Dual layer solid phase extraction based on molecular imprinting technology: Seeking a route to enhance selectivity for trace analysis of pesticide residues in olive oil.

Aiming to introduce a multiresidue analysis for the trace detection of pesticide residues belonging to organophosphorus and triazine classes from olive oil samples, a new sample preparation methodology comprising the use of a dual layer of “tailor-made” molecularly imprinted polymers (MIPs) SPE for the simultaneous extraction of both pesticides in a single procedure has been attempted. This work has focused on the implementation of a dual MIP-layer SPE procedure (DL-MISPE) encompassing the use of two MIP layers as specific sorbents. In order to achieve higher recovery rates, the amount of MIP layers has been optimized as well as the influence of MIP packaging order. The optimized DL-MISPE approach has been used in the preconcentration of spiked organic olive oil samples with concentrations of dimethoate and terbuthylazine similar to the maximum residue limits and further quantification by HPLC. High recovery rates for dimethoate (95%) and terbuthylazine (94%) have been achieved with good accuracy and precision. Overall, this work constitutes the first attempt on the development of a dual pesticide residue methodology for the trace analysis of pesticide residues based on molecular imprinting technology. Thus, DL-MISPE constitutes a reliable, robust, and sensitive sample preparation methodology that enables preconcentration of the target pesticides in complex olive oil samples, even at levels similar to the maximum residue limits enforced by the legislation.

Estimation of water use and crop coefficients for an intensive olive orchard using sap flow measurements and modeled data

Olive tree sap flow measurements were collected in an intensive orchard near Évora, Portugal, during the irrigation seasons of 2013 and 2014, to calculate daily tree transpiration rates (T_SF). Meteorological variables were also collected to calculate reference evapotranspiration (ETo). Both data were used to assess values of basal crop coefficient (Kcb) for the period of the sap flow observations. The soil water balance model SIMDualKc was calibrated with soil, biophysical ground data and sap flow measurements collected in 2013. Validated in 2014 with collected sap flow observations, the model was used to provide estimates of dual e single crop coefficients for 2014 crop growing season. Good agreement between model simulated daily transpiration rates and those obtained with sapflow measurements was observed for 2014 (R2=0.76, RMSE=0.20 mm d-1), the year of validation, with an estimation average absolute error (AAE) of 0.20 mm d-1. Olive modeled daily actual evapotranspiration resulted in atual ETc values of 0.87, 2.05 and 0.77 mm d-1 for 2014 initial, mid- and end-season, respectively. Actual crop coefficient (Kc act) values of 0.51, 0.43 and 0.67 were also obtained for the same periods, respectively. Higher Kc values during spring (initial stage) and autumn (end-stage) were published in FAO56, varying between 0.65 for Kc ini and 0.70 for Kc end. The lower Kc mid value of 0.43 obtained for the summer (mid-season) is also inconsistent with the FAO56 expected Kc mid value of 0.70 for the period. The modeled Kc results are more consistent with the ones published by Allen & Pereira [1] for olive orchards with effective ground cover of 0.25 to 0.5, which vary between 0.40 and 0.80 for Kc ini, 0.40–0.60 for Kc mid with no active ground cover, and 0.35–0.75 for Kc end, depending on ground cover. The SIMDualKc simulation model proved to be appropriate for obtaining evapotranspiration and crop coefficient values for our intensive olive orchard in southern Portugal.