Pesticide prioritization approaches and limitations in environmental monitoring studies: From Europe to Latin America and the Caribbean.

Assessment and management of issues related to pesticide residues, such as environmental fate, monitoring and toxicity, are complex and, in many cases, require costly studies. The early establishment of a priority list of pesticides that should be monitored and assigned to a restricted-use policy is an important issue of post-registration Risk Assessment (RA). Various pesticide registration approaches have been adopted by different countries with those from Europe and the USA being the most popular, constituting the major prototypes for registration approaches in other countries. Adoption of pesticide registration and monitoring systems developed in Europe or USA by Latin American and Caribbean countries may underestimate factors affecting the environmental fate and toxicity of pesticides in their own countries. Incentive for this short review was the activities undertaken during the three KNOWPEC workshops held in Costa Rica, Argentina and Bolivia where European pesticide experts met Latin American experience in the form of Costa Rica's exceptional environmental conditions and ecology, Argentina's and Uruguay's soyisation and Bolivia's contrasting climate and agricultural zones. During the parallel activities of the workshop - including scientific presentations, field trips, interviews and meetings among European partners and pesticide stakeholders in Latin America, - the whole pesticide chain (import-export, trade, application, plant protection-efficacy, residues, monitoring, remediation and risk) was studied and clarified. Recently-published chemical prioritization studies were reviewed to consider their use as a tool to support risk assessments. Differences in regional practices are highlighted as regards to the establishment of RA or prioritization strategy in European and Latin American regimes. General guidance of establishing a cost-effective pesticide monitoring scheme in water bodies of Latin America and the Caribbean (LAC) is also proposed. Moreover, we summarize the most important factors that should be taken into consideration for prioritization approaches and categorization used in pesticide environmental monitoring studies. Consideration of current RA approaches and limitations, and pesticide prioritization exercises highlighted in this Commentary could assist in the management of pesticides in Latin America and Caribbean.

Pesticide monitoring and ecotoxicological risk assessment in surface water bodies and sediments of a tropical agro-ecosystem.

A pesticide monitoring study including 80 and 60 active ingredients (in surface waters and sediments, respectively) was carried out in a river basin in Costa Rica during 2007-2012. A special emphasis was given on the exceptional ecological conditions of the tropical agro-ecosystem and the pesticide application strategies in order to establish a reliable monitoring network. A total of 135 water samples and 129 sediment samples were collected and analyzed. Long-term aquatic ecotoxicological risk assessment based on risk quotient in three trophic levels was conducted. Short-term risk assessment was used to calculate the toxic unit and prioritization of sampling sites was conducted by the sum of toxic units in both aquatic and sediment compartments. Dimethoate (61.2 µg/L), propanil (30.6 µg/L), diuron (22.8 µg/L) and terbutryn (4.8 µg/L) were detected at the highest concentrations in water samples. Carbendazim and endosulfan were the most frequently detected pesticides in water and sediment samples, respectively. Triazophos (491 µg/kg), cypermethrin (71.5 µg/kg), permethrin (47.8 µg/kg), terbutryn (38.7 µg/kg), chlorpyrifos (18.2 µg/kg) and diuron (11.75 µg/kg) were detected at the highest concentrations in sediment samples. The pesticides carbendazim, diuron, endosulfan, epoxyconazole, propanil, triazophos and terbutryn showed non-acceptable risk even when a conservative scenario was considered. Sum TUsite higher than 1 was found for one and two sampling sites in water and sediment compartments, respectively, suggesting high acute toxicity for the ecosystem. MAIN FINDING OF THE WORK: Exceptional ecological conditions of the tropical agro-ecosystem affect the fate of pesticides in water and sediment environment differently than the temperate one.

Comparison and evaluation of two methods for the pesticide residue analysis of organophosphates in yerba mate

Abstract Microwave Assisted Extraction and a modified CEN-QuEChERS methodology were evaluated as extraction and clean up procedures for the simultaneous analysis of 42 organophosphate pesticides in yerba mate (Ilex paraguaiensis). The obtained extracts were analyzed by gas chromatography using a flame photometric detector. Linearity, recovery percentages, relative standard deviations, detection and quantification limits and matrix effects were determined according to DG-SANCO guidelines for both methods. At 0.2 and 0.5 mg/kg the evaluated methods showed percentages recoveries between 70 and 120% for most of the analytes. Using Microwave Assisted Extraction methodology, 33 pesticide residues could be properly analyzed whereas only 27 could be determined with the proposed modified QuEChERS. All relative standard deviation were below 18% except for omethoate and disulfoton sulfone when evaluated by the modified QuEChERS. The limits of detection in both methodologies were 0.2 mg/kg for most of the analyzed compounds. The average detection limit for QuEChERS was 0.04 mg/kg. For 19 of the analytes determined through Microwave Assisted Extraction the lowest validated level were 0.004 mg/kg. Signal suppression/enhancement was observed for most of the pesticides, thus matrix-matched calibration curves were used for quantification. The Microwave Assisted Extraction and QuEChERS procedures studied could detect the organophosphate pesticides above the MRL fixed for "mate" by the European Union. They have been successfully applied for the determination of organophosphate pesticide residues in commercial samples and the positives were confirmed through GC–(ITD)-MS.

Simple determination of 40 organophosphate pesticides in raw wool using microwave-assisted extraction and GC-FPD analysis.

A validated analytical method for the multiresidue analysis of 40 organophosphate pesticides (OPs) and conversion products in raw wool has been developed. The method is based on the selective microwave-assisted extraction (MAE) of raw wool with acetonitrile and analysis of extracts by gas chromatography-flame photometric detector. The optimum MAE conditions were 20 min duration at 80 °C with 30 mL of acetonitrile per gram of wool. A validation study was performed according to the European SANCO guidelines 10684/2009. Limits of detection and quantification for all pesticides tested were from 0.01 to 0.2 mg/kg and from 0.2 to 1.0 mg/kg, respectively. The average recoveries of pesticides spiked at different levels were in the range of 70-120% with relative standard deviations of ≤ 20%. The extraction performance was compared to the one obtained with a reference Soxhlet extraction. The method was also applied in the analysis of real wool (after field application) samples.