Smouldering to treat PFAS in sewage sludge.

Wastewater treatment plants are accumulation points for per- and polyfluoroalkyl substances (PFAS), and are threfore important facilities for PFAS treatment. This study explored using smouldering combustion to treat PFAS in sewage sludge. Base case experiments at the laboratory scale (LAB) used dried sludge mixed with sand. High moisture content (MC) LAB tests, 75% MC sludge by mass, explored impacts of MC on treatment and supplemented with granular activated carbon (GAC) to achieve sufficient temperatures for thermal destruction of PFAS. Additional LAB tests explored using calcium oxide (CaO) to support fluorine mineralization. Further tests performed at an oil-drum scale (DRUM) assessed scale on PFAS removal. Pre-treatment sludge and post-treatment ash samples from all tests were analyzed for 12 PFAS (2C-8C). Additional emissions samples were collected from all LAB tests and analyzed for 12 PFAS and hydrogen fluoride. Smouldering removed all monitored PFAS from DRUM tests, and 4-8 carbon chain length PFAS from LAB tests. For base case tests, PFOS and PFOA were completely removed from sludge; however, high contents in the emissions (79-94% of total PFAS by mass) showed volatilization without degradation. Smouldering high MC sludge at âˆ¼ 900 °C (30 g GAC/kg sand) improved PFAS degradation compared to treatment below 800 °C (<20 g GAC/kg sand). Addition of CaO before smouldering reduced PFAS content in emissions by 97-99% by mass; with minimal PFAS retained in the ash and minimal hydrofluoric acid (HF) production, as the fluorine from the PFAS was likely mineralized in the ash. Co-smouldering with CaO had dual benefits of removing PFAS while minimizing other hazardous emission by-products.

Exploring PCDD/Fs and potentially toxic elements in sewage sludge during smouldering treatment.

Potentially toxic elements (PTEs), persistent organic pollutants, and emerging contaminants make sewage sludge management challenging. There is significant interest in thermal treatment technologies that can destroy these compounds. The most common thermal treatment, incineration, poses risks due to formation and/or release of hazardous substances in process emissions such as polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) and PTEs. Smouldering has been introduced recently as a potential treatment for managing sewage sludge. Smouldering systems present several advantages over traditional incinerators; however, there are still uncertainties regarding process by-products. This key question was investigated in three laboratory-scale tests (0.08 m radius) and five oil drum-scale tests (0.3 m radius) that were evaluated for PCDD/Fs and PTEs in the mixture before and after treatment as well as in process emissions. Volatile organic compounds (VOCs) were also measured. These experiments represent a broad spectrum of conditions to evaluate process emissions, from robust self-sustaining to extinction of smouldering. Robust smouldering had negligible PCDD/Fs in process emissions. Weak smouldering had low levels of PCDD/Fs (emissions factor: 3.3 ± 0.3 µg TEQ/Mg dried sludge destroyed), levels less than uncontrolled emissions from commercial incinerators. Overall, smouldering acted as a sink for PCDD/Fs, as only 0-3% of the PCDD/Fs originally present in the sludge were released in the emissions, and >99% of the remainder were destroyed with <1% remaining in post-treatment ash. No evidence was found to support de novo synthesis or precursor reactions forming new PCDD/Fs. In addition, 94-100% of all the PTEs analyzed were retained in the post-smouldered material. These results indicate that only minimal emissions treatment for PTEs, PCDD/Fs, and VOCs may be necessary for future sewage sludge smouldering systems. These low emissions risks combined with its unique ability to handle high moisture content waste, indicate that smouldering has significant potential as a valuable waste management technique.

Phosphorus recovery and reuse potential from smouldered sewage sludge ash.

Smouldering treatment of sewage sludge - and recapturing phosphorus - provides important steps towards a circular economy. This study reveals that bulking sludge with sand or another organic waste, e.g., woodchips, created a material that was readily converted to ash by self-sustained smouldering. Simultaneous phosphorus and regulated potentially toxic element releases from ash were evaluated using leaching methods from the USEPA Leaching Environmental Assessment Framework (LEAF). Extraction potentials were also determined to evaluate direct recovery as an alternative to land application. Compared to the parent sludge, post-treatment ash from smouldering sludge with sand contained higher quantities of inorganic phosphorus in sorbed and mineral phases, which can provide beneficial slow phosphorus release to plants and avoid early phosphorus washout during land application. Ash also released lower initial and total quantities of potentially toxic elements than virgin sludge. As an alternative to land application, approximately 42% of retained phosphorus can be recovered directly using acidic extraction, and an additional 30% from emissions. In contrast, co-smouldering sludge with woodchips was more suited for direct recovery with 78% of phosphorus potentially recoverable via emissions capture and yield increasing to 99% with acidic extraction of resulting ash. Co-smouldering also produces a single post-treatment ash and can be readily operated continuously, which aligns with current incinerator configurations at wastewater treatment plants and makes adaptation highly feasible. With phosphorus reuse opportunities for land application and direct recovery, smouldering sewage sludge creates an important opportunity for a phosphorus circular economy as part of wastewater treatment sludge management.

USEPA LEAF methods for characterizing phosphorus and potentially toxic elements in raw and thermally treated sewage sludge.

Biologically available phosphorus supports plant growth but can also cause environmental contamination. Sequential extraction methods, such as Hedley fractionation, are the most widely used to assess available phosphorus from solids. However, such methods exhibit numerous deficiencies. The USEPA Leaching Environmental Assessment Framework (LEAF) is a tiered system developed to evaluate releases of Potentially Toxic Elements (PTEs) from solids. This study compared the Hedley fractionation method to the LEAF pH-dependent, parallel batch tests (Method 1313) and dynamic leaching column test (Method 1314) to assess the bioavailability of phosphorus. The three methods were applied to wastewater treatment plant sludge before and after thermal treatment. Both methods revealed similar qualitative trends, namely that thermal treatment transformed phosphorus into less immediately available forms. However, the Hedley and LEAF methods were inconsistent in the forms and amounts of available phosphorus recovered from the solids. The Hedley method left 40% of phosphorus unextracted from sludge and 20% from ash, suggesting that it may be less appropriate for organic materials. Moreover, only 2 of the 6 Hedley phosphorus pools were within environmentally relevant pH conditions. Furthermore, the Hedley method overpredicted the readily available phosphorus. In contrast, the LEAF methods allowed for a more detailed analysis of phosphorus availability - while simultaneously assessing PTEs - across a controlled pH range. Moreover, LEAF used simpler procedures and provided more easily interpreted results. Thus, LEAF facilitates more robust and valuable assessment of organic and inorganic solids being considered for land application.

Organic liquid mobility induced by smoldering remediation.

Laboratory column experiments plus analytical and numerical modeling together suggest that, under certain conditions, downward organic liquid mobilization can occur and impact smoldering behavior. This applies for organic liquids mixed with inert sand subjected to smoldering as thermal treatment. The observed effects include increased peak temperatures (here by up to 35%) and increased treatment times (here by up to 30%). Downward organic liquid migration occurs when (i) injected Darcy air flux is less than a threshold value (here less than 3cm/s), (ii) treatment systems are tall (here 90cm, not 30cm), and (iii) the organic liquid is temperature-sensitive (viscosity less than 0.01Pas at 150°C). The developed analytical equation provides the applied air flux that can negate the downwards organic liquid gradient required for migration. Smoldering behavior is demonstrated to adjust to liquid migration and thereby still destroy all the organic waste in the system. Smoldering is a relatively new, energy-efficient thermal treatment for organic liquid waste and these results are important for designing field applications of smoldering treatment.

Self-sustaining smoldering combustion: a novel remediation process for non-aqueous-phase liquids in porous media.

Smoldering combustion, the slow burning process associated typically with porous solids (e.g., charcoal), is here proposed as a novel remediation approach for nonaqueous phase liquids (NAPLs) embedded in porous media. Several one-dimensional vertical smoldering experiments are conducted on quartz sand containing fresh coal tar at an initial concentration of 71 000 mg/kg (approximately 25% saturation) and employing an upward darcy air flux of 4.25 cm/s. Following a short-duration energy input to achieve ignition at the lower boundary, a self-sustaining combustion front is observed to propagate upward at 1.3 x 10(-2) cm/s. The process is self-sustaining because the energy released during NAPL smoldering is efficiently trapped and recirculated by the soil matrix, preheating the NAPL ahead of the reaction front. The smoldering process is observed to self-terminate when all of the NAPL is destroyed or when the oxygen source is removed. Pre- and post-soil analysis revealed that NAPL smoldering reduced the concentration of total extractable petroleum hydrocarbons (TPH) from 38 000 mg/kg to below detection limits (< 0.1 mg/kg) throughout the majority of the column. A comparable experiment in which conductive heating is applied in the absence of smoldering demonstrates a 6-fold reduction in the net energy in the system and residual TPH values of 2000-35 000 mg/kg. A further repeat in which the air supply is prematurely terminated demonstrated that the NAPL smoldering process can be extinguished via external control. A suite of 23 demonstration experiments shows that NAPL smoldering is successful across a range of soil types (including simple layered systems) and contaminants (including laboratory mixtures of dodecane, DCA/ grease, TCE/oil, vegetable oil, crude oil, and mineral oil) as well as field-obtained samples of materials containing coal tar, oil drill cutting waste, and oil sands.

Parameter and process significance in mechanistic modeling of cellulose hydrolysis.

A process-based model relevant to landfill and anaerobic digesters was developed, which included a novel approach to biomass transfer between a cellulose-bound biofilm and biomass in the bulk liquid. Model results highlighted the significance of the bacterial colonization of cellulose particles by attachment through contact in solution. Simulations revealed that both enhanced colonization and cellulose degradation are associated with reduced cellulose particle size, increased biomass populations in solution and increased cellulose-binding ability of the biomass. This suggests that transportation of biomass into the system from elsewhere and/or bacterial inoculation of such systems could enhance degradation significantly. A sensitivity analysis of the system parameters revealed the biological rate and yield properties of the hydrolyzing bacteria are most significant with regard to cellulose degradation in the system.