A Low-Cost Ecofriendly Oxidation Process to Manufacture High-Performance Polymeric Biosurfactants Derived from Municipal Biowaste.

Biosurfactants account for about 12% of the global value of the surfactant market, which is currently dominated by synthetic surfactants obtained from fossil sources. Yet, the production of biosurfactants from renewable feedstock is bound to increase, driven by the increasing pressure from both society and governments for chemistry-based industries to become more ecofriendly and economically sustainable. A photo-chemical oxidation process is reported here, yielding new biosurfactants from urban biowaste in water that perform as a solvent and terminal oxidant reagent at room temperature without the addition of conventional oxidants and catalysts. Products with 200-500 kDa molecular weight are obtained. They lower the surface tension of water down to 34 mN/m at 0.5-2 g/L concentration. The estimated cost is rather low (0.1-1.5 EUR/kg), which is competitive with the cost of synthetic surfactants but much lower than the cost of the best-performing bacterial surfactants. For the implementation of the photo-chemical oxidation process at the industrial level, the results suggest that the new biosurfactants obtained in the present work may not reach the performance level of the best-performing bacterial surfactants capable of lowering the surface tension of water down to 28 mN/m. Yet, the biosurfactants produced by the photo-chemical process have a greater chance of being marketed on large scales.

Enhancing Lettuce Yield through Innovative Foliar Spray of Biopolymers Derived from Municipal Biowastes.

Municipal waste biomass could be valorized as an alternative feedstock to produce compounds beneficial for agricultural applications. The foliar spray application of biostimulants emerges as a promising and innovative technique due to its environmental safety and ability to enhance crop yields. In recent years, the exploitation of biopolymers obtained through alkaline hydrolysis of the solid anaerobic digestate from municipal biowastes has attracted researchers' interest. The aim of this study is to investigate the effects on lettuce growth of a product obtained through alkaline hydrolysis from municipal biowaste, Biopolymers (BPs), and of a derivate subjected to a further oxidation process, Biopolymers Oxidate (BPs OX). The effects of the treatments at various concentrations were evaluated by monitoring plant growth and observing the trends in the activities of the main enzymes involved in the nitrogen metabolic pathway of lettuce. Results suggest that the best treatments in terms of fresh weight were achieved by using BPs at 10 mg/L and BPs OX at 100 mg/L, increasing yield by around 28% and 34%, respectively. The innovative aspect of this work was to make easier for farmers the biopolymers application by testing a foliar spray methodology for BPs and BPs OX, which has never been tested before in any crop.

The Autocatalytic Chemical Reaction of a Soluble Biopolymer Derived from Municipal Biowaste.

The paper discusses the perspectives of further implementation of the autocatalytic properties of a soluble biopolymer (SBP) derived from municipal biowastes for the realisation of a biorefinery producing value-added bio-products for consumer use. The reaction of an SBP and water is reported to cause the depolymerisation and oxidation of the pristine SBP organic matter with the formation of carboxyl-functionalised polymers having lower molecular weight and CO2. These findings demonstrate the oxidation of the SBP via water, which could only occur through the production of O and OH radicals catalysed by the SBP. According to the adopted experimental plan, the anaerobic digestate supplied by an Italian municipal biowaste treatment plant was hydrolysed in pH 13 water at 60 °C. The dry product was re-dissolved in plain water at pH 10 and used as a control against the same solution with hydrogen peroxide at 0.1-3 H2O2 moles per SBP carbon mole added. The control and test solutions were kept at room temperature, in the dark or in a climatic chamber under irradiation with simulated solar light, until the pH of the solutions remained constant. Afterwards, the solutions were processed to recover and analyse the crude soluble products. The present work reports the results obtained for the control solution and for the test solutions treated in the presence and absence of H2O2, with and without pH control, in the dark and under irradiation with simulated solar light.

Potentially toxic elements and lead isotopic signatures in the 10 µm fraction of urban dust: Environmental risk enhanced by resuspension of contaminated soils.

In urban environments, soils are a sink of pollutants and might become a source of contamination, as they commonly display potentially toxic elements (PTE) concentrations above the legislative limits. Particularly, the inhalable fraction of soils (<10 µm) is enriched in PTE compared to bulk soils (BS). The enrichment makes these particles an environmental hazard because of their susceptibility to resuspension and their potential contribution to road dust (RD) and atmospheric particulate matter (PM10) pollution. To gain a better insight into urban contamination dynamics we studied the BS, the resuspended <10 µm fraction of BS (Res-BS) and RD (Res-RD) in a European historically industrialized and densely populated city. Compared to BS, the Res-BS and Res-RD showed higher PTE concentrations and a higher variability for most of the elements. Lead was the only PTE showing similar concentrations in all the matrices, suggesting shared sources and redistribution pathways within the city. Chemometric elaborations identified Res-BS as a transition between BS and Res-RD or, rather, a Res-RD precursor. Also, Pb was confirmed to be ubiquitous in all the media. In all the matrices, Pb isotopic signatures were investigated and compared with PM10 fingerprints from the same city. The anthropogenic isotopic signature in Res-BS and Res-RD was evident, and samples belonging to neighboring sites showed comparable isotopic ratios. The Res-BS appeared as a key driver for Pb distribution within the city both in Res-RD and in PM10. These results demonstrate the intimate interaction between urban environmental compartments (soil, road dust and PM10), and the active contribution of fine soil fractions to anthropogenic pollution, with relevant policy implications in urban areas since soils were found to contribute directly to air pollution.

Mild Chemical Treatment of Unsorted Urban Food Wastes.

Municipal biowastes are conventionally treated by assessed anaerobic and aerobic fermentation to produce biogas, anaerobic digestate, and compost. Low-temperature hydrolysis and the oxidation of the digestate and compost, which are still at the experimental stage, are known to yield water-soluble value-added chemical specialities for use in different sectors of the chemical industry and in agriculture. The present paper reports the application of the two chemical reactions to the biowastes before fermentation. The products obtained in this manner are compared with those obtained from the chemical reactions applied to the fermented biowastes. Based on the experimental results, the paper discusses the expected environmental and economic benefits of the above chemical processes and products in comparison with the products obtained by other known biotechnologies for the valorisation of biomass as a feedstock for the biobased chemical industry. The results point out that a sustainable biowaste-based refinery that produces biofuel and biobased chemicals may be developed by integrating chemical and fermentation technologies.

Effect of municipal biowaste derived biostimulant on nitrogen fate in the plant-soil system during lettuce cultivation.

A main concern of agriculture is to improve plant nutrient efficiency to enhance crop yield and quality, and at the same time to decrease the environmental impact caused by the lixiviation of excess N fertilizer application. The aim of this study was to evaluate the potential use of biopolymers (BPs), obtained by alkaline hydrolysis of the solid anaerobic digestate of municipal biowastes, in order to face up these main concerns of agriculture. The experimental trials involved the application of BPs (at 50 and 150 kg/ha) alone or mixed with different amounts (100%, 60% and 0%) of mineral fertilizer (MF). Three different controls were routinely included in the experimental trials (MF 100%, 60% and 0%). The effect of BPs on lettuce was evaluated by monitoring growth parameters (fresh and dry weights of shoot and root, nitrogen use efficiency), and the N-flux in plant-soil system, taking into account the nitrate leached due to over irrigation events. The activities of enzymes involved in the nitrogen uptake (nitrate reductase, glutamate synthase and glutamine synthase), and the nitrogen form accumulated in the plant tissues (total N, protein and NO3-) were evaluated. The results show that the application to the soil of 150 kg/ha BPs allows to increase lettuce growth and nitrogen use efficiency, trough stimulation of N-metabolism and accumulation of proteins, and hence to reduce the use of MF by 40%, thus decreasing the nitrate leaching. These findings suggest that the use of BPs as biostimulant greatly contributes to reduce the consumption of mineral fertilizers, and to mitigate the environmental impact caused by nutrients leaching, according to European common agricultural policy, that encourages R&D of new bioproducts for sustainable eco-friendly agriculture.

The importance of presoaking to improve the efficiency of MgCl2-modified and non-modified biochar in the adsorption of cadmium.

Investigating the effect of presoaking, as one of the most important physical factors affecting the adsorption behavior of biochar, on the adsorption of heavy metals by modified or non-modified biochar and presoaking mechanism is still an open issue. In this study, the water presoaking effect on the kinetics of cadmium (Cd) adsorption by rice husk biochar (produced at 450 °C, B1, and at 600 °C, B2) and the rice husk biochar modified with magnesium chloride (B1 modified with MgCl2, MB1, and B2 modified with MgCl2, MB2) was investigated. Furthermore, the effect of pH (2, 5, and 6), temperature (15, 25, and 35 °C), and biochar particle size (100 and 500 µm) on the kinetics of Cd adsorption was also investigated. Results revealed that the content of Cd adsorbed by the presoaked biochar was significantly higher than that by the non-presoaked biochar. The highest Cd adsorption capacity of MB2 and MB1 was 98.4 and 97.6 mg g-1, respectively, which was much better than that of B1 (7.6 mg g-1) and B2 (7.5 mg g-1). The modeling of kinetics results showed that in all cases pseudo-second-order model was well-fitted (R2>0.99) with Cd adsorption data. The results also indicated that the highest Cd adsorption values were observed at pH 6 in presoaked MB1 with size of 100 µm as well as at the temperature of 35 °C in presoaked MB2, indicating the optimum conditions for this process. The presoaking process was not affected by biochar size and pH, and the difference in adsorbed Cd content between presoaked biochars and non-presoaked ones was also similar. However, the temperature had a negative effect on presoaking. The presoaking process decreased micropores (<10 µm) in the biochars but had no effect on biochar hydrophobicity. Therefore, presoaking, which could significantly increase Cd adsorption and reduce equilibrium time by reducing the micropores of biochars, is suggested as an effective strategy for improving the efficiency of modified biochars or non-modified ones in the adsorption of contaminants (Cd) from aquatic media.

Combining DGT with bioaccessibility methods as tool to estimate potential bioavailability and release of PTEs in the urban soil environment.

Potentially toxic elements (PTEs) in urban soil environments pose a noticeable risk to both ecosystem and human health; however, only a fraction of the elemental content is available for biota. To better know the potential risk of PTEs in the urban soil environment, geochemical fractionation, bioaccessibility, and potential bioavailability of four PTEs (Cd, Cu, Pb, and Zn) were investigated by the combined use of different methods. The results showed that a high non-residual chemical fraction is related to a high bioavailability of the selected elements. The ranges of labile concentration of Cu, Zn, Cd and Pb in all sampling sites measured by diffusive gradients in thin films (DGT) were 3.5-18.0, 14.2-26.5, 0.09-1.0, and 1.8-15.7 µg/L, respectively. The high non-residual contents pointed out a serious hazard to the urban environment. The bioaccessible concentrations in gastric and lung phases were closely positively correlated with DGT-measured content (r = 0.63-0.99, p < 0.05), suggesting the potential use of DGT for the prediction of PTEs risk to human health. Moreover, the correlation of DGT results with the soluble and reducible fractions of PTEs may allow DGT use for quick screenings of the PTEs fraction potentially mobilizable during flooding events in urban soil environments. Our study suggests that combing DGT, bioaccessibility and biogeochemical fractionation could provide a more accurate assessment of the urban environmental quality and be helpful for pollution control and urban planning.

Bioaccessibility of Pb in health-related size fractions of contaminated soils amended with phosphate.

Lead (Pb) contamination is one of the most significant exposure hazards to human health. Contaminated soil particles may be eroded and transferred either to the atmosphere (<10 µm) or to streams; or they may be incidentally ingested (<200 µm). Among strategies for the long-term management of this risk, one of the most cost-effective is the reduction of Pb mobility and bioavailability via amendment with phosphorus-containing materials. To clarify the effectiveness of P amendment in reducing Pb mobility and bioaccessibility in different soil size fractions, an experiment was performed by adding a soluble P compound to a historically contaminated urban soil (RO), a mining soil (MI), and an uncontaminated spiked soil (SP) at different P:Pb molar ratios (2.5:1, 5:1, and 15:1). In the <10 µm fraction of soils, P addition reduced bioaccessible Pb only in the SP soil at the highest dose, with little to no effect on RO and MI soils. Similarly, in the coarse fraction, Pb was immobilized only in the SP soil with all three P doses. These results were probably due to the higher stability of Pb in historically contaminated soils, where Pb dissolution is the limiting factor to the formation of insoluble Pb compounds. The bioaccessible proportion of Pb (using SBET method) was higher than 70 % of the total Pb in all soils and was similar in both fine and coarse particle fractions. Due to the enrichment of Pb in finer particles, this implies possible adverse effects to the environment or to human health if these particles escape from the soil. These results call for increasing attention to the effect of remediation activities on fine soil particles, considering their significant environmental role especially in urban and in historically low or moderately contaminated areas.

Pyoluteorin Produced by the Biocontrol Agent Pseudomonas protegens Is Involved in the Inhibition of Heterobasidion Species Present in Europe.

Pseudomonas protegens (strain DSMZ 13134) is a biocontrol agent with promising antagonistic activity hinging on antibiosis against the fungal forest pathogens Heterobasidion spp. Here, by using High-Performance Liquid Chromatography coupled to Mass Spectrometry (HPLC-MS), we assessed whether monocultures of P. protegens (strain DSMZ 13134) produce the three major determinants of biocontrol activity known for the genus Pseudomonas: 2,4-diacetylphloroglucinol (2,4-DAPG), pyoluteorin (PLT), and pyrrolnitrin (PRN). At the tested culture conditions, we observed the production of PLT at concentrations ranging from 0.01 to 10.21 mg/L and 2,4-DAPG at a concentration not exceeding 0.5 mg/L. Variations of culture conditions involving culture medium, incubation temperature, and incubation period had no consistent influence on PLT production by the bacterium. Assays using culture medium amended with PLT at the same concentration of that present in cell-free filtrate of the bacterium, i.e., 3.77 mg/L, previously documented as effective against Heterobasidion spp., showed a remarkable activity of PLT against genotypes of all the four Heterobasidion species present in Europe, including the non-native invasive H. irregulare. However, such antifungal activity decreased over time, and this may be a constraint for using this molecule as a pesticide against Heterobasidion spp. When the bacterium was co-cultured in liquid medium with genotypes of the different Heterobasidion species, an increased production of PLT was observed at 4 °C, suggesting the bacterium may perform better as a PLT producer in field applications under similar environmental conditions, i.e., at low temperatures. Our results demonstrated the role of PLT in the inhibition of Heterobasidion spp., although all lines of evidence suggest that antibiosis does not rely on a single constitutively produced metabolite, but rather on a plethora of secondary metabolites. Findings presented in this study will help to optimize treatments based on Pseudomonas protegens (strain DSMZ 13134) against Heterobasidion spp.

Soil PM10 emission potential under specific mechanical stress and particles characteristics.

Soil can be resuspended in the atmosphere due to wind or mechanical disturbances, such as agricultural activities (sowing, tilling, etc.), producing fine particulate matter (PM). Agriculture is estimated to be the third PM10-emitting sector in Europe, emitting more than the transportation sector. However, very few emission figures are available for the different cropping operations. Moreover, soil Emission Potential (EP) is extremely variable, since is influenced by factors such as humidity, texture, chemical composition, and wind speed. Due to their similarity to tilling emission mechanisms, Soil Resuspension Chambers (SRC) are the most suitable method to estimate the impacts of these factors on soil susceptibility to emit PM10 during cropping operations (Emission Potential, EP). The main objective of this work is to assess the EP of different agricultural soils used for maize cropping in North-Western Italy, studying the influence of soil moisture and physico-chemical characteristics. Therefore, a SRC was developed, based on previous studies, with the goal of being relatively small, easy to operate and low-cost. Using the gathered data, a log-linear multiple regression model was developed to allow soil EP estimation from few physico-chemical parameters (moisture, sand/silt ratio and organic carbon content). The model allows to tailor field Emission Factors (EF) of specific cropping operations to different soil and moisture conditions and was applied to an EF for rotary harrowing, defined in a previous study. The concentration of Potentially Toxic Elements (PTE) in soil-emitted PM10 was determined, founding an enrichment up to 16 times higher than in the original soil, evidencing a possible cause of concern for operator's safety during agricultural activities.

Soil particle size fraction and potentially toxic elements bioaccessibility: A review.

In the last decade, extensive studies have been conducted to quantify the influence of different factors on potentially toxic elements (PTE) bioaccessibility in soil; one of the most important is soil size fraction. However, there is no agreement about the size fraction and the methods to investigate bioaccessibility, as very few review articles are available on soil PTE bioaccessibility and none addressed the influence of particle size on PTE bioaccessibility. This study provides a review of the relations between PTE bioaccessibility and soil particle size fractions. The available research indicates that PTE bioaccessibility distribution across different size fractions varies widely in soil, but a general trend of higher bioaccessibility in finer size fraction was found. The different elements may exhibit different relationships between bioaccessibility and soil size fraction and, in some cases, their bioaccessibility seems to be more related to the source and to the chemico-physical form of PTE in soil. Often, soil pollution and related health risk are assessed based on PTE total concentration rather than their bioaccessible fraction, but from the available studies it appears that consensus must be pursued on the methods to determine PTE bioaccessibility in the fine soil size fractions to achieve a more accurate human health risk assessment.

Potential Release of Zinc and Cadmium From Mine-Affected Soils Under Flooding, a Mesocosm Study.

Metal-contaminated mining soils pose serious environmental and health risks if not properly managed, especially in mountainous areas, which are more susceptible to perturbation. Currently, climate change is leading to more frequent and intense rain events, which cause flooding episodes, thereby altering soil redox equilibria and contaminants stability. We evaluated the potential release of Zn and Cd (two of the most common inorganic contaminants) and the factors regulating their solubility and speciation in two heavily contaminated soils representative of a Zn-mining area. The soils were flooded under aerobic (for 24 h) and anaerobic (for 62 days) conditions using mesocosm experiments, sequential extractions, and geochemical modelling. Leaching trials under aerobic conditions showed a high release of Zn and Cd (10 times the legislative limits), with metals possibly migrating via water infiltration or runoff. Under anaerobic conditions Zn and Cd were initially released. Then, solution concentrations decreased gradually (Zn) or sharply (Cd) until the end of the experiment. Sequential extractions and multisurface modelling indicated that both metals precipitated mainly as carbonates. This was confirmed by a geochemical multisurface modelling, which also predicted the formation of sulphides after 60 days in one soil. The model calculated metals to be preferentially complexed by organic matter and well predicted the observed soil solution concentrations. The results showed that during flooding episodes contaminants could be promptly transferred to other environmental compartments. The use of multisurface modelling coupled with laboratory experiments provided useful indications on the potential release and speciation in case of anoxic conditions.

Potentially toxic elements in the Middle East oldest oil refinery zone soils: source apportionment, speciation, bioaccessibility and human health risk assessment.

In this research, fifteen potentially toxic elements (PTEs) (Al, As, Cd, Co, Cr, Cu, Fe, Hg, Mn, Mo, Ni, Pb, Sb, Sc and Zn) were analysed and quantified in samples collected at 44 sites in an urban area of Iran. Sources were apportioned using enrichment factors (EFs), modified pollution index (MPI), principal component analysis (PCA), multivariate linear regression of absolute principal component scores (MLR-APCS) and speciation, with a focus on anthropogenic PTEs in the urban and industrial soils of the Arvand Free Zone area, an oil-rich zone in the country. Furthermore, the bioaccessibility and the human health risks of PTEs were investigated. The EF revealed a significant enrichment for elements such as Cd, Cu, Hg, Mo, Pb, Sb and Zn. Values of MPI showed that Abadan industrial district and Abadan petrochemical complex are the most polluted sites in the study area.The PCA/MLR analysis revealed four main sources: natural sources, fossil fuel combustion, traffic and oil derivatives and petroleum waste. The relative contribution of each source to PTE concentration varied from 32.3% of the natural sources to 30.6% of traffic and from 20.1% of petroleum waste to 17% of fossil fuel combustion. The source apportionment of metals generated using MLR-APCS receptor modelling revealed that 85.0% of Hg was generated by oil products. Chemical speciation results were compatible with the results obtained from PCA. Bioaccessibility of PTEs decreased from gastric to intestinal phase except Mo and Sb due to their different geochemical characteristics. Hazard index (HI) for non-cancer risk of PTEs for both children and adults based on total element concentrations was estimated to range from 2-fold to more than 10-fold higher than that of bioaccessible phases.

Evaluation of particulate matter (PM10) emissions and its chemical characteristics during rotary harrowing operations at different forward speeds and levelling bar heights.

Particulate matter (PM) is an air pollutant which poses a considerable risk to human health. The agricultural sector is responsible of the 15% of the total anthropogenic emissions of PM10 (PM fraction with aerodynamic diameter below 10 µm) and soil preparation activities have been recognized as one of the main drivers of this contribution. The emission factors (EF) proposed by European environmental agency (EEA) for tilling operations are based on very few studies, none of which has been made in Italy. Moreover, few studies have considered the influence of operative parameters on PM10 emissions during tilling. The aim of this work was to assess PM10 emission and dispersion during rotary harrowing and to understand how operative parameters, such as forward speed and implement choice may affect PM release. A further objective was to assess the near field dispersion of PM10 to address exposure risks. Emission factors (EFs) were determined during two different trials (T1 and T2). During T1, the effect of tractor speeds (0.6, 1.1 and 1.7 m s-1) on PM10 emissions was investigated, while in T2 a comparative essay was made to study the influence of levelling bar height on emissions. The average ground level downwind concentrations of PM10 during harrowing operation was estimated through dispersion modelling. The observed PM10 EFs for rotary harrowing were 8.9 ± 2.0 mg m-2 and 9.5 ± 2.5 mg m-2 on T1 and T2, respectively. The heavy metal content of soil-generated PM10 was also assessed. In the generated PM, the elemental concentrations were higher than ones in soil. As, Cd and Ni concentration levels, determined in PM10 near to the tractor path, were also high, being several times higher than the annual average regulatory threshold levels in ambient air, as defined by the European regulation.

Incorporating oral bioaccessibility into human health risk assessment due to potentially toxic elements in extractive waste and contaminated soils from an abandoned mine site.

The waste rock, tailings and soil around an abandoned mine site in Gorno (northwest Italy) contain elevated concentrations of potentially toxic elements (PTE) exceeding the permissible limits for residential uses. Specifically, the maximum concentrations of As, Cd, Pb, and Zn were 107 mg/kg, 340 mg/kg, 1064 mg/kg, and 148 433 mg/kg, respectively. A site-specific human health risk assessment (HHRA) was conducted for residential and recreational exposure scenarios, using an approach based on Risk Based Corrective Action (RBCA) method, refined by incorporating oral bioaccessibility data. Oral bioaccessibility analyses were performed by simulating the human digestion process in vitro (Unified BARGE Method). Detailed analysis of oral bioaccessible fraction (BAF i.e. ratio of bioaccessible concentrations to total concentrations on <250 µm fraction) indicated BAF of As (5-33%), Cd (72-98%), Co (24-42%), Cr (3-11%), Cu (25-90%), Ni (17-60%), Pb (16-88%) and Zn (73-94%). The solid phase distribution and mineralogical analyses showed that the variation of BAF is attributed to presence of alkaline calcareous rocks and association of PTE with a variety of minerals. The HHRA for ingestion pathway, suggested that bioaccessibility-corrected cancer risk reached up to 2.7 × 10-5 and 0.55 × 10-5 for residential and recreational senarios respectively (acceptable level is 1 × 10-5). The hazard index (HI) recalculated after incorporation of oral bioaccessible concentrations for a residential scenario ranged from 0.02 to 17.9. This was above the acceptable level (>1) for 50% of the samples, indicating potential human health risks. This study provides information for site-specific risk assessments and planning future research.

Linking oral bioaccessibility and solid phase distribution of potentially toxic elements in extractive waste and soil from an abandoned mine site: Case study in Campello Monti, NW Italy.

Oral bioaccessibility and solid phase distribution of potentially toxic elements (PTE) from extractive waste streams were investigated to assess the potential human health risk posed by abandoned mines. The solid phase distribution along with micro-X-ray fluorescence (micro-XRF) and scanning electron microscopy (SEM) analysis were also performed. The results showed that the total concentrations of PTE were higher in <250 µm size fractions of waste rock and soil samples in comparison to the <2 mm size fractions. Mean value of total concentrations of chromium(Cr), copper (Cu), and nickel (Ni) in waste rocks (size fractions <250 µm) were found to be 1299, 1570, and 4010 mg/kg respectively due to the parent material. However, only 11% of Ni in this sample was orally bioaccessible. Detailed analysis of the oral bioaccessible fraction (BAF, reported as the ratio of highest bioaccessible concentration compared with the total concentration from the 250 µm fraction) across all samples showed that Cr, Cu, and Ni varied from 1 to 6%, 14 to 47%, and 5 to 21%, respectively. The variation can be attributed to the difference in pH, organic matter content and mineralogical composition of the samples. Non-specific sequential extraction showed that the non-mobile forms of PTE were associated with the clay and Fe oxide components of the environmental matrices. The present study demonstrates how oral bioaccessibility, solid phase distribution and mineralogical analysis can provide insights into the distribution, fate and behaviour of PTE in waste streams from abandoned mine sites and inform human health risk posed by such sites .

An empirical model to predict road dust emissions based on pavement and traffic characteristics.

The relative impact of non-exhaust sources (i.e. road dust, tire wear, road wear and brake wear particles) on urban air quality is increasing. Among them, road dust resuspension has generally the highest impact on PM concentrations but its spatio-temporal variability has been rarely studied and modeled. Some recent studies attempted to observe and describe the time-variability but, as it is driven by traffic and meteorology, uncertainty remains on the seasonality of emissions. The knowledge gap on spatial variability is much wider, as several factors have been pointed out as responsible for road dust build-up: pavement characteristics, traffic intensity and speed, fleet composition, proximity to traffic lights, but also the presence of external sources. However, no parameterization is available as a function of these variables. We investigated mobile road dust smaller than 10 µm (MF10) in two cities with different climatic and traffic conditions (Barcelona and Turin), to explore MF10 seasonal variability and the relationship between MF10 and site characteristics (pavement macrotexture, traffic intensity and proximity to braking zone). Moreover, we provide the first estimates of emission factors in the Po Valley both in summer and winter conditions. Our results showed a good inverse relationship between MF10 and macro-texture, traffic intensity and distance from the nearest braking zone. We also found a clear seasonal effect of road dust emissions, with higher emission in summer, likely due to the lower pavement moisture. These results allowed building a simple empirical mode, predicting maximal dust loadings and, consequently, emission potential, based on the aforementioned data. This model will need to be scaled for meteorological effect, using methods accounting for weather and pavement moisture. This can significantly improve bottom-up emission inventory for spatial allocation of emissions and air quality management, to select those roads with higher emissions for mitigation measures.

Physico-chemical characterization of playground sand dust, inhalable and bioaccessible fractions.

Dust is a mixture of natural and anthropogenic particles originated from multiple sources, which can represent an hazard for human health. Playgrounds are a site of particularly concern, due to sand dust ingestion by toddlers and inhalation. In this study, 37 sands used in public playgrounds in the city of Barcelona were physico-chemically characterized also in relation to routine maintenance activities such as disinfection and sand renewal. The analyzed sands show a felsic mineralogy dominated by Na-feldspar, quartz, and, to a lesser extent, K-feldspar, with minor amounts of clay minerals, carbonates and hematite. Particle fractions below 10, 2.5 and 1 µm represent, on average, 0.65%, 0.17% and 0.07% of bulk volume, respectively, although, due to the human grinding, these initial fractions increased every year by a 18%, 5% and 2% respectively. Disinfection of sands effectively reduced only the NH4+ concentration, among inorganic species. The average metal content was anthropogenically enriched, with respect to the upper continental crust, only for Sb and As. Both elements show high spatial variation indicating local sources such as road traffic for Sb (contributing mostly to the total concentration), and industry for As (also contributing with highly bioaccessible Sb, Cu and Zn). A clear inverse relationship between total concentrations of some elements and their leachable (Sb) and bioaccessible (Sb and Cr) fractions is observed. The most bioaccessible elements were Ca > Ni > Cu > Sr > Cd > Pb, all above the 25% of the total concentration. Bioaccessibility was higher for the carbonate-bearing particles and for the anthropic emitted metals (>50% of Ba, Cu, K, Pb and Zn).

Bioaccessibility and size distribution of metals in road dust and roadside soils along a peri-urban transect.

Road dust (RD), together with surface soils, is recognized as one of the main sinks of pollutants in urban environments. Over the last years, many studies have focused on total and bioaccessible concentrations while few have assessed the bioaccessibility of size-fractionated elements in RD. Therefore, the distribution and bioaccessibility of Fe, Mn, Cd, Cr, Cu, Ni, Pb, Sb and Zn in size fractions of RD and roadside soils (<2.5µm, 2.5-10µm and 10-200µm) have been studied using aqua regia extraction and the Simple Bioaccessibility Extraction Test. Concentrations of metals in soils are higher than legislative limits for Cu, Cr, Ni, Pb and Zn. Fine fractions appear enriched in Fe, Mn, Cu, Pb, Sb and Zn, and 2.5-10µm particles are the most enriched. In RD, Cu, Pb, Sb and Zn derive primarily from non-exhaust sources, while Zn is found in greater concentrations in the <2.5µm fraction, where it most likely has an industrial origin. Elemental distribution across soils is dependent on land use, with Zn, Ni, Cu and Pb being present in higher concentrations at traffic sites. In addition, Fe, Ni and Cr feature greater bioaccessibility in the two finer fractions, while anthropic metals (Cu, Pb, Sb and Zn) do not. In RD, only Zn has significantly higher bioaccessibility at traffic sites compared to background, and the finest particles are always the most bioaccessible; >90% of Pb, Zn and Cu is bioaccessible in the <2.5µm fraction, while for Mn, Ni, Sb, Fe and Cr, values vary from 76% to 5%. In the 2.5-10µm fraction, the values were 89% for Pb, 67% for Zn and 60% for Cu. These results make the evaluation of the bioaccessibility of size-fractionated particles appear to be a necessity for correct estimation of risk in urban areas.