Nelson W. Green

Impacts of diverted freshwater on dissolved organic matter and microbial communities in Barataria Bay, Louisiana, U.S.A.

Here we present results of an initial assessment of the impacts of a water diversion event on the concentrations and chemical composition of dissolved organic matter (DOM) and bacterioplankton community composition in Barataria Bay, Louisiana U.S.A, an important estuary within the Mississippi River Delta complex. Concentrations and spectral properties of DOM, as reflected by UV/visible absorbance and fluorescence, were strikingly similar at 26 sites sampled along transects near two western and two eastern areas of Barataria Bay in July and September 2010. In September 2010, dissolved organic carbon (DOC) was significantly higher (568.1-1043 μM C, x=755.6+/-117.7 μM C, n=14) than in July 2010 (249.1-577.1 μM C, x=383.7+/-98.31 μM C, n=14); conversely, Abs254 was consistently higher at every site in July (0.105-0.314) than in September (0.080-0.221), averaging 0.24±0.06 in July and 0.15±0.04 in September. Fluorescence data via the fluorescence index (FI450/500) revealed that only 30% (8 of 26) of the July samples had an FI450/500 above 1.36, compared to 96% (25 of 26) for the September samples. This indicates a more terrestrial origin for the July DOM. Bacterioplankton from eastern sites differed in composition from bacterioplankon in western sites in July. These differences appeared to result from reduced salinities caused by the freshwater diversion. Bacterioplankton communities in September differed from those in July, but no spatial structure was observed. Thus, the trends in bacterioplankton and DOM were likely due to changes in water masses (e.g., input of Mississippi River water in July and a return to estuarine waters in September). Discharge of water from the Davis Pond Freshwater Diversion (DPFD) through Barataria Bay may have partially mitigated some adverse effects of the oil spill, inasmuch as DOM is concerned.

Characteristics of dissolved organic matter (DOM) and relationship with dissolved mercury in Xiaoqing River-Laizhou Bay estuary, Bohai Sea, China

Because of heterogeneous properties, dissolved organic matter (DOM) is known to control the environmental fate of a variety of organic pollutants and trace metals in aquatic systems. Here we report absorptive and fluorescence properties of DOM, in concurrence with concentrations of dissolved mercury (Hg), along the Xiaoqing River-Laizhou Bay estuary system located in the Bohai Sea of China. A mixing model consisting of the two end-members terrestrial and aquatic DOM demonstrated that terrestrial signatures decreased significantly from the river into the estuary. Quasi-conservative mixing behavior of DOM sources suggests that the variations in the average DOM composition were governed by physical processes (e.g., dilution) rather than by new production and/or degradation processes. In contrast to some previous studies of river-estuary systems, the Xiaoqing River-Laizhou Bay estuary system displayed a non-significant correlation between DOM and Hg quantities. Based on this and the variation of Hg concentration along the salinity gradient, we concluded that Hg showed a non-conservative mixing behavior of suggested end-member sources. Thus, rather than mixing, Hg concentration variations seemed to be controlled by biogeochemical processes.

Fast Graphically Inspired Algorithm for Assignment of Molecular Formulae in Ultrahigh Resolution Mass Spectrometry

This study focuses on the deterministic task of assigning molecular formulae to exact masses that are generated by ultrahigh resolution mass spectrometry. A new algorithm based on low-mass moieties (LMMs) such as CH4O(-1) and C4O(-3) completely replaces conventional computational loops that explore a user-defined range of C, H, and O when searching for molecular formulae that have a given exact mass. The LMM-based algorithm has been coupled with a combinatorial algorithm that uses nested loops for N, P, S, and (13)C to assign molecular formulae. The resulting program is more than 1700 times faster than its brute-force counterpart that uses nested loops for all elements, and both programs yield identical output files. The new LMM-based program is 1050 times faster than the open-source program HR2, 60 times faster than Molecular Formula Calculator, and 3.6 times faster than MassCalc/FormCalc.

Underestimation of phosphorus fraction change in the supernatant after phosphorus adsorption onto iron oxides and iron oxide–natural organic matter complexes

The phosphorus (P) fraction distribution and formation mechanism in the supernatant after P adsorption onto iron oxides and iron oxide-humic acid (HA) complexes were analyzed using the ultrafiltration method in this study. With an initial P concentration of 20mg/L (I=0.01mol/L and pH=7), it was shown that the colloid (1kDa-0.45μm) component of P accounted for 10.6%, 11.6%, 6.5%, and 4.0% of remaining total P concentration in the supernatant after P adsorption onto ferrihydrite (FH), goethite (GE), ferrihydrite-humic acid complex (FH-HA), goethite-humic acid complex (GE-HA), respectively. The <1kDa component of P was still the predominant fraction in the supernatant, and underestimated colloidal P accounted for 2.2%, 55.1%, 45.5%, and 38.7% of P adsorption onto the solid surface of FH, FH-HA, GE and GE-HA, respectively. Thus, the colloid P could not be neglected. Notably, it could be interpreted that Fe3+ hydrolysis from the adsorbents followed by the formation of colloidal hydrous ferric oxide aggregates was the main mechanism for the formation of the colloid P in the supernatant. And colloidal adsorbent particles co-existing in the supernatant were another important reason for it. Additionally, dissolve organic matter dissolved from iron oxide-HA complexes could occupy large adsorption sites of colloidal iron causing less colloid P in the supernatant. Ultimately, we believe that the findings can provide a new way to deeply interpret the geochemical cycling of P, even when considering other contaminants such as organic pollutants, heavy metal ions, and arsenate at the sediment/soil-water interface in the real environment.

Influence of dissolved organic matter (DOM) characteristics on dissolved mercury (Hg) species composition in sediment porewater of lakes from southwest China

The origin and composition of dissolved organic matter (DOM) in porewater of lake sediments is intricate and decisive for fate of pollutants including mercury (Hg). While there are many reports on the relationship between dissolved organic carbon concentration (DOC) and mercury (Hg) concentrations in aquatic systems, there are few in which DOM compositional properties, that may better explain the fate of Hg, have been the focus. In this study, porewaters from sediments of three lakes, Caihai Lake (CH), Hongfeng Lake (HF) and Wujiangdu Lake (WJD), all located in southwest China, were selected to test the hypothesis that DOM optical properties control the fate of Hg in aquatic ecosystems. Porewater DOM was extracted and characterized by UV-Vis absorption and fluorescence spectroscopy. A two end-member (autochthonous and allochthonous DOM) mixing model was used to unveil the origin of DOM in porewaters of the three lakes. Our results show a higher input of terrestrial DOM in the pristine lake CH, as compared to lakes HF and WJD lakes, which were both influenced by urban environments and enriched in autochthonous DOM. While the relationships between the concentrations of DOC and the different chemical forms of Hg forms were quite inconsistent, we found important links between specific DOM components and the fate of Hg in the three lakes. In particular, our results suggest that allochthonous, terrestrial DOM inhibits Hg(II) availability for Hg methylating micro-organisms. In contrast, autochthonous DOM seems to have been stimulated MeHg formation, likely by enhancing the activity of microbial communities. Indeed, DOM biodegradation experiments revealed that differences in the microbial activity could explain the variation in the concentration of MeHg. While relationships between concentrations of DOC and Hg vary among different sites and provide little information about Hg cycling, we conclude that the transport and transformation of Hg (e.g. the methylation process) are more strongly linked to DOM chemical composition and reactivity.