Aqueous film-forming foams (AFFFs) are a vital tool to fight large hydrocarbon fires and can be used by public, commercial, and military firefighting organizations. In order to possess these superior firefighting capabilities, AFFFs contain fluorochemical surfactants, of which many of the chemical identities are listed as proprietary. Large-scale controlled (e.g. training activities) and uncontrolled releases of AFFF have resulted in contamination of groundwater. Information on the composition of AFFF formulations is needed to fully define the extent of groundwater contamination and the first step is to fully define the fluorochemical composition of AFFFs used by the US military. Fast atom bombardment mass spectrometry (FAB-MS) and high resolution quadrupole-time-of-flight mass spectrometry (QTOF-MS) were combined to elucidate chemical formulas for the fluorochemicals in AFFF mixtures and, along with patent-based information, structures were assigned. Sample collection and analysis was focused on AFFFs that have been designated as certified for US military use. Ten different fluorochemical classes were identified in the seven military-certified AFFF formulations, and include anionic, cationic, and zwitterionic surfactants with perfluoroalkyl chain lengths ranging from 4-12. The environmental implications are discussed and research needs are identified.

Per- and polyfluoroalkyl substances (PFASs) are important environmental contaminants, yet relatively few analytical reference standards exist for this class. Nontarget analyses performed by means of high-resolution mass spectrometry (HRMS) are increasingly common for the discovery and identification of PFASs in environmental and biological samples. The certainty of PFAS identifications made via HRMS must be communicated through a reliable and harmonized approach. Here, we present a confidence scale along with identification criteria specific to suspect or nontarget analysis of PFASs by means of nontarget HRMS. Confidence levels range from level 1a—“Confirmed by Reference Standard,” and level 1b—“Indistinguishable from Reference Standard,” to level 5—“Exact Masses of Interest,” which are identified by suspect screening or data filtering, two common forms of feature prioritization. This confidence scale is consistent with general criteria for communicating confidence in the identification of small organic molecules by HRMS (e.g., through a match to analytical reference standards, library MS/MS, and/or retention times) but incorporates the specific conventions and tools used in PFAS classification and analysis (e.g., detection of homologous series and specific ranges of mass defects). Our scale clarifies the level of certainty in PFAS identification and, in doing so, facilitates more efficient identification.

Abstract.A growing number of ambient measurements of isocyanic acid (HNCO) are being made, yet little is known about its fate in the atmosphere. To better understand HNCO's loss processes and particularly its atmospheric partitioning behaviour, we measure its effective Henry's Law coefficient K eff H with a bubbler experiment using chemical ionization mass spectrometry as the gas phase analytical technique. By conducting experiments at different pH values and temperature, a Henry's Law coefficient K H of 26 ± 2 M atm −1 is obtained, with an enthalpy of dissolution of −34 ± 2 kJ mol −1 , which translates to a K eff H of 31 M atm −1 at 298 K and at pH 3. Our approach also allows for the determination of HNCO's acid dissociation constant, which we determine to be K a = 2.1 ± 0.2 × 10 −4 M at 298 K. Furthermore, by using ion chromatography to analyze aqueous solution composition, we revisit the hydrolysis kinetics of HNCO at different pH and temperature conditions. Three pH-dependent hydrolysis mechanisms are in play and we determine the Arrhenius expressions for each rate to be k 1 = (4.4 ± 0.2) × 10 7 exp(−6000 ± 240/T ) M s −1 , k 2 = (8.9 ± 0.9) × 10 6 exp(−6770 ± 450/T ) s −1 and k 3 = (7.2 ± 1.5) × 10 8 exp(−10 900 ± 1400/T ) s −1 , where k 1 is for HNCO + H + + H 2 O → NH + 4 + CO 2 , k 2 is for HNCO + H 2 O → NH 3 + CO 2 and k 3 is for NCO − + 2 H 2 O → NH 3 + HCO − 3 . HNCO's lifetime against hydrolysis is therefore estimated to be 10 days to 28 years at pH values, liquid water contents, and temperatures relevant to tropospheric clouds, years in oceans and months in human blood. In all, a better parameterized Henry's Law coefficient and hydrolysis rates of HNCO allow for more accurate predictions of its concentration in the atmosphere and consequently help define exposure of this toxic molecule.

After the April 2010 explosion on the Deepwater Horizon oil rig, and subsequent release of millions of barrels of oil, two Corexit oil dispersant formulations were used in unprecedented quantities both on the surface and sub-surface of the Gulf of Mexico. Although the dispersant formulations contain four classes of surfactants, current studies to date focus on the anionic surfactant, bis-(2-ethylhexyl) sulfosuccinate (DOSS). Factors affecting the integrity of environmental and laboratory samples for Corexit analysis have not been systematically investigated. For this reason, a quantitative analytical method was developed for the detection of all four classes of surfactants, as well as the hydrolysis products of DOSS, the enantiomeric mixture of α- and β-ethylhexyl sulfosuccinate (α-/β-EHSS). The analytical method was then used to evaluate which practices for sample collection, storage, and analysis resulted in high quality data. Large volume, direct injection of seawater followed by liquid chromatography tandem mass spectrometry (LC-MS/MS) minimized analytical artifacts, analysis time, and both chemical and solid waste. Concentrations of DOSS in the seawater samples ranged from 71 – 13,000 ng/L, while the nonionic surfactants including Span 80, Tween 80, Tween 85 were detected infrequently (26% of samples) at concentrations from 840 – 9100 ng/L. The enantiomers α-/β-EHSS were detected in seawater, at concentrations from 200 – 1,900 ng/L, and in both Corexit dispersant formulations, indicating α-/β-EHSS were applied to the oil spill and may be not unambiguous indicator of DOSS degradation. Best practices are provided to ensure sample integrity and data quality for environmental monitoring studies and laboratory that require the detection and quantification of Corexit-based surfactants in seawater.

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