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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., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 The Authors. Published by Elsevier B.V. All rights reserved.)

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., (Copyright © 2021 Elsevier B.V. All rights reserved.)

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., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier B.V. All rights reserved.)

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., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier B.V. All rights reserved.)

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., (Copyright © 2019. Published by Elsevier B.V.)