Reducing delamination of an electron-transporting polymer from a metal oxide for electrochemical applications.

Delamination of the electron-transporting polymer N2200 from indium tin oxide (ITO) in aqueous electrolytes is mitigated by modifying ITO with an azide-functionalized phosphonic acid (PA) which, upon UV irradiation, reacts with the polymer. The optical, electrochemical, and spectroelectrochemical properties of N2200 thin films are retained in aqueous and non-aqueous media.

Iron-ozone catalytic oxidation reactive filtration of municipal wastewater at field pilot and full-scale with high-efficiency pollutant removal and potential negative CO2 e with biochar.

Iron-ozone catalytic oxidation (CatOx) shows promise in addressing challenging wastewater pollutants. This study investigates a CatOx reactive filtration (Fe-CatOx-RF) approach with two 0.4 L/s field pilot studies and an 18-month, 18 L/s full-scale municipal wastewater deployment. We apply ozone to leverage common sand filtration and iron metal salts used in water treatment into a next-generation technology. The process combines micropollutant and pathogen destructive removal with high-efficiency phosphorus removal and recycling as a soil amendment, clean water recovery, and the potential for carbon-negative operation with integrated biochar water treatment. A key process innovation is converting a continuously renewed iron oxide coated, moving bed sand filter into a "sacrificial iron" d-orbital catalyst bed after adding O3 to the process stream. Results for the Fe-CatOx-RF pilot studies show >95% removal efficiencies for almost all >5 × LoQ detected micropollutants, with removal rates slightly increasing with biochar addition. Phosphorus removal for the pilot site with the most P-impacted discharge was >98% with serial reactive filters. The long-term, full-scale Fe-CatOx-RF optimization trials showed single reactive filter 90% TP removal and high-efficiency micropollutant removals for most of the compounds detected, but slightly less than the pilot site studies. TP removal decreased to a mean of 86% during the 18 L/s, 12-month continuous operation stability trial, and micropollutant removals remained similar to the optimization trial for many detected compounds but less efficient overall. A >4.4 log reduction of fecal coliforms and E. coli in a field pilot sub-study suggests the ability of this CatOx approach to address infectious disease concerns. Life cycle assessment modeling suggests that integrating biochar water treatment into the Fe-CatOx-RF process for P recovery as a soil amendment makes the overall process carbon-negative at -1.21 kg CO2 e/m3 . Results indicate positive Fe-CatOx-RF process performance and technology readiness in full-scale extended testing. Further work exploring operational variables is essential to establish site-specific water quality limitations and responsive engineering approaches for process optimization. PRACTITIONERS POINTS: Adding ozone to WRRF secondary influent flows into tertiary ferric/ferrous salt dosed sand filtration amplifies a mature reactive filtration technology into a catalytic oxidation process for micropollutant removal and disinfection. Expensive catalysts are not used. Iron oxide compounds used to remove phosphorus and other pollutants act as sacrificial catalysts with ozone, and these rejected iron compounds can be returned upstream to aid in secondary process TP removal. Biochar addition to the CatOx process improves CO2 e sustainability and phosphorus removal/recovery for long-term soil and water health. Short duration field pilot scale and 18-month full-scale operation at three WRRFs with good results demonstrate technology readiness.

Development of a UPLC-ESI-MS/MS method to measure urinary metabolites of selected VOCs: Benzene, cyanide, furfural, furfuryl alcohol, 5-hydroxymethylfurfural, and N-methyl-2-pyrrolidone.

We report on the development of an ultra-performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS) method for simultaneously measuring eight biomarkers of volatile organic compound (VOC) exposure, with potential application to e-cigarette aerosol biomonitoring. Phenylmercapturic acid (PMA) and trans, trans-muconic acid (tt-MA) are metabolites of benzene; 2-aminothiazoline-4-carboxylic acid (ATCA) is a metabolite of cyanide; N-2-furoylglycine (N2FG) is a metabolite of furfural and furfuryl alcohol; 5-hydroxymethylfuroic acid (HMFA), 5-hydroxymethyl-2-furoylglycine (HMFG), and 2,5-furandicarboxylic acid (FDCA) are metabolites of 5-hydroxymethylfurfural; and 5-hydroxy-N-methylpyrrolidone (5HMP) is a metabolite of N-methyl-2-pyrrolidone. A pentafluorophenyl-modified silica column was used for chromatographic separation. The overall run time for the method is about 6 min per sample injection. The method has low to sub-nanograms per milliliter sensitivity, linearity over 3 orders of magnitude, and precision and accuracy within 15%. The method was used to measure human urine samples. Results showed that people with known benzene exposure (daily cigarette smokers) had higher levels of tt-MA and PMA compared with non-smokers. The method is advantageous for high-throughput analysis of selected VOC metabolites in large-scale, population-based studies such as the National Health and Nutrition Examination Survey (NHANES). Quantifying these urinary biomarkers is important to public health efforts to understand human exposure to VOCs from various sources, including tobacco products and electronic nicotine delivery systems.

Correction to: Multiple Ion Transition Summation of Isotopologues for Improved Mass Spectrometric Detection of N-Acetyl-S-(1,2-Dichlorovinyl)-L-Cysteine.

The original article has been corrected to include the missing chemical structure in Fig. 1.

Multiple Ion Transition Summation of Isotopologues for Improved Mass Spectrometric Detection of N-Acetyl-S-(1,2-dichlorovinyl)-L-cysteine.

Multiple ion transition summation of isotopologues (MITSI) is an adaptable and easy-to-implement methodology for improving analytical sensitivity, especially for halogenated compounds and otherwise abundant isotopologues. This novel application of signal summing was applied to measure and quantitate the two most abundant ion transitions of two isotopologues of N-acetyl-S-(1,2-dichlorovinyl)-L-cysteine (1DCV), a urinary metabolite of trichloroethylene (TCE). Because 1DCV is dichlorinated, only approximately half of the total potential signal is quantifiable when the monoisotopic ion transition (i.e., m/z 256 → 127 for 35Cl2) is monitored. By summing the intensity of a separate and high-abundance 1DCV isotopologue ion transition (i.e., m/z 258 → 129 to include 35Cl and 37Cl), overall signal intensity increased by over 70%. This summation technique improved the analytical sensitivity and limit of detection (LOD) by factors of 2.3 and 2.9, respectively, compared to monitoring the two transitions separately, without summation. Separation and detection were performed using liquid chromatography-tandem mass spectrometry (LC-MS/MS) in negative-ion mode with scheduled selected reaction monitoring. This approach was verified for accuracy and precision using two quality control materials. In addition, we derived a modified signal summation equation to calculate predicted signal enhancements specific to the MITSI approach. Graphical Abstract .