Role of natural attenuation in modeling the leaching of contaminants in the risk analysis framework

Natural attenuation (NA) processes occurring in the subsurface can significantly affect the impact on groundwater from contamination sources located in the vadose zone, especially when mobile and readily biodegradable compounds, such as BTEX, are present. Besides, in the last decades several studies have shown natural attenuation to take place also for more persistent compounds, such as Polycyclic Aromatic Hydrocarbons (PAHs). Nevertheless, common risk analysis frameworks, based on the ASTM RBCA (Risk Based Corrective Action) approach, do not include NA pathways in the fate and transport models, thus possibly leading to an overestimation of the calculated risk. The aim of this study was to provide an insight on the relevance of the different key natural attenuation processes usually taking place in the subsurface and to highlight for which contamination scenarios their inclusion in the risk-analysis framework could provide a more realistic risk assessment. To this end, an analytical model accounting for source depletion and biodegradation, dispersion and diffusion during leaching was developed and applied to several contamination scenarios. These scenarios included contamination by BTEX, characterized by relatively high mobility and biodegradation rate, and PAHs, i.e. a more persistent class of compounds. The obtained results showed that BTEX are likely to be attenuated in the source zone due to their mobility and ready biodegradation (assuming biodegradation constant rates in the order of 0.01-1 d(-1)). Instead, attenuation along transport through the vadose zone was found to be less important, as the residence time of the contaminant in the unsaturated zone is often too low with respect to the time required to get a relevant biodegradation of BTEX. On the other hand, heavier compounds such as PAHs, were found to be attenuated during leaching since the residence time in the vadose zone can reach values up to thousands of years. In these cases, even with the relatively slow biodegradation rate of PAHs, in the order of 0.0001-0.001 d(-1), attenuation can result significant. These conclusions were also confirmed by comparing the model results with experimental data collected at an hydrocarbon-contaminated site. The proposed model, that neglects the transport of NAPLs, could be easily included in the risk-analysis framework, allowing to get a more realistic assessment of risks, while keeping the intrinsic simplicity of the ASTM-RBCA approach. (c) 2012 Elsevier Ltd. All rights reserved

Ion exchange equilibria of arsenic in the presence of high sulfate and nitrate concentration

The aim of this work was to develop a quantitative description of the ion exchange equilibria of arsenic on a strong anionic resin, in the presence of nitrates and sulphates. First, the ion exchange equilibrium data of As(V) and NO3- on a strong anionic resin in chloride form were obtained and described with a model based on the mass action law. Namely, assuming ideal behaviour for both solution and resin phase, the thermodynamic constant of the As(V)/Cl- and NO3-/Cl- ion exchange equilibria were estimated by fitting of experimental data. Then, these equilibrium constants were used to predict the ion exchange behaviour of the ternary system As(V)/NO3-/Cl-, providing a rather good agreement with experimental results. The ion exchange equilibria involving sulphate ions were also studied, showing,a very high affinity to the resin phase. This behaviour did not allow a quantitative robust modelling of the equilibrium pattern. The results discussed in this paper represent a first step toward the development of a comprehensive modelling of the ion exchange process for the removal of As(V) from surface and groundwater in the presence of competitive, naturally occurring anions

Assessing light non-aqueous phase liquids in the subsurface using the soil gas Rn deficit technique: a literature overview of field studies

(222)Radon (Rn) was proposed in the late 1990s as a naturally occurring tracer for light non-aqueous phase liquids (LNAPLs) in the subsurface, due to its preferential partitioning behavior in the non-aqueous phase, resulting in a reduction in Rn activities in areas with LNAPLs in the subsurface compared to unimpacted areas (Rn deficit). The Rn deficit technique emerged as a cost-effective, non-invasive, and sustainable method to rapidly identify and quantify LNAPLs, for the characterization and monitoring of contaminated sites. This paper presents an overview of the technique and its field applications, with a specific focus on the use of the method in the vadose zone based on soil gas Rn measurements. Although various configurations have shown favorable outcomes, limitations persist in the application of the soil gas Rn deficit technique. Deep LNAPL contamination, soil matrix heterogeneity, and temporal variations in Rn emissions pose challenges to quantitative evaluations of LNAPL contamination. Recognizing these factors is crucial for site-specific assessments. This review aims to highlight both the strengths and limitations of the method, providing insights into potential areas for future research while acknowledging the positive outcomes achieved in different configurations over the past decades

Mineral carbonation process for CO2 sequestration

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Analysis of the effect of temperature, pH, CO2 pressure and salinity on the olivine dissolution kinetics

AbstractThe dissolution kinetics of olivine has been extensively studied under several temperatures, CO2 pressures, and solution compositions. Dissolution is an important mechanism in the aqueous mineral carbonation process. The overall carbonation reaction consists of dissolution of mineral silicate, e.g. olivine, serpentine and wollastonite, followed by carbonate precipitation, thus fixing CO2 into naturally occurring stable solids, such as magnesite and calcite. The slowness of the dissolution kinetics hinders the overall carbonation reaction and in order to make the process technically and economically feasible, such a reaction should be sped up by finding the optimum operating conditions. Experiments were performed in a flow-through reactor at 90–120–150 ∘C. The pH was adjusted by adding either acids (e.g., HCl, citric acid) or LiOH, and by changing PCO2. The salinity was changed by adding NaCl and NaNO3. From the experimental data, the dissolution rate was estimated by using the population balance equation (PBE) model coupled with a mass balance, and the obtained values were regressed with a linear model log(r)=−npH−B, where r is the specific dissolution rate (mol s−1 cm−2)

Biodegradation of 3-chlorophenol in a sequencing batch reactor

The present paper shows the results obtained through a study on the biodegradation of 3-chlorophenol (3-CP) in a Sequencing Batch Reactor (SBR). To such a purpose a lab-scale SBR was fed a synthetic wastewater containing 3-CP and nutrients (nitrogen and phosphorus) diluted in tap water. The operating strategy, in terms of both the duration of either the cycle or the react phase, was changed throughout the experimental activity in order to find out the optimal one allowing to ensure constant and high removal efficiency despite the increasing 3-chlorophenol concentration in the feed. Biomass collected from a full-scale continuous flow activated sludge facility treating domestic wastewater was used as seed, after being acclimated to 3-CP by means of several batch tests. The results showed that a periodically operated activated sludge system can be successfully used for the biodegradation of chlorophenol compounds, after the needed members of the microbiological consortium are selected and enriched

Granulation–carbonation treatment of alkali activated steel slag for secondary aggregates production

In view of the EU’s circular economy strategy, there is a need to develop treatments that may allow to improve the management of industrial residues such as steel manufacturing slag, for example by producing secondary products that may be used for different applications. This work evaluates the performance of a combined carbonation and granulation treatment applied to basic oxygen furnace (BOF) steel slag with the aim of producing secondary aggregates and of storing CO2 in a solid and stable form. In order to improve the mechanical properties of the product, a solution of sodium silicate and sodium hydroxide was tested as binder instead of water in both the granulation and combined granulation–carbonation tests. The results showed that the granules produced using the alkali activator with or without CO2 addition, presented a mean size ranging from 1 to 5 mm and adequate mechanical properties for use in civil engineering applications. The maximum CO2 uptake attained was of 4% wt. for the alkali activated and carbonated granules after 60 min of treatment and 7 days curing. As for the leaching behaviour of the produced granules, an increase in the release of Cr and V was found for the product of the granulation–carbonation treatment with alkali activation. Instead, granulation with alkali activation or granulation with carbonation showed to decrease the release of Ba and Cr with regard to the untreated residues

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The main aim of this work was to assess the potential of in situ carbonation as a treatment to modify the properties of alkaline materials such as industrial soil in terms of leaching behaviour and mineralogy and to store the CO2 generated by specific treatments applied in the context of Brownfield regeneration. The process was investigated through lab-scale column carbonation experiments, in which 100% CO2 was fed through humidified stainless steel slag under ambient temperature and pressure for set reaction times. The reaction kinetics and the maximum CO2 uptake attained (5.5%), corresponding to a Ca conversion yield of 15.6%, after 4 h treatment proved slightly lower than those resulting from batch tests carried out on the same particle size fraction at enhanced operating conditions. The mineralogy of the material showed to be affected by column carbonation, exhibiting a higher calcite content and the decrease of Ca hydroxide and silicate phases. As a result of carbonation, the material showed a decrease in pH and Ca release as well as an increase in Si mobility. Furthermore, a reduction of Cr and Ba leaching, up to 63% and 96% respectively, was achieved after 2 h of reaction. However, carbonation was observed to lead to an increased leaching of V and Mo. The effects of carbonation on the leaching behaviour of the material were also investigated performing pH-dependence leaching tests and the results indicated that in situ carbonation appears to be a promising treatment to improve the properties of alkaline materials in view of their reuse on-site

Storage of carbon dioxide captured in a pilot-scale biogas upgrading plant by accelerated carbonation of industrial residues

AbstractThis work reports the preliminary evaluations obtained within the UPGAS-LOW CO2 project (LIFE08 ENV/IT/000429) concerning innovative methods for biogas upgrading through CO2 capture and storage. One of the methods studied in this project is chemical absorption of the CO2 contained in landfill gas with a KOH solution followed by carbonation of the spent solution with selected industrial residues to regenerate the alkaline solution and store CO2 in a solid phase (calcite). This paper presents the main results of the lab scale experiments carried out to evaluate the effects o f the main operating parameters on the carbonation reaction so to identify the conditions that allow to maximize the CO2 uptake of the solid residues and the percentage of KOH that can be regenerated for the absorption process. These results provide the dataset for the design of a pilot plant unit to be built and operated in the follow-up of the project

A Score Index System for a Semi-Quantitative Assessment of Inhalation Risks at Contaminated Sites

Risk assessment of contaminated sites is typically applied following a tiered approach with increasing levels of complexity. In the standard risk-based corrective action (RBCA) procedure issued by the American Society for Testing and Materials (ASTM), the site-specific evaluation is carried out using fate and transport models that require a relatively large amount of input data. In this work, we introduce a site-specific score index system for a preliminary assessment of the inhalation risks related to contaminants in soil or groundwater that resembles the modeling approaches typically adopted for chemical risk assessment in the field of industrial hygiene. In the developed system, a risk index for the outdoor and indoor volatilization pathways is calculated as the ratio between the calculated concentration at the point of exposure for the contaminant of concern and the corresponding acceptable concentration in air. The concentration at the point of exposure for each contaminant of concern is estimated through simple algorithms that involve a limited number of indexes that depend on the parameters that affect the exposure scenario. This qualitative assessment is then converted into a semi-quantitative approach by introducing scaling factors that were calibrated using the ASTM RBCA fate and transport models. The procedure was validated against the standard RBCA procedure by performing a simple Monte Carlo analysis with 10,000 simulations with randomly varying site-specific parameters. The developed score index system resulted in a conservative estimate of the risks, with percentages of false negatives lower than 1% and false positives lower than 15%. This means that the developed system allows one to screen out sites from further evaluations in more than 80% of cases, while ensuring a conservative estimate of the expected risks. The application to a real case study of a contaminated site confirmed the suitability of the developed approach