The status of organochlorine pesticide contamination in Greek agricultural soils: the ghost of traditional agricultural history.

Inadequate information regarding pesticide contamination in Greek agricultural soils is currently available, while national soil monitoring programs have not been initiated yet. The aim of the present study was to assess the levels, compositions, and distribution of thirty three organochlorine pesticides (OCPs) in Greek agricultural soils, due to the environmental threat posed by these compounds, even after decades from their abrogation from the market. Determination of the organochlorine pesticides was achieved using gas-chromatography-mass spectrometry, following a QuEChERS sample preparation method. A total of 60 soil samples, from two soil horizons (up to 60 cm), were obtained from agricultural lands in Greece throughout 2019-2020. The major findings presented DDTs, γ-HCH, alachlor, and 4,4- DCBP in the examined soil samples, with DDTs being the major compounds with their maximum cumulative concentration (ΣDDTs) reaching 1273.4 µg kg-1 d.w. Compositional profile and diagnostic ratios suggested that the occurrence of DDT residues was due to historical inputs. Most of the samples did not exceed the target values set by the Netherlands and Canadian guidelines for DDTs in soil; however, there was one exception in the case of Aegina Island. Finally, based on the environmental exposure assessment conducted, the vast majority of the analytes presented lower concentrations compared to the predicted environmental concentrations, with an exemption for DDE metabolite where the measured and predicted concentrations were almost equal.

Validation and Simultaneous Monitoring of 311 Pesticide Residues in Loamy Sand Agricultural Soils by LC-MS/MS and GC-MS/MS, Combined with QuEChERS-Based Extraction.

Soil can be contaminated by pesticide residues through agricultural practices, by direct application or through spray-drift in cultivations. The dissipation of those chemicals in the soil may pose risks to the environment and human health. A simple and sensitive multi-residue analytical method was optimized and validated for the simultaneous determination of 311 active substances of pesticides in agricultural soils. The method involves sample preparation with QuEChERS-based extraction, and determination of the analytes with a combination of GC-MS/MS and LC-MS/MS techniques. Calibration plots were linear for both detectors over the range of five concentration levels, using matrix-matched calibration standards. The obtained recoveries from fortified-soil samples ranged from 70 to 119% and from 72.6 to 119% for GC-MS/MS and LC-MS/MS, respectively, while precision values were <20% in all cases. As regards the matrix effect (ME), signal suppression was observed in the liquid chromatography (LC)-amenable compounds, which was further estimated to be negligible. The gas chromatography (GC)-amenable compounds showed enhancement in the chromatographic response estimated as medium or strong ME. The calibrated limit of quantification (LOQ) value was 0.01 µg g-1 dry weight for most of the analytes, while the corresponding calculated limit of determination (LOD) value was 0.003 µg g-1 d.w. The proposed method was subsequently applied to agricultural soils from Greece, and positive determinations were obtained, among which were non-authorized compounds. The results indicate that the developed multi-residue method is fit for the purpose of analyzing low levels of pesticides in soil, according to EU requirements.

Experiments on Pilot-Scale Constructed Floating Wetlands Efficiency in Removing Agrochemicals.

The efficiency of constructed floating wetlands (CFWs) in their ability to remove agrochemicals (nutrients and pesticides) is here investigated in a series of pilot-scale systems. Four experimental CFWs were designed and constructed; three of them were planted with the aquatic plant species Lemna minor, Azolla pinnata and Eichhornia crassipes. The fourth did not contain any plants and was used as the control. The aim of the study was to evaluate the efficiency of CFW containing aquatic macrophytes in the reduction of pesticides and nutrients, under field conditions. The CFWs operated continuously from May 2021 to September 2021, and their removal efficiencies of nitrogen and phosphorus ions, and five commonly used pesticides were examined. The CFW systems were fed daily with agricultural wastewater which was prepared by mixing a fertilizer and predetermined doses of pesticides. The hydraulic residence time was kept at 14 days. Samples were collected on a weekly basis from both the influent and the effluent of each experimental tank, and were subsequently analyzed in the laboratory. HPLC-DAD and Ion Chromatography were implemented for sample analysis following a very simple sample preparation. Reductions for nutrient ranged from no reduction to 100% removal, whereas for pesticides these varied from no reduction to 98.8% removal, indicating that these systems can be used as efficient and low-cost pollution control technologies for agrochemical wastewater treatment. Significant reduction for certain pesticides was also observed in the algae control tank, thus, proving the efficiency of algae in organic pollution reduction, and recognizing the limitations of aquatic plant use in decontamination.

Determination of azoxystrobin, topramezone, acetamiprid, fluometuron and folpet in their commercially available pesticide formulations by liquid chromatography.

A rapid, simple, precise and accurate high performance liquid chromatographic (HPLC) analytical method was developed and validated for the determination of the active substances (a.s.) azoxystrobin, topramezone, acetamiprid, fluometuron and folpet in their respective commercially available formulations. The method was used for the analysis of samples under the frame of the national quality control program of plant protection products in the Greek market. Chromatographic separation of the active substances from additives and co-formulants is achieved using isocratic elution with acetonitrile and 0.1% phosphoric acid solution (60:40 v/v) at a flow rate of 0.4 mL min-1 on a C18 monolithic column (Chromolith Performance-RP18e 100 × 4.6 mm) and UV detection at 230 nm. Validation parameters of the method fulfilled acceptability criteria. Recovery of all individual compounds was in the range 97.8-100.9%. Precision expressed as relative standard deviation was lower than the theoretical values of the modified Horwitz equation. Correlation coefficients of linearity of response were better than 0.999. The benefits of the proposed method are significant reduction in analysis time and total cost since all analytes were determined with the same extraction procedures and chromatographic system. Analysis of real samples for all active ingredients confirmed fitness for purpose of the suggested method.

Investigation of the presence of glyphosate and its major metabolite AMPA in Greek soils.

Glyphosate is a broad-spectrum, non-selective, post-emergence herbicide that controls weeds by inhibiting their ability to synthesize amino acids. It is characterized by high persistence and adsorption to soil, with its dissipation to be highly correlated to the climatic conditions. After its degradation in soil, aminomethylphosphonic acid (AMPA) is the sole and major metabolite produced, characterized also by high persistence and adsorption. Both substances have the potential to remain in soil rather than move to other environmental compartments. Considering the recent intense debate during the EU renewal of glyphosate along with its wide use, it is apparent that both glyphosate and AMPA require further attention and information on their occurrence and distribution in EU soils. The present study does constitute the first extended soil monitoring survey of glyphosate and AMPA with samples derived during the years 2013-2015, from the highest extent of the Greek territory. Specific attention was given to areas of high agricultural production as well as to urban areas, since glyphosate-containing products are also registered for non-professional uses. The positive samples represented the 36.7% for glyphosate and 44.9% for AMPA, while the detected residues fluctuated from 0.026 to 40.6 µg g-1 and from 0.01 to 2.5 µg g-1 for glyphosate and AMPA, respectively. Our findings can constitute a basis for the determination of the background concentration levels of glyphosate and its metabolite in the Greek territory. As such, apart from being the first study for glyphosate monitoring in Greece, the most significant highlights recognized in the present work are the following:The high levels of glyphosate and AMPA residues in urban areas that indicate possible misuse of pesticidesThe generally low detection in the main agricultural basins and particularly near water recipientsThe fact that a potential for misuse of herbicides cannot be excluded even in the case of agricultural areas (considering that the maximum detection was in an olive grove and exceeded the model-predicted concentrations by 13 times).

Monitoring of glyphosate and AMPA in soil samples from two olive cultivation areas in Greece: aspects related to spray operators activities.

The persistence of glyphosate and its primary metabolite AMPA (aminomethylphosphonic acid) was monitored in two areas in Southern Greece (Peza, Crete and Chora Trifilias, Peloponnese) with a known history of glyphosate use, and the levels of residues were linked to spray operators' activities in the respective areas. A total of 170 samples were collected and analysed from both areas during a 3-year monitoring study. A new method (Impact Assessment Procedure - IAP) designed to assess potential impacts to the environment caused by growers' activities, was utilised in the explanation of the results. The level of residues was compared to the predicted environmental concentrations in soil. The ratio of the measured concentrations to the predicted environmental concentrations (MCs/PECs) was > 1 in Chora the first 2 years of sampling and < 1 in the third year, whilst the MCs/PECs ratio was < 1 in Peza, throughout the whole monitoring period. The compliance to the instructions for best handling practices, which operators received during the monitoring period, was reflected in the amount of residues and the MCs/PECs ratio in the second and especially the third sampling year. Differences in the level of residues between areas as well as sampling sites of the same area were identified. AMPA persisted longer than the parent compound glyphosate in both areas.

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

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 [Formula: see text], 79.3-100% for [Formula: see text], 76.7-100% for [Formula: see text], 79.4-100% for [Formula: see text] 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.

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

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.

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.

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 famoxadone and cymoxanil in commercial pesticide formulation by high performance liquid chromatography using a C18 monolithic rod column.

The extensive use of plant protection products in urban and rural pest control obliges to develop valid analytical methods for their successful and reliable quality control. An analytical procedure for the simultaneous determination of famoxadone and cymoxanil, by reversed phase high performance liquid chromatography based on the use of a monolithic C18 column has been developed and validated. The method involved the extraction of the active ingredients by sonication of the sample with acetonitrile and direct injection on a reversed phase liquid chromatographic system. The repeatability of the method expressed as relative standard deviation (%RSD), was lower than 1 % for both compounds. The limits of quantification for famoxadone and cymoxanil were 10 and 16 µg mL(-1) respectively. The new method involves a considerable reduction in time for both sample preparation and analysis. The proposed analytical procedure is accurate and precise.

Photodegradation of the herbicide azimsulfuron using nanocrystalline titania films as photocatalyst and low intensity Black Light radiation or simulated solar radiation as excitation source.

Aqueous solutions of the herbicide azimsulfuron have been treated by a photocatalytic process employing titania nanocrystalline films as photocatalyst. Results showed that solutions of this herbicide at maximum possible concentration can be photodegraded in a time of a few hours by using low intensity UVA radiation comparable with that of the UVA of solar noon. Similar results have also been obtained with simulated solar radiation. Thus heterogeneous photocatalysis can be employed for the treatment of waters polluted by this herbicide.

Development and single-laboratory validation of a new gas chromatographic multi-pesticide method of analysis of commercial emulsifiable concentrate formulations containing alachlor, chlorpyrifos methyl, fenthion and trifluralin as active ingredients.

A multi-pesticide (MP) method was developed and single-laboratory validated for the quality control of commercial pesticide products containing alachlor, chlorpyrifos methyl, fenthion and trifluralin as active ingredients (a.i.). A capillary gas chromatographic system with flame ionization detection (FID) and a programmable temperature vaporising split injector was used. The performance characteristics (specificity, linearity, precision and repeatability) of the method satisfied international acceptability criteria.