Mobilization of per- and poly-fluoroalkyl substances (PFAS) in soils with different organic matter contents.

There is considerable interest in addressing soils contaminated with per- and polyfluoroalkyl substances (PFAS) because of the PFAS in the environment and associated health risks. The neutralization of PFAS in situ is challenging. Consequently, mobilizing the PFAS from the contaminated soils into an aqueous solution for subsequent handling has been pursued. Nonetheless, the efficiency of mobilization methods for removing PFAS can vary depending on site-specific factors, including the types and concentrations of PFAS compounds, soil characteristics. In the present study, the removal of perfluorooctanoate (PFOA) and perfluorooctane sulfonate (PFOS) from artificially contaminated soils was investigated in a 2D laboratory setup using electrokinetic (EK) remediation and hydraulic flushing by applying a hydraulic gradient (HG) for a duration of 15 days. The percent removal of PFOA by EK was consistent (∼80%) after a 15-day treatment for all soils. The removal efficiency of PFOS by EK significantly varied with the OM content, where the PFOS removal increased from 14% at 5% OM to 60% at 50% OM. With HG, the percent removal increased for both PFOA and PFOS from about 20% at 5% OM up to 80% at 75% OM. Based on the results, the mobilization of PFAS from organic soil would be appropriate using both hydraulic flushing and EK considering their applicability and advantages over each other for site-specific factors and requirements.

Enhancing the Thermal Mineralization of Perfluorooctanesulfonate on Granular Activated Carbon Using Alkali and Alkaline-Earth Metal Additives.

Thermal treatment has emerged as a promising approach for either the end-of-life treatment or regeneration of granular activated carbon (GAC) contaminated with per- and polyfluoroalkyl substances (PFAS). However, its effectiveness has been limited by the requirement for high temperatures, the generation of products of incomplete destruction, and the necessity to scrub HF in the flue gas. This study investigates the use of common alkali and alkaline-earth metal additives to enhance the mineralization of perfluorooctanesulfonate (PFOS) adsorbed onto GAC. When treated at 800 °C without an additive, only 49% of PFOS was mineralized to HF. All additives tested demonstrated improved mineralization, and Ca(OH)2 had the best performance, achieving a mineralization efficiency of 98% in air or N2. Its ability to increase the reaction rate and shift the byproduct selectivity suggests that its role may be catalytic. Moreover, additives reduced HF in the flue gas by instead reacting with the additive to form inorganic fluorine (e.g., CaF2) in the starting waste material. A hypothesized reaction mechanism is proposed that involves the electron transfer from O2- defect sites of CaO to intermediates formed during the thermal decomposition of PFOS. These findings advocate for the use of additives in the thermal treatment of GAC for disposal or reuse, with the potential to reduce operating costs and mitigate the environmental impact associated with incinerating PFAS-laden wastes.

Field fluorometers for assessing oil dispersion at sea.

Oil dispersion by the application of chemical dispersants is an important tool in oil spill response, but it is difficult to quantify in the field in a timely fashion that is useful for coordinators and decision-makers. One option is the use of rugged portable field fluorometers that can deliver essentially instantaneous results if access is attainable. The United States Coast Guard has suggested, in their Special Monitoring of Applied Response Technologies (SMART) protocols, that successful oil dispersion can be identified by a five-fold increase in oil fluorescence. Here we test three commercial fluorometers with different excitation/emission windows (SeaOWL, Cyclops 7FO, and Cyclops 7F-G) that might prove useful for such applications. Results show that they have significantly different dynamic ranges for detecting oil and that using them (or similar instruments) in combination is probably the best option for successfully assessing the effectiveness of oil dispersion operations. Nevertheless, the rapid dilution of dispersed oil means that measurements must be made within an hour or two of dispersion, suggesting that one feasible scenario would be monitoring ship-applied dispersants by vessels following close behind the dispersant application vessel. Alternatively, autonomous submersibles might be pre-deployed to monitor aerial dispersant application, although the logistical challenges in a real spill would be substantial.

Post-Formation of Oil Particle Aggregates: Breakup and Biodegradation.

Spilled oil slicks are likely to break into droplets in the subtidal and intertidal zones of seashores due to wave energy. The nonliving suspended fine particles in coastal ecosystems can interact with the dispersed oil droplets, resulting in the formation of Oil Particle Aggregates (OPAs). Many investigations assumed that these aggregates will settle due to the particles' high density. Recent studies, however, reported that some particles penetrate the oil droplets, which results in further breakup while forming smaller OPAs that remain suspended in the water column. Here, we investigated the interaction of crude oil droplets with intertidal and subtidal sediments, as well as artificial pure kaolinite, in natural seawater. Results showed that the interaction between oil droplets and intertidal sediments was not particularly stable, with an Oil Trapping Efficiency (OTE) < 25%. When using subtidal sediments, OTE reached 56%. With artificial kaolinite, OPA formation and breakup were more significant (OTE reaching up to 67%) and occurred faster (within 12 h). Oil chemistry analysis showed that the biodegradation of oil in seawater (half-life of 485 h) was significantly enhanced with the addition of sediments, with half-lives of 305, 265, and 150 h when adding intertidal sediments, subtidal sediments, and pure kaolinite, respectively. Such results reveal how the sediments' shape and size affect the various oil-sediment interaction mechanisms, and the subsequent impact on the microbial degradation of petroleum hydrocarbons. Future studies should consider investigating the application of fine (several microns) and sharp (elongated-sheeted) sediments as a nondestructive and nontoxic technique for dispersing marine oil spills.

Effect of clay content on the mobilization efficiency of per- and polyfluoroalkyl substances (PFAS) from soils by electrokinetics and hydraulic flushing.

The need for the efficient remediation of soils impacted by per- and polyfluoroalkyl substances (PFAS) is substantially growing because of the notable upsurge in societal and regulatory awareness of this class of chemicals. To remediate PFAS-contaminated soils using mobilization approaches, the choice of appropriate techniques highly depends on the soil's composition, particularly the clay content, which significantly affects the soil's permeability. Here, we investigated the PFAS mobilization efficiency from soils with different clay contents by using two techniques: electrokinetic (EK) remediation and hydraulic flushing. Artificial kaolinite was added to a loamy sand soil to prepare four soil blends with clay contents of 5, 25, 50, and 75%, each contaminated with perfluorooctanoic acid (PFOA) and perfulorooctanesulfonic acid (PFOA) at 10,000 µg/kg. EK remediation was conducted by applying a low voltage (30 V) with a current of 100 mA, and hydraulic flushing was carried out by applying a hydraulic gradient (HG) with a slope of 6.7%. Results show that, with a 14-day treatment duration, the EK-mobilization efficiency was enhanced substantially with the increase of clay content (removal of PFOS increased from 20% at 5% clay to 80% at 75% clay), most likely due to the increase of electroosmotic flow due to the higher content of particles having a zeta potential (i.e., clay). For HG, increasing the clay content significantly suppressed the mobilization of PFAS (removal of PFOS decreased from 40% at 5% clay to 10% at 75% clay) due to a notable decrease in the soil's permeability. Based on the results, applying hydraulic flushing and washing techniques for mobilizing PFAS would be appropriate when treating permeable soils with a maximum clay content of about 25%; otherwise, other suitable mobilization techniques such as EKs should be considered.

Bioremediation of Petroleum Hydrocarbons in the Upper Parts of Sandy Beaches.

The biodegradation of dispersed crude oil in the ocean is relatively rapid (a half-life of a few weeks). However, it is often much slower on shorelines, usually attributed to low moisture content, nutrient limitation, and higher oil concentrations in beaches than in dispersed plumes. Another factor may be the increased salinity of the upper intertidal and supratidal zones because these parts of the beach are potentially subject to prolonged evaporation and only intermittent inundation. We have investigated whether such an increase in salinity has inhibitory effects on oil biodegradation in seashores. Lightly weathered Hibernia crude oil was added to beach sand at 1 or 10 mL/kg, and fresh seawater, at salinities of 30, 90, and 160 g/L, was added to 20% saturation. The biodegradation of oil was slower at higher salinities, where the half-life increased from 40 days at 30 g/L salts to 58 and 76 days at 90 and 160 g/L salts, respectively, and adding fertilizers somewhat enhanced oil biodegradation. Increased oil concentration in the sand, from 1 to 10 mL/kg, slowed the half-life by about 10-fold. Consequently, occasional irrigation with fertilization could be a suitable bioremediation strategy for the upper parts of contaminated beaches. However, dispersing oil at sea is probably the most suitable option for the optimal removal of spilled crude oil from the marine environment.

Impact of mixing and resting times on the droplet size distribution and the petroleum hydrocarbons' concentration in diluted bitumen-based water-accommodated fractions (WAFs).

The preparation of Water-accommodated Fractions (WAFs) and chemically enhanced WAFs (CEWAFs) are essential for evaluating oil toxicity. The Chemical Response to Oil Spills: Ecological Research Forum (CROSERF) method was widely adopted, with variables (e.g., mixing time, oil loading, etc.) being continuously changed among research groups, which limits the cooperation in this area. Herein, we conducted WAF and CEWAF experiments using two loadings of diluted bitumen (Dilbit): 1 g/L and 10 g/L. For the CEWAF, the dispersant to oil ratio was 1:20. We investigated the impact of three mixing durations (18 h, 42 h, and 66 h) and two resting times (6 h and 24 h) on the droplet size distribution (DSD) and accommodated oil concentration. This would be highly beneficial for analyzing toxicity from oil spills, especially when considering the toxic effect of both suspended oil droplets and dissolved hydrocarbons. The DSD results and oil chemistry analysis showed that at a low oil loading concentration (1 g/L), both WAFs and CEWAFs had the same DSD, with an average d50 (volume median diameter) of 3.38 ± 0.70 µm and 3.85 ± 0.63 µm, respectively. At a high oil loading concentration (10 g/L), the WAFs had an average d50 of 3.69 ± 0.52 µm, showing no correlation with mixing and resting time. The DSD of CEWAFs increased significantly at 42 h mixing and 24 h resting time, with oil concentration reaching equilibrium after 42 h mixing. Therefore, WAFs appears to require only 18 h mixing and 6 h resting, while it is recommended to have 42 h mixing and 24 h resting for CEWAFs at high dilbit oil loading concentrations.

Crude oil biodegradation in upper and supratidal seashores.

The salinity of the upper parts of seashores can become higher than seawater due to evaporation between tidal inundations. Such hypersaline ecosystems, where the salinity can reach up to eight-fold higher than that of seawater (30-35 g/L), can be contaminated by oil spills. Here we investigate whether such an increase has inhibitory effects on oil biodegradation. Seawater was evaporated to a concentrated brine and added to fresh seawater to generate high salinity microcosms. Artificially weathered Hibernia crude oil was added, and biodegradation was followed for 76 days. First-order rate constants (k) for the biodegradation of GC-detectable hydrocarbons showed that the hydrocarbonoclastic activity was substantially inhibited at high salt - k decreased by ~75% at 90 g/L salts and ~90% at 160 g/L salts. This inhibition was greatest for the alkanes, although it extended to all classes of compounds measured, with the smallest effect on four-ring aromatics (e.g., chrysenes). Genera of well-known aerobic hydrocarbonoclastic bacteria were only identified at 30 g/L salts in the presence of oil, and only a few halophilic Archaea showed a slight enrichment at higher salt concentrations. These results indicate that biodegradation of spilled oil will likely be slowed in supratidal ecosystems and suggest that occasional irrigation of oiled supratidal zones could be a useful supporting strategy to remediation processes.

Occurrence and biodegradation of hydrocarbons at high salinities.

Hypersaline environments are found around the world, above and below ground, and many are exposed to hydrocarbons on a continuous or a frequent basis. Some surface hypersaline environments are exposed to hydrocarbons because they have active petroleum seeps while others are exposed because of oil exploration and production, or nearby human activities. Many oil reservoirs overlie highly saline connate water, and some national oil reserves are stored in salt caverns. Surface hypersaline ecosystems contain consortia of halophilic and halotolerant microorganisms that decompose organic compounds including hydrocarbons, and subterranean ones are likely to contain the same. However, the rates and extents of hydrocarbon biodegradation are poorly understood in such ecosystems. Here we describe hypersaline environments potentially or likely to become contaminated with hydrocarbons, including perennial and transient environments above and below ground, and discuss what is known about the microbes degrading hydrocarbons and the extent of their activities. We also discuss what limits the microbial hydrocarbon degradation in hypersaline environments and whether there are opportunities for inhibiting (oil storage) or stimulating (oil spills) such biodegradation as the situation requires.

Anaerobic-aerobic sequential treatment: Temperature optimization and cost implications.

Traditionally, aeration units, used as a polishing stage after anaerobic digestion (AD) of wastes, are operated at ambient temperature. Yet, when effluent quality is the main design criterion, raising the temperature of the aeration stage can be justified by improved removal efficiencies. In this study, an anaerobic-aerobic sequential system (AASS) was operated to co-digest raw wastewater and food waste. The aerobic compartment was tested under psychrophilic and mesophilic temperatures. At the design loading rate of 2 gVS L-1 d-1, the anaerobic digester achieved removal efficiencies of 85 ± 2% of volatile solids (VS), 84 ± 3% of total chemical oxygen demand (CODT) and a biogas yield of 1,035 ± 30 mL gVSfed-1 (50% methane). The aerobic reactor achieved additional removal of 8% CODT and 7 % VS. By raising the temperature of the aerobic reactor to the mesophilic range, COD and solids concentrations of the effluent dropped to approximately half their values. This was accompanied by an increase in nitrification (from 68% to 91%) and denitrification (from 10% to 16%). The energy analysis showed that total energy consumption slightly increases (from 0.45 to 0.49 kWh kgCODfed-1) by raising the temperature of the aerobic reactor to mesophilic range. A preliminary evaluation of the sludge disposal cost, revealed a saving increase of 5-6% under mesophilic operation with respect to psychrophilic conditions. Implications: In order to cope with the globally increasing constraints on the disposal of urban wastes, efficient post-processing of effluents becomes a crucial requirement for the anaerobic digestion industry. In this context, the submitted manuscript shows that the quality of the effluent, of an anaerobic digester, treating food waste with raw wastewater, can be substantially improved by optimizing the aerobic polishing stage. Raising the temperature of the aerobic reactor to the mesophilic range resulted in a drop of solids and COD concentrations to approximately half their values. Equally important, the implications on operational costs were found to be favorable, compared to traditional psychrophilic aerobic post-treatment, when taking into consideration indirect sludge treatment costs and energy selling revenues.

Anaerobic digestion of food waste with aerobic post-treatment: Effect of fruit and vegetable content.

A mesophilic anaerobic digester, followed by a psychrophilic aerobic post-treatment, was used to treat food waste (FW) with different proportions of fruit and vegetable waste (FVW). Two types of FW were used: low fruit and vegetable mix (LFV, with 56.5% of FVW) and high fruit and vegetable mix (HFV, with 78.3% of FVW). The anaerobic digester fed with LFV failed at an organic loading rate of 1.6 g VS.L-1.d-1 (volatile fatty acid (VFA) = 6000 mg.L-1) due to high ammonia (reaching 3000 mg.L-1). It was shown that, in an unstable anaerobic environment, ammonia is highly correlated ( r2 = 0.77) with VFA and is negatively correlated with volatile solids, total solids, and chemical oxygen demand (COD) removal rates ( r2 = 0.88, r2 = 0.71, and r2 = 0.91, respectively). In contrast, the anaerobic digester fed with HFV exhibited a stable performance (VFA = 1243 mg.L-1), with limited ammonia accumulation (940 mg.L-1). Methane generation was affected by the FVW content and reached 531 ml CH4.g VS-1 (CH4 = 52%) with LFV feed and 478 ml CH4.g VS-1 (CH4 = 57.4%) with HFV. The overall TS, VS and COD removal rates (all ranging between 94% and 97%), were closely similar for LFV and HFV. Accordingly, the aerobic post-treatment seems to compensate for the reduced performance of the disturbed anaerobic system fed with LFV.