Ecological risk assessment for contaminated sites in Italy: Guidelines and path forward.

Ecological risk assessment (ERA) is defined as an iterative process that evaluates the likelihood of adverse ecological effects resulting from exposure to one or more stressors. Although ERA is recognized as a valuable procedure to better address efforts and strategies for site remediation, in Europe a common framework for the implementation of ERA in the management of contaminated sites is lacking. In Italy, there are no legally binding provisions regulating the direct assessment of potential likelihood of ecological risks. In this context, the main objective of this article was to develop a guideline to facilitate ERA application in support of an effective and sustainable management of contaminated sites in Italy and to facilitate a multistakeholder dialogue. The work was based on a critical review of existing ERA guidelines in the international context, as well as other regulatory documents and technical approaches dealing with the evaluation of ecological effects of chemical contaminants in different environmental compartments. Approaches and tools available in these documents were then used to prepare a proposed guideline for the Italian context; the proposed ERA guideline is meant to represent a flexible but robust approach that can be useful in evaluating existing data (e.g., from past investigations) as well as in the planning of site-specific investigations. To facilitate the direct application of the ERA procedure, the guideline was prepared including several templates of summary tables, checklists, and examples. The proposed ERA guideline could facilitate the decision-making process for contaminated sites with ecological values, although its application would necessarily require, at least in the initial phase, testing of its suitability to the Italian context and setting-up of a close dialogue and collaboration with local authorities and other stakeholders. Integr Environ Assess Manag 2023;19:913-919. © 2022 SETAC.

In Situ Equilibrium Polyethylene Passive Sampling of Soil Gas VOC Concentrations: Modeling, Parameter Determinations, and Laboratory Testing.

The use of low-density polyethylene (PE) sheets as equilibrium passive soil gas samplers to quantify volatile organic compounds (VOCs) such as benzene, toluene, ethylbenzene, and xylenes, and chlorinated solvents (e.g., trichloroethene and tetrachloroethene) in unsaturated subsurface environments was evaluated via modeling and benchtop testing. Two methods were devised to quantify such VOCs in PE. Key chemical properties, including PE-water (KPEw) and PE-air (KPEa) partition coefficients and diffusivities in the PE (Dpe), were determined. These KPEw, KPEa, and Dpe values were consistent with extrapolations of data based on larger compounds. Using these parameter values, field equilibration times of less than 1 day were estimated for such VOCs when using 70-100 µm thick PE sheets. Further, benchtop batch tests carried out in jars filled with VOC-contaminated soils, after 1 or 2 days, showed concentrations in soil air deduced from PE that were consistent with concentrations deduced by analyzing either water or headspace gases recovered from the same tests. Thus, PE-based measurements may overcome inaccuracies from using total soil concentrations and equilibrium partitioning models that may overestimate vapor phase concentrations up to 2 orders of magnitude.

Hybrid Forward Osmosis⁻Nanofiltration for Wastewater Reuse: System Design.

The design of a hybrid forward osmosis-nanofiltration (FO-NF) system for the extraction of high-quality water from wastewater is presented here. Simulations were performed based on experimental results obtained in a previous study using real wastewater as the feed solution. A sensitivity analysis, conducted to evaluate the influence of different process parameters, showed that an optimum configuration can be designed with (i) an influent draw solution osmotic pressure equal to 15 bar and (ii) a ratio of influent draw solution to feed solution flow rate equal to 1.5:1. With this configuration, the simulations suggested that the overall FO-NF system can achieve up to 85% water recovery using Na2SO4 or MgCl2 as the draw solute. The modular configuration and the size of the NF stage, accommodating approximately 7000 m2 of active membrane area, was a function of the properties of the membranes selected to separate the draw solutes and water, while detailed simulations indicated that the size of the FO unit might be reduced by adopting a counter-current configuration. Experimental tests with samples of the relevant wastewater showed that Cl-- and Mg2+-based draw solutes would be associated with larger membrane fouling, possibly due to their interaction with the other substances present in the feed solution. However, the results suggest that fouling would not significantly decrease the performance of the designed system. This study contributes to the further evaluation and potential implementation of FO in water reuse systems.

Performance of passive sampling with low-density polyethylene membranes for the estimation of freely dissolved DDx concentrations in lake environments.

Laboratory and field studies were used to evaluate the performance of low-density polyethylene (PE) passive samplers for assessing the freely dissolved concentrations of DDT and its degradates (DDD and DDE, together referred to as DDx) in an Italian lake environment. We tested commercially available 25 µm thick PE sheets as well as specially synthesized, 10 µm thick PE films which equilibrated with their surroundings more quickly. We measured PE-water partitioning coefficients (Kpew) of the 10 µm thick PE films, finding good correspondence with previously reported values for thicker PE. Use of the 10 µm PE for ex situ sampling of a lake sediment containing DDx in laboratory tumbling experiments showed repeatability of ±15% (= standard deviation/mean). Next, we deployed replicate 10 µm and 25 µm PE samplers (N = 4 for 10 d and for 30 d) in the water and sediment of a lake located in northern Italy; the results showed dissolved DDx concentrations in the picogram/L range in porewater and the bottom water. Values deduced from 10 µm thick PE films compared well (95% of all comparison pairs matched within a factor of 5) with those obtained using PE films of 25 µm thickness when dissolved DDx concentrations were estimated using performance reference compound (PRC) corrections, whether left at the bed-water interface for 10 or 30 days. These results demonstrated the potential of this sampling method to provide estimation of the truly dissolved DDx concentrations, and thereby the mobile and bio-available fractions in both surface waters and sediment beds.

Passive sampling of DDT, DDE and DDD in sediments: accounting for degradation processes with reaction-diffusion modeling.

Passive sampling is becoming a widely used tool for assessing freely dissolved concentrations of hydrophobic organic contaminants in environmental media. For certain media and target analytes, the time to reach equilibrium exceeds the deployment time, and in such cases, the loss of performance reference compounds (PRCs), loaded in the sampler before deployment, is one of the common ways used to assess the fractional equilibration of target analytes. The key assumption behind the use of PRCs is that their release is solely diffusion driven. But in this work, we show that PRC transformations in the sediment can have a measurable impact on the PRC releases and even allow estimation of that compound's transformation rate in the environment of interest. We found that in both field and lab incubations, the loss of the 13C 2,4'-DDT PRC from a polyethylene (PE) passive sampler deployed at the sediment-water interface was accelerated compared to the loss of other PRCs (13C-labeled PCBs, 13C-labeled DDE and DDD). The DDT PRC loss was also accompanied by accumulation in the PE of its degradation product, 13C 2,4'-DDD. Using a 1D reaction-diffusion model, we deduced the in situ degradation rates of DDT from the measured PRC loss. The in situ degradation rates increased with depth into the sediment bed (0.14 d-1 at 0-10 cm and 1.4 d-1 at 30-40 cm) and although they could not be independently validated, these rates compared favorably with literature values. This work shows that passive sampling users should be cautious when choosing PRCs, as degradation processes can affect some PRC's releases from the passive sampler. More importantly, this work opens up the opportunity for novel applications of passive samplers, particularly with regard to investigating in situ degradation rates, pathways, and products for both legacy and emerging contaminants. However, further work is needed to confirm that the rates deduced from model fitting of PRC loss are a true reflection of DDT transformation rates in sediments.