Per- and polyfluoroalkyl substances fate and transport at a wastewater treatment plant with a collocated sewage sludge incinerator.

This study aims to understand the fate and transport of per- and polyfluoroalkyl substances (PFAS) and inorganic fluoride (IF) at an undisclosed municipal wastewater treatment plant (WWTP) operating a sewage sludge incinerator (SSI). A robust statistical analysis characterized concentrations and mass flows at all WWTP and SSI primary influents/effluents, including thermal-treatment derived airborne emissions. WWTP-level net mass flows (NMFs) of total PFAS were not statistically different from zero. SSI-level NMFs indicate that PFAS, and specifically perfluoroalkyl acids (PFAAs), are being broken down. The NMF of perfluoroalkyl sulfonic acids (PFSAs; -274 ± 34 mg/day) was statistically significant. The observed breakdown primarily occurred in the sewage sludge. However, the total PFAS destruction and removal efficiency of 51 % indicates the SSI may inadequately remove PFAS. The statistically significant IF source (NMF = 16 ± 4.2 kg/day) compared to the sink of PFAS as fluoride (NMF = -0.00036 kg/day) suggests that other fluorine-containing substances are breaking down in the SSI. WWTP PFAS mass discharges were primarily to the aquatic environment (>99 %), with <0.5 % emitted to the atmosphere/landfill. Emission rates for formerly phased-out PFOS and PFOA were compared to previously reported levels. Given the environmental persistence of these compounds, the observed decreases in PFOS and PFOA discharge rates from prior reports implies regional/local differences in emissions or possibly their accumulation elsewhere. PFAS were observed in stack gas emissions, but modestly contributed to NMFs and showed negligible contribution to ambient air concentrations observed downwind.

Characterization of Printing Inks Using DART-Q-TOF-MS and Attenuated Total Reflectance (ATR) FTIR.

The rise in improved and widely accessible printing technology has resulted in an interest to develop rapid and minimally destructive chemical analytical techniques that can characterize printing inks for forensic document analysis. Chemical characterization of printing inks allows for both discrimination of inks originating from different sources and the association of inks originating from the same source. Direct analysis in real-time mass spectrometry (DART-MS) and attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR) were used in tandem to analyze four different classes of printing inks: inkjets, toners, offset, and intaglio. A total of 319 samples or ~ 80 samples from each class were analyzed directly on a paper substrate using the two methods. DART-MS was found to characterize the semi-volatile polymeric vehicle components, while ATR-FTIR provided chemical information associated with the bulk components of these inks. Complimentary data results in improved discrimination when both techniques are used in succession resulting in >96% discrimination for all toners, 95% for all inkjets, >92% for all offset, and >54% for all intaglio inks.

A Novel Forensic Tool for the Characterization and Comparison of Printing Ink Evidence: Development and Evaluation of a Searchable Database Using Data Fusion of Spectrochemical Methods.

A searchable printing ink database was designed and validated as a tool to improve the chemical information gathered from the analysis of ink evidence. The database contains 319 samples from printing sources that represent some of the global diversity in toner, inkjet, offset, and intaglio inks. Five analytical methods were used to generate data to populate the searchable database including FTIR, SEM-EDS, LA-ICP-MS, DART-MS, and Py-GC-MS. The search algorithm based on partial least-squares discriminant analysis generates a similarity "score" used for the association between similar samples. The performance of a particular analytical method to associate similar inks was found to be dependent on the ink type with LA-ICP-MS performing best, followed by SEM-EDS and DART-MS methods, while FTIR and Py-GC-MS were less useful in association but were still useful for classification purposes. Data fusion of data collected from two complementary methods (i.e., LA-ICP-MS and DART-MS) improves the classification and association of similar inks.