The photolytic conversion of 4-nonylphenol to 4-nonylcatechol within snowpack of the Palisade Glacier, Sierra Nevada, CA, USA

Abstract

4-Nonylphenol (4-NP), an environmental pollutant with potent ecotoxicological effects, has been discovered in significant quantities in glacial ice and snow of the Sierra Nevada Mountain Range, CA. Photolysis of 4-NP is suspected to be a major, if not the sole, breakdown pathway in snow. However, the photolysis process has yet to be characterized in detail for this unique environment. This study therefore seeks to (1) confirm the presence of the major photolysis product within snowpack and snowmelt samples from the Palisade Glacier, CA, (2) determine key photolysis parameters through laboratory assays in snow analogs, and (3) compute environmentally relevant photolysis rates in snowpack via a spectral solar irradiance model parameterized for the Palisade Glacier. The primary photooxidation product of 4-NP, 4-nonylcatechol (4-NC), was synthesized and characterized by NMR and GC–MS for use as a reference standard in the detection of 4-NC in environmental samples. 4-NP was detected in all snowpack (n = 4) and snowmelt (n = 5) samples, with concentrations of 1.05 (± 0.11) μg L−1 and 1.28 (± 0.12) μg L−1, respectively. 4-NC was detected in all snowmelt outflow samples and all but one snow samples (88 % detection frequency) but was below the limit of quantification for the given method. All samples were collected during a sampling regime at the Palisade Glacier in August of 2021. Quantum yields of photolysis at the 277 nm absorption band were determined to be 0.36 (±0.06) and 0.21 (±0.06) in ultrapure water and liquid snow, respectively. Under clear sky conditions at the Palisade Glacier, half-lives for 4-NP are estimated to range from 235 to 251 h (9.8–10.5 days) based on assays conducted in liquid snowmelt and irradiance modeling. These results suggest that the photolysis of 4-NP, and hence the production of 4-NC, is occurring at significant rates within the snowpack where 4-NC is inevitably released to downstream catchment areas via snowmelt. 4-NC is significantly more toxic than its precursor, thereby raising amplified concerns for downstream human and wildlife populations. Furthermore, the ubiquity of 4-NP among the Earth's environments presents this as an issue of potentially global concern.