Search for: All records

The ocean is thought to be the terminal sink for per- and polyfluoroalkyl substances (PFAS), persistent organofluorine chemicals used widely in modern commerce for decades. Industry and stewardship programs phased out the most abundantly produced legacy PFAS in the early 2000s due to toxicity concerns. However, they have since been replaced by shorter carbon chain and “novel” chemistries, and past work hypothesized likely increases in these replacement PFAS that were not previously quantifiable. To address this gap, we measured bulk extractable organofluorine (EOF) in archived liver and muscle tissues from pelagic Subarctic pilot whales over the last several decades. Results show EOF concentrations peaked in 2011 and declined by over 60% by 2023. Among a broad suite of targeted and suspect PFAS measured using high-resolution mass spectrometry, only one was consistently increasing through 2023. Tissue concentrations of four main legacy PFAS that accounted for over 75% of EOF were all decreasing by 2023. The timing of peak concentrations depended primarily on whether they were transported to the subarctic by ocean circulation or atmospheric deposition, with the latter declining much faster. Oceanic transport and bioaccumulation modeling suggests that decadal-scale lags between production and food web bioaccumulation are primarily driven by marine transport processes. Large declines in tissue concentrations in this study reinforce the effectiveness of phase-outs in chemical production. However, other work showing stable or increasing EOF in human serum suggests many emerging PFAS with more neutral physicochemical properties may be preferentially accumulating in terrestrial and nearshore environments compared to legacy PFAS. 

Ozone is commonly used as a pre-disinfectant in potable water reuse treatment trains. Nitromethane was recently found as a ubiquitous ozone byproduct in wastewater, and the key intermediate toward chloropicrin during subsequent secondary disinfection of ozonated wastewater effluent with chlorine. However many utilities have switched from free chlorine to chloramines as a secondary disinfectant. The reaction mechanism and kinetics of nitromethane transformation by chloramines, unlike free chlorine, are unknown. In this work, the kinetics, mechanism, and products of nitromethane chloramination were studied. The expected principal product was chloropicrin, because chloramines are commonly assumed to react similarly, although more slowly, compared to free chlorine. Different molar yields of chloropicrin were observed at acidic, neutral, and basic conditions, and surprisingly, transformation products other than chloropicrin were found. Monochloronitromethane and dichloronitromethane were detected at basic pH, and the mass balance was initially poor at neutral pH. Much of the missing mass was later attributed to nitrate formation, from a newly-identified pathway involving monochloramine reacting as a nucleophile rather than halogenating agent, through a presumed SN2 mechanism. The study indicates that nitromethane chloramination, unlike chlorination, is likely to produce a range of products, whose speciation is a function of pH and reaction time.