Matteo Semplice

A Dynamic Model of the Fate of Organic Chemicals in a Multilayered Air/Soil System: Development and Illustrative Application

A new site-specific, dynamic model (SoilPlus) was developed to simulate the fate of nonionized organic chemicals in the air/litter/soil system; key features of the model are the double-layered air compartment interacting dynamically with multilayered litter and soil compartments, with seasonal dissolved organic carbon (DOC) fluxes. The model describes the soil environment calculating separate mass balances for water, chemical, and organic matter. SoilPlus underwent a process of benchmarking and evaluation in order to reach a satisfying confirmation of its predictive capability. Several simulations were performed to estimate the role of litter and DOC in affecting the fate of a model contaminant for POPs (hexachlorobenzene). The model shows that litter can behave as a buffer in the process of transferring hexachlorobenzene from air to the mineral soil and as a trap when hexachlorobenzene tends to move from a contaminated field toward clean air. DOC seems to behave as a leaching-enhancer in certain climatic conditions (heavy rainfall, high DOC concentrations), but it does not appear to move significant amounts of HCB in a year calculation.

Modeling short-term variability of semivolatile organic chemicals in air at a local scale: An integrated modeling approach

Monitoring campaigns from different locations have recently shown how air concentrations of persistent semivolatile contaminants such as polychlorinated biphenyls (PCBs) often exhibit short-term (less than 24xa0h) variations. The observed patterns have been ascribed to different factors, such as temperature-mediated air-surface exchange and variability of planetary boundary layer (PBL) height and dynamics. Here, we present a new modeling approach developed in order to investigate the short-term variability in air concentrations of organic pollutants at a local scale. A new dynamic multimedia box model is supplied by a meteorological preprocessor (AERMET) with hourly values of air compartment height and wind speed. The resulting model is tested against an existing dataset of PCB air concentrations measured in Zurich, Switzerland. Results show the importance of such modeling approach in elucidating the short- and long-term behavior of semivolatile contaminants in the air/soil system.

Evaluating the temporal variability of concentrations of POPs in a glacier-fed stream food chain using a combined modeling approach

Falling snow acts as an efficient scavenger of contaminants from the atmosphere and, accumulating on the ground surface, behaves as a temporary storage reservoir; during snow aging and metamorphosis, contaminants may concentrate and be subject to pulsed release during intense snow melt events. In high-mountain areas, firn and ice play a similar role. The consequent concentration peaks in surface waters can pose a risk to high-altitude ecosystems, since snow and ice melt often coincide with periods of intense biological activity. In such situations, the role of dynamic models can be crucial when assessing environmental behavior of contaminants and their accumulation patterns in aquatic organisms. In the present work, a dynamic fate modeling approach was combined to a hydrological module capable of estimating water discharge and snow/ice melt contributions on an hourly basis, starting from hourly air temperatures. The model was applied to the case study of the Frodolfo glacier-fed stream (Italian Alps), for which concentrations of a number of persistent organic pollutants (POPs), such as polychlorinated biphenyl (PCBs) and p,p-dichlorodiphenyldichloroethylene (p,p-DDE) in stream water and four macroinvertebrate groups were available. Considering the uncertainties in input data, results showed a satisfying agreement for both water and organism concentrations. This study showed the model adequacy for the estimation of pollutant concentrations in surface waters and bioaccumulation in aquatic organisms, as well as its possible role in assessing the consequences of climate change on the cycle of POPs.

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.

Guidance on the selection of efficient computational methods for multimedia fate models.

Dynamic multimedia fate models (MFMs) have to deal with the temporal and spatial variation of physical-chemical properties, environmental scenarios, and chemical emissions. In such complex simulation tools, an analytical solution is not practically feasible, and even a numerical approach requires a suitable choice of the method in order to obtain satisfying speed and reliability, particularly when certain combinations of modeling scenarios and chemical properties occur. In this paper, considering some examples of a wide range of realistic chemical and scenario properties, some sources of stiffness in MFM equations are pinpointed. Next, a comparison of the performances of several numerical schemes (chosen as representatives of three wide classes) is performed. The accuracy and the computational effort required by each method is evaluated, illustrating the general effectiveness of automatically adapted timesteps in numerical algorithms and the pros and cons of implicit timestepping. The results show that automatic error control methods can significantly improve the quality of the computed solutions and most often lead to relevant savings in computing time. Additionally, explicit and implicit methods are compared, indicating that an implicit method of medium order (around 5) is the best choice as a general purpose MFM computing engine.

Importance of environmental and biomass dynamics in predicting chemical exposure in ecological risk assessment

In ecological risk assessment, exposure is generally modelled assuming static conditions, herewith neglecting the potential role of emission, environmental and biomass dynamics in affecting bioavailable concentrations. In order to investigate the influence of such dynamics on predicted bioavailable concentrations, the spatially-resolved dynamic model ChimERA fate was developed, incorporating macrophyte and particulate/dissolved organic carbon (POC/DOC) dynamics into a water-sediment system. An evaluation against three case studies revealed a satisfying model performance. Illustrative simulations then highlighted the potential spatio-temporal variability of bioavailable concentrations after a pulsed emission of four chemicals in a system composed of a pond connected to its inflow and outflow streams. Changes in macrophyte biomass and POC/DOC levels caused exposure variations which were up to a factor of 4.5 in time and even more significant (several orders of magnitude) in space, especially for highly hydrophobic chemicals. ChimERA fate thus revealed to be a useful tool to investigate such variations and to identify those environmental and ecological conditions in which risk is expected to be highest.

SoilPlusVeg: An integrated air-plant-litter-soil model to predict organic chemical fate and recycling in forests

Current modelling approaches often ignore the dynamics of organic chemicals uptake/release in forest compartments under changing environmental conditions and may fail in accurately predict exposure to chemicals for humans and ecosystems. In order to investigate the influence of such dynamics on predicted concentrations in forest compartments, as well as, on air-leaf-litter fluxes, the SoilPlusVeg model was developed including a forest compartment (root, stem, leaves) in an existing air-litter-soil model. The accuracy of the model was tested simulating leaf concentrations in broadleaf woods located in Northern Italy and resulted in satisfying model performance. Illustrative simulations highlighted the dual behaviour of both leaf and litter compartments. Leaves appeared to behave as filters of air contaminants but also as dispensers, being deposition flux exceeded by volatilization flux in some periods of the day. Similarly, litter seemed to behave as a dynamic compartment which could accumulate and then release contaminants recharging air and vegetation. In just 85days, litter could lose due to volatilization, diffusion to depth and infiltration processes, from 6% to 90% of chemical amount accumulated over 1year of exposure, depending on compound physical and chemical properties. SoilPlusVeg thus revealed to be a powerful tool to understand and estimate chemical fate and recycling in forested systems.

European environmental scenarios of chemical bioavailability in freshwater systems.

In exposure prediction for environmental risk assessment, the transition to more dynamic and realistic modelling approaches and scenarios has been recently identified as a major challenge, since it would allow a more accurate prediction of bioavailable concentrations and their variations in space and time. In this work, an improved version of the multimedia model ChimERA fate, including a phytoplankton compartment and equations to calculate phytoplankton, detritus and dissolved organic matter variations in time, was developed. The model was parameterized to simulate five dynamic scenarios for shallow meso-eutrophic water bodies based on a latitudinal gradient (in Europe); such scenarios include seasonal profiles of water temperature, phytoplankton biomass, detritus, and dissolved organic matter. Model runs were performed for each scenario for 8 hydrophobic chemicals (PCB congeners), with the aim of investigating the influence of scenario characteristics and compound properties on bioavailable concentrations. The key processes were adsorption/uptake by phytoplankton and deposition to sediment of detritus-bound chemicals. The northern scenarios (Scandinavia and UK) showed the highest bioavailable concentrations, with annual maximum/minimum concentration up to 25; in contrast, for example, maximum concentrations in the Mediterranean scenario were lower by a factor of 2 to 9 with respect to the northern ones (depending on chemical hydrophobicity), due to the generally higher biomass and carbon levels, and showed only limited seasonal variability (up to a factor of 4). These results highlight the importance of including biomass and organic carbon dynamics in both modelling approaches and scenarios for the evaluation of exposure concentrations in aquatic environments.