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.

Parametrization identification and characterization of the radon priority areas for indoor radon risk management.

The aim of work is to contribute to the development of methodologies concerning the selection and characterisation of radon priority areas. The selection of areas was based on risk from indoor radon exposure, expressed in terms of number of expected deaths per year. Radon data come from a survey carried out in the Lazio Region (Italy) and consist of 5297 indoor concentration measurements. Population data were also used. Data showed that dwellings with concentrations above 300 Bq/m3, taken as reference level (RL), are not confined to specific areas, but rather spread out over the territory. An absolute risk model has been chosen to predict annual deaths on a regular grid of cells 2kmx2km sized. The analysis showed that 21.7% of the territory is completely uninhabited and that another 13.9% presents a marginal risk, quantifiable in total as less than one expected death per year. The remaining territory is of interest to identify the areas where dwellings with a concentration higher than the RL would be located. It was found that: such dwellings occur with different percentage in all the cells; exposed people varies from a few to almost 2000 per cell; indoor radon risk from exposure above RL is dominated by the number of exposed people and amounts to 106 deaths per year; the number of cells where a such risk is low is far greater than where the risk is high. These findings led to restrict RPA to the smallest set of cells that retained 85% of risk, i.e. 90 expected deaths per year. This percentage has been subjectively set because the technical and economic information required for its optimal calculation was not available. Based on this assumption, the RPA were identified by applying a threshold of 43 to the number of exposed people in each cell, in order to reach 85% of risk. The other main characteristics, also expressed as percentages of the corresponding totals within the area of interest, were found to be: extension 31.5% and exposed people 84%.

Predicting the regional contamination evolution of DDT for 100-years with a new gridded spatial and dynamic multimedia fate model.

In 1996 high dichlorodiphenyltrichloroethane (DDT) concentrations were found in Lake Maggiore (Italy) fish and sediments. DDT was produced by a chemical company located in a subalpine valley (Ossola valley, Piedmont Region, Italy), and ended up in the Toce River, a tributary of Lake Maggiore. In the area surrounding the chemical plant, high DDT concentrations in soil and vegetation were found after subsequent investigations. The quantification of the release from contaminated soil and the following migration toward downwind areas, deposition to the soil, and further evaporation plays an important role in understanding future DDT trends in soil and the atmosphere. To study this phenomenon, soil, and vegetation from Ossola Valley were monitored in 2001 and 2011. The concentration values obtained (soils: 0.05 to 1 µg/g; vegetation 2-100 ng/g), allowed to reconstruct the contamination gradient in the valley and were used to develop and calibrate a spatially resolved multimedia fugacity model. The model accounts for spatial and temporal dynamicity of environmental characteristics such as wind speed and direction, variable air compartment height etc., and simulates the fate and transport of chemicals on a local scale. The dynamic emission of DDT (about 13,000 kg for the 50 y production time) to the air was estimated and utilized for a 100-year simulation (from 1948 to 2048). The results obtained allowed to understand the temporal and spatial pattern of DDT contamination for a long period at a local scale as well as the potential contribution as a source potentially affecting sites at larger distances.

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.

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.

Improving the SoilPlusVeg model to evaluate rhizoremediation and PCB fate in contaminated soils.

Tools to predict environmental fate processes during remediation of persistent organic pollutants (POPs) in soil are desperately needed since they can elucidate the overall behavior of the chemical and help to improve the remediation process. A dynamic multimedia fate model (SoilPlusVeg) was further developed and improved to account for rhizoremediation processes. The resulting model was used to predict Polychlorinated Biphenyl (PCB) fate in a highly contaminated agricultural field (1089 ng/g d.w.) treated with tall fescue (Festuca arundinacea), a promising plant species for the remediation of contaminated soils. The model simulations allowed to calculate the rhizoremediation time (about 90 years), given the available rhizoremediation half-lives and the levels and fingerprints of the PCB congeners, to reach the legal threshold, to show the relevance of the loss processes from soil (in order of importance: degradation, infiltration, volatilization, etc.) and their dependence on meteorological and environmental dynamics (temperature, rainfall, DOC concentrations). The simulations showed that the effective persistence of PCBs in soil is deeply influenced by the seasonal variability. The model also allowed to evaluate the role of DOC as a possible enhancer of PCB degradation as a microorganism "spoon feeder" of PCBs in the soil solution. Additionally, we preliminary predicted how the contribution of PCB metabolites could modify the PCB fingerprint and their final total concentrations. This shows that the SoilPlusVeg model could be used in selecting the best choices for a sustainable rhizoremediation of a POP contaminated site.

Rhizoremediation half-lives of PCBs: Role of congener composition, organic carbon forms, bioavailability, microbial activity, plant species and soil conditions, on the prediction of fate and persistence in soil.

Polychlorinated biphenyls (PCBs) are persistent organic pollutants widely produced and used in many countries until the increasing concern about their environmental risk lead to their ban in the 1980s. Although their emissions decreased, PCBs are nowadays still present in the environment and can be reemitted from reservoir compartments such as contaminated soils. In the last two decades, there has been a growing interest in bioremediation technologies that use plants and microorganisms (i.e. rhizoremediation) to degrade organic chemicals in contaminated sites. Different studies have been conducted to investigate the potential of plant-microbe interactions in the remediation of organic chemical contaminated soils. They range from short-term and laboratory/greenhouse experiments to long-term and field trials and, when correctly set up, they could provide useful data such as PCB rhizoremediation half-lives in soil. Such type of data are important input parameters for multimedia fate models that aim to estimate the time requested to achieve regulatory thresholds in a PCB contaminated site, allowing to draw up its remediation plan. This review focuses on the main factors influencing PCB fate, persistence and bioavailability in soil including PCB mixture congener composition, soil organic carbon forms, microorganism activity, plant species and soil conditions. Furthermore, it provides an estimate of rhizoremediation half-lives of the ten PCB families starting from the results of literature rhizoremediation experiments. Finally, guidance to perform appropriate experiments to obtain comparable, accurate and useful data for fate estimation is proposed.

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.

Phyto-rhizoremediation of polychlorinated biphenyl contaminated soils: An outlook on plant-microbe beneficial interactions.

Polychlorinated biphenyls (PCBs) are toxic chemicals, recalcitrant to degradation, bioaccumulative and persistent in the environment, causing adverse effects on ecosystems and human health. For this reason, the remediation of PCB-contaminated soils is a primary issue to be addressed. Phytoremediation represents a promising tool for in situ soil remediation, since the available physico-chemical technologies have strong environmental and economic impacts. Plants can extract and metabolize several xenobiotics present in the soil, but their ability to uptake and mineralize PCBs is limited due to the recalcitrance and low bioavailability of these molecules that in turn impedes an efficient remediation of PCB-contaminated soils. Besides plant degradation ability, rhizoremediation takes into account the capability of soil microbes to uptake, attack and degrade pollutants, so it can be seen as the most suitable strategy to clean-up PCB-contaminated soils. Microbes are in fact the key players of PCB degradation, performed under both aerobic and anaerobic conditions. In the rhizosphere, microbes and plants positively interact. Microorganisms can promote plant growth under stressed conditions typical of polluted soils. Moreover, in this specific niche, root exudates play a pivotal role by promoting the biphenyl catabolic pathway, responsible for microbial oxidative PCB metabolism, and by improving the overall PCB degradation performance. Besides rhizospheric microbial community, also the endophytic bacteria are involved in pollutant degradation and represent a reservoir of microbial resources to be exploited for bioremediation purposes. Here, focusing on plant-microbe beneficial interactions, we propose a review of the available results on PCB removal from soil obtained combining different plant and microbial species, mainly under simplified conditions like greenhouse experiments. Furthermore, we discuss the potentiality of "omics" approaches to identify PCB-degrading microbes, an aspect of paramount importance to design rhizoremediation strategies working efficiently under different environmental conditions, pointing out the urgency to expand research investigations to field scale.

Nondeterministic computational fluid dynamics modeling of Escherichia coli inactivation by peracetic acid in municipal wastewater contact tanks.

Wastewater disinfection processes are typically designed according to heuristics derived from batch experiments in which the interaction among wastewater quality, reactor hydraulics, and inactivation kinetics is often neglected. In this paper, a computational fluid dynamics (CFD) study was conducted in a nondeterministic (ND) modeling framework to predict the Escherichia coli inactivation by peracetic acid (PAA) in municipal contact tanks fed by secondary settled wastewater effluent. The extent and variability associated with the observed inactivation kinetics were both satisfactorily predicted by the stochastic inactivation model at a 95% confidence level. Moreover, it was found that (a) the process variability induced by reactor hydraulics is negligible when compared to the one caused by inactivation kinetics, (b) the PAA dose required for meeting regulations is dictated equally by the fixed limit of the microbial concentration as well as its probability of occurrence, and (c) neglecting the probability of occurrence during process sizing could lead to an underestimation of the PAA dose required by as much as 100%. Finally, the ND-CFD model was used to generate sizing information in the form of probabilistic disinfection curves relating E. coli inactivation and probability of occurrence with the average PAA dose and PAA residual concentration at the outlet of the contact tank.

Towards more ecologically realistic scenarios of plant uptake modelling for chemicals: PAHs in a small forest.

The importance of plants in the accumulation of organic contaminants from air and soil was recognized to the point that even regulatory predictive approaches now include a vegetation compartment or sub-compartment. However, it has recently been shown that many of such approaches lack ecological realism to properly evaluate the dynamic of air/plant/soil exchange, especially when environmental conditions are subject to sudden variations of meteorological or ecological parameters. This paper focuses on the development of a fully dynamic scenario in which the variability of concentrations of selected chemicals in air and plant leaves was studied weekly and related to the corresponding meteorological and ecological parameters, to the evaluate their influence. To develop scenarios for modelling purposes, two different sampling campaigns were performed to measure temporal variability of: 1) polycyclic aromatic hydrocarbon (PAH) concentrations in air of a clearing and a forest site, as well as in leaves of two broadleaf species and 2) two important leaf and canopy traits, specific leaf area (SLA) and leaf area index (LAI). The aim was to evaluate in detail how the variability of meteorological and ecological parameters (SLA and LAI) can influence the uptake/release of organic contaminants by plants and therefore air concentrations. A principal component analysis demonstrated how both meteorological and ecological parameters jointly influence PAH air concentrations. SLA, LAI, as well as leaf density were showed to change over time and among species and to be directly proportional to leaf/canopy uptake rate. While hazelnut had the higher leaf uptake rate, maple became the most important species when considering the canopy uptake rate due to its higher LAI. Other species specific traits, such as the seasonal variation in production of new leaves and the timing of bud burst, were also shown to influence the uptake rate of PAHs by vegetation.

Integration of an atmospheric dispersion model with a dynamic multimedia fate model: development and illustration.

Growing attention is devoted to understand the influence of the short-term variations in air concentrations on the environmental fate of semivolatile organic compounds (SVOCs) such as polycyclic aromatic hydrocarbons (PAHs). These variations are ascribable to factors such as temperature-mediated air-surface exchange and variability of planetary boundary layer (PBL) height and structure. But when investigating the fate of SVOCs at a local scale, further variability can derive from specific point source contributions. In this context, a new modeling approach (AirPlus) which integrates a previously developed model (AirFug) with an air dispersion model (AERMOD) is presented. The integrated model is illustrated for two PAHs in a Northern Italy scenario. Results show how chemical contributions deriving from background advective inflows, local emissions and a point source interact in an hourly-varying meteorological scenario to determine air concentration rapid changes and the consequent response of the soil compartment.