Distribution and fate of per- and polyfluoroalkyl substances (PFAS) in wastewater treatment facilities.

Anthropogenic compounds known as per- and polyfluoroalkyl substances (PFAS) represent a major class of contaminants of emerging concern composed of nearly 5000 chemicals. Many PFAS are persistent, bioaccumulative and toxic, and their widespread use makes their environmental distribution a growing concern. Wastewater treatment facilities (WWTFs) are a conduit of PFAS to the environment, integrating common household products from municipal sewage, industrial wastewater sources, septic materials, and firefighting wastewaters in effluent and sludge. This study investigated the distribution and fate of twenty-four PFAS within six New Hampshire municipal WWTFs applying a range of biological and disinfection unit processes. PFAS quantification was conducted using two approaches: (1) liquid chromatography with tandem mass spectrometry (LC-MS/MS) of 24 known compounds and (2) a total oxidizable precursor assay (TOP assay) followed by LC-MS/MS to determine the total oxidizable PFAS concentration. Of the 24 PFAS analyzed, up to 7 and 12 constituents were detected in influent and effluent of WWTFs, respectively, with concentrations ranging from 30 to 128 ng L-1 in March. Effluent ΣPFAS concentration increased during July, with concentrations between 70 and 198 ng L-1 for the same detected constituents. Short-chain PFAS were dominant in both influent and effluent, while long-chain compounds dominated in WWTF sludge. The increase in terminal end-products after oxidation by the TOP assay indicates the presence of unquantified PFAS precursors in both influent and effluent. A significantly lower proportion of oxidizable PFAS precursors were detected in July influent and effluent relative to March, indicating a possible role of season or temperature on microbial transformation of these compounds prior to reaching WWTFs and during treatment. These results provide new insight into PFAS distribution and fate during two seasons in New England municipal WWTFs.

The fate and removal of pharmaceuticals and personal care products within wastewater treatment facilities discharging to the Great Bay Estuary.

Pharmaceuticals and personal care products (PPCPs) are contaminants of emerging concern that derive primarily in the water environment from combined sewer overflows and discharges from industrial and municipal wastewater treatment facilities (WWTFs). Due to incomplete removal during wastewater treatment, PPCP impacts to aquatic ecosystems are a major concern. The Great Bay Estuary (New Hampshire, USA) is an important ecological, commercial, and recreational resource where upstream WWTFs have recently been under pressure to reduce nitrogen loading to the estuary and consequently upgrade treatment systems. Therefore, we investigated the distribution and abundance of 18 PPCPs and three flame retardants within the Great Bay Estuary and WWTFs discharging to the estuary to examine how WWTF type influenced PPCP removal. All 21 analytes were frequently detected at µg/L to ng/L concentrations in influent and effluent and ng/kg in sludge. WWTFs with enhanced nutrient removal and longer solids retention times correlated to higher PPCP removal, indicating facility upgrades may have benefits related to PPCP removal. Understanding PPCP fate during treatment and in downstream waters informs our ability to assess the environmental and ecological impacts of PPCPs on estuarine resources and develop mitigation strategies to better protect marine ecosystems from emerging contaminant exposure. PRACTITIONER POINTS: PPCP removal positively correlated with solids retention time and varied by treatment facility and compound. Upgrade of WWTFs for biological nitrogen removal may also increase PPCP removal. Surface water fluoxetine concentrations may present an ecological risk to the Great Bay Estuary.

KMN-159, a novel EP4 receptor selective agonist, stimulates osteoblastic differentiation in cultured whole rat bone marrow.

KMN-159 is the lead compound from a series of novel difluorolactam prostanoid EP4 receptor agonists aimed at inducing local bone formation while avoiding the inherent side effects of systemic EP4 activation. KMN-159 is a potent, selective small molecule possessing pharmacokinetic properties amenable to local administration. Unfractionated rat bone marrow cells (BMCs) were treated once at plating with escalating doses of KMN-159 (1 pM to 10 µM). The resulting elevated alkaline phosphatase (ALP) levels measured 9 days post-dose are consistent with increased osteoblastic differentiation and exposure to KMN-159 at low nanomolar concentrations for as little as 30 min was sufficient to induce complete osteoblast differentiation of the BMCs from both sexes and regardless of age. ALP induction was blocked by an EP4 receptor antagonist but not by EP1 or EP2 receptor antagonists and was not induced by EP2 or EP3 receptor agonists. Addition of BMCs to plates coated with KMN-159 24 days earlier resulted in ALP activation, highlighting the chemical stability of the compound. The expression of phenotype markers such as ALP, type I collagen, and osteocalcin was significantly elevated throughout the osteoblastic differentiation timecourse initiated by KMN-159 stimulation. An increased number of tartrate-resistant acid phosphatase-positive cells was observed KMN-159 or PGE2 treated BMCs but only in the presence of exogenous receptor activator of nuclear factor kappa-Β ligand (RANKL). No change in the number of adipocytes was observed. KMN-159 also increased bone healing in a rat calvarial defect model with a healing rate equivalent to recombinant human bone morphogenetic protein-2. Our studies show that KMN-159 is able to stimulate osteoblastic differentiation with a very short time of exposure, supporting its potential as a therapeutic candidate for augmenting bone mass.

Difluoromethylene at the γ-Lactam α-Position Improves 11-Deoxy-8-aza-PGE1 Series EP4 Receptor Binding and Activity: 11-Deoxy-10,10-difluoro-8-aza-PGE1 Analog (KMN-159) as a Potent EP4 Agonist.

A series of small-molecule full agonists of the prostaglandin E2 type 4 (EP4) receptor have been generated and evaluated for binding affinity and cellular potency. KMN-80 and its gem-difluoro analog KMN-159 possess high selectivity relative to other prostanoid receptors. Difluoro substitution is positioned alpha to the lactam ring carbonyl and results in KMN-159's fivefold increase in potency versus KMN-80. The two analogs exhibit electronic and conformational variations, including altered nitrogen hybridization and lactam ring puckering, that may drive the observed difluoro-associated increased potency within this four-compound series.

Life cycle environmental and economic implications of small drinking water system upgrades to reduce disinfection byproducts.

Many of the small drinking water systems in the US that utilize simple filtration and chlorine disinfection or chlorine disinfection alone are facing disinfection byproduct (DBP) noncompliance issues, which need immediate upgrades. In this study, four potential upgrade scenarios, namely the GAC, ozone, UV30, and UV186 scenarios, were designed for a typical small drinking water systems and compared in terms of embodied energy, carbon footprint, and life cycle cost. These scenarios are designed to either reduce the amount of DBP precursors using granular activated carbon filtration (the GAC scenario) or ozonation (the ozone scenario), or replace the chlorine disinfection with the UV disinfection at different intensities followed by chloramination (the UV30 and UV186 scenarios). The UV30 scenario was found to have the lowest embodied energy (417 GJ/year) and life cycle cost ($0.25 million US dollars), while the GAC scenario has the lowest carbon footprint (21 Mg CO2e/year). The UV186 scenario consistently presents the highest environmental and economic impacts. The major contributors of the economic and environmental impacts of individual scenarios also differ. Energy and/or material consumptions during the operation phase dominate the environmental impacts of the four scenarios, while the infrastructure investments have a noticeable contribution to the economic costs. The results are sensitive to changes in water quality. An increase of raw water quality, i.e., an increase in organic precursor content, could potentially result in the ozone scenario being the least energy intensive scenario, while a decrease of water quality could greatly reduce the overall competitiveness of the GAC scenario.

Enhanced UV inactivation of adenoviruses under polychromatic UV lamps.

Adenovirus is recognized as the most UV-resistant waterborne pathogen of concern to public health microbiologists. The U.S. EPA has stipulated that a UV fluence (dose) of 186 mJ cm(-2) is required for 4-log inactivation credit in water treatment. However, all adenovirus inactivation data to date published in the peer-reviewed literature have been based on UV disinfection experiments using UV irradiation at 253.7 nm produced from a conventional low-pressure UV source. The work reported here presents inactivation data for adenovirus based on polychromatic UV sources and details the significant enhancement in inactivation achieved using these polychromatic sources. When full-spectrum, medium-pressure UV lamps were used, 4-log inactivation of adenovirus type 40 is achieved at a UV fluence of less than 60 mJ cm(-2) and a surface discharge pulsed UV source required a UV fluence of less than 40 mJ cm(-2). The action spectrum for adenovirus type 2 was also developed and partially explains the improved inactivation based on enhancements at wavelengths below 230 nm. Implications for water treatment, public health, and the future of UV regulations for virus disinfection are discussed.

Assessment of biomarkers of protein anabolism in skeletal muscle during the life span of the rat: sarcopenia despite elevated protein synthesis.

Loss of muscle strength is a principal factor in the development of physical frailty, a condition clinically associated with increased risk of bone fractures, impairments in the activities of daily living, and loss of independence in older humans. A primary determinant in the decline in muscle strength that occurs during aging is a loss of muscle mass, which could occur through a reduction in the rate of protein synthesis, an elevation in protein degradation, or a combination of both. In the present study, rates of protein synthesis and the relative expression and function of various biomarkers involved in the initiation of mRNA translation in skeletal muscle were examined at different times throughout the life span of the rat. It was found that between 1 and 6 mo of age, body weight increased fourfold. However, by 6 mo, gastrocnemius protein synthesis and RNA content per gram of muscle were lower than values observed in 1-mo-old rats. Moreover, the relative expression of two proteins involved in the binding of initiator methionyl-tRNA to the 40S ribosomal subunit, eukaryotic initiation factors (eIF)2 and eIF2B, as well as the 70-kDa ribosomal protein S6 kinase, S6K1, was lower at 6 mo compared with 1 mo of age. Muscle mass, protein synthesis, and the aforementioned biomarkers remained unchanged until approximately 21 mo. Between 21 and 24 mo of age, muscle mass decreased precipitously. Surprisingly, during this period protein synthesis, relative RNA content, eIF2B activity, relative eIF2 expression, and S6K1 phosphorylation all increased. The results are consistent with a model wherein protein synthesis is enhanced during aging in a futile attempt to maintain muscle mass.