Helen Karasali

Pesticide residue concentration in soil following conventional and Low-Input Crop Management in a Mediterranean agro-ecosystem, in Central Greece

The present study was focused on the comparative evaluation of pesticide residues, determined in soil samples from Kopaida region, Greece before and after the implementation of Low-Input Crop Management (LCM) protocols. LCM has been suggested as an environmental friendly plant protection approach to be applied on crops growing in vulnerable to pollution ecosystems, with special focus on the site specific problems. In the case of the specific pilot area, the vulnerability was mainly related to the pollution of water bodies from agrochemicals attributed to diffuse pollution primarily from herbicides and secondarily from insecticides. A total of sixty-six soil samples, were collected and analyzed during a three-year monitoring study and the results of the determined pesticide residues were considered for the impact evaluation of applied plant protection methodology. The LCM was developed and applied in the main crops growing in the pilot area i.e. cotton, maize and industrial tomato. Herbicides active ingredients such as ethalfluralin, trifluralin, pendimethalin, S-metolachlor and fluometuron were detected in most samples at various concentrations. Ethalfluralin, which was the active ingredient present in the majority of the samples ranged from 0.01 μg g(-1) to 0.26 μg g(-1) soil dry weight. However, the amount of herbicides measured after the implementation of LCM for two cropping periods, was reduced by more than 75% in all cases. The method of analysis was based on the simultaneous extraction of the target compounds by mechanical shaking, followed by liquid chromatography mass spectrometric and gas chromatography electron capture (LC-MS/MS and GC-ECD) analysis.

PESTICIDE RESIDUES IN THERMAL MINERAL WATER IN GREECE

Eight different hot springs (SPA) in Greece were monitored over a one-year survey for priority pesticide residues. A specific and effective procedure including solid phase extraction in combination with HPLC and GC analytical methods were applied. Samples that were sensitive to nitrogen-phosphorus (NPD) and/or electron capture (ECD) detectors were analysed by capillary gas chromatography. From the twenty-six water samples, pesticide residues were detected in fourteen of them (54%) but no one exceeding the European Union Maximum Acceptable Concentration (MAC). Lindane (γ-BHC) was the most frequently detected pesticide. It was found in nine samples (35%) in concentrations from <0.005 to 0.01 μg/L. Other pesticides detected were phorate (in five samples), propachlor (in two samples) and chlorpyriphos ethyl (in three samples) but in concentrations far below the permissible levels.

Case Study To Illustrate an Approach for Detecting Contamination and Impurities in Pesticide Formulations

Counterfeit pesticides threaten public health, food trade, and the environment. The present work draws attention to the importance of regular monitoring of impurities in formulated pesticide products. General screening revealed the presence of carbaryl as a contaminant in a copper oxychloride formulated product. In this paper, as a case study, a liquid chromatographic diode array-mass spectrometric method developed for general screening of pesticide products and quantitative determination of carbaryl together with its validation is presented. The proposed testing strategy is considered suitable for use as a general approach for testing organic contaminants and impurities in solid pesticide formulations.

Rapid determination of fosetyl-aluminium in commercial pesticide formulations by high-performance liquid chromatography

An isocratic reversed-phase high-performance liquid chromatographic (RP-HPLC) method with diode array detection (DAD) was developed for the determination of aluminium tris(ethyl phosphonate) (fosetyl-aluminium, fosetyl-Al) in plant-protection products. The method involves extraction of the active ingredient by sonication of the sample with water and direct measurement by RPHPLC. The isocratic RP-HPLC method for the analysis of fosetyl-Al thus developed was then validated for specificity, linearity, precision, and accuracy. The chromatographic peak confirmation was performed by LC-MS using electron spray ionisation in the negative-ion mode. The repeatability of the method, expressed as relative standard deviation (RSD, %), was found to be 0.5 % and the limit of detection was 0.035 mg mL−1. The average recoveries of the three fortification levels varied from 96.7 % to 100.6 % and the RSDs ranged between 2.6 % and 6.3 %. The precision of the method was also considered to be acceptable as the experimental repeatability relative standard deviation (RSDr) was lower than the RSDr, calculated using the Horwitz equation. The method is rapid, simple, accurate, cost-effective, and provides a new and reliable means for the analysis of fosetyl-Al in formulated products.

Tree uptake of excess nutrients and herbicides in a maize-olive tree cultivation system

ABSTRACT Due to the extent of non-point source agricultural pollution, protective measures to control agrochemicals from entering aquatic systems are necessary. Measures may include, among others, vegetated buffer strips (VFS), no spray buffer zones, alley crops and agroforestry systems (AFS). The scope of the present work is to examine the pollution abatement potential of a maize-olive (MO) AFS. The efficiency of a combined MO trees system in reducing nutrients and herbicides is tested through soil monitoring in an experimental plot, located in Koropi, Eastern Attica, Greece, in the period May 2015 to November 2015. The monitored pollutants were nitrogen and phosphorus, as well as two herbicides: pendimethalin and nicosulfuron. Soil samples were collected every 3–5 weeks at various soil horizons and distances from the tree row. Pollutant concentrations were determined using liquid chromatography tandem mass spectrometry (LC–MS/MS), ion chromatography (IC) and spectrophotometry techniques. The studied MO tree system exhibited the potential to reduce pollutant migration, with removals ranging 36.8–78.9% for , 79.3–100% for , 76.7–100% for , 79.4–100% for and 70–100% for the examined herbicides. The higher removal percentages were observed in the upper soil layers (5–35 cm, below the crops), and where the finer tree roots extend. Thus, the results indicate that planting of trees in cultivated fields can contribute to the reduction of agrochemical pollution of the subsurface soil and in extension of groundwater.

Experimental investigation of the efficiency of triple rinsing of agricultural containers regarding their characterization as non-hazardous wastes

The efficiency of water rinsing for removing fenthion from non-combustible used pesticide containers was investigated. Four hundred empty containers from four olive oil producing areas in Greece were studied. Following triple rinsing cleaning procedures, the amount of fenthion retained in the container ranged from 0.01% to 0.1% w/w of its initial concentration. Extraction was accomplished with acetone, and the extracts were analyzed with a capillary gas chromatographic system coupled with flame ionization detector. The results obtained showed that triple rinsing is an effective procedure for removing fenthion from used pesticide containers, since the remaining pesticide concentration was below the legislated threshold value. Consequently, the containers can be handled as non-hazardous solid wastes.

Development and Validation of a Simple and Efficient Method for the Determination of Pendimethalin and Its Metabolite M455H001 in Soil by Liquid Chromatography–Tandem Mass Spectrometry (LC-MS/MS)

Abstract A new analytical method has been developed and described for the rapid determination of pendimethalin and its major metabolite M455H001 in soil by liquid chromatography coupled with ion-spray tandem mass spectrometry (LC-MS/MS) after a single acidic solvent extraction. The chromatographic separation of the analytes was achieved using a Zorbax C18 reversed phase column and water/0.1% formic acid and methanol as the mobile phase at a flow rate of 0.2 mL min−1. The recoveries of the method ranged from 78.8% to 119.8% for pendimethalin and from 73.7% to 108.8% for M455H001, and the relative standard deviation was lower than 16% for both analytes. The validated limit of quantification was 0.01 µg g−1 soil dry weight for both compounds. The matrix effects were evaluated and were less than 20% for both substances in the examined soil samples. It is concluded that the method is easy, with reasonable consumption of reagents, characterized by reliability and sensitivity, and therefore, it is suitable for monitoring the levels of pendimethalin and its major metabolite M455H001 in soils.

Occurrence and distribution of trifluralin, ethalfluralin, and pendimethalin in soils used for long-term intensive cotton cultivation in central Greece

ABSTRACT In the present study, a soil monitoring program was undertaken in Greek cotton cultivated areas in 2012. Twenty-seven soil samples were collected from the entire Thessaly plain in early summer of 2012, corresponding to approximately three months (current use of pendimethalin), up to one year (for the banned ethalfluralin), and three years (for the also banned trifluralin), after the last dinitroaniline application. Low but not negligible levels of dinitroanilines were detected, ranging from 0.01 to 0.21 μg g−1 d.w. for trifluralin and 0.01–0.048 μg g−1 d.w. for pendimethalin, respectively. Trifluralin was the herbicide most frequently detected (44.4%). The high historic application of trifluralin and its high persistence and accumulation potential is in line with the abundance of the detected residues. The present data indicate that soil samples contain extractable residues of banned trifluralin, but based on the comparison of the theoretical PECplateau for trifluralin (0.277 µg g−1) and the maximum Measured Environmental Concentration, it was concluded that the detected residues should be attributed to previous years’ application. The latter suggested the need for continual monitoring of the dinitroaniline family of pesticides, including the banned substances, aiming thus to an improved environmental profile for agricultural areas.

Determination of Arsenic in Honey, Propolis, Pollen, and Honey Bees by Microwave Digestion and Hydride Generation Flame Atomic Absorption

ABSTRACT The toxic properties of arsenic are well known. Honey has been widely used for monitoring this element. The present work reports a novel method for the determination of arsenic in honey, bees, pollen, and propolis, based on the coupling of microwave digestion and hydride generation. Method development included the quantitative reduction of arsenic(V) to arsenic(III), the acid used for dilution, and the complete removal of the gases following digestion. The method performance was satisfactory with recoveries between 83% and 111% and corresponding relative standard deviations between 3.1% and 24%. Among the 32 samples of honey, propolis, pollen, and honey bees analyzed, arsenic was detected in four out of six propolis samples at the method limit of detection (0.4 µg g−1). The results indicate that propolis may be an efficient indicator for arsenic.