Antonio Di Guardo

Past, Present, and Future Controls on Levels of Persistent Organic Pollutants in the Global Environment

Understanding the legacy of persistent organic pollutants requires studying the transition from primary to secondary source control.

Chlorinated hydrocarbons in pine needles in Europe : fingerprint for the past and recent use

Pine needles have been demonstrated as a useful monitoring matrix for the evaluation of the tropospheric contamination levels of persistent chlorinated hydrocarbons, such as DDTs, HCHs, and HCB. Global chlorinated hydrocarbon distribution has been investigated with major attention to remote areas, while the factors affecting the distribution trends in regions of major use are less known. Six countries in Europe were analyzed by the transect sampling mode. Homogeneous contamination intensities were present within each transect, and correspondence factor analysis was used for the characterization of the typical distribution patterns

Conifer needles as passive biomonitors of the spatial and temporal distribution of DDT from a point source

Needles of two conifer species, Picea abies and Pinus nigra, were used as passive samplers for monitoring air contamination by sampling at increasing distances from a suspected point source of DDT. Needle concentrations declined with increasing distance downwind of the point source allowing to identify spatial and temporal trends of accumulation. This suggested that conifer needles are effective biomonitors of contamination levels in areas characterized by the presence of semi-volatile substances. Differences in uptake were apparent between the species. Needle morphology and structure were studied with scanning electron microscope (SEM) as were dimensional parameters (surface area, volume). The results suggest that the concentrations depend on a mechanism involving the inner structure of the needles, specifically the number and accessibility of resin channels rather than their surface area. Pine needles have more channels with greater accessibility than spruce. The results suggest that spruce is more suitable for short term measurement while pine for determining long term cumulative exposure.

Screening of pesticides for environmental partitioning tendency

The partitioning tendency of chemicals, in this study pesticides in particular, into different environmental compartments depends mainly on the concurrent relevance of the physico-chemical properties of the chemical itself. To rank the pesticides according to their distribution tendencies in the different environmental compartments we propose a multivariate approach: the combination, by principal component analysis, of those physico-chemical properties like organic carbon partition coefficient (Koc), n-octanol/water partition coefficient (Kow), water solubility (Sw), vapour pressure and Henrys law constant (H) that are more relevant to the determination of environmental partitioning. The resultant macrovariables, the PC1 and PC2 scores here named leaching index (LIN) and volatality index (VIN), are proposed as preliminary environmental partitioning indexes in different media. These two indexes are modeled by theoretical molecular descriptors with satisfactory predictive power. Such an approach allows a rapid pre-determination and screening of the environmental distribution of pesticides starting only from the molecular structure of the pesticide, without any a priori knowledge of the physico-chemical properties.

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.

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.

Species interactions and chemical stress: combined effects of intraspecific and interspecific interactions and pyrene on Daphnia magna population dynamics.

Species interactions are often suggested as an important factor when assessing the effects of chemicals on higher levels of biological organization. Nevertheless, the contribution of intraspecific and interspecific interactions to chemical effects on populations is often overlooked. In the present study, Daphnia magna populations were initiated with different levels of intraspecific competition, interspecific competition, and predation and exposed to pyrene pulses. Generalized linear models were used to test which of these factors significantly explained population size and structure at different time points. Pyrene had a negative effect on total population densities, with effects being more pronounced on smaller D. magna individuals. Among all species interactions tested, predation had the largest negative effect on population densities. Predation and high initial intraspecific competition were shown to interact antagonistically with pyrene exposure. This was attributed to differences in population structure before pyrene exposure and pyrene-induced reductions in predation pressure by Chaoborus sp. larvae. The present study provides empirical evidence that species interactions within and between populations can alter the response of aquatic populations to chemical exposure. Therefore, such interactions are important factors to be considered in ecological risk assessments.

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.

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.

Predicting pesticide fate in small cultivated mountain watersheds using the DynAPlus model: Toward improved assessment of peak exposure

The use of plant protection products (PPPs) in agricultural areas implies potential chemical loadings to surface waters, which can pose a risk to aquatic ecosystems and human health. Due to the spatio-temporal variability of PPP applications and of the processes regulating their transport to surface waters, aquatic organisms are typically exposed to pulses of contaminants. In small mountain watersheds, where runoff fluxes are more rapid due to the steep slopes, such exposure peaks are particularly likely to occur. In this work, a spatially explicit, dynamic model for predicting pesticide exposure in surface waters of cultivated mountain basins (DynAPlus) has been developed. The model has been applied to a small mountain watershed (133km2) located in the Italian Eastern Alps and characterized by intensive agriculture (apple orchards) around the main river and its tributaries. DynAPlus performance was evaluated for chlorpyrifos through experimental monitoring, using samples collected during the 2011 and 2012 productive seasons. The comparison between predictions and measurements resulted in a good agreement (R2=0.49, efficiency factor 0.60), although a more accurate spatial information in the input scenario (e.g., field-specific applications, rainfall amount, soil properties) would dramatically improve model performance. A set of illustrative simulations performed for three PPPs highlighted the potential role of DynAPlus in improving exposure predictions for ecological risk assessment and pesticide management practices (e.g., for active ingredient and application rate selection), as well as for planning efficient monitoring campaigns and/or interpreting monitoring data. However, some model improvements (e.g., solid erosion and transport) and a more thorough model validation are desirable to enlarge the applicability domain.