Risk-based imprecise post-remediation soil quality objectives.

While risk-based contaminated land management is an essential component of sustainable remediation, uncertainty is an unavoidable aspect of risk assessment, since most of the parameters that influence risk are typically affected by uncertainty. Uncertainty may be of different origins; i.e., stochastic or epistemic. Stochastic (or aleatoric) uncertainty arises from random variability related to natural processes, while epistemic uncertainty arises from the incomplete/imprecise nature of available information. But the latter is rarely considered in risk assessments, with the result that risk-based soil quality objectives are almost invariably presented as precise (unique) threshold values. In this paper it is shown: (i) how the joint treatment of stochastic and epistemic uncertainty in risk assessment can lead to soil quality objectives presented as intervals rather than precise values and (ii) how this provides an upper risk-based safeguard for post-remediation monitoring values. The proposed method is illustrated by a real case of soils contaminated by arsenic located in the North-East of France. At this site steel manufacturers have gradually filled up a small valley with slag and dust, over more than a century. These materials are enriched in various metal(loid)s, including arsenic and lead. As the environmental authority has asked for a conversion of the site to other uses that may involve access by the general public, an investigation of human health risk was performed based on a sampling campaign and chemical characterizations including various types of extractions and an analysis of bioaccessibility. While further investigations are required to improve the bioaccessibility model, the human health risk presented herein shows how partial or imprecise information can be incorporated in the analysis while taking into account underlying uncertainties.

Permanganate oxidation of polycyclic aromatic compounds (PAHs and polar PACs): column experiments with DNAPL at residual saturation.

Permanganate is an oxidant usually applied for in situ soil remediation due to its persistence underground. It has already shown great efficiency for dense nonaqueous phase liquid (DNAPL) degradation under batch experiment conditions. In the present study, experimental permanganate oxidation of a DNAPL - coal tar - sampled in the groundwater of a former coking plant was carried out in a glass bead column. Several glass bead columns were spiked with coal tar using the drainage-imbibition method to mimic on-site pollution spread at residual saturation as best as possible. The leaching of organic pollutants was monitored as the columns were flushed by successive sequences: successive injections of hot water, permanganate solution for oxidation, and ambient temperature water, completed by two injections of a tracer before and after oxidation. Sixteen conventional US-EPA PAHs and selected polar PACs were analyzed in the DNAPL remaining in the columns at the end of the experiment and in the particles collected at several steps of the flushing sequences. Permanganate oxidation of the pollutants was rapidly limited by interfacial aging of the DNAPL drops. Moreover, at the applied flow rate chosen to be representative of in situ injections and groundwater velocities, the reaction time was not sufficient to reach high degradation yields but induced the formation and the leaching of oxygenated PACs.

FerrateVI oxidation of polycyclic aromatic compounds (PAHs and polar PACs) on DNAPL-spiked sand: degradation efficiency and oxygenated by-product formation compared to conventional oxidants.

In situ chemical oxidations are known to remediate PAH contaminations in groundwater and soils. In this study, batch-scale oxidations aim to compare the PAC (polycyclic aromatic compound) degradation of three oxidation processes traditionally applied for soil treatment: permanganate, heat-activated persulfate (60 °C) and Fenton-like activated by magnetite, to results obtained with ferrates (FeVI). Widely studied for water treatments, ferrates are efficient on a wide range of pollutants with the advantage of producing nontoxic ferric sludge after reaction. However, fewer works focus on their action on soil, especially on semi-industrial grade ferrates (compatible with field application). Oxidations were carried out on sand spiked with dense non-aqueous phase liquid (DNAPL) sampled in the groundwater of a former coking plant. Conventional 16 US-EPA PAHs and polar PACs were monitored, especially potential oxygenated by-products that can be more harmful than parent-PAHs. After seven reaction days, only the Fenton-like showed limited degradation. Highest efficiencies were obtained for heat-activated persulfate with no O-PAC ketones formed. Permanganate gave important degradation, but ketones were generated in large amount. The tested ferrates not only gave slightly lower yields due to their auto-decomposition but also induced O-PAC ketone production, suggesting a reactional pathway dominated by oxidoreductive electron transfer, rather than a radical one.

Metal availability in a highly contaminated, dredged-sediment disposal site: field measurements and geochemical modeling.

Two complementary approaches were used to characterize arsenic and metal mobilizations from a dredged-sediment disposal site: a detailed field study combined with hydrogeochemical modeling. Contaminants in sediments were found to be mainly present as sulfides subject to oxidation. Secondary phases (carbonates, sulfates, (hydr)oxides) were also observed. Oxidative processes occurred at different rates depending on physicochemical conditions and contaminant contents in the sediment. Two distinct areas were identified on the site, each corresponding to a specific contaminant mobility behavior. In a reducing area, Fe and As were highly soluble and illustrated anoxic behavior. In well-oxygenated material, groundwater was highly contaminated in Zn, Cd and Pb. A third zone in which sediments and groundwater were less contaminated was also characterized. This study enabled us to prioritize remediation work, which should aim to limit infiltration and long-term environmental impact.

Changes in the geochemistry and ecotoxicity of a Zn and Cd contaminated dredged sediment over time after land disposal.

The management of dredged sediments is of environmental concern worldwide since they may be overloaded with myriads of pollutants. For inland waters' sediments, disposal on land is a common practice. For the long-term risks assessment of such a management, a better understanding of the fate of pollutants over time and an assessment of possible associated biological consequences are needed. Here, we studied the geochemical distribution of Fe, Mn, Zn and Cd in sediment dredged from the Scarpe canal (Nord-Pas-de-Calais Region, France). Analyses were carried out immediately after dredging and 12, 18 and 24 months after disposal in field conditions. In parallel, ecotoxicity of sediment leachates was assessed using standardized bioassays. The results reflected an initial oxidation of sulphides (first year) followed by changes explained by a reversible binding of metals to organic matter in winter and to Fe oxihydroxides in summer. The water-leachable fraction represented less than 2% of the total metal and its ecotoxicity was higher for deposited sediments than for the fresh one. After first year of disposal, sediment ecotoxicity remained stable. A long-term natural attenuation of metals within disposed sediment seemed unlikely since their speciation seemed to fluctuate seasonally without any time trend over years.