Efeitos tardios dos praguicidas organoclorados no homem

Procurou-se relacionar as informações disponíveis sobre os organoclorados e os efeitos crônicos provocados pela exposição. Os compostos organoclorados são os praguicidas mais persistentes já fabricados. Embora sejam geralmente eficientes no controle das pragas, são importantes poluentes ambientais e potenciais causas de problemas de saúde para o homem, tendo sido proibidos ou controlados na maioria dos países. Com poucas exceções, os efeitos tardios desses compostos sobre a saúde humana são difíceis de detectar, em função de dificuldades metodológicas e da extrapolação dos resultados. A genotoxicidade está entre os mais sérios dos possíveis danos causados por esses compostos e merece atenção especial, devido à natureza irreversível do processo. Outro ponto a ser considerado é o aumento na incidência de alterações no desenvolvimento do trato reprodutivo e na fertilidade masculina observada nas últimas décadas provavelmente decorrente do aumento da exposição intra-uterina a compostos estrogênicos e anti-androgênicos, como os organoclorados.

ORGANOCHLORINE PESTICIDE-RESIDUES IN HUMAN-MILK IN THE RIBEIRAO-PRETO REGION, STATE OF SAO-PAULO, BRAZIL

Thirty-seven samples of human milk (colostrum) from donors living in the Ribeirao Preto region were analyzed to determine the levels of organochlorine pesticide residues. Donors were classified into two groups, i.e., occupationally exposed and non-exposed to pesticides. Other factors such as age, previous lactations, race, smoking habit, occupation, family income and educational level were also considered. Analysis was performed by preliminary lipid extraction followed by fractional partition on a column and finally by gas chromatography with an electron capture detector. Lindane was found in 32% of the samples in amounts of less than 0.001 mg/kg; heptachlor was found in 65% of the samples at mean levels of 0.001 mg/kg, i.e., a level five-fold lower than that established by FAO/WHO (1970) for cow's milk. Aldrin and endrin were not detected in any of the samples. Dieldrin was detected in only one sample at a level of 0.038 mg/kg, which is considered high. DDT and DDE amounts are reported as total DDT and at least one of these compounds was present in every sample. Amounts detected in donors occupationally exposed to pesticides ranged from 0.008 to 0.455 mg/kg (mean, 0.149 mg/kg), i.e., three times the limit established by FAO/WHO (1970), while values for donors who had not been exposed ranged from 0.002 to 0.072 mg/kg (mean, 0.025 mg/kg), i.e., half the limit. Considering the level of acceptable daily intake proposed by FAO/WHO (1973), lactents ingested 1% of the acceptable intake of lindane (all donors), 30% of the acceptable intake of heptachlor (all donors), 60% of the acceptable intake of DDT (non-exposed donors), and 3.7 times the acceptable intake of DDT (exposed donors). Comparing the present results with those obtained 10 years ago, the total DDT level in human milk is decreasing in this part of the country. The mean amount of organochlorine residues in non-exposed women's milk was one of the lowest levels among those recorded in the literature. DDT levels of occupationally exposed women's milk were comparable with those reported for developed countries and lower than those detected in Latin American countries. When the results of this survey are considered in relation to the advantages of breast-feeding, the risk-benefit balance is still favorable to breast-feeding. However, given the lack of long-term epidemiological studies, undesirable or harmful long-lasting effects cannot be excluded.

Extraction and clean-up procedure for analysis of organochlorine pesticide residues in ethoxylated lanolin

In the present study an evaluation was made of a method for the determination of organochlorine pesticide residues in ethoxylated lanolin. Samples were homogenized with Celite, transferred to chromatographic columns, prepacked with silica gel deactivated to 10%. The pesticide elution was processed with n-hexane-dichloromethane and the concentrated eluate was analyzed using gas-liquid chromatography (GC) with electron capture detection (ECD). The composition of the elution solvent was a significant factor for the recovery of the pesticides. Mean recoveries obtained for fortified samples ranged from 87 to 94% for p,p'-DDE, dieldrin, endrin, p,p'-DDD and p,p'-DDT. Optimization of the experimental conditions resulted in a small-scale method that combines extraction and cleanup in a single step. (C) 2000 Elsevier B.V. S.A. All rights reserved.

Assessment of aquatic plants in the reservoirs of AES-Tiete and development of an integrated control model for the most important species

The general objective of this work was to develop a monitoring and management model for aquatic plants that could be used in reservoir cascades in Brazil, using the reservoirs of AES-Tiete as a study case. The investigations were carried out at the reservoirs of Barra-Bonita, Bariri, Ibitinga, Promissao, and Nova-Avanhandava, located in the Tiete River Basin; Agua Vermelha, located in the Grande River Basin; Caconde, Limoeiro, and Euclides da Cunha, which are part of the Pardo River Basin; and the Mogi-Guacu reservoir, which belongs to the Mogi-Guacu River basin. The main products of this work were: development of techniques using satellite-generated images for monitoring and planning aquatic plant control; planning and construction of a boat to move floating plant masses and an airboat equipped with a DGPS navigation and application flow control system. Results allowed to conclude that the occurrence of all types of aquatic plants is directly associated with sedimentation process and, consequently, with nutrient and light availability. Reservoirs placed at the beginning of cascades are more subject to sedimentation and occurrence of marginal, floating and emerged plants, and are the priority when it comes to controlling these plants, since they provide a supply of weeds for the other reservoirs. Reservoirs placed downstream show smaller amounts of water-suspended solids, with greater transmission of light and occurrence of submerged plants.

Determination of carbofuran and 3-hydroxycarbofuran residues in coconut water by solid-phase extraction and liquid chromatography with UV detection

A simple method was developed to determine carbofuran and 3-hydroxycarbofuran in coconut water. The procedure involved solid-phase extraction using C-18 cartridges with acetonitrile for elution. The analysis of these compounds was carried out by liquid chromatography with UV detection at 275 nm using a gradient solvent system. The method was validated with fortified samples at different concentration levels (0.01-2.5 mu g/mL). Average recoveries ranged from 81 to 95% with relative standard deviation between 1.6 and 12.5%. Each recovery analysis was repeated at least five times. Detection limits ranged from 0.008 to 0.01 mu g/mL. The analytical procedure was applied to coconut water samples from palms submitted to treatment with commercial formulation under field conditions.

On-line extraction and determination of carbofuran in raw milk by direct HPLC injection on an ISRP column

A method has been developed for extraction and determination of carbofuran in milk. The method involved direct injection of raw milk on to a human serum albumin dimethyloctyl-silica gel (HSA-Cs) column and the use of 80:20 (v/v) 0.01 M phosphate buffer pH 5.5 - acetonitrile as mobile phase. UV spectrophotometric detection was performed at 220 nm. Identification was based on retention time. Quantification was performed by automatic peak-area determination and was calibrated by use of an external standard.

Pesticide residues in plums from field treatment to the drying process

The fate of three pesticides (vinclozolin, dimethoate, cyproconazole) in plums, from field treatment to the drying process, was studied. Only vinclozolin showed measurable residue concentrations at harvest, while dimethoate was completely degraded after two weeks and cyproconazole was present at negligible levels just after treatment. During the drying process into prunes, the residues were not reduced during the fruit washing stage, but the drying stage led to complete elimination of vinclozolin residues.

Determination of herbicides and a metabolite in human urine by liquid chromatography-electrospray ionization mass spectrometry

A method was developed to determine simazine, atrazine and their metabolite, 2-chloro-4,6-diamino-1,3,5-triazine, in urine. The presence of these herbicides in urine may reflect possible exposure to pesticides. Sample preparation involved protein precipitation and solid-phase extraction. The samples were analyzed by high-performance liquid chromatography-mass spectrometry. The detection limits were 0.4 mug/l and the analytes have a linear response in the interval 6-800 mug/l. The precision of the method was reflected in the RSD of <2.4% for the herbicides studied. Based on the detectable herbicide levels from spiked urine samples collected from unexposed volunteers, this method can be used to determine the low levels necessary for establishing reference values of the selected herbicides and the metabolite. (C) 2002 Elsevier B.V. B.V. All rights reserved.

Metodologia rápida e eficiente para análise de pesticidas organoclorados em fubá

A rapid and efficient analytical method is presented for the quantitative analysis of 10 organochlorine pesticides in corn meal. The extraction and clean up steps are combined into one step by transferring the sample to a chromatographic column prepacked with alumina and silica gel. The pesticides are eluted with n-hexane-dichloromethane 9:1 (v/v) and the extracts analized by gas-liquid chromatography with electron capture detection, the average recoveries were between 78% and 98% and the detection limits were between 1 and 5 ng/g.

Persistence of insecticide residues in olives and olive oil

The decay rate of six insecticides (azinphos methyl, diazinon, dimethoate, methidathion, parathion methyl, and quinalphos) used to control Dacus oleae was studied. Degradation of pesticides showed pseudo-first-order kinetics with correlation coefficients ranging between -0.936 and -0.998 and half-lives between 4.3 days for dimethoate and 10.5 days for methidathion. Residues in olive oil were greater than on olives, with a maximum concentration factor of 7. Dimethoate was the only pesticide with lower residues in the oil than on the fruits. Olive washing affects pesticide residues ranging from no reduction to a 45% decrease. During 8 months of storage of the olive oil, diazinon, dimethoate, parathion methyl, and quinalphos did not show any remarkable difference, while methidathion and azinphos methyl showed a moderate decrease.

Comparison of different clean-up procedures for the determination of N-methylcarbamate insecticides in vegetable matrices by high-performance liquid chromatography with UV detection

Several clean-up procedures which included the use of glass chromatography columns (silica gel, alumina, Florisil, silanized Celite-charcoal), Sep-Pak cartridges and standard solutions were compared for the determination of the following N-methylcarbamate (NMC) insecticides: aldicarb, carbaryl, carbofuran, methomyl and propoxur. According to recovery results of the compounds after elution in a glass column, the most efficient systems employed 4.6% deactivated alumina and a silanized Celite-charcoal (4:1) as adsorbents, using dichloromethane-methanol (99:1) and toluene-acetonitrile (75:25) mixtures, respectively, as binary eluents. The recoveries of the compounds studied varied from 84 to 120%. Comparable recoveries (75-100%) for Sep-Pak cartridges in normal phase (NH2, CN) and reversed phase (C-8) were observed. Different temperatures were tested during the concentration step in a rotary evaporator, and we verified a strong influence of this parameter on the stability of some compounds, such as carbofuran and carbaryl. Recovery studies employing the best clean up procedures were performed at the Brazilian agricultural level in potato and carrot samples; Validation methodology of the US Food and Drug Administration was adapted for the N-methylcarbamate analysis. Their recoveries ranged between 79 and 93% with coefficients of variation of 2.3-8%. (C) 1998 Elsevier B.V. B.V.

Evaluation of a highly sensitive amperometric biosensor with low cholinesterase charge immobilized on a chemically modified carbon paste electrode for trace determination of carbamates in fruit, vegetable and water samples

A highly sensitive amperometric biosensor for determination of carbamate pesticides directly in water, fruit and vegetable samples has been evaluated, electrochemically characterized and optimized. The biosensor strip was fabricated in screen printed technique on a ceramic support using silver-based paste for reference electrode, and platinum-based paste for working and auxiliary electrodes. The working electrode was modified by a layer of carbon paste mixed with cobalt(II) phthalocyanine and acetylcellulose. Cholinesterase (ChE) enzymes with low enzymatic charge were immobilized on this layer. The operational simplicity of the biosensor consists in that a small drop (similar to 50 mu l) of substrate or sample is deposited on a horizontally positioned biosensor strip representing the microelectrochemical cell. The working potential of the biosensor was 370 mV versus Ag/AgI on a ship reference electrode preventing the interference of electroactive species which are oxidable at more positive potentials. The biosensor was applied to investigate the degradation of two reference ChE inhibitors in freeze dried water under different storage conditions and for direct determination of some N-methylcarbamates (NMCs) in fruit and vegetable samples at ppb concentration levels without any sample pretreatment. A comparison of the obtained results for the total carbamate concentration was done against those obtained using HPLC measurements. (C) 1999 Elsevier B.V. B.V. All rights reserved.

Catechol biosensing using a nanostructured layer-by-layer film containing Cl-catechol 1,2-dioxygenase

dThe detection of aromatic compounds from pesticides and industrial wastewater has become of great interest, since these compounds withstand chemical oxidation and biological degradation, accumulating in the environment. In this work, a highly sensitive biosensor for detecting catechol was obtained with the immobilization of Cl-catechol 1,2-dioxygenase (CCD) in nanostructured films. CCD layers were alternated with poly(amidoamine) generation 4 (PAMAM G4) dendrimer using the electrostatic layer-by-layer (LbL) technique. Circular dichroism (CD) measurements indicated that the immobilized CCD preserved the same conformation as in solution. The thickness of the very first CCD layers in the LbL films was estimated at ca. 3.6 nm, as revealed by surface plasmon resonance (SPR). PAMAM/CCD 10-bilayer films were employed in detecting diluted catechol solutions using either an optical or electrical approach. Due to the mild immobilization conditions employed, especially regarding the pH and ionic strength of the dipping solutions, CCD remained active in the films for periods longer than 3 weeks. The optical detection comprised absorption experiments in which the formation of cis-cis muconic acid, resulting from the reaction between CCD and catechol, was monitored by measuring the absorbance at 260 nm after film immersion in catechol solutions. The electrical detection was carried out using LbL films deposited onto gold-interdigitated electrodes immersed in aqueous solutions at different catechol concentrations. Using impedance spectroscopy in a broad frequency range (1Hz-1kHz), we could detect catechol in solutions at concentrations as low as 10(-10) M. (c) 2005 Elsevier B.V. All rights reserved.

Diuron lacks promoting potential in a rat liver bioassay

The promoting activity of the herbicide Diuron was evaluated in a medium-term rat liver carcinogenesis bioassay that uses as endpoint immunohistochemically identified glutathione S-transferase positive (GST-P+) foci. Male Wistar rats were allocated to the following groups: G1 to G6 were initiated for liver carcinogenesis by a single dose of diethylnitrosamine (DEN, 200 mg/kg) while groups G7 and G8 received only 0.9% NaCl (DEN vehicle). From the 2nd week animals were fed a basal diet (G1 and G7) or a diet added with Diuron at 125, 500, 1250, 2500 and 2500 ppm (G2 to G5 and G8, respectively) or 200 ppm Hexaclorobenzene (HCB; G6). The animals were submitted to 70% partial hepatectomy at the 3rd week and sacrificed at the 8th week. The herbicide did not alter ALT or creatinine serum levels. No conspicuous GST-P+ foci development was registered in non-initiated rats fed Diuron at 2500 ppm. While DEN-initiated animals fed Diuron at 1250 or 2500 ppm developed mild centrilobular hypertrophy, DEN-initiated HCB-fed animals showed severe liver centrilobular hypertrophy and significant GST-P+ foci development. These findings indicate that the medium-term assay adopted in this study does not reveal any liver carcinogenesis initiating or promoting potential of Diuron in the rat.

Eucalyptus ESTs related to genes for oxidative stress

Oxidative stress generating active oxygen species has been proved to be one of the underlying agents causing tissue injury after the exposure of Eucalyptus (Eucalyptus spp.) plants to a wide variety of stress conditions. The objective of this study was to perform data mining to identify favorable genes and alleles associated with the enzyme systems superoxide dismutase, catalase, peroxidases, and glutathione S-transferase that are related to tolerance for environmental stresses and damage caused by pests, diseases, herbicides, and by weeds themselves. This was undertaken by using the eucalyptus expressed-sequence database (https//forests.esalq.usp.br). The alignment results between amino acid and nucleotide sequences indicated that the studied enzymes were adequately represented in the ESTs database of the FORESTs project.