Determination of parathion and carbaryl pesticides in water and food samples using a self assembled monolayer/acetylcholinesterase electrochemical biosensor

An acetylcholinesterase (AchE) based amperometric biosensor was developed by immobilisation of the enzyme onto a self assembled modified gold electrode. Cyclic voltammetric experiments performed with the SAM-AchE biosensor in phosphate buffer solutions ( pH = 7.2) containing acetylthiocholine confirmed the formation of thiocholine and its electrochemical oxidation at E-p = 0.28 V vs Ag/AgCl. An indirect methodology involving the inhibition effect of parathion and carbaryl on the enzymatic reaction was developed and employed to measure both pesticides in spiked natural water and food samples without pre-treatment or pre-concentration steps. Values higher than 91-98.0% in recovery experiments indicated the feasibility of the proposed electroanalytical methodology to quantify both pesticides in water or food samples. HPLC measurements were also performed for comparison and confirmed the values measured amperometrically.

Effectiveness of two systems for the spraying of pesticides in citrus trees

Citriculture normally uses high application volumes in pesticide solutions (of 2.000 to 5.000 L ha(-1)) to control pests and diseases that affect the crop, which generates an increase in operational costs. For this reason, diverse systems of application are being developed to reduce application volumes and improve the uniformity of pesticide deposition. The goal of this work was to evaluate the efficiency of two application systems of pesticides in citrus trees. One system used a prototype for terrestrial application with rotary disc atomizers that are widely used in agricultural aviation, and the other system used hollow cone tip hydraulics. For the treatment of the trees the insecticide Metidation was used at the dose of 180 gr per hectare. To study the droplet spectrum, water-sensitive papers were installed at different positions in the trees canopy, and for the study of insecticide deposition leaves of the treated plants were collected. The water-sensitive papers were collected and analyzed using a computerized image analysis system (e-Sprinkle, EMBRAPA, Sao Paulo, Brazil), and the leaves analyzed by the technique of gas chromatography. Pesticide deposition was similar in both application system, although the solution volume used by the application system equipped with rotary disc atomizers was one quarter of the volume used by the application system equipped with hydraulic tips, reducing considerably the cost of the phytosanitary treatments.

Environmental Risk Factors for Parkinson's Disease

Parkinson’s disease (PD) is a progressive, degenerative, neurological disease. The progressive disability associated with PD results in substantial burdens for those with the condition, their families and society in terms of increased health resource use, earnings loss of affected individuals and family caregivers, poorer quality of life, caregiver burden, disrupted family relationships, decreased social and leisure activities, and deteriorating emotional well-being. Currently, no cure is available and the efficacy of available treatments, such as medication and surgical interventions, decreases with longer duration of the disease. Whilst the cause of PD is unknown, genetic and environmental factors are believed to contribute to its aetiology. Descriptive and analytical epidemiological studies have been conducted in a number of countries in an effort to elucidate the cause, or causes, of PD. Rural residency, farming, well water consumption, pesticide exposure, metals and solvents have been implicated as potential risk factors for PD in some previous epidemiological studies. However, there is substantial disagreement between the results of existing studies. Therefore, the role of environmental exposures in the aetiology of PD remains unclear. The main component of this thesis consists of a case-control study that assessed the contribution of environmental exposures to the risk of developing PD. An existing, previously unanalysed, dataset from a local case-control study was analysed to inform the design of the new case-control study. The analysis results suggested that regular exposure to pesticides and head injury were important risk factors for PD. However, due to the substantial limitations of this existing study, further confirmation of these results was desirable with a more robustly designed epidemiological study. A new exposure measurement instrument (a structured interviewer-delivered questionnaire) was developed for the new case-control study to obtain data on demographic, lifestyle, environmental and medical factors. Prior to its use in the case-control study, the questionnaire was assessed for test-retest repeatability in a series of 32 PD cases and 29 healthy sex-, age- and residential suburb-matched electoral roll controls. High repeatability was demonstrated for lifestyle exposures, such as smoking and coffee/tea consumption (kappas 0.70-1.00). The majority of environmental exposures, including use of pesticides, solvents and exposure to metal dusts and fumes, also showed high repeatability (kappas >0.78). A consecutive series of 163 PD case participants was recruited from a neurology clinic in Brisbane. One hundred and fifty-one (151) control participants were randomly selected from the Australian Commonwealth Electoral Roll and individually matched to the PD cases on age (± 2 years), sex and current residential suburb. Participants ranged in age from 40-89 years (mean age 67 years). Exposure data were collected in face-to-face interviews. Odds ratios and 95% confidence intervals were calculated using conditional logistic regression for matched sets in SAS version 9.1. Consistent with previous studies, ever having been a regular smoker or coffee drinker was inversely associated with PD with dose-response relationships evident for packyears smoked and number of cups of coffee drunk per day. Passive smoking from ever having lived with a smoker or worked in a smoky workplace was also inversely related to PD. Ever having been a regular tea drinker was associated with decreased odds of PD. Hobby gardening was inversely associated with PD. However, use of fungicides in the home garden or occupationally was associated with increased odds of PD. Exposure to welding fumes, cleaning solvents, or thinners occupationally was associated with increased odds of PD. Ever having resided in a rural or remote area was inversely associated with PD. Ever having resided on a farm was only associated with moderately increased odds of PD. Whilst the current study’s results suggest that environmental exposures on their own are only modest contributors to overall PD risk, the possibility that interaction with genetic factors may additively or synergistically increase risk should be considered. The results of this research support the theory that PD has a multifactorial aetiology and that environmental exposures are some of a number of factors to contribute to PD risk. There was also evidence of interaction between some factors (eg smoking and welding) to moderate PD risk.

Spray drift of pesticides arising from aerial application in cotton

This paper presents results from field studies carried out during the 1993-1998 Australian cotton (Gossypium hirsutum L.) seasons to monitor off-target droplet movement of endosulfan (6,7,8,9,10,10-hexachloro-1,5,5a,6,9,9a-hexahydro-6,9-methano-2,4,3-benzodioxathiepin 3-oxide) insecticide applied to a commercial cotton crop. Averaged over a wide range of conditions, off-target deposition 500 m downwind of the field boundary was approximately 2% of the field-applied rate with oil-based applications and 1% with water-based applications. Mean airborne drift values recorded 100 m downwind of a single flight line were a third as much with water-based application compared with oil-based application. Calculations using a Gaussian diffusion model and the U.S. Spray Drift Task Force AgDRIFT model produced downwind drift profiles that compared favorably with experimental data. Both models and data indicate that by adopting large droplet placement (LDP) application methods and incorporating crop buffer distances, spray drift can be effectively managed.

Why farmers continue to use pesticides despite environmental, health and sustainability costs

Use of chemical inputs such as pesticides has increased agricultural production and productivity. However, negative externalities from such use have increased too. These externalities include damage to agricultural land, fisheries, fauna and flora. Another major externality is the unintentional destruction of beneficial predators of pests thereby increasing the virulence of many species of agricultural pests. Furthermore, increased mortality and morbidity of humans due to exposure to pesticides are recorded especially in developing countries. The costs from these externalities are large and affect farmers' returns. However, despite these high costs, farmers continue to use pesticides and in most countries in increasing quantities. In this paper, we examine this paradox and show why farmers continue to use pesticides despite the increasing costs. We also emphasize 'lock-in' aspects of pesticide use. (C) 2001 Elsevier Science B.V. All rights reserved.

Mango stem-end rot (Botryosphaeria dothidea) disease control by partial-pressure infiltration of fungicides

The in vitro efficacy of several fungicides against Botryosphaeria dothidea (syn. Dothiorella dominicana) and their in vivo efficacy in controlling mango cv. Kensington Pride stem-end rot on partial-pressure infiltration v. dip treatment of green mature fruit was evaluated. In vitro sensitivity of B. dothidea to Benlate (benomyl), Sportak (prochloraz) and Scala (pyrimethanil) at 10 dilutions of the manufacturer's recommended rate was first determined at typical cold (13degreesC) and shelf (23degreesC) storage temperatures. The effectiveness of partial-pressure infiltration and conventional hot (52degreesC) or cold (26degreesC) dipping of fruit after harvest was then evaluated using the commercially recommended rate for each fungicide. In vitro, Benlate and Sportak prevented the growth of B. dothidea at both storage temperatures and at all concentrations, while Scala partially controlled growth of the pathogen. Benlate was the most effective fungicide for stem-end rot control. Sportak and Scala resulted in stem-end rot control when applied by partial-pressure infiltration, but not as dips. Partial-pressure infiltration holds promise for enhancing the efficacy of otherwise less effective but alternative fungicides for control of stem-end rot diseases.

Efficacy, timing and method of application of fungicides for management of sorghum ergot caused by Claviceps africana

Trials conducted in Queensland, Australia between 1997 and 2002 demonstrated that fungicides belonging to the triazole group were the most effective in minimising the severity of infection of sorghum by Claviceps africana, the causal agent of sorghum ergot. Triadimenol ( as Bayfidan 250EC) at 0.125 kg a. i./ha was the most effective fungicide. A combination of the systemic activated resistance compound acibenzolar-S-methyl ( as Bion 50WG) at 0.05 kg a. i./ha and mancozeb ( as Penncozeb 750DF) at 1.5 kg a. i./ha has the potential to provide protection against the pathogen, should triazole-resistant isolates be detected. Timing and method of fungicide application are important. Our results suggest that the triazole fungicides have no systemic activity in sorghum panicles, necessitating the need for multiple applications from first anthesis to the end of flowering, whereas acibenzolar-S-methyl is most effective when applied 4 days before flowering. The flat fan nozzles tested in the trials provided higher levels of protection against C. africana and greater droplet deposition on panicles than the tested hollow cone nozzles. Application of triadimenol by a fixed wing aircraft was as efficacious as application through a tractor-mounted boom spray.

Pesticides and respiratory symptoms among farmers

OBJECTIVE: Despite the intensive use of pesticides in agriculture there are few studies assessing the risk of respiratory conditions from this exposure. The study aimed at quantifying the prevalence of respiratory symptoms among farmers and evaluating its relationship with occupational use of pesticides and the prevalence of respiratory symptoms. METHODS: A cross-sectional study was conducted among 1,379 farmers from two municipalities of Southern Brazil in 1996. Frequency and type of chemical exposure and pesticide poisoning were recorded for both sexes. All subjects aged 15 years or older with at least 15 weekly hours of agricultural activity were interviewed. An adapted questionnaire developed by the American Thoracic Society was used for the assessment of respiratory symptoms. Multivariate logistic regression analysis was carried out. RESULTS: More than half (55%) of interviewees were male. The prevalence of asthma symptoms was 12% and chronic respiratory disease symptoms was 22%. Higher odds ratios for both asthma (OR=1.51; 95% CI: 1.07-2.14) and chronic respiratory disease (OR=1.34; 95% CI 1.00-1.81) symptoms were found in women. Logistic regression analysis identified associations between many forms of exposure to pesticides and increased respiratory symptoms. Occurrence of pesticide poisoning was associated with higher prevalence of asthma symptoms (OR=1.54; 95% CI: 1.04-2.58) and chronic respiratory disease symptoms (OR=1.57; 95% CI: 1.08-2.28). CONCLUSIONS: In spite of causality limitations, the study results provide evidence that farming exposure to pesticides is associated with higher prevalence of respiratory symptoms, especially when the exposure is above two days per month.

Analysis of six fungicides and one acaricide in still and fortified wines using solid-phase microextraction-gas chromatography/tandem mass spectrometry

A multiresidue gas chromatographic method for the determination of six fungicides (captan, chlorthalonil, folpet, iprodione, procymidone and vinclozolin) and one acaricide (dicofol) in still and fortified wines was developed. Solid-phase microextraction (SPME) was chosen for the extraction of the compounds from the studied matrices and tandem mass spectrometry (MS/MS) detection was used. The extraction consists in a solvent free and automated procedure and the detection is highly sensitive and selective. Good linearity was obtained with correlation coefficients of regression (R2) > 0.99 for all the compounds. Satisfactory results of repeatability and intermediate precision were obtained for most of the analytes (RSD < 20%). Recoveries from spiked wine ranged from 80.1% to 112.0%. Limits of quantification (LOQs) were considerably below the proposedmaximumresidue limits (MRLs) for these compounds in grapes and below the suggested limits for wine (MRLs/10), with the exception of captan.

Analysing organochlorine pesticides in strawberry jams using GC-ECD, GC-MS/MS and QuEChERS sample preparation

This paper describes a comparison of adaptations of the QuEChERS (quick, easy, cheap, effective, rugged and safe) approach for the determination of 14 organochlorine pesticide (OCP) residues in strawberry jam by concurrent use of gas chromatography (GC) coupled to electron capture detector (ECD) and GC tandem mass spectrometry (GC-MS/MS). Three versions were tested based on the original QuEChERS method. The results were good (overall average of 89% recoveries with 15% RSD) using the ultrasonic bath at five spiked levels. Performance characteristics, such as accuracy, precision, linear range, limits of detection (LOD) and quantification (LOQ), were determined for each pesticide. LOD ranged from 0.8 to 8.9 microg kg-1 ; LOQ was in the range of 2.5–29.8 microg kg- 1; and calibration curves were linear (r2>0.9970) in the whole range of the explored concentrations (5–100 microg kg- 1). The LODs of these pesticides were much lower than the maximum residue levels (MRLs) allowed in Europe for strawberries. The method was successfully applied to the quantification of OCP in commercially available jams. The OCPs were detected lower than the LOD.

The development and optimization of a modified single-drop microextraction method for organochlorine pesticides determination by gas chromatography-tandem mass spectrometry

We have developed a new method for single-drop microextraction (SDME) for the preconcentration of organochlorine pesticides (OCP) from complex matrices. It is based on the use of a silicone ring at the tip of the syringe. A 5 μL drop of n-hexane is applied to an aqueous extract containing the OCP and found to be adequate to preconcentrate the OCPs prior to analysis by GC in combination with tandem mass spectrometry. Fourteen OCP were determined using this technique in combination with programmable temperature vaporization. It is shown to have many advantages over traditional split/splitless injection. The effects of kind of organic solvent, exposure time, agitation and organic drop volume were optimized. Relative recoveries range from 59 to 117 %, with repeatabilities of <15 % (coefficient of variation) were achieved. The limits of detection range from 0.002 to 0.150 μg kg−1. The method was applied to the preconcentration of OCPs in fresh strawberry, strawberry jam, and soil.

Optimization of QuEChERS method for the analysis of organochlorine pesticides in soils with diverse organic matter

A QuEChERS method has been developed for the determination of 14 organochlorine pesticides in 14 soils from different Portuguese regions with wide range composition. The extracts were analysed by GC-ECD (where GC-ECD is gas chromatography-electron-capture detector) and confirmed by GC-MS/MS (where MS/MS is tandem mass spectrometry). The organic matter content is a key factor in the process efficiency. An optimization was carried out according to soils organic carbon level, divided in two groups: HS (organic carbon>2.3%) and LS (organic carbon<2.3%). Themethod was validated through linearity, recovery, precision and accuracy studies. The quantification was carried out using a matrixmatched calibration to minimize the existence of the matrix effect. Acceptable recoveries were obtained (70–120%) with a relative standard deviation of ≤16% for the three levels of contamination. The ranges of the limits of detection and of the limits of quantification in soils HS were from 3.42 to 23.77 μg kg−1 and from 11.41 to 79.23 μg kg−1, respectively. For LS soils, the limits of detection ranged from 6.11 to 14.78 μg kg−1 and the limits of quantification from 20.37 to 49.27 μg kg−1. In the 14 collected soil samples only one showed a residue of dieldrin (45.36 μg kg−1) above the limit of quantification. This methodology combines the advantages of QuEChERS, GC-ECD detection and GC-MS/MS confirmation producing a very rapid, sensitive and reliable procedure which can be applied in routine analytical laboratories.