Arsenic movement and fractionation in agricultural soils which received wastewater from an adjacent industrial site for 50 years.

Arsenic (As) is an element with important environmental and human health implications due to its toxic properties. It is naturally occurring since it is contained in minerals, but it can also be enriched and distributed in the environment by anthropogenic activities. This paper reports on the historic As contamination of agricultural soils in one of the most important national relevance site for contamination in Italy, the so-called SIN Brescia-Caffaro, in the city of Brescia, northern Italy. These agricultural areas received As through the use of irrigation waters from wastewater coming from a factory of As-based pesticides (lead and calcium arsenates, sodium arsenite). Pesticide production started in 1920 and ended in the '70. Concentrations in the areas are generally beyond the legal threshold values for different soil uses and are up to >200 mg/kg. Arsenic contamination was studied to assess the long-time trend and the dynamics related to the vertical movement of As down to 1 m depth and its horizontal diffusion with surface irrigation in the entire field. Arsenic fractionation analysis (solid phase speciation by sequential extraction procedure) was also performed on samples collected from these areas and employed in greenhouse experiments with several plant species to evaluate the long-term contamination and the role of plant species in modifying As availability in soil. The results of this work can help in the evaluation of the conditions controlling the vertical transfer of As towards surface aquifers, the bioaccumulation likelihood in the agricultural food chain and the selection of sustainable remediation techniques such as phytoextraction.

Mulching in lowland hay meadows drives an adaptive convergence of above- and below-ground traits reducing plasticity and improving biomass: A possible tool for enhancing phytoremediation.

We aimed to understand the effect of mulching (i.e., cutting and leaving the crushed biomass to decompose in situ) on above- and below-ground plant functional traits and whether this practice may be a potential tool for enhancing the phytoremediation of lowland hay meadows. To this aim, we evaluated at the community level seven years of mulching application in a PCBs and HMs soil-polluted Site of National Interest (SIN Brescia-Caffaro) through the analysis of the floristic composition and the above- and below-ground plant traits. We found that the abandonment of agricultural activities led to a marked increase in the soil organic carbon and pH, and the over-imposed mulching additionally induced a slight increase in soil nutrients. Mulching favored the establishment of a productive plant community characterized by a more conservative-resource strategy, a higher biomass development, and lower plasticity through an adaptative convergence between above- and below-ground organs. In particular, the analysis of the root depth distribution highlighted the key role of roots living in the upper soil layer (10 cm). Mulching did not show a significant effect on plant species known to be effective in terms of PCB phytoremediation. However, the mulching application appears to be a promising tool for enhancing the root web that functions as the backbone for the proliferation of microbes devoted to organic contaminants' degradation and selects a two-fold number of plant species known to be metal-tolerant. However, besides these potential positive effects of the mulching application, favoring species with a higher biomass development, in the long term, may lead to a biodiversity reduction and thus to potential consequences also on the diversity of native species important for the phytoremediation.

Pollution and edaphic factors shape bacterial community structure and functionality in historically contaminated soils.

Studies about biodegradation potential in soils often refer to artificially contaminated and simplified systems, overlooking the complexity associated with contaminated sites in a real context. This work aims to provide a holistic view on microbiome assembly and functional diversity in the model site SIN Brescia-Caffaro (Italy), characterized by historical and uneven contamination by organic and inorganic compounds. Here, physical and chemical analyses and microbiota characterization were applied on one-hundred-twenty-seven soil samples to unravel the environmental factors driving bacterial community assembly and biodegradation potential in three former agricultural fields. Chemical analyses showed a patchy distribution of metals, metalloids and polychlorinated biphenyls (PCB) and allowed soil categorization according to depth and area of collections. Likewise, the bacterial community structure, described by molecular fingerprinting and 16S rRNA gene analyses, was significantly different according to collection site and depth. Pollutant concentrations (i.e., hexachloro-biphenyls, arsenic and mercury), nitrogen content and parameters related to soil texture were identified as main drivers of microbiota assembly, being significantly correlated to bacterial community composition. Moreover, bacteria putatively involved in the aerobic degradation of PCBs were enriched over the total bacterial community in topsoils, where the highest activity was recorded using fluorescein hydrolysis as proxy. Metataxonomic analyses revealed the presence of bacteria having metabolic pathways related to PCB degradation and tolerance to heavy metals and metalloids in the topsoil samples collected in all areas. Overall, the provided dissection of soil microbiota structure and its degradation potential in the SIN Brescia-Caffaro can contribute to target specific areas for rhizoremediation implementation. Metagenomics studies could be implemented in the future to understand if specific degradative pathways are present in historically polluted sites characterized by the co-occurrence of multiple classes of contaminants.

Life cycle exposure of plants considerably affects root uptake of PCBs: Role of growth strategies and dissolved/particulate organic carbon variability.

Plant roots can accumulate organic chemicals, including PCBs, and this could be relevant in spreading chemicals through the food chain. To estimate such uptake, several equations are available in the literature, mostly developed in lab conditions, to obtain the root concentration factor (RCF). Here, a long-term (18 months) greenhouse experiment, using an aged, contaminated soil, was performed to reproduce root uptake in field-like conditions and to account for the ecological variability of exposure during the entire life cycle. Specific growth strategies (i.e., annual vs. perennial), root development (e.g., timing of root production and decaying), and soil parameters (e.g., dissolved organic carbon (DOC), and the particulate organic carbon (POC)) may interfere with the uptake of contaminants into the roots of plants. In this study, we investigate the effects of these factors on the RCF, obtained for 79 PCBs. New predictive equations were calculated for 5 different plants species at four different growth times (from few months to 1.5 years) and stages (growing vs maturity). The relationships highlighted a species-specific and time-dependent accumulation of PCB in plants roots, with higher RCFs in summer than in fall for some species, and the relevant influence of DOC and POC in affecting root uptake.

Solid Oxide Cell Electrode Nanocomposites Fabricated by Inkjet Printing Infiltration of Ceria Scaffolds.

The enhancement of solid oxide cell (SOC) oxygen electrode performance through the generation of nanocomposite electrodes via infiltration using wet-chemistry processes has been widely studied in recent years. An efficient oxygen electrode consists of a porous backbone and an active catalyst, which should provide ionic conductivity, high catalytic activity and electronic conductivity. Inkjet printing is a versatile additive manufacturing technique, which can be used for reliable and homogeneous functionalization of SOC electrodes via infiltration for either small- or large-area devices. In this study, we implemented the utilization of an inkjet printer for the automatic functionalization of different gadolinium-doped ceria scaffolds, via infiltration with ethanol:water-based La1-xSrxCo1-yFeyO3-δ (LSCF) ink. Scaffolds based on commercial and mesoporous Gd-doped ceria (CGO) powders were used to demonstrate the versatility of inkjet printing as an infiltration technique. Using yttrium-stabilized zirconia (YSZ) commercial electrolytes, symmetrical LSCF/LSCF-CGO/YSZ/LSCF-CGO/LSCF cells were fabricated via infiltration and characterized by SEM-EDX, XRD and EIS. Microstructural analysis demonstrated the feasibility and reproducibility of the process. Electrochemical characterization lead to an ASR value of ≈1.2 Ω cm2 at 750 °C, in the case of nanosized rare earth-doped ceria scaffolds, with the electrode contributing ≈0.18 Ω cm2. These results demonstrate the feasibility of inkjet printing as an infiltration technique for SOC fabrication.

Mercury vertical and horizontal concentrations in agricultural soils of a historically contaminated site: Role of soil properties, chemical loading, and cultivated plant species in driving its mobility.

The long term vertical and horizontal mobility of mercury (Hg) in soils of agricultural areas of a historically contaminated Italian National Relevance Site (SIN Brescia-Caffaro) was investigated. The contamination resulted from the continuous discharge of Hg in irrigation waters by an industrial plant (Caffaro S.p.A), equipped with a mercury-cell chlor-alkali process. The contamination levels with depth ranged from about 20 mg/kg dry weight (d.w.) of soil in the top (plow) layer to less than 0.1 mg/kg d.w. at 1 m depth. The concentrations varied also spatially, up to one order of magnitude within the same field and showing a decreasing trend from the Hg source (i.e., irrigation ditches). The concentration profiles and gradients measured were explained considering Hg loading, soil properties, such as the texture, organic carbon content, pH and cation exchange capacity. A Selective Sequential Extraction (SSE) was also applied on soil samples from an ad hoc greenhouse experiment to investigate the role of different plant species in influencing Hg speciation in soils. Although most of the extracted Hg was included in scarcely mobile or immobile forms, some plant species (i.e., alfalfa) showed to importantly increase the soluble and exchangeable fractions with respect to the unplanted control soils, thus affecting mobility and potential bioavailability of Hg.

A new dataset of PCB half-lives in soil: Effect of plant species and organic carbon addition on biodegradation rates in a weathered contaminated soil.

This paper presents a new dataset of Polychlorinated Biphenyls (PCBs) half-lives in soil. Data were obtained from a greenhouse experiment performed with an aged contaminated soil under semi-field conditions, collected from a National Relevance Site (SIN) located in Northern Italy (SIN Brescia-Caffaro). Ten different treatments (combination of seven plant species and different soil conditions) were considered together with the respective controls (soil without plants). PCB concentration reduction in soil was measured over a period of 18 months to evaluate the ability of plants to stimulate the biodegradation of these compounds. Tall fescue, tall fescue cultivated together with pumpkin and tall fescue amended with compost reduced more than the 50% of the 79 measured PCB congeners, including the most chlorinated ones (octa to deca-PCBs). However, the data obtained showed that no plant species was uniquely responsible for the effective degradation of all isomeric classes and congeners. The obtained half-lives ranged from 1.3 to 5.6 years and were up to a factor of 8 lower compared to generic HL values reported in literature. This highlighted the importance of cultivation and plant-microbe interactions in speeding up the PCB biodegradation. This new dataset could contribute to substantially improve the predictions of soil remediation time, multimedia fate and the long-range transport of PCBs. Additionally, the half-lives obtained here can also be used in the evaluation of the food chain transfer of these chemicals, and finally the exposure and potential for effects on ecosystems.

PCB vertical and horizontal movement in agricultural soils of a highly contaminated site: Role of soil properties, cultivation history and PCB physico-chemical parameters.

The agricultural areas of a historically contaminated National Relevance Site (SIN Brescia Caffaro) in Italy are an ideal case for studying the long term vertical and horizontal movement of polychlorinated biphenyls (PCBs) in soil. Here, a former large producer of PCBs (Caffaro S.p.A.) discharged its wastewaters, contaminated by PCBs and other chemicals, to a ditch used for about 80 years as source of irrigation waters for the adjacent agricultural areas. This caused a spread of contamination along both a vertical and a horizontal soil gradient. PCB concentrations of about 80 congeners, including PCB 209, peculiar of Caffaro production, were measured in three areas, selected for their different soil properties and cultivation history. The contamination levels with depth ranged from about 30 mg/kg dry weight (d.w.) of soil in the top (plow) layer to less than 0.1 mg/kg d.w. at the depth of 1 m. The concentrations varied also horizontally, since each field was surface irrigated from the short edge of each field, showing that PCBs could spread with length halving the initial concentrations in the topsoil only after about 30-35 m. The concentration gradients detected were explained considering the historic soil use and its change with time, the pedological properties as well as PCB physico-chemical parameters and halflives, developing equations which could be employed as guidance tools for evaluating PCBs (and similar chemicals) movement and direct further studies.

New Data Set of Polychlorinated Dibenzo-p-dioxin and Dibenzofuran Half-Lives: Natural Attenuation and Rhizoremediation Using Several Common Plant Species in a Weathered Contaminated Soil.

In this paper, a new data set of polychlorinated dibenzo-p-dioxin and dibenzofuran (PCDD/Fs) half-lives (HLs) in soil is presented. Data are derived from a greenhouse experiment performed with an aged contaminated soil under semi-field conditions, obtained from a National Relevance Site (SIN) located in Northern Italy (SIN Brescia-Caffaro). Ten different treatments (combination of seven plant species with different soil conditions) were considered together with the respective controls (soil without plants). The ability of the plants to stimulate the biodegradation of these compounds was evaluated by measuring the PCDD/F concentration reduction in soil over a period of 18 months. The formation of new bound residues was excluded by using roots as a passive sampler of bioaccessible concentrations. The best treatment which significantly reduced PCDD/F concentrations in soil was the one with Festuca arundinacea (about 11-24% reduction, depending on the congener). These decreases reflected in HLs ranging from 2.5 to 5.8 years. Simulations performed with a dynamic air-vegetation-soil model (SoilPlusVeg) confirmed that these HLs were substantially due to biodegradation rather than other loss processes. Because no coherent PCDD/F degradation HL data sets are currently available for soil, they could substantially improve the predictions of soil remediation time, long-range transport, and food chain transfer of these chemicals using multimedia fate models.

Rhizoremediation of weathered PCBs in a heavily contaminated agricultural soil: Results of a biostimulation trial in semi field conditions.

This paper describes the results of a rhizoremediation greenhouse experiment planned to select the best plant species and soil management for the bioremediation of weathered polychlorinated biphenyls (PCBs). We evaluated the ability of different plant species to stimulate activity and diversity of the soil microbial community leading to the reduction of PCB concentrations in a heavily contaminated soil (at mg kg-1 dw level), of the national priority site for remediation (SIN) "Brescia-Caffaro" in Italy. Biostimulation was determined in large size (6kg) pots, to reflect semi-field conditions with a soil/root volume ratio larger than in most rhizoremediation experiments present in the literature. In total, 10 treatments were tested in triplicates comparing 7 plant species (grass and trees) and 5 soil/cultivation conditions (i.e., only one plant species, plant consociation, redox cycle, compost or ammonium thiosulfate addition) with the appropriate unplanted controls. After 18months of biostimulation the overall reduction of total PCBs varied between 14 and 20%. Microbial analysis revealed a shift in the microbial community structure over time and showed that all the planted treatments significantly enhanced microbial hydrolytic activity and the abundance of bacterial populations, including potential PCB degraders, in the soil surrounding plant roots. The plant species most effective in reducing the contaminant concentrations were Festuca arundinacea cultivated adding compost or in consociation with Cucurbita pepo ssp. pepo and Medicago sativa cultivated with Rhizobium spp. and mycorrhizal fungi; they reduced total PCB concentrations of about 20% and showed the significant depletion of a high number of PCB congeners (29, 37 and 23, respectively, out of the 79 measured). Our results suggest that these plant species are particularly efficient in increasing soil PCB bioavailability and in stimulating microbial degradation. They could be used in field rhizoremediation strategies to enhance the natural attenuation process and reduce PCB levels in historically contaminated sites.

Differentiating current and past PCB and PCDD/F sources: The role of a large contaminated soil site in an industrialized city area.

Cities and contaminated areas can be primary or secondary sources of polychlorinated biphenyls (PCBs), dibenzo-p-dioxins (PCDDs), dibenzofurans (PCDFs), and other chemicals, into air and soil and can influence the regional level of some of these pollutants. In a contaminated site, the evaluation of such emissions can be crucial in the choice of the remediation technology to be adopted. In the city of Brescia (Northern Italy), more than 100 ha of agricultural areas were contaminated with PCBs, PCDD/Fs and heavy metals, originating from the activities of a former PCB factory. In order to evaluate the current emissions of PCBs and PCDD/Fs from the contaminated site, in a location where other current sources are present, we compared measured and predicted air concentrations, resulting from chemical volatilization from soils as well as fingerprints of Brescia soils and of soils contaminated by specific sources. The results confirm that the contaminated area is still a current and important secondary source of PCBs to the air, and to a lesser extent of PCDFs (especially the more volatile), but not for PCDDs. PCBs in soils have fingerprints similar to highly chlorinated mixtures, indicating contamination by these mixtures and/or a long weathering process. PCB 209 is also present at important levels. PCDD fingerprints in soil cannot be related to current emission sources, while PCDFs are compatible to industrial and municipal waste incineration, although weathering and/or natural attenuation may have played a role in modifying such soil fingerprints. Finally, we combined chemical and microbiological analyses to provide an integrated approach to evaluate soil fingerprints and their variation in a wider perspective, which accounts for the mutual effects between contamination and soil microbiota, a pivotal hint for addressing in situ bioremediation activities.