Discovery of Polar Ozonation Byproducts via Direct Injection of Effluent Organic Matter with Online LC-FT-ICR-MS.
Elaine K JenningsArina KremserLimei HanThorsten ReemtsmaOliver Jens LechtenfeldPublished in: Environmental science & technology (2022)
Effluent organic matter (EfOM), a major ozone consumer during wastewater ozonation, is a complex mixture of natural and anthropogenic organic molecules. Ozonation of EfOM adds to molecular complexity by introducing polar and potentially mobile ozonation byproducts (OBPs). Currently, nontargeted direct infusion (DI) ultrahigh resolution mass spectrometry (e.g. FT-ICR-MS) is used to study OBPs but requires sample extraction, limiting the accessible polarity range of OBPs. To better understand the impact of ozonation on EfOM and the formation of polar OBPs, nonextracted effluent was analyzed by direct injection onto a reversed-phase liquid chromatography system (RP-LC) online hyphenated with an FT-ICR-MS. Over four times more OBPs were detected in nonextracted EfOM compared to effluent extracted with solid phase extraction and measured with DI-FT-ICR-MS (13817 vs 3075). Over 1500 highly oxygenated OBPs were detected exclusively in early eluting fractions of nonextracted EfOM, indicating polar OBPs. Oxygenation of these newly discovered OBPs is higher than previously found, with an average molecular DBE-O value of -3.3 and O/C ratio of 0.84 in the earliest eluting OBP fractions. These polar OBPs are consistently lost during extraction but may play an important role in understanding the environmental impact of ozonated EfOM. Moreover, 316 molecular formulas classified as nonreactive to ozone in DI-FT-ICR-MS can be identified with LC-FT-ICR-MS as isomers with varying degrees of reactivity, providing for the first time experimental evidence of differential reactivity of complex organic matter isomers with ozone.
Keyphrases
- mass spectrometry
- liquid chromatography
- organic matter
- high resolution mass spectrometry
- solid phase extraction
- high performance liquid chromatography
- tandem mass spectrometry
- gas chromatography
- wastewater treatment
- simultaneous determination
- ultra high performance liquid chromatography
- capillary electrophoresis
- multiple sclerosis
- anaerobic digestion
- high resolution
- ionic liquid
- ms ms
- molecularly imprinted
- liquid chromatography tandem mass spectrometry
- health information
- particulate matter
- drinking water
- social media
- small molecule
- hydrogen peroxide
- gas chromatography mass spectrometry
- single molecule
- healthcare
- biofilm formation
- low dose
- nitric oxide
- single cell
- high throughput
- cystic fibrosis
- risk assessment