Complex Mixture Analysis of Emerging Contaminants Generated from Coal Tar- and Petroleum-Derived Pavement Sealants: Molecular Compositions and Correlations with Toxicity Revealed by Fourier Transform Ion Cyclotron Resonance Mass Spectrometry.

Pavement sealants are of environmental concern because of their complex petroleum-based chemistry and potential toxicity. Specifically, coal tar-derived sealants contain high concentrations of toxic/carcinogenic polycyclic aromatic hydrocarbons (PAHs) that, when weathered, can be transferred into the surrounding environment. Previous studies have demonstrated the effects of coal tar sealants on PAH concentration in nearby waterways and their harmful effects in aquatic ecosystems. Here, we investigate and compare the molecular composition of two different pavement sealants, petroleum asphalt- and coal tar-derived, and their photoproducts, by positive-ion (+) atmospheric pressure photoionization (APPI) and negative-ion (-) electrospray ionization (ESI) coupled with ultrahigh-resolution Fourier transform ion cyclotron resonance mass spectrometry to address species (high-boiling and/or high oxygen content) that lie outside the analytical window of other techniques due to ultra-high molecular complexity. In addition, we evaluate the toxicity of the water-soluble photoproducts by use of Microtox bioassay. The results demonstrate that the coal tar sealant contains higher amounts of PAHs and produces abundant water-soluble compounds, relative to unweathered materials, with a high abundance of PAH-like molecules of high toxicity. By comparison, the asphalt sealant produces fewer toxic water-soluble species, with molecular compositions that are consistent with natural dissolved organic matter. These results capture the mass, chemical diversity, toxicity, and source/photoproduct relationship of these compositionally complex emerging contaminants from the built environment.

Time-dependent molecular progression and acute toxicity of oil-soluble, interfacially-active, and water-soluble species reveals their rapid formation in the photodegradation of Macondo Well Oil.

Photodegradation is a significant weathering process that transforms spilled oil, yet, the fate, degradation rate, and molecular transformations that occur through photoinduced pathways remain relatively unknown. The molecular complexity combined with the increased polarity of photoproducts challenges conventional analytical techniques. Here, we catalogue the molecular progression of photochemical transformation products of Macondo Well Oil by negative-ion electrospray ionization (ESI) Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS). We track the molecular compositions of oil-soluble, interfacially-active, and water-soluble oil species formed at varying time intervals in photomicrocosm experiments. Short photoirradiation periods (<24 h), not previously reported, are included to reveal rapid photooxidation of native oil components. Surface oil films exposed to solar irradiation were shown to increasingly contribute to the dissolved organic carbon pool as a function of increased irradiation time. FT-ICR MS analysis of acidic species of each fraction identifies tens of thousands of oil-soluble, interfacially-active, and water-soluble phototransformation products, including Ox, NOx, and SOx species. Oil-soluble species incorporate oxygen as a function of irradiation periods. After 96 h of irradiation, ~14 wt% of the photooxidized oil film was interfacially active and contained phototransformed species with up to 12 oxygen atoms per molecule. Water-soluble species correspond to highly oxygenated compounds. Importantly, photochemical oxidation is shown to occur within the first hour. Beyond 24 h, photoproducts remain compositionally similar, highlighting the rapid effect of photodegradation to transform oil species into water-soluble compounds. Molecular fingerprints provided by FT-ICR MS highlight the oxygen dependence on oil/water solubility. Microtox® analysis indicates that the toxicity of water-soluble photoproducts rapidly increases at early irradiation time points (first 24 h) compared to the dark control and reaches a maximum at 6 h of irradiation. Results highlight the temporal, molecular progression of photoproducts as they partition from oil-soluble to oil-soluble interfacially-active, and finally to water-soluble species.