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 broadspectrum 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.

Remediation interventions based on the native bacteria's capability to reduce Cr(VI) represent a valid strategy in terms of economic and environmental sustainability. In this study, a bioremediation test was carried out using viable microcosms set with groundwater and deep soil (4:1), collected from the saturated zone of an industrial site in Southern Italy that was polluted by ~130 µg L of Cr(VI). Conditions simulating the potential natural attenuation were compared to the enhanced natural attenuation induced by supplying yeast extract or polyhydroxybutyrate. Sterile controls were set up to study the possible Cr(VI) abiotic reduction. No pollution attenuation was detected in the unamended viable reactors, whereas yeast extract provided the complete Cr(VI) removal in 7 days, and polyhydroxybutyrate allowed ~70% pollutant removal after 21 days. The incomplete abiotic removal of Cr(VI) was observed in sterile reactors amended with yeast extract, thus suggesting the essential role of native bacteria in Cr(VI) remediation. This was in accordance with the results of Pearson's coefficient test, which revealed that Cr(VI) removal was positively correlated with microbial proliferation (n = 0.724), and also negatively correlated with pH (n = -0.646), dissolved oxygen (n = -0.828) and nitrate (n = -0.940). The relationships between the Cr(VI) removal and other monitored parameters were investigated by principal component analysis, which explained 76.71% of the total variance.

The exponential growth of the human population requires an increasing application of nitrogen (N) fertilizers, causing environmental pollution. Biochar (B) amended soil has been suggested as a sustainable agricultural practice to improve crop yield and mitigate agricultural pollutants' contamination. Evaluating the effect of fertilization on Brassica crops, in combination with spectral analysis, may specify changes in the chemical composition of the vegetable as a result of N fertilization. This study characterized cauliflower tissues treated with N fertilizer and biochar, employing Fourier Transform Infrared spectroscopy. The experiment was conducted in cauliflower mesocosms treated with two doses of N fertilizer (130 and 260 kg N ha?1) with or without B. Attenuated total reflectance fractions were used to characterize fractions of curds, leaves, stems, and roots in the infrared using a Fourier transform. Principal component analysis was performed to classify the main differences among cauliflower tissues concerning treatments. FTIR spectra of Brassica oleracea L. var. botrytis tissues were related to nitrogen-based agricultural practices. The specific molecules associated with functional groups in cauliflower tissues were phenols, amides, proteins, amines, and glucosinolates. Biochar amended soil resulted in higher peaks that correspond to the stretching of phenols and proteins. The application of sustainable nitrogen fertilizers might influence the absorption bands characteristic of cauliflower's typical metabolites. The research allows the identification of Brassicaceae's functional molecules with a potential agronomic application.

Over the years, many plant species have been studied to find the ones that can best be used in PlantAssisted BioRemediation (PABR) techniques. The PABR has established itself as one of the most ecosustainable and effective methods to recovery contaminated areas, thanks to the processes promoted by the interactions established between root system and soil rhizosphere microorganisms (Ancona et al. 2022). Plant species belonging to the Brassicaceae family are the most studied for the recovery of contaminated areas. The interest is due to their capability to be moderate tolerant to the contaminants present in the environment and to phytoextract pollutants (especially heavy metals), accumulating them in their epigeal tissues (Belouchrani et al. 2016; Angelova et al. 2017). Among these, the use of Brassica napus L. has been particularly thorough also due to the possibility of reusing its biomass for the production of secondary valuable products, such as oil for biofuel and ethanol (Park et al. 2012; Dhiman et al. 2016). To enhance the efficiency of PABR, the addition of organic amendments was extensively tested. In fact, it was studied that organic matters, such as compost or biochar, are useful to improve soil chemical-physical and microbiological properties and, consequently, to stimulate the pollutants' degradation or extraction (Ancona et al. 2022). In the present study, three series of soil microcosms have been performed at greenhouse scale. Brassica napus L. was growth in a soil historically contaminated by polychlorobyphenils (PCBs) and heavy metals (HMs). Compost and biochar were tested as amendments (10% and 2.5%, respectively). Three conditions were set up, each with and without plant, as control (Fig.1): contaminated soil, contaminated soil + compost, contaminated soil + biochar. At each sampling times (0, 60 and 90 days) each condition was analysed in triplicate. Chemical-physical analyses (pH, electric conductivity, available phosphorus, organic carbon), microbiological and molecular analyses (microbial abundance, community structure and dehydrogenase activity) and contaminants analyses (PCBs, HMs) were carried out on soil at the different sampling times. To evaluate the uptake, contaminants were also investigated in plant tissues (roots, stem, leaves and flowers).

The presence of Cr (VI) in groundwater, at concentrations significantly higher than legal limits, represents a widespread environmental problem. Environmental contamination is mainly related to the incorrect management of process water and byproducts coming from numerous industrial processes involving chromium. Groundwater remediation can be conveniently achieved by reducing Cr (VI) to Cr (III), since the latter is less soluble and less mobile through environmental matrices, as well as a hundredfold less toxic for living organisms than Cr(VI). Biological reduction is potentially advantageous in terms of economic and environmental sustainability, especially in the case of large volumes of water. Ubiquitous organisms, characterized by high metabolic plasticity, such as bacteria, are able to detoxify the environment surrounding the cell by reducing Cr (VI). However, these microorganisms are generally heterotrophic and need an external source of nutrients to support their growth and reproduction, especially in oligotrophic environments such as groundwater. Enhanced natural attenuation can be achieved by supplying suitable amendments that can both support bacterial biomass production and provide electrons for reductive processes. The NGS technologies applied to the 16S rDNA region can provide the structure of the native bacterial community, highlighting changes before and after treatment. This approach also allows investigating a possible amendment-driven enrichment of chromium-reducing bacteria. The capability of indigenous bacterial consortia to remediate Cr(VI)-polluted groundwater was investigated by a bioremediation test carried out at a microcosm scale. Microcosms setup was performed using deep saturated soil and groundwater collected from an industrial site in the territory of Barletta Municipality, where Cr(VI) was detected in groundwater at a concentration of about 140 µg L -1 . The effectiveness of two different amendments for Cr(VI) removal was tested. Results showed a clear dependence of Cr(VI) decay on the amendment used. Notably, yeast extract (200 mg L -1 ) provided the highest Cr(VI) removal, in comparison with polyhydroxybutirrate (180 mg L -1 ), whereas no removal was detected in the not amended control reactors. Bioinformatic analyses are ongoing in order to investigate changes in the bacterial community structure.

Plant-assisted bioremediation (PABR) is a strategy based on interactions between plants and microorganisms in the rhizosphere, which promotes a reduction in soil contaminants. In fact, the plant root system can stimulate microbial activity in the rhizosphere favoring decontamination processes (biodegradation of organic xenobiotics and removal/transformation of the inorganic ones). In the last few years, several laboratory, greenhouse, and field studies were carried out to assess the effectiveness of PABR technology in recovering multi-contaminated soils. At laboratory scale, microcosm experiments allow studying natural soil microbial populations under controlled environmental conditions (e.g., temperature, light, humidity, and so on). Recently, sunflower has been proposed for plant-assisted bioremediation purposes. This plant species was demonstrated to be able to absorb various heavy metals (e.g., Zn, Cu, Pb, etc) through its root system. Moreover, sunflower effectiveness in degradation of Persistent Organic Pollutants (e.g., DDT, endosulfan, different chlorinated compounds, and polychlorinated biphenyl-PCBs) was verified recently. In this work, a sunflower microcosm experiment was carried out for 3 months to assess sunflower capability in restoring soil historically contaminated by PCBs and heavy metals (HM). The soil was collected from a survey site located close to Taranto city (Southern Italy). Four different experimental conditions (presence/absence of compost and/or plant) have been set up. Chemical analyses of soil properties (e.g., pH, EC, OC, available phosphorous) and pollutants (PCBs and HMs) were performed at two sampling times (45, 90 days). Moreover, microbial abundance, dehydrogenase activity, and qPCR assays were performed for evaluating the autochthonous microbial community composition, structure, and functioning. Finally, a root exudates screening was carried out on planted pots in order to investigate the potential microbial-plant interactions occurring in sunflower-assisted bioremediation microcosm experiments.

In agriculture, biochar (B) application has been suggested as a green technology to reduce nitrate pollution from agricultural origins and improve crop yield. The agronomic impact of B use on soil has been extensively studied, while knowledge of its possible effects on horticultural cultivation is still scarce. A greenhouse experiment was conducted to evaluate the effect of using biochar in soils treated with two different rates of nitrogen fertilizers on soil properties and nitrogen (N) leachate. This study also investigated the vegetative parameters during the crop growing season of Brassica oleracea L. var. botrytis. Soil mesocosms were set up to test the following treatments: untreated/control (C); normal dose of N fertilizer (130 kg N ha-1) (ND); ND+B; high dose of N fertilizer (260 kg N ha-1) (HD); and HD+B. Principal component analysis and cluster analysis were exploited to assess biochar's ability to reduce nitrate leaching and enhance soil-vegetative properties. Biochar addition affected the soil chemical properties of the fertilized microcosms (ND and HD). Biochar increased the NH+4 content in HD soil and the NO-3 content in ND soil by 26 mg/L and 48.76 mg/L, respectively. The results showed that biochar application increased the marketable cauliflower yield. In ND+B and HD+B, the curd weight was 880.68 kg and 1097.60 kg, respectively. In addition, a small number of nitrogenous compounds in the leachate were quantified in experimental lines with the biochar. Therefore, biochar use improves the marketable yield of horticulture, mitigating the negative impacts associated with the mass use of N fertilizers in agriculture.

This paper reports the application of organic amendments, such as biochar (BC) or compost (CMP) in a Plant-assisted bioremediation (PABR) strategy of a soil contaminated by polychlorinated biphenyls (PCBs) and heavy metals (HM). BC and CMP were applied for improving PABR in specific plots where the highest amounts of PCBs were present. Before the organic treatments and six months after it, soil samples and plant tissue (leaves, shoots and roots) were collected from each investigated plot and chemical and microbiological analyses performed. Moreover, micro-X ray fluorescence (µXRF) analysis was performed on soil and biomass (leaves, roots). Preliminary results evidenced different effects of the CMP or BC on promoting PCB and HM removal, depending on the initial pollutant concentrations

Nitrogen is a vital nutrient helpful to plants and crop growth. However, among the leading causes of water resources pollution is the excess nitrogen from agricultural sources. In European Union countries, the Nitrates Directive has been approved to reduce this problem monitoring of water bodies with regard to nitrate concentrations, designation of Nitrate Vulnerable Zones (NVZs), and establishing codes of good agricultural practices and measures to prevent and reduce water pollution from nitrates. In light of this, we propose an integrated methodological approach to better manage a environmental issue as the perimeter of NVZs with the prospective that our approach could be used in the future by other member states representing a Best Practice in that direction. The methodology is based on data integration applied in a GIS environment. Different available data representing the knowledge of the territory were harmonised, systematised and georeferenced, in order to increase the environmental framework, preserve the contamination of the water resource and give indications on the measures to be implemented to apply in the best way possible the Nitrates Directive. Finally, it was also possible to overcome the infringement procedure in progress for Italy and the Puglia region and proceed to new designation of NVZs

In this review, we examined the European legislative context on water protection concerning pesticide residues monitoring and the relevant National Action Plans and strategies that were undertaken in European countries to better identify and manage the problem in water bodies. Furthermore, we illustrated the development of analytical methodologies and criticalities connected to determine pesticide residues in water matrices, including sampling, sample preparation approaches, instrumental techniques and specific applications emphasising those works published after 2015. Details about sampling strategies, analytical feasibility, official methods, degradation products and behaviour in the environment for a subset of 160 pesticides are also provided.

La Regione Puglia con Deliberazione di Giunta n.2273 del 02.12.2019, in adempimento a quanto previsto dalla Direttiva 91/676/CEE relativa alla protezione delle acque dall'inquinamento provocato dai nitrati provenienti da fonti agricole e dal D.Lgs. n.152/2006, ha provveduto alla periodica Revisione delle Zone Vulnerabili da Nitrati di origine agricola (ZVN) approvando la proposta motivata di revisione delle Zone Vulnerabili ai Nitrati di origine agricola (contenuta nel documento "Workflow metodologico finalizzato alla perimetrazione delle nuove ZVN"). Con tale revisione si è provveduto alla rivalutazione dell'inquinamento da nitrati nelle acque superficiali e sotterranee, nonché alla prima valutazione dell'eutrofizzazione nelle acque superficiali che ha comportato un notevole incremento dell'estensione territoriale delle zone vulnerabili. Successivamente, con Deliberazione di Giunta n.389 del 19.03.2020 si è provveduto alla rettifica di meri errori materiali rilevati nell'Appendice in coda all'allegato 1 della DGR 2273/2019, contenente l'elenco dei fogli catastali interessati dal vincolo.

Nitrogen (N) is a fundamental nutrient for plant growth and for the performance of biological functions. In agroecosystems, nitrogen fertilization is aimed at providing a suitable N dose for crop growth, avoiding the impoverishment or the improper enrichment of nitrogen compounds in soil. The high application of nitrogen fertilizers is the main cause of the increase in nitrate leaching and loss of the quality of natural resources (groundwater and soil). In the last decades, new sustainable technological approaches have been developed and applied on laboratory and field scales to reduce the impacts of nitrogen pollution on the environmental matrices and to improve the sustain-ability of agricultural management. This review highlights the results of the implementation of sustainable remediation new strategies to reduce pollution from a main agricultural contaminant (nitrate) and describes the benefits obtained from the use of these solutions in agroecosystems.

The growth of horticultural species is closely related to the availability of nitrogen (N), whose physiological role is of great importance. Considering both the demand for nitrogen for agricultural yield and the easy leaching of nitrogen compounds, the amount of this soil nutrient is carefully assessed for implementing suitable fertilization programs. Excessive use of nitrogen fertilizers causes nitrate pollution with quality loss of drinking water aquifers and eutrophication phenomena. In recent years, the slow release of nitrate by the application of carbon-rich amendment (i.e. biochar) has been suggested as a potential strategy for increasing the bioavailability of nitrogen nutrients and reducing nitrate leaching. Biochar is a promising sustainable tool to improve the yield of horticultural crops and reduce the use of mineral fertilizers in agroecosystems. The incorporation of biochar along with controlled doses of nitrogen mineral fertilizers could have a potential for mitigation of leached nitrates in surface water bodies and groundwater. The aim of this work is to assess the effect of different levels of N in soil with and without amendment of virgin wood biochar on crop yield, quality, and release of nitrates into the soil. The main objective is the characterization of plant materials of Brassica oleracea L. var. botrytis, in different doses of nitrogen and treatments with biochar, by analysis of Fourier Transform Infrared spectra. In this study, cauliflower was grown in mesocosms using two types of fertilization regimes: (1) dose of conventional inorganic fertilizer with and without biochar, (2) dose of high inorganic fertilizer with and without biochar. Soil biological and physicochemical properties and, the quantification of nitrogenous compounds in the percolation water, are studied in samples collected 10 days after each fertilization and at the end of the experiment (complete ripening of the corymb). Biomass samples are characterized by ATRFTIR spectroscopy. The experimental approach tested in this work intends to evaluate the biochar capabilities in preventing the loss of nitrates in horticultural systems, reducing the demand for nitrogen fertilizers, and improving agricultural yield.

Plant-assisted bioremediaton (PABR) is an effective green technology for removing contaminants from soils. It relies on the sinergistic interactions between roots and microrganisms of the rhizosphere for removing, transforming and contain toxic compounds. Poplars were proved to be very efficient in promoting degradation of chloride organic pollutants such as lindane and polychlorobyphenils (PCBs) in both laboratory and field scale experiments. Due to their high molecular stability, low solubility in water and high tendency to adsorb on particulate phase, PCBs are extremely hard to remove from soil. In this work, some crucial aspects of the PABR strategy in recovering two historically contaminated areas, located in Southern Italy, characterized by different PCB amounts (medium and high concentrations, respectively), are illustrated.Two poplar treated areas, inside the survey site, were set up at a distance of two years from each other (2013 and 2015, respectively). In the first one, characterized by a medium PCB contamination level (PCB ~250 ng/g) about 600 poplar cuttings were planted; instead, in the second one, affected by high PCB contamination (PCB >2000 ng/g), about 750 poplar cuttings were planted.Chemical investigations of soil properties and pollutants (PCB congeners) were carried out before plantation and at different times after poplar planting, in both the PABR treated areas. Moreover, microbial analyses such as the total microbial abundance (DAPI counts), cell viability (live/dead method), microbial activity (dehydrogenase activity) and the sequencing of 16S DNA (Miseq-Illumina) were performed for evaluating microbial community structure and functioning in the poplar rhizosphere. Moreover, in March 2019, a compost (CMP) or biochar (BC) treatment was also performed on some contaminated plots inside the highest polluted poplar treated area in order to increase soil quality and promote PCB degradation.The results obtained in the first poplar treated area, affected by medium PCB contamination, showed the effectiveness of PABR in restoring this area, promoting active bacteria able to degrade and contain pollutants and increase soil quality. In the second poplar treated area, the high PCB levels and the soil nutrient impoverishment favouring stress conditions for poplars limiting their growth. The addition of the fertilizers (compost or biochar) promoted an increase in soil quality and microbial activity promoting the bioremediation processes.

Documento di scoping della VAS

Chromium is a potentially toxic metal occurring in water and groundwater as a result of natural and anthropogenic sources. Microbial interaction with mafic and ultramafic rocks together with geogenic processes release Cr (VI) in natural environment by chromite oxidation. Moreover, Cr (VI) pollution is largely related to several Cr (VI) industrial applications in the field of energy production, manufacturing of metals and chemicals, and subsequent waste and wastewater management. Chromium discharge in European Union (EU) waters is subjected to nationwide recommendations, which vary depending on the type of industry and receiving water body. Once in water, chromium mainly occurs in two oxidation states Cr (III) and Cr (VI) and related ion forms depending on pH values, redox potential, and presence of natural reducing agents. Public concerns with chromium are primarily related to hexavalent compounds owing to their toxic effects on humans, animals, plants, and microorganisms. Risks for human health range from skin irritation to DNA damages and cancer development, depending on dose, exposure level, and duration. Remediation strategies commonly used for Cr (VI) removal include physico-chemical and biological methods. This work critically presents their advantages and disadvantages, suggesting a site-specific and accurate evaluation for choosing the best available recovering technology.