Biosensor based on multi-walled carbon nanotubes paste electrode modified with laccase for pirimicarb pesticide quantification

This study focused on the development of a sensitive enzymatic biosensor for the determination of pirimicarb pesticide based on the immobilization of laccase on composite carbon paste electrodes. Multi- walled carbon nanotubes(MWCNTs)paste electrode modified by dispersion of laccase(3%,w/w) within the optimum composite matrix(60:40%,w/w,MWCNTs and paraffin binder)showed the best performance, with excellent electron transfer kinetic and catalytic effects related to the redox process of the substrate4- aminophenol. No metal or anti-interference membrane was added. Based on the inhibition of laccase activity, pirimicarb can be determined in the range 9.90 ×10- 7 to 1.15 ×10- 5 molL 1 using 4- aminophenol as substrate at the optimum pH of 5.0, with acceptable repeatability and reproducibility (relative standard deviations lower than 5%).The limit of detection obtained was 1.8 × 10-7 molL 1 (0.04 mgkg 1 on a fresh weight vegetable basis).The high activity and catalytic properties of the laccase- based biosensor are retained during ca. one month. The optimized electroanalytical protocol coupled to the QuEChERS methodology were applied to tomato and lettuce samples spiked at three levels; recoveries ranging from 91.0±0.1% to 101.0 ± 0.3% were attained. No significant effects in the pirimicarb electro- analysis were observed by the presence of pro-vitamin A, vitamins B1 and C,and glucose in the vegetable extracts. The proposed biosensor- based pesticide residue methodology fulfills all requisites to be used in implementation of food safety programs.

Analysis of pesticide residues in strawberries and soils by GC-MS/MS, LC-MS/MS and two-dimensional GC-timeof- flight MS comparing organic and integrated pest management farming

This study analysed 22 strawberry and soil samples after their collection over the course of 2 years to compare the residue profiles from organic farming with integrated pest management practices in Portugal. For sample preparation, we used the citrate-buffered version of the quick, easy, cheap, effective, rugged, and safe (QuEChERS) method. We applied three different methods for analysis: (1) 27 pesticides were targeted using LC-MS/MS; (2) 143 were targeted using low pressure GC-tandem mass spectrometry (LP-GC-MS/MS); and (3) more than 600 pesticides were screened in a targeted and untargeted approach using comprehensive, two-dimensional gas chromatography time-of-flight mass spectrometry (GC × GC-TOF-MS). Comparison was made of the analyses using the different methods for the shared samples. The results were similar, thereby providing satisfactory confirmation of both similarly positive and negative findings. No pesticides were found in the organic-farmed samples. In samples from integrated pest management practices, nine pesticides were determined and confirmed to be present, ranging from 2 μg kg−1 for fluazifop-pbutyl to 50 μg kg−1 for fenpropathrin. Concentrations of residues in strawberries were less than European maximum residue limits.

The fast atom bombardment mass spectrometric analysis of the carbamate pesticide carbaryl

The carbamate pesticide, carbaryl, was quantitatively studied using fast atom bombardment mass spectrometry (FAB-MS). Mass spectra were obtained in the positive ion-mode using both 2-nitrophenyloctyl ether (NPOE) and 3-nitrobenzyl alcohol (NBA) as matrix liquids. The sample was applied by three different techniques; simple mixing, solvent mixing and surface precipitation. Smaller volumes of matrix liquid were found to produce more favourable ion currents. Detection limits were largely independent of the matrix or application technique used. The relationship between ion current and the mass of analyte was found to be intricately related to the choice of matrix liquid.

Biochemical effects of the pesticide Chlorpyrifos on the fish Oreochromis mossambicus (Peters)

Man uses a variety of synthetic material for his comfortable materialistic life. Thus human interactions may become harmful for various terrestrial and aquatic lives. This is by contaminating their habitat and by becoming a threat to organisms itself. Thus the application and dispersal of several organic pollutants can lead to the development of several mutated forms of the species when exposed to sublethal concentrations of the pollutants. Otherwise, a decrease in number or extinction of these exposed species from earth's face may happen. Pesticides, we use for the benefit of crop yield, but its persistence may become havoc to non-target organism. Pesticides reaching a reservoir can subsequently enter the higher trophic levels. Organophosphorus compounds have replaced all other pesticides, due to its acute toxicity and non-persistent nature.Hence the present study has concentrated on the toxicity of the largest market-selling and multipurpose pesticide, chlorpyrifos on the commonly edible aquatic organism, fish. The euryhaline cichlid Oreochromis mossambicus was selected as animal model. The study has concentrated on investigating biochemical parameters like tissue-specific enzymes, antioxidant and lipid-peroxidation parameters, haematological and histological observations and pesticide residue analysis.Major findings of this work have indicated the possibility of aquatic toxicity to the fish on exposure to the insecticide chlorpyrifos. The insecticide was found as effective to induce structural alteration, depletion in protein content, decrease in different metabolic enzyme levels and to progress lipid peroxidation on a prolonged exposure of 21 days. The ion-transport mechanism was found to be adversely affected. Electrophoretic analysis revealed the disappearance of several protein bands after 21days of exposure to chlorpyrifos. Residue, analysis by gas chromatography explored the levels of chlorpyrifos retaining on the edible tissue portions during exposure period of 21days and also on a recovery period of 10 days.

Paddy Field Cyanobacteria : Diversity and Pesticide Tolerance

School of Environmental Studies, Cochin University of Science and Technology

The influence of organophosphorus pesticide-methylparathion on protein, lipid metabolism and detoxifying enzymes in rohu (Labeo rohita)

Methylparathion (MP) is an organophosphorus insecticide used world wide in agriculture due to its high activity against a broad spectrum of insect pests. The aim of the study is to understand the effect of methylparathion on the lipid peroxidation, detoxifying and antioxidant enzymes namely catalase (CAT), glutathione peroxidase (GPx), superoxide dismutase (SOD), glutathione Stransferase (GST), total reduced glutathione (GSH), lipid peroxidation (LPO), acetylcholinesterase (AChE) and disease diagnostic marker enzymes in liver, sarcoplasmic (SP) and myofirbirllar (MF) proteins in muscles, lipids and histopathlogical changes in various organs of Labeo rohita of size 75 i 6g at lethal and sublethal level of exposure. The probit analysis showed that the lethal concentration (LC 50%) for 24, 48, 72 and 96h were 15.5mg/L, 12.3mg/L, 11.4mg/L and 10.2mg/L respectively which is much higher compared to the LC50 for juvenile fish. The LPO level and GST activity increased five folds and two folds respectively on exposure to methylparathion at 10.2 mg/L and the level of the enzymes increased, on sub lethal exposure beyond 0.25mg/L. AChE activity was inhibited by 74% at a concentration of 1.8mg/L and 90% at 5.4mg/L. The disease diagnostic marker enzymes AST, ALT, ALP and LDH increased by about 2, 3 ,3 and 2 folds respectively at pesticide concentration of 10.2mg/L when compared to control. On sub lethal exposure, however the enzymes did not show any significant changes up to 0.5mg/L. At a concentration of 10.2 mg/L, there was a three fold increase in myofibrillar proteins while the increase in sarcoplasmic protein was above 1.5 fold. On sub lethal exposure, significant alteration was noticed up to 30 days up to 1mg/L of methylparathion concentration. Further exposure up to 45 days increased sarcoplasmic proteins (upto 0.5mg/L). ln the case of myofibrillar proteins, noticeable changes were observed at 1mg/L concentration right from 15th day. The cholesterol content in brain tissues increased by about 27% at methylparathion concentration of 5.4 mglL. However at 0.25mg/L sub lethal concentration, no significant alteration was observed in enzyme activity, muscle proteins, lipids and histopathology of the tissues. The results suggest that methylparathion has the potential to induce oxidative stress in fish, and that liver, muscle and brains are more sensitive organs of Labeo rohita, with poor antioxidant potentials at higher concentrations of the pesticide. The various parameters studied in this investigation can also be used as biomarkers of methylparathion exposure.

Studies on the effect of the organophosphorus pesticide Eka(Rlu) x EC 25 on the bacterial flora of Villorita cyprinoides var. cochinensis (Han1ey)

The thesis is Studies on the Effect or the Obganophosphorus Pesticide Ekalux(R) EC 25 on the Bacterial Flora or Villorita Cyprinoides Var.Cochinensis (Hanley). For the present investigation, the black clam Villorita gyprinoides var. cochinensis (Hanley), a most common clam genus present in this estuarine system has been selected as test organaism and Ekalux (R) EC 25 as toxicant. The aspects dealt with are 1. Total heterotrophic bacterial population, 2. Generic composition, 3. Hydrolytic enzyme producing bacteria, 4. Antibiotic resistance, 5. Heavy metal resistance, 6. The effect of pesticide concentration on the growth of the bacteria and 7. Effect of temperature, pH and sodium chloride on the growth and phosphate release of selected isolates.The samples for the experiment were collected from the Vembanad Lake, near Kumbalam Island during the period of September 1985 to May '86. The THB of the estuarine water and clams contained 6.5 x I04/ml and 2.975 x l06/g respectively, immediately after collection. Untreated water and clam samples showed enormous increase in THB from 0 hr population. The treated samples (water and clams) contained higher THB than 0 hr. In general, THB was observed to increase tremendously in the samples treated with pesticide when compared to their native flora. With reference to various concentrations of pesticides, THB recorded an increase with increase of concentration in water and clam samples.

Pesticide-handling practices of smallholder coffee farmers in Eastern Jamaica

Pesticide use among smallholder coffee producers in Jamaica has been associated with significant occupational health effects. Research on pesticide handling practices, however, has been scarce, especially in eastern Jamaica. This explorative study aims at filling this gap and provides a first basis to develop effective interventions to promote a safer pesticide use. A random sample of 81 coffee farmers was surveyed. The majority of farmers reported to suffer from at least one health symptom associated with pesticide handling, but safety practices were scarcely adopted. There was also the risk that other household members and the wider local community are exposed to pesticides. The lack of training on pesticide management, the role of health services and the cost for protective equipment seemed to be the most significant factors that influence current pesticide handling practices in eastern Jamaica. Further research is recommended to develop a systemic understanding of farmer’s behaviour to provide a more solid basis for the development of future intervention programmes.

Survey of Agricultural Practices and Alternatives to Pesticide Use to Conserve Water Resources in the Mojanda Watershed, Ecuador

Agriculture in the Mojanda Watershed is facing rainfall reductions caused by climate change. Reductions of water availability in the Watershed are also due to constant extension of the agricultural activities into the páramo ecosystem above 3000m a.s.l., with this ecosystem having immanently important functions in the local water balance. The application of pesticides threatens the quality of water and with less precipitation contaminations will further concentrate in the outflow. To analyze problems associated with agricultural practices in the area a questionnaire about agricultural practices (28) was conducted and fields (20) were surveyed for pests and diseases with a focus on potatoes (Solanum tuberosum L.), tree tomatoes (Solanum betaceum Cav.) and peas (Pisum sativum L.). Potatoes were infected to a low degree with Phytophthora infestans and according to the farmers the Andean potato weevil (Premnotrypes spec.) caused biggest losses. To combat the weevil the soils are disinfected with toxic Carbofuran (WHO Class 1B). Tree tomatoes showed symptoms of various fungal diseases. Most important was Fusarium solani causing the branches to rot and Anthracnosis (Colletotrichum gloeosporioides) causing the fruits to rot. Fungicide applications were correspondingly high. Peas were only minorly affected by Ascochyta blight (Mycosphaerella pinodes) and a root rot. Overall 19 active ingredients were applied of which fungicide Mancozeb (WHO class table 5) and insecticide Carbofuran (WHO Class 1B) were applied the most. Approved IPM methods are advised to reduce pesticide use. For tree tomatoes regular cutting of branches infected with F. solani and regular collection and disposal of infected fruits with Anthracnosis are advised. For potatoes plastic barriers around the fields prevent the Andean potato weevil from laying eggs thus reducing infestation with the larvae in the tubers. Local bioinsecticide “Biol” seems effective and without harm to the environment, although not used by many farmers. Organic fertilization promises to restore decreasing soil fertility, water holding capacity and reduce erosion. The here presented alternatives and strategies to reduce pesticide use pose an opportunity to preserve the water resources of the region.

Compromiso neurológico periférico y exposición a plaguicidas en cultivadores de arroz en una zona rural, Colombia.

Objetivos Mediante un estudio descriptivo transversal, establecer la presencia de una relación entre los niveles de exposición a plaguicidas con la presencia de hallazgos clínicos neurológicos periféricos en personas expuestas ocupacionalmente a estos. Resultados La muestra poblacional fue de 59 trabajadores, en el área rural del municipio del Espinal, Tolima. El 52% de la población refirió usar organofosforados, 32 % carbamatos, 16% organoclorados, y 66% otros grupos de plaguicidas. Los niveles sanguíneos de carbamatos estuvieron presentes en el 7% de la población, organofosforados en el 66% y organoclorados en el 100%. En el 42% de la población se estableció sospecha de neuropatía a partir de los síntomas y en el 92% a partir de los signos. Se estableció asociación estadísticamente significativa entre los niveles sanguíneos de determinados organoclorados con la sospecha de neuropatía periférica a partir de síntomas; la presencia de sensación de pérdida de la fuerza en extremidades y la presencia de alteraciones en los reflejos osteotendinosos. Conclusiones El presente estudio permitió identificar los plaguicidas a los cuales está expuesta la población agrícola del municipio del Espinal así como corrobora el efecto de bioacumulación y biomagnificación de los organoclorados. Adicionalmente, se detectó la presencia de hallazgos sugestivos de compromiso neurológico periférico, con asociaciones significativas entre ciertas anormalidades y determinados organoclorados. Este estudio es una aproximación a la relación entre la exposición a plaguicidas de la población agrícola de la zona rural del municipio del Espinal con la secuelas neurológicos periféricas asociadas a esta.

Effect of Community of Residence on Neurobehavioral Development in Infants and Young Children in a Flower-Growing Region of Ecuador

In this study we compared neurobehavioral development in Ecuadoran children living in two communities with high potential for exposure to organophosphate (OP) and carbamate pesticides to that of children living in a community with low potential for exposure. Residence in communities with high potential for exposure to OP and carbamate pesticides was associated with poorer neurobehavioral development of the child even after controlling for major determinants of delayed development. Malnourished populations may be particularly vulnerable to neurobehavioral effects of pesticide exposure.

Chronic pesticide poisoning from persistent low-dose exposures in Ecuadorean floriculture workers: toward validating a low-cost test battery

Chronic pesticide poisoning is difficult to detect. We sought to develop a low-cost test battery for settings such as Ecuador’s floriculture industry. First we had to develop a case definition; as with all occupational diseases a case had to have both sufficient effective dose and associated health effects. For the former, using canonical discriminant analysis, we found that adding measures of protection and overall environmental stressors to occupational category and duration of exposure was useful. For the latter, factor analysis suggested three distinct manifestations of pesticide poisoning. We then determined sensitivity and specificity of various combinations of symptoms and simple neurotoxicity tests from the Pentox questionnaire, and found that doing so increased sensitivity and specificity compared to use of acethylcholinesterase alone – the current screening standard. While sensitivity and specificity varied with different case definitions, our results support the development of a low-cost test battery for screening in such settings.

Production risk, pesticide use and GM crop technology in South Africa

Technology involving genetic modification of crops has the potential to make a contribution to rural poverty reduction in many developing countries. Thus far, pesticide-producing Bacillus thuringensis (Bt) varieties of cotton have been the main GM crops under cultivation in developing nations. Several studies have evaluated the farm-level performance of Bt varieties in comparison to conventional ones by estimating production technology, and have mostly found Bt technology to be very successful in raising output and/or reducing pesticide input. However, the production risk properties of this technology have not been studied, although they are likely to be important to risk-averse smallholders. This study investigates the output risk aspects of Bt technology by estimating two 'flexible risk' production function models allowing technology to independently affect the mean and higher moments of output. The first is the popular Just-Pope model and the second is a more general 'damage control' flexible risk model. The models are applied to cross-sectional data on South African smallholders, some of whom used Bt varieties. The results show no evidence that a 'risk-reduction' claim can be made for Bt technology. Indeed, there is some evidence to support the notion that the technology increases output risk, implying that simple (expected) profit computations used in past evaluations may overstate true benefits.

Impacts of a pesticide on pollinator species richness at different spatial scales

Pesticides are an important potential cause of biodiversity and pollinator decline. Little is known about the impacts of pesticides on wild pollinators in the field. Insect pollinators were sampled in an agricultural system in Italy with the aim of detecting the impacts of pesticide use. The insecticide fenitrothion was over 150 times greater in toxicity than other pesticides used in the area, so sampling was set up around its application. Species richness of wild bees, bumblebees and butterflies were sampled at three spatial scales to assess responses to pesticide application: (i) the ‘field’ scale along pesticide drift gradients; (ii) the ‘landscape’ scale sampling in different crops within the area and (iii) the ‘regional’ scale comparing two river basins with contrasting agricultural intensity. At the field scale, the interaction between the application regime of the insecticide and the point in the season was important for species richness. Wild bee species richness appeared to be unaffected by one insecticide application, but declined after two and three applications. At the landscape scale, the species richness of wild bees declined in vine fields where the insecticide was applied, but did not decline in maize or uncultivated fields. At the regional scale, lower bumblebee and butterfly species richness was found in the more intensively farmed basin with higher pesticide loads. Our results suggest that wild bees are an insect pollinator group at particular risk from pesticide use. Further investigation is needed on how the type, quantity and timing of pesticide application impacts pollinators.

Consumer attitudes towards and willingness to pay for pesticide residue limit compliant 'safe' vegetables in Northeast Thailand

Pesticide residue in vegetables is a major food safety issue in Thailand. A range of vegetable products (organic/pesticide-free/ hydroponic) has emerged in Thai markets that guarantee compliance with maximum residue limits. The Government of Thailand is eager to extend the benefits of this suite of alternative vegetables to the entire population, particularly the semi-urban/rural segments that are often bypassed by such speciality products. However, little information is available to guide such an effort, particularly with regard to up-country consumer attitudes, shopping and consumption habits and willingness to pay premiums for such produce. This research aims to fill this gap in knowledge. It reports the results of a survey of vegetable consumption and shopping habits and attitudes of 608 consumers in northeast Thailand. Willingness to pay premiums for pesticide residue limit compliant vegetables is also assessed by using a contingent valuation method, and determinants of willingness to pay are examined using an ordered probit empirical model. Results indicate that, given adequate awareness of relative risks, even up-country consumers are willing to pay market premium levels for these products, and that inadequate availability, rather than lack of demand is the constraining factor. Willingness to pay is found to increase with income, age and supermarket sourcing of vegetables. We also discuss the challenge of improving availability at mainstream outlets.