Adsorption and leaching of fluorotelomer compounds and perfluoroalkyl acids in aqueous media by activated carbon prepared from municipal biosolids.

Perfluoroalkyl acids (PFAAs) are ubiquitous in nature and pose serious health risks to humans and animals. Limiting PFAA exposure requires novel technology for their effective removal from water. We investigated the efficacy of biosolid-based activated carbon (Bio-SBAC) in removing frequently detected PFAAs and their precursor fluorotelomer compounds at environmentally relevant concentrations (∼50 µg/L). Batch experiments were performed to investigate adsorption kinetics, isotherms, and leachability. Bio-SBAC achieved >95% removal of fluorotelomeric compounds, indicating that the need for PFAA removal from the environment could be minimised if the precursors were targeted. Kinetic data modelling suggested that chemisorption is the dominant PFAA adsorption mechanism. As evidenced by the isotherm modelling results, Freundlich adsorption intensity, n-1, values of <1 (0.707-0.938) indicate chemisorption. Bio-SBAC showed maximum capacities for the adsorption of perfluorooctanoic acid (1429 µg/g) and perfluorononanoic acid (1111 µg/g). Batch desorption tests with 100 mg/L humic acid and 10 g/L NaCl showed that Bio-SBAC effectively retained the adsorbed PFAA with little or no leaching, except perfluorobutanoic acid. Overall, this study revealed that Bio-SBAC is a value-added material with promising characteristics for PFAA adsorption and no leachability. Additionally, it can be incorporated into biofilters to remove PFAAs from stormwater, presenting a sustainable approach to minimise biosolid disposal and improve the quality of wastewater before discharge into receiving waters.

Using circular economy principles in the optimisation of sludge-based activated carbon production for the removal of perfluoroalkyl substances.

Massive sewage sludge (SS) production from municipal wastewater treatment plants and the presence of numerous pollutant types render the process of SS treatment and disposal costly and complex. Here, resource recovery from SS was maximised via the optimisation of sludge-based activated carbon (SBAC) production for the removal of poly- and perfluoroalkyl substances (PFASs), while considering economic factors and minimising environmental impacts. SBAC production optimisation was realised under different operating conditions (different ZnCl2 impregnation ratios and different pyrolysis activation temperatures and durations). The sorption capacity of the optimised SBAC with respect to the removal of nine commonly detected PFASs, with environmentally relevant concentrations (∽50 µg/L), from simulated wastewater was evaluated. Economic analysis and life-cycle assessment (LCA) were also performed to determine the feasibility of the process and its potential role in the circular economy. Batch adsorption tests confirmed the high efficiency of the optimised SBACs for PFAS removal (93-100 %), highlighting the possibility of converting SS to SBAC. Economically speaking, the optimised SBAC at 1.5 M ZnCl2, 500 °C, and 0.75 h reduced total production cost by 49 %. Further, the cost could be reduced to as little as 1087 US $/metric-ton compared with that corresponding to the original conditions (2.5 M ZnCl2, 500 °C, 2 h; 2144 US $/metric-ton). LCA results also showed that freshwater ecotoxicity, marine ecotoxicity, and human non-carcinogenic toxicity were the most affected environmental impact indicators, showing a 49 % decrease when ZnCl2 impregnation ratio was reduced from 2.5 to 1.5 M. These findings highlighted the optimal conditions for the production of SBAC with high sorption capacity at a reduced cost and with reduced environmental impacts. Thus, they can serve as valuable tools for decision making regarding the selection of the most sustainable and economically feasible process for PFAS removal.

Sludge-based activated carbon and its application in the removal of perfluoroalkyl substances: A feasible approach towards a circular economy.

This study explores the recovery of resources and energy from sewage sludge through the production of sludge-based activated carbon (SBAC) considering circular economy principles. The SBAC production costs were estimated under three scenarios considering various sludge dewatering/drying schemes to determine the production feasibility and its role in the circular economy. SBAC was tested in the removal of a mixture of nine commonly detected poly- and perfluoroalkyl substances (PFASs) in environmentally relevant concentrations of ∽50 µg/L in comparison to commercially available activated carbon (AC) using 5 mg of sorbent and 5 mL of a nine-PFAS mixture in deionised water. SBAC can be produced at approximately 1.2 US $/kg, which is substantially lower than the average production cost of commercial AC of >3 US $/kg. A net revenue ranging from 2 to 7 US $/kg SBAC was estimated by recycling the produced non-condensable gases and bio-oil to produce energy and selling the SBAC. Batch adsorption tests showed that the PFASs removal of SBAC was superior to that of granular AC and similar to that of powdered AC, reaching >91% to below the detection limit. The kinetics tests revealed that adsorption by SBAC and AC occurred within 15 min. The overall results demonstrate the potential of SBAC as an effective sorbent for PFASs, achieving waste-to-resources circular economy via resource and energy recovery from sewage sludge, eliminating sludge disposal and contaminant-leaching to the environment, and in enhancing the quality of wastewater effluent before discharge.

Exploring indirect photolysis of 6:2 fluorotelomer sulfonate in landfill leachate under simulated sunlight: effect of humic acid and nitrate.

Landfill leachate is exposed to sunlight through on- and off-site leachate treatment and disposal to surface water bodies. Very little is known about the potential phototransformation of fluorotelomer compounds in landfill leachates, which can undergo environmental oxidation and produce perfluorocarboxylic acids (PFCAs). This study investigated phototransformation of spiked 6:2 fluorotelomer sulfonate (FTS) (∼ 100 µg/L) in leachate under simulated sunlight, using a metal halide lamp (wavelength, 390 to 750 nm). To understand the effects of nitrate and humic acid (HA), phosphate buffer (pH 7.1) containing nitrate and HA were spiked with 6:2 FTS and irradiated under simulated sunlight for 72 h. Following irradiation, 6:2 FTS and known transformation products (i.e., PFCAs) were quantified in the samples using LC-MS/MS. The results showed that 6:2 FTS was undergoing indirect photolysis in leachate (half-life of ∼ 15 days), suggesting that indirect photolysis of 6:2 FTS is likely a relevant transformation pathway in sunlit aquatic environments. However, the spiked 6:2 FTS did not show any observable decrease in the presence of nitrate and HA over 72 h. Perfluorohexanoic acid (PFHxA) increased in irradiated leachate background samples (without 6:2 FTS spike) suggesting that phototransformation in sunlit leachate could lead to the formation of persistent PFCAs at environmental concentrations of the precursors. Future studies using probe compounds are recommended to better understand the roles of reactive species in phototransformation of 6:2 FTS.

Formation of perfluorocarboxylic acids from 6:2 fluorotelomer sulfonate (6:2 FTS) in landfill leachate: Role of microbial communities.

Fluorotelomer compounds in landfill leachate can undergo biotransformation under aerobic conditions and act as a secondary source of perfluorocarboxylic acids (PFCAs) to the environment. Very little is known about the role of various microbial communities towards fluorotelomer compounds biotransformation. Using an inoculum prepared from the sediment of a leachate collection ditch, 6:2 fluorotelomer sulfonate (6:2 FTS) biotransformation experiments were carried out. Specific substrates (i.e., glucose, ammonia) and ammonia-oxidizing inhibitor (allylthiourea) were used to produce two experimental runs with heterotrophic (HET) growth only and heterotrophic with ammonia-oxidizing and nitrite- oxidizing bacteria (HET + AOB + NOB). After 10 days, ∼20% of the spiked 6:2 FTS removal was observed in HET + AOB + NOB, compared to ∼7% under HET condition. Higher 6:2 FTS removal in HET + AOB + NOB likely resulted from ammonia monooxygenase enzyme that catalyzes the first step of ammonia oxidation. The HET + AOB + NOB condition also showed higher PFCA (C4-C6) formation (∼2% of initially spiked 6:2 FTS), possibly due to higher overall bioactivity. Microbial community analysis through 16s rRNA sequencing confirmed that Proteobacteria and Bacteroidetes were the most abundant phyla (>75% relative abundance) under all experimental conditions. High abundance of Actinobacteria (>17%) was observed under the HET + AOB + NOB condition on day 7. Since Actinobacteria can synthesize a wide range of enzymes including monooxygenases, they likely play an important role in 6:2 FTS biotransformation and PFCA production.

Effect of substrate concentrations on aerobic biotransformation of 6:2 fluorotelomer sulfonate (6:2 FTS) in landfill leachate.

Biotransformation of 6:2 fluorotelomer sulfonate (FTS) results in the formation of short-chain (C4 - C6) perfluorocarboxylic acids (PFCAs) in landfill leachate. Although leachate substrate concentrations (i.e., organic carbon, ammonia) vary widely, their effects on 6:2 FTS biotransformation and PFCAs formation are unknown. This study investigated the effect of organic carbon and ammonia concentration in 6:2 FTS aerobic biotransformation and PFCA formation in leachate. Biotransformation experiments were conducted with sediment collected from a landfill leachate ditch, to which deionized (DI) water and various amounts of leachate were added. Microbial community analysis using 16S rRNA indicated that while phylum Proteobacteria dominated the bacterial composition throughout the 60 days, Actinobacteria increased with time. Many genera from Proteobacteria and Actinobacteria can synthesize a wide array of enzymes, indicating that these phyla are likely to play an important role in 6:2 FTS biotransformation. Higher biotransformation of 6:2 FTS was observed in leachate-added microcosms (∼21%), compared to DI water microcosm (∼14%), likely reflecting the substrate dependency of 6:2 FTS biotransformation. Substrate limiting conditions in DI water microcosm resulted in slightly greater formation of ∑(C4 - C6) PFCAs (∼14 mol%), compared with leachate added microcosms (10-13 mol%). The findings suggest that dilution of landfill leachate, (e.g., during wet seasons), likely results in reduced 6:2 FTS biotransformation and increased PFCAs formation compared to dry conditions. Observed formation of C7 - C8 PFCAs in the live microcosms suggested that landfills act as secondary sources of legacy PFCAs (e.g., perfluorooctanoic acid) in the environment.

Aerobic biotransformation of fluorotelomer compounds in landfill leachate-sediment.

Consumer products containing fluorotelomer polymers are a source of fluorotelomer compounds to the environment following their disposal at landfills. The fate and transformation of fluorotelomer compounds are unknown in landfill leachates. This study investigates the aerobic biotransformation of 8:2 fluorotelomer alcohol (FTOH) and 6:2 fluorotelomer sulfonate (FTS) in landfill leachate-sediment microcosms using batch tests. Spiked 8:2 FTOH, 6:2 FTS and their known biotransformation products were quantified in sediment-leachate and headspace over 90 days under aerobic conditions. 8:2 FTOH and 6:2 FTS biotransformation was slow (half-life >>30 d) in landfill leachate-sediment microcosm, suggesting persistence of fluorotelomer compounds under the conditions investigated. Significant volatilization (>20%) of 8:2 FTOH was observed in the microcosm headspace after 90 days. C6 - C8 and C4 - C6 perfluorocarboxylic acids (PFCAs) were the most abundant products for 8:2 FTOH and 6:2 FTS, respectively. PFCAs accounted for 4-9 mol% of the initially spiked parent compounds at 90 days. Perfluorooctanoic acid (PFOA) was the single most abundant product of 8:2 FTOH (>2.8 mol% at 90 days). The unaccounted mass (20 to 35 mol%) of the initially spiked parent compounds indicated formation of fluorotelomer intermediates and sediment-bound residue. Overall the findings suggest that aerobic biotransformation of fluorotelomer compounds acts as a secondary source of long- and short-chain (≤C7) PFCAs in the environment. Partitioning of semi-volatile fluorotelomer compounds (e.g., 8:2 FTOH) to the gas-phase indicates possible long-range transport and subsequent release of PFCAs in pristine environments. Short-chain fluorotelomer replacements (e.g., 6:2 FTS) result in a higher abundance of short-chain PFCAs in landfill leachate. Future research is needed to understand the long-term exposure effects of short-chain PFCAs to humans, aquatic life and biota.

Fate of perfluorooctanoic acid (PFOA) in sewage sludge during microwave-assisted persulfate oxidation treatment.

The fate of perfluorooctanoic acid (PFOA) has been investigated for an emerging sludge treatment technique using microwave heating-assisted persulfate (PS) oxidation. The effect of heating temperature (20, 50, and 70 °C) and PS dose (PS1: 0.01; PS2: 0.1; PS3: 0.2 g/g wet sludge) was studied in sludge spiked with PFOA at an environmentally relevant concentration (200 ng/g wet weight). Control degradation experiments using spiked sludge without PS addition and background sludge (no PFOA spike) with PS addition were also conducted at each temperature. Sludge samples were analyzed for eight perfluorocarboxylic acids (PFCAs) (C4 - C11) using LC-MS/MS. At 20 °C (PS2 dose), minimal (~ 5%) removal of the spiked PFOA was observed after 72 h, suggesting the need for elevated treatment temperature. For the same PS dose (0.1 g /g sludge), treatment at 50 and 70 °C showed a decrease in PFOA concentration with increasing temperature, with ~ 28 and ~ 42% removal following 4 h of treatment. No significant increase in degradation was observed for the highest dose (PS3) after 2 h, possibly indicating self-scavenging of PS at high dosage. Due to the low initial spiking concentration of PFOA and low extraction recovery, all shorter-chain PFCAs (< C8), the degradation products of PFOA, were below quantification limits in all sludge samples.

Review of the fate and transformation of per- and polyfluoroalkyl substances (PFASs) in landfills.

A critical review of existing publications is presented i) to summarize the occurrence of various classes of per- and polyfluoroalkyl substances (PFASs) and their sources in landfills, ii) to identify temporal and geographical trends of PFASs in landfills; iii) to delineate the factors affecting PFASs in landfills; and iv) to identify research gaps and future research directions. Studies have shown that perfluoroalkyl acids (PFAAs) are routinely detected in landfill leachate, with short chain (C4-C7) PFAAs being most abundant, possibly indicating their greater mobility, and reflecting the industrial shift towards shorter-chain compounds. Despite its restricted use, perfluorooctanoic acid (PFOA) remains one of the most abundant PFAAs in landfill leachates. Recent studies have also documented the presence of PFAA-precursors (e.g., saturated and unsaturated fluorotelomer carboxylic acids) in landfill leachates at concentrations comparable to, or higher than, the most frequently detected PFAAs. Landfill ambient air also contains elevated concentrations of PFASs, primarily semi-volatile precursors (e.g., fluorotelomer alcohols) compared to upwind control sites, suggesting that landfills are potential sources of atmospheric PFASs. The fate of PFASs inside landfills is controlled by a combination of biological and abiotic processes, with biodegradation releasing most of the PFASs from landfilled waste to leachate. Biodegradation in simulated anaerobic reactors has been found to be closely related to the methanogenic phase. The methane-yielding stage also results in higher pH (>7) of leachates, correlated with higher mobility of PFAAs. Little information exists regarding PFAA-precursors in landfills. To avoid significant underestimation of the total PFAS released from landfills, PFAA-precursors and their degradation products should be determined in future studies. Owing to the semi-volatile nature of some precursor compounds and their degradation products, future studies also need to include landfill gas to clarify degradation pathways and the overall fate of PFASs.

Effect of microwave hydrolysis on transformation of steroidal hormones during anaerobic digestion of municipal sludge cake.

Fate and removal of 16 steroidal (estrogenic, androgenic and progestogenic) hormones were studied during advanced anaerobic digestion of sludge cake using microwave (MW) pretreatment. Effect of pretreatment temperature (80, 120, 160 °C), operating temperature (mesophilic at 35 ± 2 °C, thermophilic at 55 ± 2 °C) and sludge retention time (SRT: 20, 10, 5 days) were studied employing eight lab-scale semi-continuously fed digesters. To determine the potential effect of MW hydrolysis, hormones were quantified in total (sorbed + soluble) and supernatant (soluble) phases of the digester influent and effluent streams. Seven of 16 hormones were above the method reporting limit (RL) in one or more of the samples. Hormone concentrations in total phase of un-pretreated (control) and pretreated digester feeds ranged in <157-2491 ng/L and <157-749 ng/L, respectively. The three studied factors were found to be statistically significant (95% confidence level) in removal of one or more hormones from soluble and/or total phase. MW hydrolysis of the influent resulted in both release (from sludge matrix) and attenuation of hormones in the soluble phase. Accumulation of estrone (E1) as well as progesterone (Pr) and androstenedione (Ad) in most of the digesters indicated possible microbial transformations among the hormones. Compared to controls, all pretreated digesters had lower total hormone concentrations in their influent streams. At 20 days SRT, highest total removal (E1+E2+Ad +Pr) was observed for the thermophilic control digester (56%), followed by pretreated mesophilic digesters at 120 °C and 160 °C with around 48% efficiency. In terms of conventional performance parameters, relative (to control) improvements of MW pretreated digesters at a 5-d SRT ranged in 98-163% and 57-121%, for volatile solids removal and methane production, respectively.

Fate of estrogenic hormones in wastewater and sludge treatment: A review of properties and analytical detection techniques in sludge matrix.

Estrogenic hormones (estrone (E1), 17ß-estradiol (E2), estriol (E3), 17α-ethinylestradiol (EE2)) are the major contributor to the total estrogenicity in waterways. Presence of these compounds in biosolids is also causing concern in terms of their use as soil amendment. In comparison with wastewater treatment, removal of estrogenic compounds in sewage sludge has received less attention. This paper presents a literature review regarding the source and occurrence of these pollutants in our environment. The removal pathways of estrogenic compounds in engineered systems, such as full-scale wastewater treatment plants (WWTPs), are also discussed. Review of the fate studies revealed that activated sludge system with nutrient removal shows very high (>90%) removal of estrogenic hormones in most of the cases. Although, aerobic digestion showed better attenuation of estrogenic compounds, anaerobic digestion increased the overall estrogenicity of biosolids. Finally, this paper highlights the challenges involved in analytical determination of these compounds in sewage sludge matrix.