Impacts of the COVID-19 pandemic on pharmaceuticals in wastewater treated for beneficial reuse: Two case studies in central Pennsylvania.

During the COVID-19 pandemic, wastewater surveillance was leveraged as a powerful tool for monitoring community-scale health. Further, the well-known persistence of some pharmaceuticals through wastewater treatment plants spurred concerns that increased usage of pharmaceuticals during the pandemic would increase the concentrations in wastewater treatment plant effluent. We collected weekly influent and effluent samples from May 2020 through May 2021 from two wastewater treatment plants in central Pennsylvania, the Penn State Water Reclamation Facility and the University Area Joint Authority, that provide effluent for beneficial reuse, including for irrigation. Samples were analyzed for severe acute respiratory syndrome coronavirus 2 (influent only), two over-the-counter medicines (acetaminophen and naproxen), five antibiotics (ampicillin, doxycycline, ofloxacin, sulfamethoxazole, and trimethoprim), two therapeutic agents (remdesivir and dexamethasone), and hydroxychloroquine. Although there were no correlations between pharmaceutical and virus concentration, remdesivir detection occurred when the number of hospitalized patients with COVID-19 increased, and dexamethasone detection co-occurred with the presence of patients with COVID-19 on ventilators. Additionally, Penn State decision-making regarding instruction modes explained the temporal variation of influent pharmaceutical concentrations, with detection occurring primarily when students were on campus. Risk quotients calculated for pharmaceuticals with known effective and lethal concentrations at which 50% of a population is affected for fish, daphnia, and algae were generally low in the effluent; however, some acute risks from sulfamethoxazole were high when students returned to campus. Remdesivir and dexamethasone persisted through the wastewater treatment plants, thereby introducing novel pharmaceuticals directly to soils and surface water. These results highlight connections between human health and water quality and further demonstrate the broad utility of wastewater surveillance.

Trace organic contaminant removal in six full-scale integrated fixed-film activated sludge (IFAS) systems treating municipal wastewater.

Trace organic contaminants (TrOCs) often pass through conventional activated sludge wastewater treatment plants (CAS-WWTPs) and are discharged into surface waters, where they can threaten aquatic ecosystems and human health, largely due to the hormone disrupting effects of certain TrOCs. The integrated fixed-film activated sludge (IFAS) process is a cost-effective means of upgrading CAS-WWTPs by adding free-floating carrier media, which promotes biofilm formation in the well-mixed suspended growth reactors, providing a potential niche for slow-growing microorganisms. Although IFAS upgrades are typically aimed at enhancing nutrient removal, limited bench- and pilot-scale data indicate that TrOC removal may also be improved. However, only limited reports which focus on a small number of compounds in individual full-scale IFAS-WWTPs have been published to date, and no data is available regarding the removal of estrogenic activity in full-scale IFAS-WWTPs. In this study, six full-scale IFAS-WWTPs were surveyed to quantify TrOC and estrogenic activity removal. Twenty-four hour composite samples of secondary influent and effluent (pre-disinfection) were analyzed for total suspended solids (TSS), chemical oxygen demand (COD), ammonia, total nitrogen (TN), total phosphorus (TP), estrogenic activity, and 98 TrOCs. The biomass distribution between the suspended growth phase (i.e. mixed liquor) and IFAS media was also assessed. All IFAS-WWTPs performed well in terms of TSS, COD, and ammonia removal. TN removal varied in accordance with nitrate removal. Total solids per liter of wetted reactor volume ranged from 2.5 to 7.6 g, with 40-60% attached to media. TrOCs with no detection (17) and those with high median removal (23, ≥90% average removal) were observed. Other TrOCs had lower and more variable removal efficiencies. Qualitative comparison with CAS literature shows potentially higher IFAS removal efficiencies for a number of compounds including several which have been previously indicated in bench- or pilot-scale studies (atenolol, diclofenac, gemfibrozil, DEET, 4-nonylphenol, and 4-tert-octylphenol), as well as the chlorinated flame retardants TCIPP and TDCIPP. Effluent estrogenic activity was found to be similar to that reported for full-scale CAS-WWTPs. These results provide the first survey of multiple full-scale IFAS-WWTPs employing mobile plastic carrier media in terms of basic chemical endpoints (removal of ammonia, TN, TP, and COD), the distribution of solids within the systems, and the removal of TrOCs and estrogenic activity.

Effect of pH and temperature on microbial community structure and carboxylic acid yield during the acidogenic digestion of duckweed.

BACKGROUND: Duckweeds (Lemnaceae) are efficient aquatic plants for wastewater treatment due to their high nutrient-uptake capabilities and resilience to severe environmental conditions. Combined with their rapid growth rates, high starch, and low lignin contents, duckweeds have also gained popularity as a biofuel feedstock for thermochemical conversion and alcohol fermentation. However, studies on the acidogenic anaerobic digestion of duckweed into carboxylic acids, another group of chemicals which are precursors of higher-value chemicals and biofuels, are lacking. In this study, a series of laboratory batch experiments were performed to determine the favorable operating conditions (i.e., temperature and pH) to maximize carboxylic acid production from wastewater-derived duckweed during acidogenic digestion. Batch reactors with 25 g/l solid loading were operated anaerobically for 21 days under mesophilic (35 °C) or thermophilic (55 °C) conditions at an acidic (5.3) or basic (9.2) pH. At the conclusion of the experiment, the dominant microbial communities under various operating conditions were assessed using high-throughput sequencing. RESULTS: The highest duckweed-carboxylic acid conversion of 388 ± 28 mg acetic acid equivalent per gram volatile solids was observed under mesophilic and basic conditions, with an average production rate of 0.59 g/l/day. This result is comparable to those reported for acidogenic digestion of other organics such as food waste. The superior performance observed under these conditions was attributed to both chemical treatment and microbial bioconversion. Hydrogen recovery was only observed under acidic thermophilic conditions, as 23.5 ± 0.5 ml/g of duckweed volatile solids added. More than temperature, pH controlled the overall structure of the microbial communities. For instance, differentially abundant enrichments of Veillonellaceae acidaminococcus were observed in acidic samples, whereas enrichments of Clostridiaceae alkaliphilus were found in the basic samples. Acidic mesophilic conditions were found to enrich acetoclastic methanogenic populations over processing times longer than 10 days. CONCLUSIONS: Operating conditions have a significant effect on the yield and composition of the end products resulting from acidogenic digestion of duckweed. Wastewater-derived duckweed is a technically feasible alternative feedstock for the production of advanced biofuel precursors; however, techno-economic analysis is needed to determine integrated full-scale system feasibility and economic viability.

Synthesis and polymerization of renewable 1,3-cyclohexadiene using metathesis, isomerization, and cascade reactions with late-metal catalysts.

Synthesis and subsequent polymerization of renewable 1,3-cyclohexadiene (1,3-CHD) from plant oils is reported via metathesis and isomerization reactions. The metathesis reaction required no plant oil purification, minimal catalyst loading, no organic solvents, and simple product recovery by distillation. After treating soybean oil with a ruthenium metathesis catalyst, the resulting 1,4-cyclohexadiene (1,4-CHD) was isomerized with RuHCl(CO)(PPh3)3. The isomerization reaction was conducted for 1 h in neat 1,4-CHD with [1,4-CHD]/[RuHCl(CO)(PPh3)3] ratios as high as 5000. The isomerization and subsequent polymerization of the renewable 1,3-CHD was examined as a two-step sequence and as a one-step cascade reaction. The polymerization was catalyzed with nickel(II)acetylacetonate/methaluminoxane in neat monomer, hydrogenated d-limonene, and toluene. The resulting polymers were characterized by FTIR, DSC, and TGA.