Pharmaceuticals account for a significant proportion of the extractable organic fluorine in municipal wastewater treatment plant sludge

Fluorine mass balance studies have shown that monomeric per- and polyfluoroalkyl substances (PFAS) with perfluoroalkyl chain lengths of ~5-14 carbon atoms (i.e., “conventional” PFAS) account for a fraction (~2%) of the extractable organic fluorine (EOF) in municipal wastewater treatment plant (WWTP) sludge. The identity of the remaining EOF has thus far been unclear, but may be partly attributable to fluorine-containing pharmaceuticals and pesticides used throughout society. To test this hypothesis, we applied high resolution mass spectrometry-based suspect screening to samples of municipal WWTP sludge which had been previously subjected to a fluorine mass balance. Sixteen pharmaceutical substances (including transformation products [TPs]), one pesticide, and thirteen conventional PFAS were confirmed at confidence levels 1-4, with concentrations ranging from 0.07-155 ng/g dw. Notably, eight pharmaceutical substances did not meet the OECD definition of PFAS. When converted to fluorine equivalents, the newly detected organofluorine substances increased the percentage of known EOF from ~2% to ~27%, of which ~22% was attributed to pharmaceutical- and pesticide substances, with the greatest contributions from a ticagrelor TP (4.0%), ezetimibe (3.9%), and bicalutamide (3.5%). These data highlight the importance of considering both unconventional- and non-PFAS organofluorine substances in addition to conventional PFAS when closing the organofluorine mass balance in WWTP sludge

Characterizing the Organohalogen Iceberg: Extractable, multi-halogen mass balance determination in municipal wastewater treatment plant sludge

The large number and diversity of organohalogen compounds (OHCs) occurring in the environment poses a grand challenge to analytical chemists. Since no single targeted method can identify and quantify all OHCs, the size of the OHC iceberg may be underestimated. We sought to address this problem in municipal wastewater treatment plant (WWTP) sludge by quantifying the unidentified fraction of the OHC iceberg using targeted analyses of major OHCs together with measurements of total- and extractable (organo)halogen (TX and EOX, respectively; where X=F, Cl, or Br). In addition to extensive method validation via spike/recovery and combustion efficiency experiments, TX and/or EOX were determined in reference materials (BCR-461 and NIST SRMs 2585 and 2781) for the first time. Application of the method to WWTP sludge revealed that chlorinated paraffins (CPs) accounted for most (~92%) of the EOCl, while brominated flame retardants and per- and polyfluoroalkyl substances (PFAS) accounted for only 54% of the EOBr and 2% of the EOF, respectively. Moreover, unidentified EOF in non-polar CP extracts points to the existence of organofluorine(s) with physical-chemical properties unlike those of target PFAS. This study represents the first multi-halogen mass balance in WWTP sludge, and offers a novel approach to prioritization of sample extracts for follow-up investigation

The Role of Polymeric Biomaterials in the Treatment of Articular Osteoarthritis

Osteoarthritis is a high-prevalence joint disease characterized by the degradation of cartilage, subchondral bone thickening, and synovitis. Due to the inability of cartilage to self-repair, regenerative medicine strategies have become highly relevant in the management of osteoarthritis. Despite the great advances in medical and pharmaceutical sciences, current therapies stay unfulfilled, due to the inability of cartilage to repair itself. Additionally, the multifactorial etiology of the disease, including endogenous genetic dysfunctions and exogenous factors in many cases, also limits the formation of new cartilage extracellular matrix or impairs the regular recruiting of chondroprogenitor cells. Hence, current strategies for osteoarthritis management involve not only analgesics, anti-inflammatory drugs, and/or viscosupplementation but also polymeric biomaterials that are able to drive native cells to heal and repair the damaged cartilage. This review updates the most relevant research on osteoarthritis management that employs polymeric biomaterials capable of restoring the viscoelastic properties of cartilage, reducing the symptomatology, and favoring adequate cartilage regeneration properties.This research was funded by the Spanish MICINN (PID2020-114086RB-100) and CIBERBBN, ISCIII, Spain. M.R.A., L.G.-F., B.V.-L. and L.R are members of the Interdisciplinary Platform SusPlast+, CSIC. This research work was performed in the framework of the Nanomedicine CSIC HUB (ref 202180E048)