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Seasonal factors driving biochemical biomarkers in two fish species from a subtropical reservoir in southern Brazil: An integrated approach
2020
Blank do Amaral, Aline Monique | Kuhn de Moura, Letícia | de Pellegrin, Dionatan | Guerra, Luciana Joner | Cerezer, Felipe Osmari | Saibt, Nathália | Prestes, Osmar Damian | Zanella, Renato | Loro, Vania Lucia | Clasen, Barbara
Reservoirs are lentic man-made waterbodies resulting from river damming processes. Pollutants coming from adjacent areas can accumulate in the water and sediment of these modified freshwater environments. Fish are often found in reservoirs occupying several trophic niches. Biochemical biomarkers are early warning signals of environmental disturbance to an organism. It is essential to understand how pollutants, abiotic variables and biochemical biomarker responses behave throughout the seasons to implement biomonitoring programs. Loricariichthys anus and Geophagus brasiliensis were collected, and abiotic variables were seasonally measured for one year, at six sampling sites in Passo Real reservoir, in a subtropical region of Southern Brazil. Biochemical biomarkers were analyzed in four tissues of both fish species, as well as metal and pesticide concentrations in the reservoir’s water and sediment. Redundancy analysis (RDA) was carried out to find the temporal relationship between biomarkers and environmental variables. RDA has clearly shown the separation of seasons for both species. Azoxystrobin, simazine and propoxur were the pesticides mostly contributing to the variation, whereas metals had lesser contribution to it. Seasonality appears to be the main factor explaining biomarkers’ variability. PERMANOVA has confirmed the effect of temperature and dissolved oxygen on biomarkers of both fish species. Thus, it is hard to differentiate if the fluctuation in biomarkers’ responses only reflects the normal state of organisms or it is a biological consequence from negative effects of fish exposure to several types of pollution (sewage, pesticides, and fertilizers) entering this aquatic system. In this study, to circumvent the seasonality issue on biomonitoring, the analysis of biomarkers on these fish should not be carried out in organs directly affected by temperature (such as liver and gills), or during reproduction periods (mainly in Spring).
Show more [+] Less [-]Toxicity of carbamates to the brine shrimp Artemia salina and the effect of atropine, BW284c51, iso-OMPA and 2-PAM on carbaryl toxicity
1999
Barahona, M.V. | Sanchez-Fortun, S. (Departamento de Toxicologia y Farmacologia, Facultad de Veterinaria, Universidad Complutense de Madrid, 28040 Madrid (Spain))
Evaluation of pesticide residues in commercial Swiss beeswax collected in 2019 using ultra-high performance liquid chromatographic analysis
2022
Marti, Joshua N. G. | Kilchenmann, Verena | Kast, Christina
The aim of this study was to determine residue levels of pesticides in Swiss commercial beeswax. Foundation samples were collected in 2019 from nine commercial manufacturers for analysis of 21 pesticides using ultra-high performance liquid chromatography. Individual samples showed the variability and residue ranges and pooled samples represented the average annual residue values of the Swiss production. In total, 17 pesticides were identified and 13 pesticides were quantified. They included 13 acaricides and/or insecticides, two fungicides as well as a synergist and a repellent. The means calculated from individual samples were similar to the average annual residue values for most tested pesticides. Mean values of 401, 236, 106 and 3 μg·kg⁻¹ were obtained for the beekeeping-associated contaminants coumaphos, tau-fluvalinate, bromopropylate and N-(2,4-Dimethylphenyl)-formamide (DMF; breakdown product of amitraz), respectively. For the other pesticides, the mean values were 203 μg·kg⁻¹ (synergist piperonyl butoxide), 120 μg·kg⁻¹ (repellent N,N-Diethyl-3-methylbenzamide, DEET), 19 μg·kg⁻¹ (chlorfenvinphos) and 4 μg·kg⁻¹ ((E)-fenpyroximate), while the means for acrinathrin, azoxystrobin, bendiocarb, boscalid, chlorpyrifos, flumethrin, permethrin, propoxur and thiacloprid were below the limit of quantification (< LOQ). Individual samples contained from seven to 14 pesticides. The ranges of values for coumaphos and piperonyl butoxide (from 14 to 4270 μg·kg⁻¹; from 6 to 1555 μg·kg⁻¹, respectively) were larger as compared to the ranges of values for DEET and tau-fluvalinate (from < LOQ to 585 μg·kg⁻¹; from 16 to 572 μg·kg⁻¹, respectively). In conclusion, the most prominent contaminants were the pesticides coumaphos and tau-fluvalinate, which are both acaricides with previous authorization for beekeeping in Switzerland, followed by piperonyl butoxide, a synergist to enhance the effect of insecticides.
Show more [+] Less [-]Degradation of the insecticide propoxur by electrochemical advanced oxidation processes using a boron-doped diamond/air-diffusion cell
2017
Guelfi, Diego Roberto Vieira | Gozzi, Fábio | Sirés, Ignasi | Brillas, Enric | Machulek, Amílcar Jr | de Oliveira, Silvio César
A solution with 0.38 mM of the pesticide propoxur (PX) at pH 3.0 has been comparatively treated by electrochemical oxidation with electrogenerated H₂O₂ (EO-H₂O₂), electro-Fenton (EF), and photoelectro-Fenton (PEF). The trials were carried out with a 100-mL boron-doped diamond (BDD)/air-diffusion cell. The EO-H₂O₂ process had the lowest oxidation ability due to the slow reaction of intermediates with •OH produced from water discharge at the BDD anode. The EF treatment yielded quicker mineralization due to the additional •OH formed between added Fe²⁺ and electrogenerated H₂O₂. The PEF process was the most powerful since it led to total mineralization by the combined oxidative action of hydroxyl radicals and UVA irradiation. The PX decay agreed with a pseudo-first-order kinetics in EO-H₂O₂, whereas in EF and PEF, it obeyed a much faster pseudo-first-order kinetics followed by a much slower one, which are related to the oxidation of its Fe(II) and Fe(III) complexes, respectively. EO-H₂O₂ showed similar oxidation ability within the pH range 3.0–9.0. The effect of current density and Fe²⁺ and substrate contents on the performance of the EF process was examined. Two primary aromatic products were identified by LC-MS during PX degradation.
Show more [+] Less [-]Part I: Temporal and spatial distribution of multiclass pesticide residues in lake waters of Northern Greece: application of an optimized SPE-UPLC-MS/MS pretreatment and analytical method
2014
Kalogridi, Eleni-Chrysoula | Christophoridis, Christophoros | Bizani, Erasmia | Drimaropoulou, Garyfallia | Fytianos, Konstantinos
The present work describes the application of an analytical procedure, utilizing ultra performance liquid chromatography (UPLC) coupled with mass spectrometry instrumentation, for the determination of 253 multiclass pesticides, classified in six different groups. Solid phase extraction was applied for the isolation and pre-concentration of target compounds in water samples. Surface waters of the lakes located in Northern Greece (Volvi, Doirani, and Kerkini), were collected in two time periods (fall/winter 2010 and spring/summer 2011) and analyzed, applying the developed analytical methods. Spatial distribution of detected pesticides was visualized using interpolation methods and geographical information systems (GIS). Pesticides with maximum concentrations were amitrole, propoxur, simazine, chlorpyrifos, carbendazim, triazophos, disulfoton-sulfone, pyridaben, sebuthylazine, terbuthylazine, atrazine, atrazine-desethyl, bensulfuron-methyl, metobromuron, metribuzin, rotenone, pyriproxyfen, and rimsulfuron. In Lake Kerkini, mainly carbamates and triazines were determined at elevated concentrations, near the coastal point of the NW side of the lake. Seasonal variations were strong among the applied pesticide classes and determined concentrations, indicating the contribution of pesticide application patterns and rainfall. Lake Doirani exhibited organophosphate pesticides at higher concentrations mainly at coastal points, while triazines emerged as the main pollutant during spring sampling. Lake Volvi exhibited the highest pesticide concentrations, mostly triazines and ureas at the central part of the lake. The occurrence of extreme values and nonconstant seasonal variations indicated that the concentrations were increased disproportionately during the second sampling, as a result of the varying contribution of pollution sources right after the application period. In all cases, the total concentration of pesticides increased during the second sampling period.
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