Grower reported pesticide poisonings among Florida citrus fieldworkers

In a 1981 survey of 436 Florida citrus growers, 27 pesticide related poisoning incidents were reported that were to have taken place within one year of the interview date. From these reports it is possible to estimate that there are 376 citrus fieldworker related poisonings per year in Florida. This number of estimated poisonings may be developed into an incidence rate of 113 fieldworker poisonings per 10,000 fieldworkers.     

Estimating pesticide runoff in small streams

Surface runoff is one of the most important pathways for pesticides to enter surface waters. Mathematical models are employed to characterize its spatio-temporal variability within landscapes, but they must be simple owing to the limited availability and low resolution of data at this scale. This study aimed to validate a simplified spatially-explicit model that is developed for the regional scale to calculate the runoff potential (RP). The RP is a generic indicator of the magnitude of pesticide inputs into streams via runoff. The underlying runoff model considers key environmental factors affecting runoff (precipitation, topography, land use, and soil characteristics), but predicts losses of a generic substance instead of any one pesticide. We predicted and evaluated RP for 20 small streams. RP input data were extracted from governmental databases. Pesticide measurements from a triennial study were used for validation. Measured pesticide concentrations were standardized by the applied mass per catchment and the water solubility of the relevant compounds. The maximum standardized concentration per site and year (runoff loss, R_Loss) provided a generalized measure of observed pesticide inputs into the streams. Average RP explained 75% (p < 0.001) of the variance in R_Loss. Our results imply that the generic indicator can give an adequate estimate of runoff inputs into small streams, wherever data of similar resolution are available. Therefore, we suggest RP for a first quick and cost-effective location of potential runoff hot spots at the landscape level.     

Bound residues of organic compounds in the soil: the significance of pesticide persistence in soil and water: a European regulatory view

The paper discusses key aspects of the European Union (EU) regulatory policy for persistence of agricultural pesticide active substances (a.s.) in soil, which is examined in the context of the EU Authorisations Directive (91/414/EEC). For agricultural pesticide regulation within EU Member States (MS), the Authorisations Directive will gradually replace existing national systems. Discussion is concentrated on this directive, looking in particular at the Uniform Principles therein and the possible ways that these decision-making guidelines could be developed into a regulatory framework. The aim in this process of negotiated development is to identify any questions or data requirements that will be needed for persistent pesticides, over and above those generally required for all compounds. The present European regulatory position on soil non-extractable or bound residues is discussed. Finally, a brief mention of pesticide persistence in water and sediment is made.     

Pesticide persistence and bound residues in soil--regulatory significance

The paper discusses key aspects of the European Union (EU) regulatory policy related to the persistence and bound residues of agricultural pesticide active substances in soil. This is examined in the context of the EU Authorisations Directive (91/414/EEC) which will gradually replace existing national systems of agricultural pesticide regulation within EU Member States. Discussion is concentrated on this directive, looking in particular at the Uniform Principles therein and the possible ways that these decision-making guidelines could be developed into a regulatory framework. The aim in this process of negotiated development is to identify any questions or data requirements that will be needed for persistent pesticides or soil bound residues, over and above those generally required for all compounds. The present EU regulatory position on soil non-extractable or bound residues is examined and possible future improvements to the system are described and discussed.     

Sister chromatid exchange and proliferative rate index in the longitudinal risk assessment of occupational exposure to pesticides

At present, there are more than 1,000 chemicals classified as pesticides and many reports have shown that some of them have genotoxic properties. In the present longitudinal study, possible genetic damage on a population of workers occupationally exposed to a mixture of pesticides by using sister chromatid exchange (SCE) analysis has been evaluated. As an additional cytogenetic parameter, the proportion of lymphocytes that undergo one, two or three cell divisions as well as proliferative rate index have been determined. This study was performed on the exposed group of workers employed in pesticide production, simultaneously exposed to a complex mixture of pesticides (atrazine, alachlor, cyanazine, 2,4-dichlorophenoxyacetic acid, and malathion). The blood samples of the exposed subjects were collected in three different periods: before the beginning of the new pesticide production period, after 8 months of everyday work in the pesticide production, and 8 months after the removal of subjects out of the production. In all three samplings, the mean value of SCE and number of cells with high sister chromatid exchange frequency (HFC) in the exposed group was significantly higher in the comparison with the control group. There were no differences in the proliferative rate index (PRI) between the control and exposed group, regardless of the sampling period. In both groups examined, the majority of lymphocytes were found in the second cell division, following cultivation. These results suggest that the increase in the number of SCE found in the exposed subjects is not the result of either cytotoxic or epigenetic action of pesticide mixture, but chronic occupational exposure to mixture of pesticides.     

Persistence and distribution of pesticide residues in fresh agricultural food consumed in the province of Bologna

The presence of pesticide residues in fresh vegetables and fruit have been qualitatively and quantitatively determined at the laboratories of the Regional Agency for Environmental Protection (ARPA), Division of the Province of Bologna. More than 1,700 samples have been tested by routine analyses. The possible risks for consumers have been evaluated by various parameters. The most important ones were: the amount of each residue; the respective ADI (Acceptable Daily Intake) limit; the contemporary presence of different residues; an estimation of the daily intake, based on the amount of fruit and vegetables consumed per person. It has been possible to evaluate that the daily intake of pesticide residues in the province of Bologna during the period 2003–06 resulted lower than the ADI limits concerning the vegetables. According to the information on fruit consumption the daily intake of omethoate (O,O-dimethyl S-methylcarbamoylmethyl phosphorothioate) resulted higher than its ADI limit, of dicofol (2,2,2-trichloro-1,1-bis(trichloromethyl)benzenemethanol) very close to the admitted limit, under the respective limits for all the other residues.     

Lesions induced by 2,4-D and chlorpyrifos in tench (Tinca tinca L.): implication in toxicity studies

This study was undertaken to demonstrate the toxicity of two pesticides, chlorpyrifos (O,O-diethyl 0-3,5,6-trichloro-2-pyridyl phosphorothioate) and 2,4-D (Dichlorophenoxyacetic acid) to tench (Tinca tinca Linnaeus). Pathological samples of damaged tench kidney showing lesions were taken for statistical analysis in order to quantify different parameters. Analysis revealed differences in the action and/or action time of the two pesticides. These differences were more acute in the case of 2,4-D thereby indicating a greater toxicity. These differences, expressed by mathematical formulae of numerical variables, would enable, a priori, the identification of the responsible pesticide and the time of acting in new natural cases of poisonings with these substances.     

Modelling pesticide volatilization after soil application using the mechanistic model Volt'Air

Volatilization of pesticides participates in atmospheric contamination and affects environmental ecosystems including human welfare. Modelling at relevant time and spatial scales is needed to better understand the complex processes involved in pesticide volatilization. Volt'Air-Pesticides has been developed following a two-step procedure to study pesticide volatilization at the field scale and at a quarter time step. Firstly, Volt'Air-NH₃ was adapted by extending the initial transfer of solutes to pesticides and by adding specific calculations for physico-chemical equilibriums as well as for the degradation of pesticides in soil. Secondly, the model was evaluated in terms of 3 pesticides applied on bare soil (atrazine, alachlor, and trifluralin) which display a wide range of volatilization rates. A sensitivity analysis confirmed the relevance of tuning to K_h. Then, using Volt'Air-Pesticides, environmental conditions and emission fluxes of the pesticides were compared to fluxes measured under 2 environmental conditions. The model fairly well described water temporal dynamics, soil surface temperature, and energy budget. Overall, Volt'Air-Pesticides estimates of the order of magnitude of the volatilization flux of all three compounds were in good agreement with the field measurements. The model also satisfactorily simulated the decrease in the volatilization rate of the three pesticides during night-time as well as the decrease in the soil surface residue of trifluralin before and after incorporation. However, the timing of the maximum flux rate during the day was not correctly described, thought to be linked to an increased adsorption under dry soil conditions. Thanks to Volt'Air's capacity to deal with pedo-climatic conditions, several existing parameterizations describing adsorption as a function of soil water content could be tested. However, this point requires further investigation. Practically speaking, Volt'Air-Pesticides can be a useful tool to make decision about agricultural practices such as incorporation or for the estimation of overall pesticide volatilization rates, and it holds promise for time specific dynamics.     

The relationship between dermal pesticide exposure by fruit harvesters and dislodgeable foliar residues

Dermal pesticide exposure rates, expressed in mg/hr, by strawberry and blueberry harvesters and dislodgeable foliar pesticide residues were determined in 7 separate field experiments during 1981-1983 in California and Oregon. The pesticides which were studied included captan, vinclozolin, carbaryl, and methiocarb. A positive correlation between these two parameters was found and compared with literature values involving different pesticides and tree crops. The ratio between dermal exposure rate and dislodgeable foliar residues, the units of which are area/time, may have a possible use as an empirical factor for a first approximation of dermal exposure rates by fruit harvesters without the involvement of human subjects.     

Results of the monitoring program of pesticide residues in organic food of plant origin in Lombardy (Italy)

Organic agriculture, with its restrictions on the use of synthetic chemical inputs, seems to offer a low-residue alternative to conventional methods. In Europe, the Council Regulation n. 2092/91/EEC regulates the production and trade of organic products and foodstuffs; national and regional legislation in Italy gives specific guidance on the surveillance of organic agriculture. However, monitoring of specific chemical residues in organic foodstuffs is part of the regular controls on food, aiming to safeguard consumer's health. Monitoring programs are coordinated at the national level by the Ministry of Health and at local level by Regional authorities. In Lombardy, in accordance with the provisions of the General Directorate of Health of the Region and under the supervision of the 15 Local Health Units, a monitoring program of pesticide residues in food of plant origin is undertaken every year. The International Centre for Pesticides and Health Risk Prevention (ICPS), on behalf of the General Directorate of Health of the Region of Lombardy, has been collecting and elaborating the data resulting from the analysis of food samples, carried out by the local laboratories. During the period 2002–2005, a total of 3508 samples food of plant origin were analyzed for pesticide residues, among which were 266 samples of organic farming products. Commodities were classified into groups (citrus fruits, legumes, vegetables, potatoes, processed products, cereals, and fruit other than citrus) and the outcomes of the analyses were reported by year, origin of the sample and presence/absence of pesticide residues. Results showed that the vast majority of organic farming products were in conformity with the relevant legislation and did not contain detectable pesticide residues. A limited amount of samples had residues at concentration below the Maximum Residue Limit (MRL). Only in one sample the residue level was above the MRL, however it did not pose a concern for public health, as demonstrated by the outcomes of dietary risk assessment. Organic fruits and vegetables can be expected to contain fewer agrochemical residues than conventionally grown alternatives. There is a widespread belief that organic agriculture products are safer and healthier than conventional foods. It is difficult to come to conclusions, but what should be made clear to the consumer is that “organic” does not automatically equal “safe”. In the absence of adequate comparative data, additional studies in this area of research are required.     

Results of the monitoring program of pesticide residues in organic food of plant origin in Lombardy (Italy)

Organic agriculture, with its restrictions on the use of synthetic chemical inputs, seems to offer a low-residue alternative to conventional methods. In Europe, the Council Regulation n. 2092/91/EEC regulates the production and trade of organic products and foodstuffs; national and regional legislation in Italy gives specific guidance on the surveillance of organic agriculture. However, monitoring of specific chemical residues in organic foodstuffs is part of the regular controls on food, aiming to safeguard consumer's health. Monitoring programs are coordinated at the national level by the Ministry of Health and at local level by Regional authorities. In Lombardy, in accordance with the provisions of the General Directorate of Health of the Region and under the supervision of the 15 Local Health Units, a monitoring program of pesticide residues in food of plant origin is undertaken every year. The International Centre for Pesticides and Health Risk Prevention (ICPS), on behalf of the General Directorate of Health of the Region of Lombardy, has been collecting and elaborating the data resulting from the analysis of food samples, carried out by the local laboratories. During the period 2002-2005, a total of 3508 samples food of plant origin were analyzed for pesticide residues, among which were 266 samples of organic farming products. Commodities were classified into groups (citrus fruits, legumes, vegetables, potatoes, processed products, cereals, and fruit other than citrus) and the outcomes of the analyses were reported by year, origin of the sample and presence/absence of pesticide residues. Results showed that the vast majority of organic farming products were in conformity with the relevant legislation and did not contain detectable pesticide residues. A limited amount of samples had residues at concentration below the Maximum Residue Limit (MRL). Only in one sample the residue level was above the MRL, however it did not pose a concern for public health, as demonstrated by the outcomes of dietary risk assessment. Organic fruits and vegetables can be expected to contain fewer agrochemical residues than conventionally grown alternatives. There is a widespread belief that organic agriculture products are safer and healthier than conventional foods. It is difficult to come to conclusions, but what should be made clear to the consumer is that "organic" does not automatically equal "safe". In the absence of adequate comparative data, additional studies in this area of research are required.     

Assessment of a potential preventive ability of amygdalin in mycotoxin-induced ovarian toxicity

The possible effects of a natural substance amygdalin and its combination with the mycotoxin deoxynivalenol (DON) on the steroid hormone secretion (progesterone and 17-β-estradiol) by porcine ovarian granulosa cells (GCs) were examined in this in vitro study. Ovarian GCs were incubated without (control group) and with amygdalin (1, 10, 100, 1,000 and 10,000 μg mL¹), or its combination with DON (1 μg mL¹) for 24 h. The release of steroid hormones was determined by ELISA. The progesterone secretion by porcine ovarian GCs was not affected by amygdalin in comparison to the control. However, the highest amygdalin dose (10,000 μg mL¹) caused a significant stimulation of the 17-β-estradiol release. A combination of amygdalin with DON significantly (P < 0.05) increased the progesterone release at all concentrations. Similarly, a stimulatory effect of amygdalin co-administered with DON was detected with respect to the 17-β-estradiol secretion at the highest dose (10,000 μg mL¹) of amygdalin and 1 μg mL¹ of DON. Noticeable differences between the effects of amygdalin alone and its combination with DON on the progesterone release were detected. In contrast, no differences between the stimulatory effects of amygdalin and its combination with DON on the 17-β-estradiol synthesis by porcine GCs were observed. Findings from this in vitro study did not confirm the expected protective effect of amygdalin on mycotoxin induced reprotoxicity. Our results indicate that the stimulatory effect of amygdalin combined with DON on the progesterone release was clearly caused by the DON addition, not by the presence amygdalin per se. On the other hand, the stimulation of 17-β-estradiol production was solely caused by the presence of amygdalin addition. These findings suggest a possible involvement of both natural substances into the processes of steroidogenesis and appear to be endocrine modulators of porcine ovaries.     

Measurements of surface contamination of spray equipment with pesticides after various methods of application

A traditional method to determine operator dermal exposure is to quantify the amount of pesticide coming into contact with specific body regions and then to integrate the deposition density values with the total body surface. It is known that extremely high deposition values may occur in the hand region; however, the source of contamination is generally assumed to be direct splash or contact with the pesticide container. One of the parameters affecting operator/pilot exposure could be the transfer of pesticide residue, particularly in the case of pesticides with a longer half-life, from contaminated surfaces of spray equipment by direct contact over extended periods. If the rate of skin absorption of pesticide is readily known, the expected values of daily dose for an operator or pilot may significantly rise due to the extended contact period. This study produced field data on the surface contamination of spray equipment used for ground and aerial applications. If field data on precise work practice (time-motion) observations are incorporated, it may be possible to estimate the potential exposure of operator/pilot due to hand contact with contaminated surfaces.     

Influence of humic substances on the photolysis of aqueous pesticide residues

The present work investigated the direct and indirect photolysis of pesticide residues (atrazine, imazaquin, iprodione), in aqueous solutions and under UV-visible radiation (280-480nm). Different kinds of humic substances (HS) were added to samples in order to evaluate their behaviour as possible photocatalysts and their effect on the photolysis of pesticides. The fulvic acids were purchased from the International Humic Substances Society, and they were added to samples in concentrations ranging from 1 to 150 mgl(-1). Titanium dioxide was used as the photocatalyst, in concentration ranging from 10 to 150 mgl(-1). Pesticides photolysis were measured by UV-visible absorption spectroscopy and differential pulse polarography with all used pesticides, reaching total degradation after 2h of irradiation, thus indicating a fast direct photolysis. Photocatalysis by TiO(2) could increase the pesticides photolysis rate up to 40%. This effect, however, was not observed for imazaquin photolysis. Again, except for imazaquin, HS presence showed a positive effect in increasing pesticide degradation, but only within specific concentration ranges (below 10mg l(-1) for iprodione and about 30mgl(-1) for atrazine). Above these ranges HS induce a decrease in the pesticides photolysis rate. Spin-trapping measurements by electronic paramagnetic resonance spectroscopy, using the spin-trap DMPO, showed that HS are able to photogenerate hydroxyl radicals, increasing the pesticides molecule degradation. However, the HS also react with the photogenerated hydroxyl radical, influencing the pesticide photolysis, leading to a decrease in the photolysis rate and causing it to be strongly dependent on the nature and concentration of residues in the water to be treated.     

A comparison of five pesticides adsorption and desorption processes in thirteen contrasting field soils

Batch adsorption and desorption experiments were performed using thirteen agricultural soil samples and five pesticides. Experimental data indicated a gradient in pesticide adsorption on soil: trifluralin > 2,4-D > isoproturon> atrazine > bentazone. Atrazine, isoproturon and trifluralin adsorption were correlated to soil organic matter content (r2 = 0.7, 0.82, 0.79 respectively). Conversely, bentazone adsorption was governed by soil pH (r2 = 0.68) while insignificant effect has been shown in the case of 2,4-D. Multiple linear regressions were used to combine relationships between the various soil parameters and the Freundlich adsorption coefficient (K(f)) of each pesticide. Then desorption was assessed since it may reflect some of the interactions involved between the pesticides and the soil components. Adsorbed molecules were released into aqueous solution in the following order: bentazone > atrazine> isoproturon> 2,4-D > trifluralin. The occurrence of hysteresis did not allow an accurate interpretation of the pesticide desorption data because of the possible interplay of several processes.     

Determination of the residue dynamics and dietary risk of thiamethoxam and its metabolite clothianidin in citrus and soil by LC-MS/MS

A modified quick, easy, cheap, effective, rugged and safe (QuEChERS) method was developed for the determination of thiamethoxam and its metabolite clothianidin in citrus (including the whole citrus, peel and pulp) and soil samples by liquid chromatography-tandem mass spectrometry. The sample was extracted with acetonitrile and purified with octadecylsilane. The detection limits of both compounds were 0.0001–0.0002?mg kg^–1, while the limit of quantification of thiamethoxam was 0.002?mg kg^–1 and the limit of quantitation of metabolites was 0.001?mg kg^–1. The recovery was 70.37%–109.76%, with inter-day relative standard deviations (RSD) (n?=?15) values ≤9.46% for the two compounds in the four matrices. The degradation curve of thiamethoxam in whole citrus and soil was plotted using the first-order kinetic model. The half-life of the whole citrus was 1.9–6.2?days, and the half-life of the soil was 3.9–4.2?days. The terminal residue of thiamethoxam (the sum of thiamethoxam and clothianidin, expressed as thiamethoxam) was found to be concentrated on the peel. The final residual amount of thiamethoxam in the edible portion (pulp) was less than 0.061?mg kg^–1. The risk quotient values were all below 1, indicating that thiamethoxam as a citrus insecticide does not pose a health risk to humans at the recommended dosage.     

Measurements of surface contamination of spray equipment with pesticides after various methods of application

Abstract

A traditional method to determine operator dermal exposure is to quantify the amount of pesticide coming into contact with specific body regions and then to integrate the deposition density values with the total body surface. It is known that extremely high deposition values may occur in the hand region; however, the source of contamination is generally assumed to be direct splash or contact with the pesticide container. One of the parameters affecting operator/pilot exposure could be the transfer of pesticide residue, particularly in the case of pesticides with a longer half‐life, from contaminated surfaces of spray equipment by direct contact over extended periods. If the rate of skin absorption of pesticide is readily known, the expected values of daily dose for an operator or pilot may significantly rise due to the extended contact period. This study produced field data on the surface contamination of spray equipment used for ground and aerial applications. If field data on precise work practice (time‐motion) observations are incorporated, it may be possible to estimate the potential exposure of operator/pilot due to hand contact with contaminated surfaces.     

Simultaneous gas chromatographic determination of chlorpyrifos and its impurity sulfotep in liquid pesticide formulations

An analytical method for simultaneous determination of the active substance (chlorpyrifos) and its relevant impurity (sulfotep) in commercial pesticide formulations has been developed and validated. The proposed method entails extraction of the analytes from samples by sonication with acetone and analysis by gas chromatography-flame ionization detection (GC-FID). The proposed method was characterized by satisfactory accuracy and precision. The repeatability expressed as relative standard deviation (RSD) was lower than the acceptable values calculated from the modified Horwitz equation whereas individual recoveries were in the range of 98–102% and 80–120% for chlorpyrifos and sulfotep, respectively. The limit of quantification (LOQ) for the impurity (sulfotep) was 0.003 mg mL^?1 corresponding to the maximum permitted level according to Food and Agricultural Organization of the United Nations (FAO) specifications for the active substance (chlorpyrifos) being 3 g kg^?1 of the chlorpyrifos content found. The main advantage of the proposed method was a considerable reduction in the analysis time since both analytes were determined based on a single injection into the GC-FID. Analysis of real samples of commercial pesticide formulations confirmed fitness-for-purpose of the proposed method.     

Pesticide bioconcentration modelling for fruit trees

The model presented allows simulating the pesticide concentration evolution in fruit trees and estimating the pesticide bioconcentration factor in fruits. Pesticides are non-ionic organic compounds that are degraded in soils cropped with woody species, fruit trees and other perennials. The model allows estimating the pesticide uptake by plants through the water transpiration stream and also the time in which maximum pesticide concentration occur in the fruits. The equation proposed presents the relationships between bioconcentration factor (BCF) and the following variables: plant water transpiration volume (Q), pesticide transpiration stream concentration factor (TSCF), pesticide stem-water partition coefficient (K(Wood,W)), stem dry biomass (M) and pesticide dissipation rate in the soil-plant system (k(EGS)). The modeling started and was developed from a previous model "Fruit Tree Model" (FTM), reported by Trapp and collaborators in 2003, to which was added the hypothesis that the pesticide degradation in the soil follows a first order kinetic equation. The FTM model for pesticides (FTM-p) was applied to a hypothetic mango plant cropping (Mangifera indica) treated with paclobutrazol (growth regulator) added to the soil. The model fitness was evaluated through the sensitivity analysis of the pesticide BCF values in fruits with respect to the model entry data variability.