Identifying pesticide use patterns among flower growers to assess occupational exposure to mixtures

Objectives Exposure assessment to a single pesticide does not capture the complexity of the occupational exposure. Recently, pesticide use patterns analysis has emerged as an alternative to study these exposures. The aim of this study is to identify the pesticide use pattern among flower growers in Mexico participating in the study on the endocrine and reproductive effects associated with pesticide exposure. Methods A cross-sectional study was carried out to gather retrospective information on pesticide use applying a questionnaire to the person in charge of the participating flower growing farms. Information about seasonal frequency of pesticide use (rainy and dry) for the years 2004 and 2005 was obtained. Principal components analysis was performed. Results Complete information was obtained for 88 farms and 23 pesticides were included in the analysis. Six principal components were selected, which explained more than 70% of the data variability. The identified pesticide use patterns during both years were: 1. fungicides benomyl, carbendazim, thiophanate and metalaxyl (both seasons), including triadimephon during the rainy season, chlorotalonyl and insecticide permethrin during the dry season; 2. insecticides oxamyl, biphenthrin and fungicide iprodione (both seasons), including insecticide methomyl during the dry season; 3. fungicide mancozeb and herbicide glyphosate (only during the rainy season); 4. insecticides metamidophos and parathion (both seasons); 5. insecticides omethoate and methomyl (only rainy season); and 6. insecticides abamectin and carbofuran (only dry season). Some pesticides do not show a clear pattern of seasonal use during the studied years. Conclusions The principal component analysis is useful to summarise a large set of exposure variables into smaller groups of exposure patterns, identifying the mixtures of pesticides in the occupational environment that may have an interactive effect on a particular health effect.

Comparison of the insecticide susceptibilities of laboratory strains of Aedes aegypti and Aedes albopictus

A susceptible strain of Aedes albopictus derived from the Gainesville strain (Florida, USA) was established in our laboratory. The larvicidal efficacies of the neurotoxic insecticides temephos, permethrin and the pure cis and trans-permethrin isomers and the microbial insecticide Bacillus thuringiensis israelensis (Bti) against Ae. albopictus were estimated and compared to a susceptible strain of Aedes aegypti. The larvicidal effect of insect growth regulator pyriproxyfen was also evaluated in both mosquito strains. The median lethal concentration/median emergency inhibition values for Ae. aegypti and Ae. albopictus, respectively, were: temephos, 3.058 and 6.632 ppb, permethrin, 3.143 and 4.933 ppb, cis-permethrin, 4.457 and 10.068 ppb, trans-permethrin, 1.510 and 3.883 ppb, Bti, 0.655 and 0.880 ppb and pyriproxyfen, 0.00774 and 0.01642 ppb. Ae. albopictus was more tolerant than Ae. aegypti to all six larvicides evaluated. The order of susceptibility for Ae. aegypti was pyriproxyfen > Bti > trans-permethrin > temephos > permethrin > cis-permethrin and for Ae. albopictus was pyriproxyfen > Bti > trans-permethrin > permethrin > temephos > cis-permethrin. Because both species can be found together in common urban, suburban and rural breeding sites, the results of this work provide baseline data on the susceptibility of Ae. albopictus to insecticides commonly used for controlling Ae. aegypti in the field.

Extração em fase sólida (SPE) e micro extração em fase sólida (SPME) de piretróides em água

The pyrethroids bifenthrin, permethrin, cypermethrin and deltamethrin were extracted by solid phase extraction (SPE) and solid phase microextraction (SPME). The analysis were performed on a gas chromatograph with electron capture detection (GC-ECD). Octadecil Silano-C18, Florisil and Silica stationary phases were studied for SPE. Better results were obtained for Florisil which gave recoveries from 80% to 108%. Pyrethroids extraction by SPME showed a linear response and a detection limit of 10 pg ml-1. Although the data showed that the two extraction methods were able to isolate the pesticide residues from water samples, the best results were obtained by using SPME which is more sensitive, faster, cheeper, being a more useful technique for the analysis of pyrethroids in drinking water.

Desenvolvimento de métodos analíticos para determinação de agrotóxicos em sedimentos por cromatografia gasosa monodimensional e bidimensional abrangente com micro detector de captura de elétrons

The development of analytical methods for determination of eight pesticides of different chemical classes (trichlorfon, propanil, fipronil, propiconazole, trifloxystrobin, permethrin, difenoconazole and azoxystrobin) in sediments with gas chromatography-micro-electron capture detector (GC/µECD) and comprehensive two-dimensional gas chromatography with micro-electron capture detector (GCxGC/µECD) is described. These methods were applied to real sediment samples, and the best results were obtained using a 5% diphenyl-methylpolysiloxane column for 1D-GC. For GCxGC the same column was employed in the first dimension and a 50%-phenyl-methylpolysiloxane stationary phase was placed in the second dimension. Due to the superior peak capacity and selectivity of GCxGC, interfering matrix peaks were separated from analytes, showing a better performance of GCxGC.

Análise de agrotóxicos em água usando extração líquido-líquido com partição em baixa temperatura por cromatografia líquida de alta eficiência

This study optimized and validated the liquid-liquid extraction technique with partition at low temperature (LLE-PLT) for identification and quantification of four pesticides (chlorpyrifos, λ-cyhalothrin, permethrin, bifenthrin) in water samples. Analyses were performed by HPLC-UV. The technique was efficient for pesticide recovery with extraction exceeding 86%. Chromatographic response was linear for the four compounds in the 10-45 µg L-1 range, with correlation coefficients greater than 0.99. Limits of detection and quantitation were less than 3.5 µg L-1 and equal to 10 µg L-1, respectively. The proposed method was applied to 29 water samples from the Jaíba Project in northern Minas Gerais.

Associações entre o herbicida glyphosate e inseticidas na cultura da soja Roundup Ready®

Este trabalho teve o objetivo de avaliar os efeitos da associação do herbicida glyphosate com 10 inseticidas de diferentes grupos químicos sobre a cultura da soja Roundup Ready® (cultivar Monsoy 8585 RR®), o controle de plantas daninhas e o controle da lagarta-da-soja (Anticarsia gemmatalis). O experimento foi realizado em lavoura no município de Nova Xavantina - MT, no período de novembro de 2005 a abril de 2006, em solo classificado como Latossolo Vermelho distrófico. O delineamento experimental utilizado foi o de blocos ao acaso, em esquema fatorial 11 x 2, sendo os fatores constituídos por 11 tratamentos inseticidas [lambdacyhalothrin (3,75 g ha-1); permethrin (12,50 g ha-1); methamidophos (300,00 g ha-1); chlorpyriphos (240,00 g ha-1); acephate (150,00 g ha-1); endosulfan (175,00 g ha-1); methomyl (107,50 g ha-1); lufenuron (7,50 g ha-1); triflumuron (14,40 g ha-1); spinosad (24,00 g ha-1); e testemunha sem inseticida], com ou sem a adição (mistura em tanque) de 960 g e.a. ha-1 de glyphosate, formando 22 tratamentos, conduzidos em quatro repetições. Os tratamentos foram aplicados 30 dias depois da emergência da cultura. A mistura do herbicida glyphosate com o inseticida chlorpyriphos causou fitotoxicidade inicial à cultura da soja RR®. O controle das plantas daninhas Chamaesyce hirta, Alternanthera tenella, Euphorbia heterophylla e Cenchrus echinatus não foi afetado pelas misturas de glyphosate com todos os inseticidas avaliados. A adição do glyphosate à calda de aplicação prejudicou a eficiência inicial dos inseticidas methomyl, methamidophos, chlorpyriphos e acephate no controle de Anticarsia gemmatalis, porém incrementou o controle dessa praga quando associado aos inseticidas spinosad, lambdacyhalothrin e lufenuron. A combinação de glyphosate com os inseticidas methamidophos, chlorpyriphos, lufenuron, triflumuron e spinosad proporcionou os maiores níveis de produtividade de grãos da soja RR®.

Seletividade de cultivares de soja RR® submetidos a misturas em tanque de glyphosate + chlorimuron-ethyl associadas a óleo mineral e inseticidas

O uso de glyphosate para o controle de plantas daninhas em soja RR® apresenta características essenciais no conceito de praticabilidade. Entretanto, apesar de não permitido na legislação brasileira, tem-se aumentado a associação com outros herbicidas para manejo de espécies de difícil controle, assim como a sua mistura em tanque em combinação com inseticidas e adjuvantes. Com o objetivo de avaliar a seletividade de cultivares de soja RR® submetidos a misturas em tanque de formulações de glyphosate (Polaris®, Roundup Ready® e Roundup WG®) com chlorimuron-ethyl (Classic®), e suas associações com óleo mineral (Joint Oil®) e inseticidas novaluron (Gallaxy 100 EC®), permethrin (Piredan®) e methomyl (Lannate BR®), um experimento foi conduzido a campo na cidade de Maracaí-SP, na safra 2006/2007. O delineamento experimental utilizado foi o de blocos ao acaso, com quatro repetições, em esquema fatorial 16 x 4, sendo 16 as associações das misturas em tanque entre as formulações de glyphosate, óleo mineral e inseticidas e quatro cultivares: Monsoy 7210RR®, Monsoy 7979RR®, BRS 245RR® e CD 214RR®. Sintomas visuais de intoxicação inicial dos cultivares estudados foram caracterizados por clorose e encarquilhamento nas folhas para todas as misturas em tanque das formulações de glyphosate + chlorimuron-ethyl, associadas ou não ao óleo mineral e inseticidas novaluron, permethrin e methomyl. Todas as misturas em tanque não promoveram reduções significativas de produtividade para os cultivares Monsoy 7210RR®, Monsoy 7979RR® e BRS 245RR® e controlaram Ipomoea spp. com eficácia apenas satisfatória a partir dos 21 DAA (dias após aplicação).

Étude de la cinétique de biomarqueurs d’exposition à la perméthrine dans des conditions d’exposition réelles chez les travailleurs agricoles au Québec

La perméthrine fait partie de la famille des pyréthrinoïdes qui sont abondamment utilisés en agriculture. Le but de cette étude était d'obtenir des données sur la cinétique des biomarqueurs d'exposition à la perméthrine en condition réelle d'exposition chez les travailleurs agricoles. Douze travailleurs (un applicateur, un superviseur et dix cueilleurs) exposés à la perméthrine dans le cadre de leur emploi ont été recrutés dans une ferme maraichère de la Montérégie (Québec). Ils ont fourni toutes leurs urines sur une période de trois jours suivant le début des travaux dans un champ traité. Les trois principaux métabolites de la perméthrine, l'acide cis-/trans-3-(2,2-dichlorovinyle)-2,2-diméthylecyclopropane carboxylique (cis-/trans-DCCA) et l'acide 3-phénoxybenzoïque (3-PBA) ont été analysés par chromatographie liquide à ultra-haute performance couplée à la spectrométrie de masse à temps de vol. Pour l'applicateur, une augmentation progressive des valeurs d'excrétion a été observée avec un pic unique atteint environ 30 h après le début de l'exposition d'une durée de 3,5 h suivi d'une élimination avec une demi-vie de 8 h. Pour le superviseur et l'un des cueilleurs, les profils d'excrétion de trans-DCCA et de 3-PBA étaient compatibles avec de multiples entrées dans la zone traitée pendant la période d'échantillonnage accompagné d'une élimination rapide entre les épisodes d'exposition.L'applicateur aurait été exposé indirectement par contact main-bouche, alors que les autres travailleurs auraient été exposés par la voie cutanée. Pour une surveillance biologique adéquate, nous recommandons de mesurer deux biomarqueurs de la perméthrine, soit le trans-DCCA et le 3-PBA et de prendre un minimum de trois échantillons urinaires, un avant et deux pendant ou suivant la période d'exposition.

Étude de la cinétique des pesticides pyréthrinoïdes en conditions contrôlées et en milieu de travail dans un objectif de biosurveillance

Les pyréthrinoïdes sont des insecticides largement utilisés. La population générale y est exposée par l’alimentation tandis que les travailleurs agricoles y sont exposés lors de tâches diverses en champs. Leurs effets neurotoxiques, immunitaires et endocriniens potentiels en font des composés à surveiller pour assurer la santé de la population. La mesure de biomarqueurs d’exposition, qui consiste à quantifier la concentration dans l’organisme d’une substance ou de ses métabolites, permet d’estimer les doses absorbées. Les biomarqueurs peuvent également être des molécules répondant à un stress physiologique, identifiées comme des biomarqueurs d’effets. Pour raffiner les stratégies de biosurveillance de l’exposition, on se doit de bien connaître la toxicocinétique d’un xénobiotique; actuellement, les études de biosurveillance considèrent rarement la variabilité temporelle, intra-invidivuelle et inter-individuelle, qui pourrait influencer l’estimation de l’exposition. L’objectif de la thèse est donc d’appliquer une approche cinétique pour l’évaluation de l’exposition aux pyréthrinoïdes en conditions contrôlées et en milieu de travail. Dans un volet exploratoire, l’effet de cette exposition sur des changements métaboliques précoces a également évalué. Trois métabolites finaux (cis-DCCA, trans-DCCA et 3-PBA) de deux pyréthrinoïdes les plus utilisés, soient la perméthrine et la cyperméthrine, ont été mesurés dans le plasma et l’urine de six volontaires oralement exposés à une dose équivalente à la dose de référence. Une demi-vie moyenne (t½) d’élimination apparente du trans-DCCA, cis-DCCA et 3-PBA dans le plasma de 5,1, 6,9 et 9,2 h, respectivement, a été obtenue après exposition orale à la cyperméthrine, comparativement à 7,1, 6,2 et 6,5 h après exposition à la perméthrine. Dans l’urine, la demi-vie d'élimination apparente (t½) était de 6,3, 6,4 et 6,4 h pour le trans-DCCA, cis-DCCA et 3-PBA, respectivement, après administration de la cyperméthrine comparé à 5,4, 4,5 et 5,7 h après administration de la perméthrine. Les profils temporels étaient semblables suite à l’exposition à la cyperméthrine et perméthrine. Ensuite, une étude en milieu agricole a été réalisée avec la participation de travailleurs pour évaluer leur exposition et raffiner les stratégies de biosurveillance. La variabilité intra-individuelle dans les niveaux de biomarqueurs d’exposition chez plusieurs travailleurs était plus importante que la variabilité inter-individuelle. Les échantillons urinaires ont également été utilisés pour identifier des modifications du métabolome pouvant fournir de nouveaux biomarqueurs d’effets précoces. Chez les travailleurs, une augmentation de l'hippurate urinaire (p <0,0001) a été observée après exposition aux pyréthrinoïdes, un biomarqueur de la conjugaison de l’acide benzoïque. En conclusion, cette étude a permis de mieux documenter la cinétique de biomarqueurs d’exposition aux pyréthrinoïdes dans des conditions contrôlées et réelles afin de raffiner les stratégies de biosurveillance. Elle a aussi contribué à renseigner sur les niveaux d’exposition agricole québécois et sur les paramètres professionnels associés à une plus forte exposition. Ce projet s’insère dans une démarche d’analyse de risque en santé au travail.

Induction of cytochrome P-450 activity in individual Chironomus riparius Meigen larvae exposed to xenobiotics

Cytochrome P450 activity in individual Chironomus riparius larvae was measured using a microtiter plate adaptation of the ethoxyresorufin-O-deethylase (EROD) assay. The sensitivity of this biomarker was tested by exposing larvae to phenobarbital (0.5 and 1.0 mM) and permethrin (1 and 10 mug/g). Both chemicals induced EROD activity in C. riparius larvae by up to 1.58-fold with PB and 2.47-fold with permethrin. EROD induction was more pronounced after 48 h. The initially high EROD activity in the controls suggested that P450s are induced by stress. Feeding levels prior to exposure also had a significant effect on EROD activity. EROD activity compared to the control was highest when larvae were fed double the normal ration. These results indicate that EROD activity in individual C. riparius may be a useful biomarker to add to a suite of biomarkers for the detection of freshwater pollution. (C) 2002 Elsevier Science (USA). All rights reserved.

Knockdown resistance in pyrethroid-resistant horn fly (Diptera: Muscidae) populations in Brazil

To investigate the kdr (knockdown resistance) resistance-associated gene mutation and determine its frequency in pyrethroid-resistant horn fly (Haematobia irritans) populations, a total of 1,804 horn flies of 37 different populations from all Brazilian regions (North, Northeast, Central-West, Southeast, and South) were molecular screened through polymerase chain reaction (PCR). The kdr gene was not detected in 87.08% of the flies. However, the gene was amplified in 12.92% of the flies, of which 11.70% were resistant heterozygous and 1.22% were resistant homozygous. Deviation from Hardy-Weinberg equilibrium (HWE) was found only in 1 ranch with an excess of heterozygous. When populations were grouped by region, three metapopulations showed significant deviations of HWE (Central-West population, South population and Southeast population). This indicates that populations are isolated one from another and kdr occurrence seems to be an independent effect probably reflecting the insecticide strategy used by each ranch. Although resistance to pyrethroids is disseminated throughout Brazil, only 48% of resistant populations had kdr flies, and the frequency of kdr individuals in each of these resistant populations was quite low. But this study shows that, with the apparent exception of the Northeast region, the kdr mechanism associated with pyrethroid resistance occurs all over Brazil.

Decreased Sperm Motility in Rats Orally Exposed to Single or Mixed Pesticides

The Brazilian Agency of Sanitary Vigilance (ANVISA) conducted a study that demonstrated the presence of residues of several pesticides in fresh fruits and vegetables that were available for purchase by the general populace. In order to evaluate potential adverse health effects of low-level exposure to agrochemicals, the reproductive toxicity of the pesticides dicofol, dichlorvos, permethrin, endosulfan, and dieldrin was evaluated in rats dosed with these chemicals individually or as mixtures. Sixty male Lewis rats (6 wk old, 200 x g) were randomly allocated to 8 groups: (1) control group, received basal diet; (2) 5 groups designated a to e received the diet containing each pesticide individually, at the respective effective doses: lowest-observed-adverse-effect level (LOAEL) for dieldrin and endosulfan, lowest-observed-effect level (LOEL) for dicofol, and lowest effect level (LEL) for dichlorvos and permethrin, respectively, depending on the published data; (3) effective dose group, which received a mixture of pesticides added to basal diet at the respective doses reported to produce adverse effects; and (4) low dose group, which received a pesticide mixture added to the basal diet, where each pesticide was at its no-observed-effect level (NOEL). After 8 wk of treatment, reproductive parameters were evaluated. Sperm morphology, daily sperm production (DSP), sperm transit time through the epididymis, hormonal levels, and histopathological evaluation of testis and epididymis did not differ significantly among the groups. However, sperm motility was significantly decreased in animals that received a mixture of dieldrin, endosulfan, dicofol, dichlorvos, and permethrin, as well as in the group receiving dicofol alone. Exposure to the individual pesticides endosulfan, dichlorvos, and permethrin did not markedly affect sperm motility. The impairment of sperm motility in the mixture of pesticides at the NOEL level indicates that reproductive effects not seen with individual pesticides may occur in presence of several pesticides due to an additive effect. However, the pesticide mixtures did not appear to affect DSP or spermatogenesis despite reduced sperm motility.

A rapid, environmentally friendly, and reliable method for pesticide analysis in high-fat samples

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Macrophage activity and histopathology of the lymphohematopoietic organs in male Wistar rats orally exposed to single or mixed pesticides

The noxious effects of low or effective dose exposure to single or mixed pesticides on macrophage activity and the lymphohematopoietic organs were investigated. Male Wistar rats were orally exposed to dichlorvos, dicofol, endosulfan, dieldrin and permethrin, either as single or combined mixtures during a 28-day study containing eight groups: one group received a semipurified diet (non-treated); two groups received a semipurified diet containing low dose mixture (dieldrin 0.025 mg/kg, endosulfan, 0.6 mg/kg, dicofol 0.22 mg/kg, dichlorvos 0.23 mg/kg, permethrin 5 mg/kg) or an effective dose mixture (dichlorvos 2.3 mg/kg, dicofol 2.5 mg/kg, endosulfan 2.9 mg/kg, dieldrin 0.05 mg/kg and permethrin 25.0 mg/kg), respectively; the other five groups received a semipurified diet containing each single pesticide in effective doses. At sacrifice, the thymus, spleen, mesenteric lymph nodes, Payer's patches and bone marrow were removed for histological analysis. Peritoneal macrophages were obtained to determine the phagocytosis and spreading indexes and tumoral necrosis factor alpha (TNF-α), nitric oxide (NO) and H2O2 production. Exposure to pesticide mixtures did not alter the percentage of macrophage phagocytosis and spreading, TNF-α production or the NO and H2O2 release when compared to the non-treated group. Neither was there any apparent evidence that a pesticide mixture at low or effective doses altered the histological structure of the lymphohematopoietic organs. The findings indicate that short-term treatment with pesticide mixtures did not induce an apparent immunotoxic effect in male Wistar rats. © 2013 Copyright Taylor and Francis Group, LLC.

Efeitos cardiovasculares da exposição pré-natal à permetrina, isoladamente ou em associação à desnutrição intra-uterina, em ratos adultos e o comportamento materno nessas condições

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)