ABSTRACT
The expansion of agricultural activities causes habitat loss and fragmentation and the pollution of natural ecosystems through the intense use of pesticides, which may affect the populations of amphibian anurans that inhabit agricultural areas. The present study evaluated the in situ bioaccumulation of pesticides in a population of Leptodactylus luctator that occupies farmland in southern Brazil. We also compared the genotoxicity of L. luctator populations from farmland and forested areas in the same region. We analyzed the micronuclei and nuclear abnormalities of 34 adult anurans, 19 from farmland, and 15 from the forested area. We also assessed the presence of 32 pesticides in liver samples obtained from 18 farmland-dwelling anurans, using chromatographic analysis. We recorded significantly higher rates of nuclear abnormalities in the individuals from the farmland, in comparison with the forest. We detected nine pesticides in the liver samples, of which, deltamethrin was the most common and carbosulfan was recorded at the highest concentrations. The bioaccumulation of pesticides and the higher levels of genotoxic damage found in the anurans from agricultural areas, as observed in the present study, represent a major potential problem for the conservation of these vertebrates, including the decline of their populations and the extinction of species.
Subject(s)
Pesticides , Animals , Anura , Bioaccumulation , Brazil , DNA Damage , EcosystemABSTRACT
Monitoring of triphenyltin (TPhT) in the environment, particularly to control its misuse in agriculture, is of great importance because of its high toxicity. In this work, methods for determination of TPhT residues in surface water and soil samples by liquid chromatography with tandem mass spectrometry (LC-MS/MS) were developed and validated. Different sample volumes and pH and elution solvent types and volumes were evaluated for solid phase extraction (SPE) of TPhT in surface water samples. The optimized conditions were 500 mg sorbent Strata C18-E, 100 mL of the sample, pH adjusted to 9.0 and 1 mL of methanol containing acetic acid as the eluent. For a 10 g soil sample, the extraction was established using a modified QuEChERS method with 10 mL of acidified acetonitrile followed by a clean-up step by dispersive solid phase extraction (dSPE) with C18. A full factorial 23 design of experiments was applied to optimize the sample preparation method for soil samples. Practical method limits of quantification were 0.1 µg L-1 and 10 µg kg-1 for surface water and soil samples, respectively. Satisfactory accuracy, with recoveries from 86 to 107% for surface water and 72 to 87% for soil samples, as well as good precision, with an overall relative standard deviation (RSD) from 3 to 8% was observed. The validated methods were applied to real samples and some residues of TPhT were found, especially in soil samples (30 to 190 mg kg-1), indicating the suitability for routine analysis.
ABSTRACT
The use of pesticides has been associated with the increase of productivity of crops and control of vectors that cause diseases. However, excessive use of these compounds can cause human health and environmental problems, especially regarding to water resources. In this work, a method for multiresidue determination of 62 pesticides in surface water using the rotating disk sorptive extraction (RDSE) technique for sample preparation and ultra-high-performance liquid chromatography with tandem mass spectrometry (UHPLC-MS/MS) for analysis was optimized and validated. The parameters time and rotational disk velocity for the extraction step, types and amounts of sorbents, sample pH, ionic strength, time and velocity of the rotating disk in the desorption step, as well different desorption solvents were evaluated. The best results were obtained using 50mL of sample, acidified at pH 2.0, and 2.5g of sodium chloride. The selected velocity of rotation in the extraction step was 1600rpm for 80min. Inside the disk cavity, a small amount (20mg) of the polymeric sorbent Oasis® HLB was used. The desorption step was performed immerging the disk in 3mL of methanol and rotating the disk at 1600rpm for 60min. Procedural calibration curves showed linearity between 0.05 or 0.1-2µgL-1, with r2>0.99 for all compounds. The method presented practical limit of quantification of 0.05 or 0.1µgL-1 and suitable accuracy and precision, with recoveries from 70.1 to 119.9% and RSD≤20% for the levels 0.05, 0.1, 0.5 and 2µgL-1. The validated method was applied to surface water samples from different river and residues of atrazine, azoxystrobin, clomazone, difenoconazole, epoxiconazole, propoxur, simazine and tebuconazole were found in the range of 0.06-0.35µgL-1. The results indicate that the proposed method is suitable for the determination of pesticide residues in surface water, allowing an easy and simultaneously preparation of several samples with low material consumption.
