Bisphenol A (BPA) is an endocrine-disrupting compound widely used in the plastic industry and found in natural waters at concentrations considered harmful for aquatic life. BPA is susceptible to oxidation by Mn(III/IV) oxides, which are commonly found in near-surface environments. Here, we quantify BPA oxidation rates and the formation of its predominant product, 4-hydroxycumyl alcohol (HCA), in tandem with transformation of a synthetic, Mn(III)-rich δ-MnO. To investigate the effect of Mn oxide structural changes on BPA oxidation rate, 12 sequential additions of 80 μM BPA are performed at pH 7. During the additions, BPA oxidation rate decreases by 3 orders of magnitude, and HCA yield decreases from 40% to 3%. This is attributed to the accumulation of interlayer Mn(II/III) produced during the reaction, as observed using X-ray absorption spectroscopy, as well as additional spectroscopic and wet chemical techniques. HCA is oxidized at a rate that is 12.6 times slower than BPA and accumulates in solution. These results demonstrate that BPA degradation by environmentally relevant Mn(III/IV) oxides is inhibited by the buildup of solid-phase Mn(II/III), specifically in interlayer sites. Nevertheless, Mn oxides may limit BPA migration in near-surface environments and have potential for use in drinking and wastewater treatment.

Transport of per- and polyfluoroalkyl substances (PFAS) to the Great Lakes is of great importance as this large freshwater system provides drinking water to over 40 million people. Tributary PFAS loading to the Great Lakes is poorly characterized, and the role of sediments as a source or sink of PFAS is largely unknown. We quantified 10 perfluoroalkyl acids (PFAAs) in water (4–1310 ng/L) and sediment (below detection to 3255 ng/kg) of 41 tributaries to Green Bay of Lake Michigan. We demonstrate that tributary discharge plays a major role in PFAS contribution to receiving waters. In this system, three large rivers (i.e., Fox, Menominee, and Peshtigo Rivers) contribute two-thirds of the total tributary PFAA loading to Green Bay despite their relatively low concentrations. This circumvents the current regulatory focus on sites with high concentrations. Tributary PFAA composition is linked to likely sources, including a fire-fighting foam manufacturer, other industrial activities, and airports. In addition to tributary discharge, we show that tributary sediments can contribute to PFAA transport via desorption. Perfluorooctanesulfonate rapidly desorbs from contaminated riverbed sediments when equilibrated with Lake Michigan water, indicating that sediments may act as a PFAS source if water concentrations are reduced by pollution mitigation methods.

This study combines analysis of both organic and inorganic components in bisphenol A oxidation by MnO2 in a stirred flow reactor.

Many phenolic compounds found as contaminants in natural waters are susceptible to oxidation by manganese oxides. However, there is often variability between oxidation rates reported in pristine matrices and studies using more environmentally relevant conditions. For example, the presence of cations generally results in slower phenolic oxidation rates. However, the underlying mechanism of cation interference is not well understood. In this study, cation co-solutes inhibit the transformation of four target phenols (bisphenol A, estrone, p-cresol, and triclosan) by acid birnessite. Oxidation rates for these compounds by acid birnessite follow the same trend (Na + > K + > Mg 2+ > Ca 2+) when cations are present as co-solutes. We further demonstrate that the same trend applies to these cations when they are absent from solution but pre-exchanged with the mineral. We analyze valence state, surface area, crystallinity, and zeta potential to characterize changes in oxide structure. The findings of this study show that preexchanged cations have a large effect on birnessite reactivity even in the absence of cation co-solutes, indicating that the inhibition of phenolic compound oxidation is not due to competition for surface sites, as previously suggested. Instead, the reaction inhibition is attributed to changes in aggregation and the mineral microstructure.

Forensic analysis can potentially be used to determine per-and polyfluoroalkyl substance (PFAS) sources at contaminated sites. However, fluorotelomer aqueous film-forming foam (AFFF) sources are difficult to identify because the polyfluorinated active ingredients do not have authentic standards and because the parent compounds can undergo transformation and differential transport, resulting in alteration of the PFAS distribution or fingerprint. In this study, we investigate changes in the PFAS fingerprint of fluorotelomer-derived AFFF due to environmental and engineered processes, including groundwater transport, surface water flow, and land application of contaminated biosolids. Fingerprint analysis supplemented by quantification of precursors and identification of suspected active ingredients shows a clear correlation between a fluorotelomer AFFF manufacturer and surface water of nearby Lake Michigan, demonstrating contamination (>100 ng/L PFOA) of the lake due to migration of an AFFF-impacted groundwater plume. In contrast, extensive processing during wastewater treatment and environmental transport results in large changes to the AFFF fingerprint near agricultural fields where contaminated biosolids were spread. At biosolids-impacted sites, the presence of active ingredients confirms contamination by fluorotelomer AFFF. While sediments can retain longer-chain PFAS, this study demonstrates that aqueous samples are most relevant for PFAS fingerprinting in complex sites, particularly where shorter-chain compounds have been used.

No abstract