Quantitative Separation of Unknown Organic–Metal Complexes by Liquid Chromatography–Inductively Coupled Plasma-Mass Spectrometry

Dewey, Christian; Kaplan, Daniel I.; Fendorf, Scott; Boiteau, Rene M.

doi:10.1021/acs.analchem.3c00696

Quantitative Separation of Unknown Organic–Metal Complexes by Liquid Chromatography–Inductively Coupled Plasma-Mass Spectrometry

Journal Article · Wed May 10 00:00:00 EDT 2023 · Analytical Chemistry

DOI:https://doi.org/10.1021/acs.analchem.3c00696· OSTI ID:2350669

^[1]; Kaplan, Daniel I. ^[2]; ^[3]; ^[4]

Oregon State Univ., Corvallis, OR (United States); Stanford Univ., CA (United States); Savannah River Ecology Laboratory - University of Georgia
Univ. of Georgia, Aiken, SC (United States). Savannah River Ecology Laboratory (SREL)
Stanford Univ., CA (United States)
Oregon State Univ., Corvallis, OR (United States)

Dissolved organic matter (DOM) is widely recognized to control the solubility and reactivity of trace metals in the environment. However, the mechanisms that govern metal-DOM complexation remain elusive, primarily due to the analytical challenge of fractionating and quantifying metal–organic species within the complex mixture of organic compounds that comprise DOM. Here, we describe a quantitative method for fractionation and element-specific detection of organic–metal complexes using liquid chromatography with online inductively coupled plasma mass spectrometry (LC–ICP-MS). The method implements a post-column compensation gradient to stabilize ICP–MS elemental response across the LC solvent gradient, thereby overcoming a major barrier to achieving quantitative accuracy with LC–ICP-MS. With external calibration and internal standard correction, the method yields concentrations of organic–metal complexes that were consistently within 6% of their true values, regardless of the complex’s elution time. We used the method to evaluate the effects of four stationary phases (C18, phenyl, amide, and pentafluoroylphenyl propyl) on the recovery and separation of environmentally relevant trace metals (Mn, Fe, Co, Ni, Cu, Zn, Cd, and Pb) in Suwannee River Fulvic Acid and Suwannee River Natural Organic Matter. The C18, amide, and phenyl phases generally yielded optimal metal recoveries (>75% for all metals except Pb), with the phenyl phase separating polar species to a greater extent than C18 or amide. We also fractionated organic-bound Fe, Cu, and Ni in oxidized and reduced soils, revealing divergent metal-DOM speciation across soil redox environments. Finally, by enabling quantitative fractionation of DOM-bound metals, our method offers a means for advancing a mechanistic understanding of metal–organic complexation throughout the environment.

View Accepted Manuscript (DOE)

Research Organization:: Savannah River Site (SRS), Aiken, SC (United States). Savannah River Ecology Laboratory (SREL)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Environmental Management (EM)

Grant/Contract Number:: EM0005228; SC0020205; AC02-06CH11357

OSTI ID:: 2350669

Journal Information:: Analytical Chemistry, Journal Name: Analytical Chemistry Journal Issue: 20 Vol. 95; ISSN 0003-2700

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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