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.

Measuring the level of environmental performance in insular areas, through key performed indicators, in the framework of waste strategy development.

To measure "something that is not there", is not easy and at the same time not fully understandable and perceived by the citizens. Several elements (such as, waste production, waste management cost, social attitude and behaviour, etc.) interrupt and disturb any strategy in the framework of waste management. Additionally, through the European Green Deal (EGD), Europe is trying to achieve climate neutrality by 2050, taking into account the Circular Economy Strategy (CES) and the United Nations Sustainable Development Goals (UNSDGs). A Driving Force-Pressure-State-Impact-Response (DPSIR) breakdown was applied, to establish and organize key information's on the environmental performance (E.P) taking into consideration the existing pollution, reviewing the contemporary knowledge and existing implemented waste strategies on the driving forces, pressures, states and impacts. This paper includes several key performed indicators (KPIs), in order to evaluate the E.P of an area, through hybrid approach which cover among others, the waste compositional analysis, SWOT and PESTEL analysis, waste recycling and waste accumulation index, prevention activities, awareness activities etc. The results indicate that, the selected areas implement periodic measures, but they need to put more effort to boost their citizens to participate in any proposed waste strategy. Furthermore, the results are very valuable and helpful to policy makers, consultants, scientists, competent authorities, stakeholders etc., in order to design and promote synergies and activities (mainly in Local Authorities), to reach the proposed figures that EGD, proposed in relation with the CES as well as with the SDGs.

Nematicidal Amendments and Soil Remediation.

The intensification of agriculture has created concerns about soil degradation and toxicity of agricultural chemicals to non-target organisms. As a result, there is great urgency for discovering new ecofriendly tools for pest management and plant nutrition. Botanical matrices and their extracts and purified secondary metabolites have received much research interest, but time-consuming registration issues have slowed their adoption. In contrast, cultural practices such as use of plant matrices as soil amendments could be immediately used as plant protectants or organic fertilizers. Herein, we focus on some types of soil amendments of botanical origin and their utilization for nematicidal activity and enhancement of plant nutrition. The mode of action is discussed in terms of parasite control as well as plant growth stimulation.

Use of clinoptilolite to improve and protect soil quality from the disposal of olive oil mills wastes.

In the framework of LIFE07 ENV/GR/000280 Project "Strategies to improve and protect soil quality from the disposal of olive oil mills wastes in the Mediterranean-PROSODOL", a laboratory experiment was conducted in order to investigate to which extent the natural zeolite clinoptilolite is capable of limiting environmental degradation caused by the uncontrolled disposal of olive oil mills wastes (OOMW). Clinoptilolite was added in various ratios (from 0% up to 30%w/w) to soil samples, which were collected from four OOMW disposal sites (from both the interior of the disposal ponds and the surroundings) located in a pilot Municipality in Rethymno, Crete, Greece. Water soluble K, Ca, Mg, Mn, Zn, Fe, Cu, polyphenols, NO3-, Cl-, SO4(2-) and PO4(3-) were measured in leachates after equilibration of the soil samples with clinoptilolite It was observed that water soluble K, NO3-, Cl-, SO4(2-) and polyphenols were decreased with an increase in zeolite percentage; Ca leaching was slightly increased or remained nearly constant; Mg leaching remained constant or increased, especially for pond soils; and PO4(3-) leaching was very low. Although the soil samples' content in available Mn, Cu, Zn, Fe was high, the metals were not detected in the leachates.

Simultaneous removal of Cu, Mn and Zn from drinking water with the use of clinoptilolite and its Fe-modified form.

Zeolites have been widely used in water treatment and especially clinoptilolite, due to its low cost and high abundance. It has large cation-exchange capacity and is capable of removing large quantities of heavy metals from contaminated water samples. By loading the surface of clinoptilolite with amorphous Fe-oxide species, a total improvement in adsorption capacity could be achieved. Thus, the Clin-Fe oxide system is capable of adsorbing significantly higher heavy metal concentrations than untreated clinoptilolite with simultaneous noticeable decrease in water hardness. Batch adsorption experiments have shown that Clin-Fe system has very large Cu, Zn and Mn adsorption capacity and for most of the cases the treated water samples were suitable for human consumption or agricultural use. New experiments were conducted to study the effectiveness of clinoptilolite and of the Clin-Fe system in removal of Cu, Mn, Zn, present simultaneously in water samples, so that the study of metal-sorbent chemical behavior and of the adsorption selectivity would be feasible. Desorption of metals was also examined and an integrated approach of the effectiveness of such materials in drinking water treatment is presented.

Synthesis of a clinoptilolite-Fe system with high Cu sorption capacity.

An iron oxide-clinoptilolite system was synthesized by adding natural clinoptilolite in an iron nitrate solution under strongly basic condition. The newly synthesized material has a red-brown color. A combination of XRD, FTIR and EPR spectroscopies, as well as specific surface area measurements and TG/DSC thermal analyses provided information on the type of Fe species located on the zeolite surface. Clinoptilolite seems to maintain its structure, while Fe(3+) species are in a symmetric environment (Th or Oh). The new material has a noteworthy high value of specific surface area (151 m(2)g(-1)) and is fully iron exchanged (Fe/Al=1.23). Differences in FTIR and TG/DSC spectrograms between the Fe-Clin system and untreated Clin were reported and explained. According to Cu adsorption/desorption experiments, carried out after the synthesis and characterization procedures, the Fe-Clin system is a promising new material since it adsorbs significantly larger Cu concentrations than clinoptilolite. This fact is owed to its high specific surface area and to its high negative surface charge. Desorption of Cu was also examined and it was observed that the Fe-Clin system desorbs smaller Cu amounts than untreated clinoptilolite.

Removal of Mn2+ ions from drinking water by using Clinoptilolite and a Clinoptilolite-Fe oxide system.

Clinoptilolite, a natural zeolite, was used for the synthesis of a high surface area Clinoptilolite-Iron oxide system, in order to be used for the removal of Mn2+ ions from drinking water samples. The new system was obtained by adding natural clinoptilolite in an iron nitrate solution under strongly basic conditions. The Clin-Fe system has specific surface area equal to 151.0 m2/g and is fully iron exchanged (Fe/Al = 1.23). Batch adsorption experiments were carried out to determine the effectiveness of the Clin and the Clin-Fe system in removal of manganese from drinking water. Adsorption experiments were conducted by mixing 1.00 g of each of the substrates with certain volume of water samples contaminated with 10 different Mn concentrations (from 3.64 x 10(-6) to 1.82 x 10(-2) M or from 0.2 to 1000 ppm). For the present experimental conditions, the Mn adsorption capacity of Clin was 7.69 mg/g, whereas, of Clin-Fe system was 27.12 mg/g. The main factors that contribute to difference adsorption capacity of the two solids are due to new surface species and negative charge of Clin-Fe system. In addition, the release of counterbalanced ions (i.e., Ca2+, Mg2+, Na+ and K+) was examined as well as the dissolution of framework Si and Al. It was found that for the most of the samples the Clin-Fe system releases lower concentrations of Ca, Mg and Na and higher concentrations of K than Clin, while the dissolution of Si/Al was limited. Changes in the composition of water samples as well as in their pH and conductivities values were reported and explained.