Dithiocarbamates (DTCs) are a group of chemicals used primarily as fungicides, although they are exploited for various other applications. DTCs represent one of the oldest classes of broad-spectrum fungicides employed worldwide to control fungal diseases on many crops. Due to their ease of synthesis, low production costs (cheap and readily available starting materials) and a fungicidal activity with a multi-site mode of action, they are still among modern agriculture’s most extensively used pesticides. Although the environmental degradation in air, water, and soil is relatively rapid due to photolysis and/or hydrolysis, they are among the most frequently detected pesticides in the European Union (EU), also with a high frequency of maximum residue level (MRL) exceedances. The current review aims to comprehensively survey all aspects of DTCs, including the environmental fate, toxicity and analytical methods for determining parental compounds and degradation products in environmental and food samples. Furthermore, the accumulation of carbamate and dithiocarbamate pesticides in vegetables, fruits, bioindicator organisms and human biological samples, as well as their health effects on humans, are also considered in this study.
Karst aquifers are essential drinking water sources, representing about 25% of the total available sources globally. Groundwater ecosystems consist of fissured carbonate rocks commonly covered with canopy collapse sinkholes. The open nature of karst aquifers makes them susceptible to rapidly transporting contaminants from the surface in dissolved and particulate forms. The principal aim of this review is to contribute to filling the gap in knowledge regarding major concerns affecting karst aquifers and understanding their vulnerabilities and dynamics. The principal groundwater pollutants of relevance are detailed in the present work, including well-known issues, such as the input of agriculture and its role in water quality. Emerging pollutants such as microplastics, still poorly studied in the groundwater systems, were also considered. Case studies for each typology of pollutant were highlighted, as their relative concerns for karst environments. Final considerations underlined an approach for studying karst environments more focused on understanding dynamics and links among different pollutants inputs and their drivers than on individual sources and impacts.
Glyphosate is the best-selling herbicide worldwide. The toxicity on ecosystems and the possible effects on human health have long been at the centre of a complex controversy concerning the authorisation for its use. The peculiar chemical-physical properties of glyphosate, AMPA and glufosinate make their determination at trace levels in the water a real analytical challenge. All three compounds can be derivatised to less polar ones and FMOC-Cl (9-fluorenylmethyl chloroformate) is the most common pre-column derivatisation reagent used for this analysis. It can be successfully combined with Ultra-High-Performance Liquid Chromatography with Mass Spectrometry (UHPLC-MS/MS) to determine all three analytes in one method as part of water monitoring programs. The developed method aims to determine glyphosate with AMPA and glufosinate at sub-micrograms/L levels in groundwater, surface and water by UHPLC-MS/MS after derivatisation with FMOC-Cl. The novelty of this method is its high simplicity, robustness and sensitivity allowing the identification and quantification of the compounds at the detection limits required by the European regulations (0.1 µg /L). No pre-concentration or purification steps (by using Solid Phase Extraction cartridges) are necessary for our method saving time and consumables costs. The method demonstrated an excellent linear relationship (R2 ≥ 0.999) in the concentration range from 0.025 to 10 µg /L for glyphosate and AMPA and 0.025 to 5 µg /L for glufosinate. The method Limit Of Quantification (LOQ) is 0.025 µg/L, the lowest among all previously published studies, and it was demonstrated according to the European SANTE guidelines.
Environmental pollution is caused by the unsustainable use of nitrogen (N) fertilizers and pesticides. Biochar (BC) is a carbon-based material applied to remove excess nutrients and pesticides from the environment. In pot experimental research, N fertilizer and pesticides alone and different biochar types were applied in the soil to evaluate cauliflower growth, soil quality, and leaching of agricultural contaminants. BC addition had increased nutrient availability based on feedstock origin. The surface structure results by SEM showed that the BC pore size was equal to 8.94 and 7.24 µm for mixed biochar and wood biochar, respectively. Nitrate concentrations in percolation water were 43.78 and 76.82 mg/L in mixed biochar and wood biochar, respectively. In soil treated with fertilizer and pesticides, was equal to 106.76 mg/L. Biochar’s binding with pesticides depends on its nature and structure. Adding wood biochar significantly reduced the leaching of fungicide compared to unamended soil, with a contraction of 327.86 and 3576 ng/L. Mixed biochar was more efficient for herbicide mitigation. FTIR was used to identify the functional groups on biochar-amended soil that play a role in the adsorption of agricultural compounds. Research shows that the BC application greatly affects the pesticide fate and N compounds of agricultural origin in soil.
Recently modern methodologies allowed the improvement of conventional bioventing strategies in an engineering technology known as smart passive bioventing (S-PBv). The latter is an increasingly used application to reduce the concentrations of organic contaminants below the relative value of contamination threshold concentration (CSC). The S-PBv exploits the natural fluctuations of atmospheric pressure, which allow air to enter into the subsoil, to facilitate natural remediation processes. In this way, the efforts in terms of economics resources in the remediation process are minimised, the risk of pollutants volatilization is drastically reduced, and the degradation favoured by microorganisms is promoted. Our study aims to provide the essential information to plan a series of in situ tests (pilot test) to verify the applicability of this remediation technology, through the use of intelligent sensors designed and engineered using open-source hardware and software.
The topic of diffuse pollution is of particular interest from technical, scientific, and administrative management points of view. Diffuse pollution is defined as the contamination or chemical, physical, or biological alterations of environmental matrices caused by diffuse sources and not attributable to a single origin. In this study, various sources of diffuse pollution such as nitrates, pesticides, metals, and plastics were analysed. This was aimed at the implementation of a decision support system able to represent the state of environmental matrices degradation, with particular attention to water resources, and to make decisions evaluating similar environmental contexts. The potential of the developed system makes it possible to identify areas with the same environmental characteristics, referring to the various activities that create diffuse pollution and areas with the same pressure values on the environmental matrices. The system provides the political decision-maker with greater awareness of the environmental state, thus enabling him to apply more accurate land management policies. The created system, based on open-source software, which can be implemented with additional available data sources, is characterised by a data processing workflow that provides output information at the municipal level, so that it can be managed both by mayors and regional managers who are able to share the same information with all.