Supramolecular Answers to the Organic Matter Controversy

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Abstract
The foundation of separation science is the division or deconvolution of a mixture into constituent parts. To do so greatly informs our understanding of complex systems. Equally important is consideration of the behavior of a mixture as a whole—to consider if the whole is the sum of the parts or if individual components interact synergistically or antagonistically when combined. Application of separation science has seldom assumed greater importance than in consideration of the controversy surrounding the traditional and emergent views of the complex chemical system of natural organic matter (NOM). Analyses of simulated and actual environmental water samples using noninvasive separation techniques including flow field‐flow fractionation (flow FFF), excitation–emission matrix (EEM) fluorescence spectroscopy with parallel factor (PARAFAC) analyses, and dynamic light scattering (DLS) are discussed. The data are used to explore whether a distinct chemical category of humic (diagenetic) substances exists in NOM; whether separation of organic matter into fulvic and humic extracts has relevant meaning translatable to actual environmental water samples; whether extraction procedures alter the chemistry of NOM extracts; and, if humic and fulvic acids exist, what physicochemical property or properties make humic substances unique among other forms of NOM. A fluorescence‐based nonoperational definition of humic substances is introduced. The underexplored role of supramolecular, self‐assembled aggregation is presented as a NOM conceptual model. Responses are provided to questions raised in the great NOM debate within a supramolecular context.Core Ideas: A new supramolecular conceptual model invokes strong near‐covalent hydrogen bonding. A nonoperational definition of diagenetic (humic) substances is proposed. Alkali extracts are valid, though imperfect, organic matter proxies. A mechanism for intrinsic chemical recalcitrance of natural organic matter exists. Protection is a “function” of the supramolecular “form.”

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