Kyriaki Machera

Pesticide residues in honeybees, honey and bee pollen by LC–MS/MS screening: Reported death incidents in honeybees

The aim of this study was to investigate reported cases of honeybee death incidents with regard to the potential interrelation to the exposure to pesticides. Thus honeybee, bee pollen and honey samples from different areas of Greece were analyzed for the presence of pesticide residues. In this context an LC-ESI-MS/MS multiresidue method of total 115 analytes of different chemical classes such as neonicotinoids, organophosphates, triazoles, carbamates, dicarboximides and dinitroanilines in honeybee bodies, honey and bee pollen was developed and validated. The method presents good linearity over the ranges assayed with correlation coefficient values r(2)≥0.99, recoveries ranging for all matrices from 59 to 117% and precision (RSD%) values ranging from 4 to 27%. LOD and LOQ values ranged - for honeybees, honey and bee pollen - from 0.03 to 23.3 ng/g matrix weight and 0.1 up to 78 ng/g matrix weight, respectively. Therefore this method is sufficient to act as a monitoring tool for the determination of pesticide residues in cases of suspected honeybee poisoning incidents. From the analysis of the samples the presence of 14 active substances was observed in all matrices with concentrations ranging for honeybees from 0.3 to 81.5 ng/g, for bee pollen from 6.1 to 1273 ng/g and for honey one sample was positive to carbendazim at 1.6 ng/g. The latter confirmed the presence of such type of compounds in honeybee body and apicultural products.

EVALUATION OF POTENTIAL DERMAL EXPOSURE OF PESTICIDE SPRAY OPERATORS IN GREENHOUSES BY USE OF VISIBLE TRACERS

In the present study, the potential dermal and inhalation exposure of the operator was measured, following simulation of insecticide application with the dye tracer Sunset Yellow in greenhouse cucumbers and tomatoes. For the monitoring of operator exposure, the whole body technique was used. The potential inhalation exposure was measured with a personal air sampler equipped with a glass fiber filter. The potential dermal operator exposure ranged from 84.4 to 526.7 ml of spray solution (s.s.)/h for the whole body and from 18.5 to 62.5 ml s.s./h for hands in the case of greenhouse cucumbers. The respective inhalation exposure was between 0.17 and 1.0 ml s.s./h. For greenhouse tomatoes, the potential body exposure was in the range of 22.4 to 62.1 ml s.s./h. The hand exposure varied from 5.5 to 6.1 ml s.s./h. The potential inhalation exposure was in the range of 0.33 to 0.43 ml s.s./h. The potential dermal operator exposure is a highly variable parameter, with a variation factor higher than 100% in many cases. One of the most critical factors for the determination of both potential dermal and inhalation exposure is the application pressure. Other field and operational conditions, including unpredictable factors, are also important for the determination of operator exposure levels. The measured potential dermal operator exposure values were above the levels of exposure estimated with mathematical models.

Dermal Exposure of Pesticide Applicators as a Measure of Coverall Performance Under Field Conditions

In this study, the field performance of two coverall designs used by pesticide applicators was determined. Two coverall types were selected based on data from previously conducted comfort testing under field conditions in southern Europe. Dermal exposure was measured during 22 applications conducted with 11 operators using similar hand-held spray guns in greenhouse pepper crops in the Ierapetra region of Crete, Greece. One of the coverall designs studied was made from a cotton/polyester material treated with a water-repellent Resist Spills(R) finish, which was compared in the field study to a coverall of similar design, but using a woven, untreated cotton material. An in-house analytical method was developed and validated for determining residues of the active substance (a.s.) malathion on the dosimeters. The derived levels of dermal exposure were used as a measure of the protection provided by the two types of coveralls. In addition, by comparing the total amount of the a.s. recovered from outer and inner dosimeters (potential dermal exposure = 238.8 mg kg(-1) a.s. for the cotton coverall and 160.44 mg kg(-1) a.s. for the Resist Spills coverall), a value could be determined for the degree of coverall penetration. The mean penetration (milligrams per kilogram a.s.) of the outer coveralls, calculated as a percentage of the total contamination, was 0.4% for the water-repellent coverall and 2.3% for the cotton coverall. The mean recovery from the laboratory and field-fortified samples was >91 and 74%, respectively and used as the main criterion for quality control of the analytical data. Under the field trial conditions evaluated, both the coverall designs gave better protection than the default values used in the most relevant predictive exposure model. Therefore, they could be considered as appropriate tools of personal protection when both comfort and field performance is taken into account under the specific application scenario.

Determination of operator exposure levels to insecticide during bait applications in olive trees: Study of coverall performance and duration of application

In this study the operator exposure levels during bait applications of an insecticide in olive groves were determined using a whole body dosimetry method for dermal exposure. The study design allowed the roles of application task duration and coverall type to be evaluated as factors influencing operator exposure. Twenty applications were carried out with knapsack sprayers in the Tanagra region of Viotia, Greece, ten of which were for a 1h and ten for a 3h duration. An in-house GC-NPD analytical method was developed and validated for the determination of malathion, the active substance (a.s.) of the insecticide formulation used in field trials. The mean recovery of field-fortified samples was 84% (%RSD=3.0). Field trial results generally indicated lower operator exposure levels than indicated by the most relevant operator exposure predictive model. Residues of malathion on internal dosimeters were compared to those measured on the respective outer coveralls (potential dermal exposure) to evaluate the protective factor of each one of the two coverall types used. Both coverall types provided satisfactory levels of protection and can be considered as suitable protection for the conditions of the application scenario studied. Furthermore, the results indicated that there is not a strong correlation between exposure levels and duration of application.

Comparative toxicities of fungicide and herbicide formulations on freshwater and marine species.

The estimation of the toxic effects of plant protection products on non-target aquatic organisms is essential for risk assessment evaluation. In this study the acute toxicity of two fungicide and two herbicide formulations was determined in four marine species in comparison with the toxicity assessed for the freshwater crustacean Daphnia magna. From the study it is indicated that the marine crustacean species are effectively protected when acute toxicity data on Daphnia magna are used as surrogate for risk assessment while the comparative sensitivity of the unicellular green algae may vary considerably, depending on the mode of action of the specific formulation.

Perceptions of pesticides exposure risks by operators, workers, residents and bystanders in Greece, Italy and the UK

The EU Directive on the sustainable use of pesticides (EU128/2009/EC) requires European Member States to develop training activities targeting occupational exposure to pesticides, and communication material aimed at residents and bystanders. Risk perceptions, knowledge and attitudes associated with passive and occupational exposure to pesticide potentially influence the extent to which different stakeholders adopt self-protective behaviour. A methodology for assessing the link between attitudes, adoption of self-protective behaviours and exposure was developed and tested. A survey was implemented in the Greece, Italy and the UK, and targeted stakeholders associated with pesticide exposure linked to orchards, greenhouse crops and arable crops respectively. The results indicated that the adoption of protective measures is low for residents and bystanders, with the exception of residents in Greece, when compared to operators and workers, who tend to follow recommended safety practices. A regression analysis was used to examine the factors affecting the probability of adopting protective measures as well the as the level of exposure in the case of operators and workers where data are available. The results indicate that the likelihood of engaging in self-protective behaviour is not significantly affected by perceptions of own health being affected by pesticides for residents and bystanders. However, operators who perceive that their heath has been negatively affected by the use of pesticides are found to be more likely to adopt self-protective behaviours. Gender and country differences, in perceptions, attitudes and self-protection are also observed. Recommendations for improved communication, in particular for vulnerable groups, are provided.

Dermal & inhalation exposure of operators during fungicide application in vineyards. Evaluation of coverall performance.

In the present study the dermal and the inhalation exposure of five operators during fungicide applications in vineyards were determined. The produced exposure datasets can be used as surrogate for the estimation of the actual and the potential dermal as well as inhalation operator exposure levels for this application scenario. The dermal exposure was measured using the whole body dosimetry method while the inhalation exposure with the use of personal air sampling devices with XAD tubes located on the operators breathing zone. Ten field trials were carried out by 5 different operators using a tractor assisted hand-held lance with spray gun at the Tanagra region of Viotia, Greece. An in-house GC-ECD analytical method was developed and validated for the determination of penconazole, which was the active substance (a.s.) of the fungicide formulation used in field trials. The mean recovery of field-fortified samples was 81%. The operator exposure results showed expected variability and were compared to those derived from the German model for prediction of operator exposure. The comparison of the 75th percentile values for an operator wearing personal protection equipment has shown that the measured levels were 2.2 times lower than those estimated by the German model. The levels of actual dermal exposure ranged from 2 to 19 mg/kg a.s. applied. The protection provided by the two types of coveralls was evaluated and in comparison to the existing reduction factors used for other types of PPE (coveralls) was found satisfactory for the operator under the conditions of the specific applications.

Monitoring of systemic exposure to plant protection products and DNA damage in orchard workers

The systemic exposure of plum tree growers and operators to plant protection products (PPPs) and effects on DNA were assessed. Specifically, a GC-MS/MS method was developed and validated for the analysis of serum samples for the presence of seven active substances of PPPs. The analytical results verified the presence of myclobutanil, propargite, cypermethrin and deltamethrin in 7 out of 19 serum samples. The incidence of DNA damage was monitored using the single cell electrophoresis assay (comet assay). A paired Students t-test revealed a statistically significant increase of SSBs in the blood samples collected at the end of the cropping period as compared to the samples collected from the same subjects before the start of PPPs application period. Moreover, the group of seven subjects with detectable serum pesticides levels revealed statistically significant increase of SSBs as compared to the group of subjects with no detectable PPP levels. The results of the present study demonstrate that the agriculture workers may exhibit detectable level of systemic exposure to the applied PPPs which are correlated to increased DNA damage during the cultivation period.

Headspace Solid Phase Micro Extraction Gas Chromatographic Determination of Fenthion in Human Serum

A simple and effective analytical procedure was developed for the determination of fenthion residues in human serum samples. The sample treatment was performed using the headspace solid-phase micro extraction with polyacrylate fiber, which has the advantage to require low amount of serum (1 mL) without tedious pre-treatment. The quantification of fenthion was carried out by gas chromatography-mass spectrometry and the recoveries ranged from 79 to 104% at two spiking levels for 6 replicates. Detection and quantification limits were calculated as 1.51 and 4.54 ng/mL of serum respectively. Two fenthion metabolites fenoxon and fenthion–sulfoxide were also identified.

A Review of the Use of Pictograms for Communicating Pesticide Hazards and Safety Instructions: Implications for EU Policy

ABSTRACT The literature was reviewed to assess the understanding and interpretation of pictograms used in pesticide exposure risk communication, and to assess the results in the context of the new European Union (EU) regulatory context for the sustainable use of pesticides. The results indicate that the understanding of pictograms used on pesticide labels by workers and operators is generally low. Standardized approaches, contrary to their claims, are not easily understandable, culturally neutral, or universally understood. Although there is scope for the greater use of pictograms in training, it is important to stress that they should never replace the full and frequent verbal training in a language understood by the trainee. They can, however, be used to complement training, facilitate recall, and encourage compliance. While the policy affecting the handling, labeling, and use of pesticides is applied across the EU, there has been no analysis of the different types of pictograms that have been used in the European context, nor the different ways that they are employed (e.g., on labels, on signs, during training), nor understanding of their meaning by European workers and operators. Furthermore, the implications for risk with residents and bystanders are less clear than for workers and operators.