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.

Composition of dissolved organic matter (DOM) from periodically submerged soils in the Three Gorges Reservoir areas as determined by elemental and optical analysis, infrared spectroscopy, pyrolysis-GC-MS and thermally assisted hydrolysis and methylation.

Soil-derived dissolved organic matter (DOM) has a major influence in biogeochemical processes related to contaminant dynamics and greenhouse gas emissions, due to its reactivity and its bridging role between the soil and aquatic systems. Within the Three Gorges Reservoir (TGR, China) area, an extensive water-fluctuation zone periodically submerges the surrounding soils. Here we report a characterization study of soil-derived DOM across the TGR areas, using elemental and optical analysis, infrared spectroscopy (FTIR), pyrolysis-GC-MS (Py-GC-MS) and thermally assisted hydrolysis and methylation (THM-GC-MS). The results showed that the soil DOM from the TGR area is a mixture of "allochthonous" (i.e., plant-derived/terrigenous) and "autochthonous" (i.e., microbial) origins. The terrigenous DOM is composed primarily of phenolic and aliphatic structures from lignin and aliphatic biopolymers (i.e. cutin, suberin), respectively. Multivariate statistics differentiated between two fractions of the microbial DOM, i.e. chitin-derived, perhaps from fungi and arthropods in soil, and protein-derived, partially sourced from algal or aquatic organisms. Molecular proxies of source and degradation state were in good agreement with optical parameters such as SUVA254, the fluorescence index (FI) and the humification index (HIX). The combined use of elemental analysis, fluorescence spectroscopy, and Py-GC-MS provides rigorous and detailed DOM characterization, whereas THM-GC-MS is useful for more precise but qualitative identification of the different phenolic (cinnamyl, p-hydroxyphenyl, guaiacyl, syringyl and tannin-derived) and aliphatic materials. With the multi-methodological approach used in this study, FTIR was the least informative, in part, because of the interference of inorganic matter in the soil DOM samples. The soil DOM from the TGR's water fluctuation zone exhibited considerable compositional diversity, mainly related to the balance between DOM source (microbial- or plant-derived), local vegetation and anthropogenic activities (e.g., agriculture). Finally, the relationship between DOM composition and its potential reactivity with substances of environmental concerns in the TGR area are also discussed.

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.

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.

Isobaric molecular formulae of C, H, and O: a view from the negative quadrants of van Krevelen space.

When compositions of an isobaric series of molecular formulae consisting of C, H, and O are displayed in a van Krevelen plot, a remarkable number of nonparallel lines of compositions can be observed. Each group of related lines converge at a point in a negative quadrant of van Krevelen space (e.g., H/C = 4, O/C = -1). These points of convergence have H/C and O/C ratios that correspond to "molecular formulae" in which the stoichiometric coefficients of some of the isotopes are negative. In this manner, a group of related low-mass moieties have been identified (CH4O(-1), C4O(-3), C2H(-8)O(-1), CH(-12), etc.). Each of these moieties has a nominal mass of zero and a very small exact mass. Furthermore, all of these low-mass moieties have compositions that fall on the line H/C = -12 - 16(O/C), which lies entirely in the negative quadrants of van Krevelen space. This paper demonstrates that all low-mass moieties consisting of C, H, and O can be expressed formally as linear combinations of any two moieties. Likewise, all molecular formulae that fall on a line that passes through a given low-mass moiety must differ compositionally by a multiple of the composition of that moiety, and their exact masses must differ by a multiple of the exact mass of the moiety. This latter relationship has been invoked for very rapid assignment of a molecular formula to an exact mass. Finally, a more comprehensive and theoretically based understanding of family scores has been developed around the concept of low-mass moieties.