Elisa Terzaghi

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.

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.

Estimation of Polycyclic Aromatic Hydrocarbon Variability in Air Using High Volume, Film, and Vegetation as Samplers

Organic films and leaves provide a medium into which organic contaminants, such as polycyclic aromatic hydrocarbons (PAHs), can accumulate, resulting in a useful passive air sampler. In the present work, the temporal variability (weekly) in PAH concentrations and the fingerprint of films developed on window surfaces were investigated. Moreover, films and leaves of two tree species (Acer pseudoplatanus and Cornus mas) collected at the same time were used to derive PAH air concentrations and investigate their short-term variability. In general, the most abundant chemicals found in films were phenanthrene and pyrene (22%), followed by perylene (21%) and fluoranthene (16%), but the fingerprint (in contrast to leaves and air) changed over time. Leaf derived air concentrations were within a factor of 2 to 9 from measured values, while air concentrations back-calculated from films were within a factor of 2 to 53. This happened because predicted air concentrations using films and vegetation samplers (especially for low KOA chemicals) generally reflect only the last few hours (due to the fast equilibrium) of the weekly integrated samples obtained employing the high-volume sampler. This means that films and leaves can be usefully employed for predicting the short-term variability of low KOA organic contaminant air concentrations.

How good are the predictions of mobility of aged polychlorinated biphenyls (PCBs) in soil? Insights from a soil column experiment

A column leaching experiment was performed to evaluate the influence of some relevant environmental factors (soil/water contact time, temperature, saturation) on mobility of aged polychlorinated biphenyls (PCBs) in soil together with transport mediated by dissolved organic carbon (DOC) and mobile organic carbon (OC) coated fine particles/colloids. Consecutive fractions of leachates were collected after a variable pre-equilibration time (2, 5, 7, 48 days), using leaching solutions with different DOC content (tap water vs. Aldrich humic acid), in saturated vs. field capacity conditions and at different temperatures (25 °C vs. 15 °C). The data obtained were compared to the predicted values using a multimedia model (SoilPlusVeg) to evaluate model behaviour. Contact time and temperature determined a relevant effect on DOC and particle/colloid availability, with significant variations in leachate concentrations (up to 1 order of magnitude), typically overlooked by most environmental fate models. Results obtained at different temperatures show a modulation of the DOC/particles production with temperature and therefore the role of temperature changes in the environmental scenarios (e.g. seasonal variations). Transport of PCBs enhanced by Aldrich DOC was not linearly correlated to chemical hydrophobicity but revealed a threshold to ~Log KOW 6.5, likely because of the slow sorption kinetics of more hydrophobic chemicals. Additionally, variation of the saturation conditions (e.g. drying-wetting cycles) can determine contamination peaks at the beginning of an irrigation/rainfall event because of the soil/water equilibration. Model simulations, even when including DOC in the water phase, but not accounting for the particle/colloidal transport and sorption/desorption kinetics, mismatched the ratio of dissolved vs. DOC-associated and particle-associated PCBs and substantially underpredicted concentrations, especially for the high chlorinated congeners. The results indicated that some of the common assumptions and paradigms in fate modelling of such hydrophobic compounds should be revisited and models updated.