Complexation of trace organic contaminants with fractionated dissolved organic matter: Implications for mass spectrometric quantification

Selene Hernandez Ruiz, Samanthi Wickramasekara, Leif Abrell, Xiaodong Gao, Benny Chefetz, Jon Chorover*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

31 Scopus citations


Interaction with aqueous phase dissolved organic matter (DOM) can alter the fate of trace organic contaminants of emerging concern once they enter the water cycle. In order to probe possible DOM binding mechanisms and their consequences for contaminant detection and quantification in natural waters, a set of laboratory experiments was conducted with aqueous solutions containing various operationally-defined "hydrophilic" and "hydrophobic" freshwater DOM fractions isolated by resin adsorption techniques from reference Suwannee River natural organic matter (SROM). Per unit mass of SROM carbon, hydrophobic acids (HoA) comprised the largest C fraction (0.63±0.029), followed by hydrophilic-neutrals (HiN, 0.11±0.01) and acids (HiA, 0.09±0.017). Aqueous solutions comprising 8mgL-1 DOC of each SROM fraction were spiked with a concentration range (10-1000μgL-1) of bisphenol A (BPA), carbamazepine (CBZ), or ibuprofen (IBU) as model target compounds in 24mM NH4HCO3 background electrolyte at pH 7.4. Contaminant interaction with the SROM fractions was probed using fluorescence spectroscopy, and effects on quantitative analysis of the target compounds were measured using direct aqueous-injection liquid chromatography tandem mass spectrometry (LC-MS/MS). Total quenching was greater for the hydrophilic fractions of SROM and associations were principally with protein-like and fulvic acid-like constituents. Whereas LC-MS/MS recoveries indicated relatively weak interactions with most SROM factions, an important exception was the HiA fraction, which diminished recovery of CBZ and IBU by ca. 30% and 70%, respectively, indicating relatively strong molecular interactions.

Original languageAmerican English
Pages (from-to)344-350
Number of pages7
Issue number3
StatePublished - Apr 2013

Bibliographical note

Funding Information:
Research support was provided by the Binational Agricultural Research and Development (BARD) fund, Grant # IS-3822-06 , the Water Research Foundation (Award #4269) and the University of Arizona Water Sustainability Program. The comments and views detailed herein may be necessarily reflecting the views of the Water Research Foundation, its officers, directors, affiliates, or agents. Analyses in the ALEC were supported by NSF Grant CBET-0722579.


  • EDC
  • Fluorescence quenching
  • LC-MS/MS
  • PPCP
  • Suwannee River natural organic matter


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