Publications

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2017
Kumar, A, Borgen M, Aluwihare LI, Fenical W.  2017.  Ozone-activated halogenation of mono- and dimethylbipyrrole in seawater. Environmental Science & Technology. 51:589-595.   10.1021/acs.est.6b03601   AbstractWebsite

Polyhalogenated N-methylbipyrroles of two different structure classes have been detected worldwide in over 100 environmental samples including seawater, bird eggs, fish, dolphin blubber, and in the breast milk of humans that consume seafood. These molecules are concentrated in the fatty tissues in comparable abundance to some of the most important anthropogenic contaminants, such as the halogenated flame-retardants and pesticides. Although the origin of these compounds is still unknown, we present evidence that the production of these materials can involve the direct ozone activated seawater halogenation of N-methylbipyrrole precursors. This observation shows that environmental polyhalogenated bipyrroles can be produced via an abiotic process, and implies that the ozone activated halogenation of a variety of natural and anthropogenic seawater organics may be a significant process occurring in surface ocean waters.

2015
Arakawa, N, Aluwihare L.  2015.  Direct identification of diverse alicyclic terpenoids in Suwannee River fulvic acid. Environmental Science & Technology. 49:4097-4105.   10.1021/es5055176   AbstractWebsite

The chemical complexity of dissolved organic matter (DOM) obstructs our ability to definitively recover source compounds from within DOM, an objective which has the capacity to alter our understanding, of carbon sequestration on a. global scale. To advance compositional studies of DOM we have applied a previously published reduction method to an environmental standard, Suwannee River Fulvic Acid (SRFA). The reduction products, comprising 12% of the prereduced carbon, were then separated by comprehensive two-dimensional gas chromatography time-of-flight mass spectrometry (GCXGC-TOF-MS). estilts indicate that the majority of obsetved reduced compounds corresponded to alicyclic hydrocarbons in the size range C-10 to C-17. Cyclic terpenoids are the only biomolecule class with contiguous, alicyclic carbon backbones of this size. These terpenoid reduction products contain series offset by CH2 and exhibit great isomeric diversity, features previously inferred from ultrahigh resolution mass spectrometry and NMR studies of unreduced SRFA. Reduction of Taxodium leaf litter as a Source material to SRFA confirmed the prevalence of tetpenoids in SRFA and provided insight into the parent compounds that must be diagenetically modified on relatively short time scales. These data corroborate several recent studies that suggest alicydic hydrocarbons to be important components of longer-lived DOM.

1999
Aluwihare, LI, Repeta DJ.  1999.  A comparison of the chemical characteristics of oceanic DOM and extracellular DOM produced by marine algae. Marine Ecology-Progress Series. 186:105-117.   10.3354/meps186105   AbstractWebsite

The chemical characteristics of extracellular high molecular weight (HMW) dissolved organic matter (DOM) from 3 species of marine phytoplankton were compared to HMW DOM in seawater. Thalassiosira weissflogii, Emiliania huxleyi and Phaeocystis sp., were grown in nutrient enriched seawater that had been previously ultrafiltered to remove HMW DOM. The extracellular HMW DOM produced in these cultures was isolated by ultrafiltration and characterized using nuclear magnetic resonance (NMR) spectroscopy, and molecular level analyses. All species exude DOM rich in polysaccharides, and the exudates of T. weissflogii and E. huxleyi closely resemble acyl heteropolysaccharides (APS) previously identified as major constituents of naturally occurring marine HMW DOM. Degradation of the T. weissflogii exudate alters the chemical composition of the DOM, which we attribute to differences in the reactivity of specific polysaccharides. The component within the exudate that most resembles seawater DOM has a slower degradation rate relative to the total polysaccharide fraction. Our study indicates that APS isolated from the surface ocean can have a direct algal source and that APS may accumulate in seawater as a result of its metabolic resistance.