Burning questions: Current practices and critical gaps in evaluating removal of per- and polyfluoroalkyl substances (PFAS) during pyrolysis treatments of biosolids.

Concerns surrounding potential health and environmental impacts of per- and polyfluoroalkyl substances (PFAS) are growing at tremendous rates because adverse health impacts are expected with trace-level exposures. Extreme measures are required to mitigate potential PFAS contamination and minimize exposures. Extensive PFAS use results in the release of diverse PFAS species from domestic, industrial, and municipal effluents to wastewater, which partition to biosolids throughout secondary treatment. Biosolids generated during municipal wastewater treatment are a major environmental source of PFAS due to prevailing disposal practices as fertilizers. Pyrolysis is emerging as a viable, scalable technology for PFAS removal from biosolids while retaining nutrients and generating renewable, raw materials for energy generation. Despite early successes of pyrolysis in PFAS removal, significant unknowns remain about PFAS and transformation product fates in pyrolysis products and emissions. Applicable PFAS sampling methods, analytical workflows, and removal assessments are currently limited to a subset of high-interest analytes and matrices. Further, analysis of exhaust gases, particulate matter, fly ashes, and other pyrolysis end-products remain largely unreported or limited due to cost and sampling limitations. This paper identifies critical knowledge gaps on the pyrolysis of biosolids that must be addressed to assess the effectiveness of PFAS removal during pyrolysis treatment.

A comparative study of ultrasonic pretreatment and an internal recycle for the enhancement of mesophilic anaerobic digestion.

The objective of this study was to investigate the use of ultrasonic energy in an internal recycle and pretreatment mode of operation relative to a conventional mode of mesophilic anaerobic digestion. The primary focus was to determine if using ultrasonics in a pretreatment mode and in an internal recycle line produced changes in performance relative to each other and the control. Using a relatively low-energy sonication system, the data showed that the addition of ultrasonic energy, in either a recycle line or as a pretreatment technology, improved anaerobic digestion efficiency for waste-activated sludge. There was a 13 to 21% increase in biogas yield and an increase in total and volatile solids destruction of 3 to 10.3 additional percentage points, depending on the ultrasonic dose and location. Dewatering of the biosolids following ultrasonic treatment was poorer, as measured by an increase in the optimum polymer conditioning dose. The addition of ultrasonics to the digestion systems generated a more stable biosolids product, with a 2 to 58% reduction in organo-sulfur gas production from dewatered biosolids cakes.

Application of mechanical shear in an internal-recycle for the enhancement of mesophilic anaerobic digestion.

A combination of bench- and full-scale studies were conducted to determine the effectiveness of high-intensity mechanical shear in an internal recycle loop to enhance mesophilic anaerobic digestion and the implications of this process for routine operations of a digestion system. During short-term batch digestion (56 hours), a 46% increase in biogas production was observed. However, it was found that the degree of digestion enhancement was sludge-specific, with increases in volatile solids destruction ranging from 16.6 to 110%. A full-scale demonstration showed increased total and volatile solids destruction of 22 and 21% for the primary digester and 17.2 and 11% for the secondary digester, respectively. The data also suggest that increased protein degradation is one of the major mechanisms associated with the observed increases in volatile solids destruction. The full-scale demonstration also determined that shear enhanced digestion can be operated without process upset, based on volatile fatty acid profile and headspace biogas composition (methane and carbon dioxide). Dewatering properties, as measured by polymer demand, deteriorated in the primary digester, but there was improvement in the secondary digester. High-intensity shear does not appear to enhance pathogen reduction based on total and fecal coliform bacterial enumeration.

The effect of wastewater cations on activated sludge characteristics: effects of aluminum and iron in floc.

Wastewater samples collected from seven wastewater treatment plants (WWTPs) were characterized to assess the impacts of wastewater cations on the activated sludge process. The cations included in this study were sodium (Na+), potassium, ammonium, calcium, magnesium, aluminum (Al), and iron (Fe). Among the selected cations, Al and Fe were of most interest to this study because their role in bioflocculation has not been extensively studied and remains largely unknown. The data showed that WWTPs contained highly varying concentrations of Na+, Al, and Fe in the wastewater and that these cations were responsible for differences between WWTPs as to sludge dewatering rates and effluent quality. In general, a high influent Na+ concentration caused poor sludge dewatering and effluent characteristics. However, when sufficient Al and Fe were present in floc, the deleterious effects of Na+ were offset. The data associated with Al further revealed that waste activated sludge with low Al contained high concentrations of soluble and colloidal biopolymer (protein + polysaccharide), resulting in a high effluent chemical oxygen demand, high conditioning chemical requirements, and poor sludge dewatering properties. These results suggest that Al will improve activated sludge effluent quality by scavenging organic compounds from solution and binding them to floc.

The digestibility of waste activated sludges.

Laboratory digestion studies using waste activated sludges (WAS) were conducted to compare the digestion performance between anaerobic and aerobic processes. Nine samples of WAS from seven wastewater treatment plants were collected and batch-digested under both anaerobic and aerobic conditions for 30 days at 25 degrees C. The cation content of wastewater (both floc and solution phases) and solution biopolymer (protein and polysaccharide) was measured before and after digestion and compared with volatile solids destruction data. The study revealed that each digestion process was associated with a distinct biopolymer fraction, which accounted for differences in volatile solids reduction under anaerobic and aerobic conditions. The anaerobic digestion data showed strong correlations between soluble protein generation, ammonium production, percent volatile solids reduction, and floc iron (Fe). These data suggest that the amount of volatile solids destroyed by anaerobic digestion depends on the Fe content of floc. In aerobic digestion, polysaccharide accumulated in solution along with calcium and magnesium. For aerobic digestion, correlations between divalent cation release and the production of inorganic nitrogen were found. This implies that divalent cation-bound biopolymer, thought to be lectin-like protein, was the primary organic fraction degraded under aerobic conditions. The results of the study show that the cation content in wastewater is an important indicator of the material that will digest under anaerobic or aerobic conditions and that some of the volatile solids will digest only under either anaerobic or aerobic conditions.

Alkylamine odors from degradation of flocculant polymers in sludges.

The cationic organic polymers used to enhance thickening and dewatering processes are potential sources of strong odors. These polymers vary in chemical structure, and some may be more susceptible to biotic or abiotic degradation than others. The product organic amines will be volatilized most noticeably at high pH, as in lime addition. These possibilities were examined using several structural types of polymers combined with anaerobically digested sludge. Two commonly used polymers gave significant production of trimethylamine (TMA), which was released upon lime addition. Their structures were correlated with reactions that yield TMA. An initial ester hydrolysis step appears to be biologically mediated, but subsequent steps can occur due to alkaline conditions. An alternative cationic polymer structure did not generate TMA but required a much higher dose to effect sufficient conditioning of the sludge. The acrylamide-based polymers were shown to be the predominant source of TMA in limed sludges.

Sequential polymer dosing for effective dewatering of ATAD sludges.

Dewatering problems associated with the sludge from autothermal thermophilic aerobic digestion (ATAD) of sludge, result in large chemical conditioning costs for effective dewatering. A variety of chemical conditioners were used to improve dewatering, but none of them were able to dewater the sludge as desired at acceptable conditioning doses. It was found that during the digestion process, chemical precipitation of divalent cations occurred. Some of the ATAD sludge colloids were found to have a positive zeta potential and these were thought to be the precipitated divalent cations. Sequential polymer dosing using either iron or cationic polymer, followed by anionic polymer, was found to improve dewatering. The use of anionic polymer is essential and allows the use of smaller amounts of iron or cationic polymer for effective dewatering. The use of the less expensive anionic polymer along with cationic polymers has the potential to make the use of the ATAD process more economical.

Characterization of odors from limed biosolids treated with nitrate and anthraquinone.

Complaints from the public due to odor emissions are one of the biggest problems associated with any biosolids land application program. Chemical additives to reduce or mask odors are one option for producers; however, many chemicals are too expensive or are too unstable to use safely. This project provides a preliminary evaluation of nitrate or nitrate + anthraquinone as additives in controlling odors from limed biosolids. Over a twenty-four day period, odors were measured in the headspace over several treatment levels using two different chemical analysis tools along with olfactometric evaluation of odor intensity and hedonic tone. On six days during the sample period, hydrogen sulfide was measured using a Jerome 631X, a sensor that also responds to other reduce sulfur gases. Other specific sulfides, amines, and mercaptans were also determined using solid phase microextraction with gas chromatography-mass spectrometry. A simple sniff test approach was used with six panelists on five days during the project. The chemical analysis results revealed that the addition of nitrate and especially nitrate + anthraquinone was effective in reducing concentrations of hydrogen sulfide and methylmercaptan when compared to untreated limed biosolids. However, the olfactometric results did not reveal any significant differences between treatments. The panelists also found that all treatments exhibited a fishy or ammonical character, indicative of amines, or ammonia. More advance olfactometric analysis utilizing dilution techniques might have been able to distinguish between treatments, but it is likely that amines were the dominant odorant released from all treatments. This preliminary project suggests that chemical addition of nitrate or nitrate + anthraquinone would be most effective in controlling odors from unlimed biosolids such as anaerobically digested materials.