludge

The aim of the study was to establish whether the repeated application of sewage sludge to an acid forest soil (Dystric Cambisol) would lead to short-term groundwater contamination. Sludge was applied at four loading rates (0, 2.4, 17 and 60 Mg ha⁻¹) in two consecutive years and leachates were analysed. Heavy metal inputs to soils at the lowest dose were below EC regulations but, at higher doses, limits for Zn, Cd, Cr and Ni were exceeded. Repeated application of sludge at 60 Mg ha⁻¹ resulted in significantly (P < 0.05) higher concentrations of Zn, Cd, Cr and Ni in the leachates than with other treatments. The drinking water standards for Cd and Ni were surpassed in all treatments. Control plots were contaminated by groundwater flow despite the existence of buffer zones between plots. This complicated interpretation of the results, highlighting the importance of careful design of this type of experiment.