Assessing glyphosate and AMPA pesticides in the Ofanto River waters and sediments.

In the present study, we determined glyphosate (GPS) and aminomethylphosphonic acid (AMPA) in the water and sediments of the Ofanto River (Italy), evaluating their transport from the mouth to the sea. Sediments were collected twice in 2021 during low and high tide; waters were sampled on a seasonal basis. The results showed the prevalence of GPS and AMPA in the water with concentrations equal to 190 and 3053 ng/l, respectively. We also found GPS and AMPA in the sediments with values of 0.95 and 11.34 ng/g. In water, pesticides were detected in all seasons with peaks in concentrations during summer and spring. A significant positive correlation between the pesticides in the sediments and the water pH and a negative correlation with salinity was observed. An estimation of the average loads revealed a discharge of 64.11 kg/yr. of GPS and 958.37 kg/yr. of AMPA from the river to the marine environment.

Dithiocarbamates: Properties, Methodological Approaches and Challenges to Their Control.

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.

Fourier Transform Infrared Spectroscopy to Assess the Degree of Alteration of Artificially Aged and Environmentally Weathered Microplastics.

Fourier transform infrared (FTIR) is a spectroscopy technique widely used to identify organic materials. It has recently gained popularity in microplastic (MP) pollution research to determine the chemical composition of unknown plastic fragments. However, it could also be used to evaluate the degree of ageing of MPs collected from the environment. In this context, the principal aim of our research has been to qualitatively evaluate the natural weathering of environmental MPs collected in an Italian freshwater body (the Ofanto River) using ATR-FTIR technology. Furthermore, we compared environmental particles to weathered artificial MPs under controlled light and temperature conditions and to unaltered pristine materials to assess the results. FTIR spectra were acquired using a Nicolet Summit FTIR (ThermoFisher Scientific) equipped with an Everest ATR with a diamond Crystal plate and a DTGS KBr detector (wavenumber range 4000-500 cm-1, 32 scans per spectrum, spectral resolution of 4 cm-1). The degree of ageing was assessed using three different indexes known to be related to changes in MPs: Carbonyl Index (CI), Hydroxyl Index (HI), and Carbon-Oxygen Index (COI). The overall results showed that the regions reflecting changes (hydroxyl groups, peaks from 3100 to 3700 cm-1, alkenes or carbon double bonds, 1600 and 1680 cm-1, and carbonyl groups, 1690 and 1810 cm-1) appeared significantly modified in artificial and natural weathered particles compared to the pristine materials. The indexes calculated for polymers degraded under the artificial photo and thermo ageing conditions displayed a general tendency to increase with the time in contact with irradiation time. Particular enhancements of CI of PS fragment and PE pellet, HI of PE and PS fragments and PE pellet, and COI of PS fragment were observed. Otherwise, the following incubation of the same particles at a constant temperature of 45 °C did not further affect the chemical composition of the particles. Moreover, new unique peaks were also observed in the freshwater particles, almost all in the fingerprint region (1500-500 cm-1). Differences in CI, HI, and COI were evidenced among the different morphological MP shapes. On the one hand, the CI calculated for the environmental PE pellets showed values ranging from 0.05 to 0.26 with a mean value of 0.17 ± 0.10. Most samples (57%) presented a CI with values between 0.16 and 0.30. On the other hand, fragments presented slicer modifications in the carbonyl region with CI values lower than pellets (0.05 ± 0.05). This index helps evaluate the degradation of PE MPs by UV light, increasing with enhancing residence time in the environment. Conversely, fragments showed greater values of HI (5.90 ± 2.57) and COI (1.04 ± 0.48) than pellets, as well as lines, which presented the maximum value of HI (11.51). HI is attributed to the bond vibrations of hydroxyl, carboxyl, or phenol groups. In contrast, COI is frequently attributed to the vibrations of C_O bonds found in carbohydrates, alkanes, secondary alcohols, and ketones. In conclusion, our results showed characteristics spectra acquired from environmental particles compared to pristine and artificial aged ones. The interpretation of our main results emphasizes the need to conduct ecotoxicological experimental studies using naturally weathered particles due to the unicity of their properties, which are more helpful for understanding microplastic pollution effects.

Assessment of metals associated with virgin pre-production and freshwater microplastics collected by an Italian river.

Recently, microplastics (MPs) have been detected in almost all environmental matrices (water, soil, air, biota). Their presence is of concern due to high environmental persistence and their ability to release or bind pollutants. In light of this, the present work aimed to quantify a poorly studied pollutant category associated with MPs: metals. This analysis was conducted on virgin MPs, used as raw materials in the plastics' production process and on environmental MPs taken from the Ofanto river in Southern Italy. The MP samples were initially grouped for colour, shape and ageing and following mineralised by a microwave digestor. The metals and metalloids Pb, Ba, Sb, Sn, Cd, Mo, Se, Zn, Cu, Ni, Co, Cr, Fe, Mn, Ti, Al, V, Ca, K, Mg, Na were subsequently quantified with ICP-MS. All the analysed elements were found on both types of samples (virgin and environmental MPs), with higher concentrations detected on environmental samples (above 14,400 µg/g-1) rather than on pristine ones (above 5000 µg/g-1). Many of these inorganic compounds are probably adsorbed by the surrounding environment, and others are intentionally added during the plastic production process to improve their properties (e.g. additives). Noticeable differences were detected concerning the metal's distribution and amount observed in the two types of MP particles analysed. Moreover, trace element concentrations were also linked to the colour and shape of the environmental particles analysed. Most abundant levels of metals were quantified on aged black fragments, followed by coloured and transparent fragments and black pellets. Our concluding remarks underline the role of MPs as a vehicle for the transport of metals, with significant differences between the high abundance of these pollutants examined in our particles collected in a freshwater environment and the significantly lower concentrations revealed previously in marine MPs.

Effects and Impacts of Different Oxidative Digestion Treatments on Virgin and Aged Microplastic Particles.

Although several sample preparation methods for analyzing microplastics (MPs) in environmental matrices have been implemented in recent years, important uncertainties and criticalities in the approaches adopted still persist. Preliminary purification of samples, based on oxidative digestion, is an important phase to isolate microplastics from the environmental matrix; it should guarantee both efficacy and minimal damage to the particles. In this context, our study aims to evaluate Fenton's reaction digestion pre-treatment used to isolate and extract microplastics from environmental matrices. We evaluated the particle recovery efficiency and the impact of the oxidation method on the integrity of the MPs subjected to digestion considering different particles' polymeric composition, size, and morphology. For this purpose, two laboratory experiments were set up: the first one to evaluate the efficacy of various digestion protocols in the MPs extraction from a complex matrix, and the second one to assess the possible harm of different treatments, differing in temperatures and volume reagents used, on virgin and aged MPs. Morphological, physicochemical, and dimensional changes were verified by Scanning Electron Microscope (SEM) and Fourier Transformed Infrared (FTIR) spectroscopy. The findings of the first experiment showed the greatest difference in recovery rates especially for polyvinyl chloride and polyethylene terephthalate particles, indicating the role of temperature and the kind of polymer as the major factors influencing MPs extraction. In the second experiment, the SEM analysis revealed morphological and particle size alterations of various entities, in particular for the particles treated at 75 °C and with major evident alterations of aged MPs to virgin ones. In conclusion, this study highlights how several factors, including temperature and polymer, influence the integrity of the particles altering the quality of the final data.

Development of a UHPLC-MS/MS method to enhance the detection of Glyphosate, AMPA and Glufosinate at sub-microgram / L levels in water samples.

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.

Microplastics pollution in the terrestrial environments: Poorly known diffuse sources and implications for plants.

Research on microplastics (MPs) in the terrestrial environment is currently at a still embryonal stage. The current knowledge concerning poorly known diffuse sources of MPs pollution in terrestrial ecosystems have been considered in this work. In addition, a particular focus on the presence, mechanism of absorption and effects of MPs in plants has also been provided. Research concerning microplastics in urban areas and their intake by Tyre and Road Wear Particulates (TWRP) demonstrated a high contribution of this plastic debris to microplastic pollution, although quantification of these inputs is challenging to assess because studies are still very few. Around 50% of particles are expected to remain in the roadside soil, while the rest is transported away by the runoff with high concentrations of TRWP with a size ranging between 0.02 and 0.1 mm. Natural and anthropic environments like temporary ponds, stormwater retention ponds and small waterbodies were considered sensitive connecting ecosystems rich in biodiversity between terrestrial and aquatic environments. Even if studies are not yet exhaustive and just eight studies were currently published concerning these ecosystems, considerable values of MPs were already observed both in the sediment and water phase of ponds. Although still poorly explored, agricultural environments were already demonstrated to hide a significant number of microplastics linked mainly to agricultural activities and practices (e.g. mulch, sewage and compost fertilisation). However, the microplastics transportation processes into the soil are still understudied, and a few works are available. Microplastics and primarily nanoplastics presence was also observed in common edible plants (fruit and vegetables) with alarming Estimated Daily Intakes ranging from 2.96 × 1004 to 4.62 × 1005 (p kg-1 day-1) for adults depending on species. In addition, adverse effects on plants growth, photosynthetic activity, antioxidant system and nutritional values of several common fruits and vegetables were also demonstrated by several studies.

Protection of Water Resources from Agriculture Pollution: An Integrated Methodological Approach for the Nitrates Directive 91-676-EEC Implementation.

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.

A Relevant Screening of Organic Contaminants Present on Freshwater and Pre-Production Microplastics.

Microplastics (MPs) have recently been discovered as considerable pollutants of all environmental matrices. They can contain a blend of chemicals, some of them added during the manufacture of plastic to improve their quality (additives) and others adsorbed from the surrounding environment. In light of this, a detailed study about the identification and quantification of target organic pollutants and qualitative screening of non-target compounds present on MPs was carried out in different types of samples: environmental MPs, collected from an Italian river, and pre-production MPs, taken from the plastic industry. Polychlorobiphenyls (PCBs), organochlorine pesticides (OCPs), and polycyclic aromatic hydrocarbons (PAHs) were chosen as target compounds to be quantified by Gas Chromatography-Mass Spectrometry (GC-MS), while the non-target screening was carried out by High Resolution Gas Chromatography-Mass Spectrometry (HRGC-MS). The target analysis revealed concentrations of 16 priority Polycyclic Aromatic Hydrocarbons by Environmental Protection Agency (EPA-PAHs) in the range of 29.9-269.1 ng/g; the quantification of 31 PCBs showed values from 0.54 to 15.3 ng/g, identifying CB-138, 153, 180, 52, and 101 primarily; and the detected OCPs (p,p'-DDT and its metabolites) ranged between 14.5 and 63.7 ng/g. The non-target screening tentatively identified 246 compounds (e.g., phthalates, antioxidants, UV-stabilizers), including endocrine disruptors, toxic and reprotoxic substances, as well as chemicals subjected to risk assessment and authorisation. The large assortment of plastic chemicals associated with MPs showed their role as a presumable source of pollutants, some of which might have high bioaccumulation potential, persistence, and toxicity.

Characterization of the Belowground Microbial Community in a Poplar-Phytoremediation Strategy of a Multi-Contaminated Soil.

Due to their widespread use in industrial applications in recent decades, Polychlorobiphenyls (PCBs) and heavy metals (HMs) are the most common soil contaminants worldwide, posing a risk for both ecosystems and human health. In this study, a poplar-assisted bioremediation strategy has been applied for more than 4 years to a historically contaminated area (PCBs and HMs) in Southern Italy using the Monviso poplar clone. This clone was effective in promoting a decrease in all contaminants and an increase in soil quality in terms of organic carbon and microbial abundance. Moreover, a significant shift in the structure and predicted function of the belowground microbial community was also observed when analyzing both DNA and cDNA sequencing data. In fact, an increase in bacterial genera belonging to Proteobacteria able to degrade PCBs and resist HMs was observed. Moreover, the functional profiling of the microbial community predicted by PICRUSt2 made it possible to identify several genes associated with PCB transformation (e.g., bphAa, bphAb, bphB, bphC), response to HM oxidative stress (e.g., catalase, superoxide reductase, peroxidase) and HM uptake and expulsion (e.g., ABC transporters). This work demonstrated the effectiveness of the poplar clone Monviso in stimulating the natural belowground microbial community to remove contaminants and improve the overall soil quality. It is a practical example of a nature based solution involving synergic interactions between plants and the belowground microbial community.

Chromium Pollution in European Water, Sources, Health Risk, and Remediation Strategies: An Overview.

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.

A Detailed Review Study on Potential Effects of Microplastics and Additives of Concern on Human Health.

The distribution and abundance of microplastics into the world are so extensive that many scientists use them as key indicators of the recent and contemporary period defining a new historical epoch: The Plasticene. However, the implications of microplastics are not yet thoroughly understood. There is considerable complexity involved to understand their impact due to different physical-chemical properties that make microplastics multifaceted stressors. If, on the one hand, microplastics carry toxic chemicals in the ecosystems, thus serving as vectors of transport, they are themselves, on the other hand, a cocktail of hazardous chemicals that are added voluntarily during their production as additives to increase polymer properties and prolong their life. To date, there is a considerable lack of knowledge on the major additives of concern that are used in the plastic industry, on their fate once microplastics dispose into the environment, and on their consequent effects on human health when associated with micro and nanoplastics. The present study emphasizes the most toxic and dangerous chemical substances that are contained in all plastic products to describe the effects and implications of these hazardous chemicals on human health, providing a detailed overview of studies that have investigated their abundance on microplastics. In the present work, we conducted a capillary review of the literature on micro and nanoplastic exposure pathways and their potential risk to human health to summarize current knowledge with the intention of better focus future research in this area and fill knowledge gaps.

Microplastics and their possible sources: The example of Ofanto river in southeast Italy.

Monitoring studies have quantified microscopic plastic debris, so-called microplastics, in freshwater systems, including banks, surface waters and sediments. However, there is a lack of knowledge of freshwater and terrestrial environments. When microplastics are released in freshwater environments, they will be transported and will not remain stationary. Moreover, their transport from sink to source (land-based to river systems) may depend on several factors such as weather conditions and river hydrology. The present study aims to investigate the abundance and composition of microplastics in the most important river of Apulia Region (Southeast Italy) evaluating the main drivers and possible input sources of microplastic debris. The following work is the first study showing an Italian river context. For this research five sampling campaigns have been conducted west of the Ofanto river mouth. Microplastics were collected by three surface plankton nets fixed in the middle of the river in order to reduce the spatial and temporal variability. For each campaign, a total of six replicates were sampled during two time slots. Microplastic concentrations ranged from 0.9 ±â€¯0.4 p/m3 to 13 ±â€¯5 p/m3 showing comparable values to or greater than those ones reported in other studies. A statistically significant difference in the average microplastic concentrations in different campaigns of this study has been observed, suggesting thus a temporal variation in plastic abundances. These significant differences could be explained by the hydrology of the river that influences the particle concentration with its physical forces such as flow velocity, water level and seasonal variability. Microplastics were found at higher concentrations during wet periods indicating a land-based origin probably connected to waste produced by the surroundings agricultural areas. In fact, Spearman's correlation results show a strong positive statistically significant correlation between the concentration of microplastics and the water level (R = 0.8475, p < 0.0001).

Enhancement of Chromium (VI) Reduction in Microcosms Amended with Lactate or Yeast Extract: A Laboratory-Scale Study.

A laboratory-scale study was carried out to evaluate the groundwater bioremediation potential of hexavalent chromium (Cr(VI)), taking into account the chromate pollution of an industrial site located in Southern Italy (Apulia Region). The reduction of Cr(VI) was studied on laboratory microcosms, set up in different experimental conditions, namely: ABIO (soil and water sterilized), BIO (soil and water not sterilized), LATT (with the addition of lactate), and YE (with the addition of yeast extract). Control test lines, set up by using sterilized matrices and amendments, were employed to assess the occurrence of the pollutant reduction via chemical processes. By combining molecular (microbial abundance, specific chromate reductase genes (ChR) and the Shewanella oinedensis bacterial strain) with chemical analyses of chromium (VI and III) in the matrices (water and soil) of each microcosm, it was possible to investigate the response of microbial populations to different experimental conditions, and therefore, to assess their bioremediation capability in promoting Cr(VI) reduction. The overall results achieved within this work evidenced the key role of amendments (lactate and yeast extract) in enhancing the biological reduction of hexavalent chromium in the contaminated aqueous phase of laboratory microcosms. The highest value of Cr(VI) removal (99.47%) was obtained in the YE amended microcosms at seven days.

Gasification treatment of poplar biomass produced in a contaminated area restored using plant assisted bioremediation.

Remediation of polluted soils using phytoremediation techniques is an effective strategy. However, the use of the biomass from these soils for energy purposes may raise efficiency and pollution emission problems and there is currently little research on this issue. In this work, the main results of a fluidized-bed gasification treatment conducted on poplar biomass pruning residues from a multi-contaminated area are presented. The samples were collected from an experimental site in which a plant-assisted bioremediation (PABR) technology has been applied since 2013 to reduce the soil heavy metal (HM) and polychlorinated biphenyl (PCB) contents. The main goal of this study was to identify the specific treatment necessary, in addition to conventional tar reforming, for trapping possible residues of HMs and PCBs in ashes during the gasification process. In our study, we demonstrate that gasification of contaminated biomass coming from PABR (where contaminant residues are concentrated mainly in the roots and are insignificant in the shoots) produces syngas whose characteristics are similar to those obtained using non-contaminated biomass. The results showed that contaminant concentrations in the prunings were negligible; the total amount of PCBs was 1.63 ng/g, while HMs ranged from 0.01 to 0.70 mg/kg, except for Cu and Zn (∼20 mg/kg). Furthermore, the presence in the biomass of Ca and traces of other metals showed a possible catalytic effect with an improvement in the tar conversion in the gasifier leading to a reduction of 5-10% in tar content. The overall results suggest that a specific treatment for pollutant capture is necessary only when the roots, the part of the plants where these contaminants are concentrated, are sampled and used for the gasification process. Although energy from biomass produced on a contaminated site is currently considered waste and involves disposal costs, this paper shows that the poplar biomass grown on a multi-contaminated soil can be used for energy purposes without any impact on the environment.

Lewis-Brønsted acid catalysed ethanolysis of the organic fraction of municipal solid waste for efficient production of biofuels.

A combined Lewis-Brønsted acid ethanolysis of sugars was thoroughly investigated with the aim of producing ethyl levulinate (EL) in a single step. Ethanolysis carried out at 453 K for 4 h using H2SO4 (1 wt%) and AlCl3·6H2O (30 mol % with respect to sugars) produced a yield of 60 mol % of EL respect to glucose and starch. Such optimised conditions were positively applied directly on different food waste, preliminarily characterised and found to be mainly composed by simple (10-15%) and relatively complex sugars (20-60%), besides proteins (6-10%) and lipids (4-10%), even in their wet form. The catalytic system resulted robust enough to the point that the copresence of proteins, lignin, lipids and mineral salts not only did not negatively affect the overall reactivity, but resulted efficiently converted into soluble species, and specifically, into other liquid biofuels of different nature.

Plant-assisted bioremediation of a historically PCB and heavy metal-contaminated area in Southern Italy.

A plant-assisted bioremediation strategy was applied in an area located in Southern Italy, close to the city of Taranto, historically contaminated by polychlorinated biphenyls (PCBs) and heavy metals. A specific poplar clone (Monviso) was selected for its ability to promote organic pollutant degradation in the rhizosphere, as demonstrated elsewhere. Chemical and microbiological analyses were performed at the time of poplar planting in selected plots at different distances from the trunk (0.25-1m) and at different soil depths (0-20 and 20-40cm), at day 420. A significant decrease in PCB congeners and a reduction in all heavy metals was observed where the poplar trees were present. No evidence of PCB and heavy metal reduction was observed in the non poplar-vegetated soil. Microbial analyses (dehydrogenase activity, cell viability, microbial abundance) of the autochthonous microbial community showed an improvement in soil quality. In particular, microbial activity generally increased in the poplar-rhizosphere and a positive effect was observed in some cases at up to 1m distance from the trunk and up to 40cm depth. The Monviso clone was effective in promoting both a general decrease in contaminant occurrence and an increase in microbial activity in the chronically polluted area a little more than one year after planting.