Thiamethoxam in soybean seed treatment: Plant bioactivation and hormesis, besides whitefly control?

Amid concerns on the myriad of existing chemical stressors in agroecosystems, pesticides and particularly neonicotinoid insecticides are in the forefront. Despite that, these neurotoxic compounds remain the dominant group of insecticides in worldwide use with the added versatility of use in seed coatings. Such use sparks environmental concerns counterbalanced by their reported insecticidal efficacy and potential plant bioactivation. Nonetheless, this alleged double benefit and interconnection expected with neonicotinoids has been little explored particularly when the whole plant phenology is considered. Regardless of the expected efficacy against targeted insect pest species, like whiteflies, neonicotinoids may spark dual effect on plants - negative at higher concentrations, positive at low concentrations, which is consistent with the hormesis phenomenon that may be expressed as a plant bioactivation. This effect may also cascade to the targeted insect species, what deserves attention. Therefore, soybean seeds treated with increasing concentrations of the neonicotinoid thiamethoxam were followed throughout their development in greenhouse, recording the plant response and yield, besides their effect in whiteflies (Bemisia tabaci MEAM1). Thiamethoxam application was correlated to leaf contents of thiamethoxam and its metabolite clothianidin. Plant hormesis was found for leaf area and root growth, but not for other plant morphological or physiological parameters, nor plant yield. The insecticide concentration-dependency compromised whitefly population growth without evidence of cascading any plant-mediated hormesis to the insects. Thus, although plant hormesis was recognized with thiamethoxam in treated soybean seeds in relevant parameters, no evidence of plant bioactivation was observed to justify its use with such a secondary objective, nor did this hormesis impair whitefly control.

Environmentally Relevant Concentrations of Atrazine and Ametrine Induce Micronuclei Formation and Nuclear Abnormalities in Erythrocytes of Fish.

A rapid and sensitive method using liquid chromatography coupled with mass spectrometry triple quadrupole direct aqueous injection for analysis of atrazine and ametrine herbicides in surface waters was developed. According to the validation method, water samples from six different locations in the Piracicaba River were collected monthly from February 2011 to January 2012 and injected into a liquid chromatographer/dual mass spectrometer without the need for sample extraction. The method was validated and shown to be precise and accurate; limits of detection and quantification were 0.07 and 0.10 µg L(-1) for atrazine and 0.09 and 0.14 µg L(-1) for ametrine. During the sampling period, concentrations of atrazine ranged from 0.11 to 1.92 µg L(-1) and ametrine from 0.25 to 1.44 µg L(-1). After analysis of the herbicides, Danio rerio were exposed a range of concentrations found in the river water to check the induction of micronuclei and nuclear abnormalities (NAs) in erythrocytes. Concentrations of atrazine and ametrine >1.0 and 1.5 µg L(-1), respectively, induced MN formation in D. rerio. Ametrine was shown to be more genotoxic to D. rerio because a greater incidence of NAs was observed compared with atrazine. Therefore, environmentally relevant concentrations of atrazine and ametrine found in the Piracicaba River are dangerous to the aquatic biota.

Liquid chromatography-electrospray ionization tandem mass spectrometry and dynamic multiple reaction monitoring method for determining multiple pesticide residues in tomato.

A quick and sensitive liquid chromatography-electrospray ionization tandem mass spectrometry method, using dynamic multiple reaction monitoring and a 1.8-µm particle size analytical column, was developed to determine 57 pesticides in tomato in a 13-min run. QuEChERS (quick, easy, cheap, effective, rugged, and safe) method for samples preparations and validations was carried out in compliance with EU SANCO guidelines. The method was applied to 58 tomato samples. More than 84% of the compounds investigated showed limits of detection equal to or lower than 5 mg kg(-1). A mild (<20%), medium (20-50%), and strong (>50%) matrix effect was observed for 72%, 25%, and 3% of the pesticides studied, respectively. Eighty-one percent of the pesticides showed recoveries ranging between 70% and 120%. Twelve pesticides were detected in 35 samples, all below the maximum residue levels permitted in the Brazilian legislation; 15 samples exceeded the maximum residue levels established by the EU legislation for methamidophos; and 10 exceeded limits for acephate and four for bromuconazole.

Estudo do inseticida carbofurano em solo e sedimento de área de produção de arroz irrigado e controle do gorgulho aquático Oryzophagus oryzae, Taubaté, São Paulo, Brasil / Study of the insecticide carbofuran in the soil and sediment of paddy rice fields with control of the weevil Oryzophagus oryzae, in Taubaté, state of São Paulo, Brazil

Resíduos do inseticida e nematicida carbofurano e de seu principal metabólito 3-hidroxicarbofurano foram averiguados em tabuleiros de arroz irrigado e em áreas adjacentes para controle do gorgulho aquático da espécie Oryzophagus oryzae Lima, 1936. As amostras foram coletadas no período de 6/9/1999 a 4/5/2000 e analisadas por cromatografia a líquido de alta eficiência (HPLC) utilizando-se detector de fluorescência. Não foram detectados resíduos de carbofurano e de seu metabólito 3-hidroxicarbofurano dentro dos limites de determinação do método.

The presence of residues of the insecticide and nematicide carbofuran, used for weevil (Oryzophagus oryzae Lima 1936) control, and its principal metabolite 3-hydroxycarbofuran were evaluated in soil and sediment plots from paddy rice fields and adjacent areas. The samples were analyzed using a high-performance liquid chromatography and fluorescence detector. Carbofuran and 3-hydroxycarbofuran residues were not detected in any sample in amounts above the method’s detection threshold.

Pesticide residues in some commodities: dietary risk for children.

The objective of this study was to identify pesticides found in infants' and children's diets. Fruits and vegetables were collected from 2004 to 2007 and analyzed using a multiresidue method. The most frequently detected residues were procymidone, captan, chlorpyrifos and chlorothalonil. Twenty-eight percent of the samples contained pesticide residues. Strawberry, pear, apple, peach and tomato contained pesticide levels of concern. Twenty-one pesticides were found with the estimated total mean daily intake greater than the acceptable daily intake for four of the pesticides. Residues of carbaryl, diazinon and methidathion exceeded regulatory levels in (apple, strawberry, and orange).

Structure-function relationship of new crotamine isoform from the Crotalus durissus cascavella.

In this work we isolated a novel crotamine like protein from the Crotalus durissus cascavella venom by combination of molecular exclusion and analytical reverse phase HPLC. Its primary structure was:YKRCHKKGGHCFPKEKICLPPSSDLGKMDCRWKRK-CCKKGS GK. This protein showed a molecular mass of 4892.89 Da that was determined by Matrix Assisted Laser Desorption Ionization Time-of-flight (MALDI-TOF) mass spectrometry. The approximately pI value of this protein was determined in 9.9 by two-dimensional electrophoresis. This crotamine-like protein isolated here and that named as Cro 2 produced skeletal muscle spasm and spastic paralysis in mice similarly to other crotamines like proteins. Cro 2 did not modify the insulin secretion at low glucose concentration (2.8 and 5.6 mM), but at high glucose concentration (16.7 mM) we observed an insulin secretion increasing of 2.7-3.0-fold than to control. The Na+ channel antagonist tetrodoxin (6 mM) decreased glucose and Cro 2-induced insulin secretion. These results suggested that Na+ channel are involved in the insulin secretion. In this article, we also purified some peptide fragment from the treatment of reduced and carboxymethylated Cro 2 (RC-Cro 2) with cyanogen bromide and protease V8 from Staphylococcus aureus. The isolated pancreatic beta-cells were then treated with peptides only at high glucose concentration (16.7 mM), in this condition only two peptides induced insulin secretion. The amino acid sequence homology analysis of the whole crotamine as well as the biologically-active peptide allowed determining the consensus region of the biologically-active crotamine responsible for insulin secretion was KGGHCFPKE and DCRWKWKCCKKGSG.

Active and inactive renin in the plasma of the snake Bothrops jararaca.

1. Complementing the work of Gervitz R. K., Hiraichi E., Fichman M. and Lavras A. A. C. Comp. Biochem. Physiol. 86A, 503-507 (1987), conditions have been established for measuring plasma renin activity (PRA) of the venomous snake Bothrops jararaca (Bj). 2. It corresponded to 115.9 +/- 11.5 ng equivalents of angiotensin II (AII) per ml of plasma (N = 13). 3. PRA did not increase when Bj plasma was submitted to acid-cryo-trypsin Bitis arietans venom activation of inactive renin. 4. This may indicate either absence of inactive renin in this plasma or lack of its activation, due to the already demonstrated (Nahas L., Kamiguti A. S., Betti F., Martins I. S. S. and Rodrigues M. I., Comp. Biochem. Physiol. 69A, 739-743, 1981; Prezoto B. C., Hiraichi E., Abdalla F. M. F. and Picarelli Z. P., Comp. Biochem. Physiol. 99C, 135-139, 1991) absence of factor XII.