Interactions Of Dissolved Organic Matter Research Articles

Microbial degradation of dissolved organic matter (DOM) and its influence on phenanthrene–DOM interactions

Microbial degradation-induced changes in the characteristics of dissolved organic matter (DOM), and the subsequent effects on phenanthrene–DOM interactions were investigated based on the microbial incubation of DOM collected from four different sources for 28 d. Partially biodegraded DOM presented higher specific UV absorbance (SUVA), lower protein-like fluorescence, higher humic-like fluorescence, lower aliphatic carbon fraction, and higher hydrophobic neutral fractions compared to the original DOM. Microbial changes in DOM led to an increase in the isotherm nonlinearity as well as the extent of phenanthrene binding. A negative relationship between SUVA and the Freundlich n values was established for the original and the biodegraded DOM, suggesting that aromatic condensed structures may play important roles in providing nonlinear strong binding sites irrespective of microbial degradation. In contrast, there were two separate slopes of the correlations between the percentage of hydrophobic acid (HoA) fraction and the n values for the original and the biodegraded DOM with a higher slope exhibited for the latter, implying that the microbial utilization of oxygen-containing structures in the HoA fractions may contribute to enhancing the associated isotherm nonlinearity.

Changes in water extractable organic matter during incubation of forest floor material in the presence of quartz, goethite and gibbsite surfaces

The release of dissolved organic matter (DOM) from forest floor material constitutes a significant flux of C to the mineral soil in temperate forest ecosystems, with estimates on the order of 120–500 kg C ha −1 year −1. Interaction of DOM with minerals and metals results in sorptive fractionation and stabilization of OM within the soil profile. Iron and aluminum oxides, in particular, have a significant effect on the quantity and quality of DOM transported through forest soils due to their high surface area and the toxic effects of dissolved aluminum on microbial communities. We directly examined these interactions by incubating forest floor material, including native microbiota, for 154 days in the presence of (1) goethite (α-FeOOH), (2) gibbsite (γ-Al(OH) 3), and (3) quartz (α-SiO 2) sand (as a control). Changes in molecular and thermal properties of water extractable organic matter (WEOM, as a proxy for DOM) were evaluated. WEOM was harvested on days 5, 10, 20, 30, 60, 90, and 154, and examined by thermogravimetry/differential thermal analysis (TG/DTA) and diffuse reflectance Fourier transform infrared (DRIFT) spectroscopy. Results indicated significant differences in WEOM quality among treatments, though the way in which oxide surfaces influenced WEOM properties did not seem to change significantly with increasing incubation time. Dissolved organic C concentrations were significantly lower in WEOM from the oxide treatments in comparison to the control treatment. Incubation with goethite produced WEOM with mid-to-high-range thermal lability that was depleted in both protein and fatty acids relative to the control. The average enthalpy of WEOM from the goethite treatment was significantly higher than either the gibbsite or control treatment, suggesting that interaction with goethite surfaces increases the energy content of WEOM. Incubation with gibbsite produced WEOM rich in thermally recalcitrant and carboxyl-rich compounds in comparison to the control treatment. These data indicate that interaction of WEOM with oxide surfaces significantly influences the composition of WEOM and that oxides play an important role in determining the biogeochemistry of forest soil DOM.

The effect of ionic strength and pH on the stability of tannic acid-facilitated carbon nanotube suspensions

Carbon nanotubes (CNTs) are prone to aggregation and precipitation in water due to their high hydrophobicity and aspect ratio. However, the addition of dissolved organic matter (DOM) has been reported to disperse and stabilize certain CNTs, suggesting the potential transport and bioavailability of CNTs in natural aqueous environments. For a better understanding of the CNT–DOM interaction, five multiwalled CNTs with outer diameters of <10 (MWCNT10), 10–20 (MWCNT20), 20–40 (MWCNT40), 40–60 (MWCNT60), and 60–100 nm (MWCNT100) were used to investigate their sorptive and suspension behavior in tannic acid (TA, as a DOM surrogate) solution; the effects of ionic strength and pH on the TA–CNT interaction were examined. Suspension of MWCNTs sharply improved with increasing TA concentration and leveled off at an initial TA concentration ca. 20 mg/L. Suspension of MWCNTs was in the order of MWCNT40 > MWCNT60 > MWCNT20 > MWCNT100 > MWCNT10. The TA-stabilized CNTs were stable within pH 5–11, while they quickly precipitated at pH < 5. Different ions (Na +, Mg 2+, Ca 2+, or La 3+) aggregated the stabilized CNTs, with a critical coagulation concentration exponentially correlated to ionic valence. Changes of steric repulsion and electrostatic interaction with the added TA could account for the variation of CNT stability.

Interactions of diuron with dissolved organic matter from organic amendments

Diuron is frequently detected in some drinking water reservoirs under the Burgundy vineyards, where organic amendments are applied. The environmental effect of these amendments on pesticide transport is ambiguous: on the one hand it could enhance their retention by increasing soil organic carbon content; on the other hand, dissolved organic matter (DOM) could facilitate their transport. Elutions were performed using columns packed with glass beads in order to investigate DOM–diuron interactions, and the possible co-transport of diuron and DOM. Four organic amendments (A, B, C and D) were tested; C and D were sampled at fresh (F) and mature (M) stages. An increase in diuron leaching was observed only for A and D F amendments (up to 16% compared to the DOM-free blank samples), suggesting a DOM effect on diuron transport. These results could be explained by the higher DOM leaching for A and D F compared to B, C F, C M and D M increasing diuron–DOM interactions. These interactions seem to be related to the aromatic and aliphatic content of the DOM, determining formation of hydrogen and non-covalent bonds. The degree of organic matter maturity does not seem to have any effect with amendment C, while a reduction in diuron leaching is observed between D F and D M. After equilibrium dialysis measurement of diuron–DOM complexes, it appeared that less than 3% of the diuron applied corresponded to complexes with a molecular weight > 1000 Da. Complexes < 1000 Da could also take part in this facilitated transport.

Characterizing the Interactions between Trace Metals and Dissolved Organic Matter Using Excitation−Emission Matrix and Parallel Factor Analysis

Natural dissolved organic matter (DOM) is composed of a variety of organic compounds, which can interact with metals in aquatic environments. The interactions between DOM and two metals of environmental concern (Cu(II) and Hg(II)) were studied using fluorescence quenching titrations combined with excitation-emission matrix (EEM) spectra and parallel factor analysis (PARAFAC). This allowed characterizing the specific interactions between eight fluorescent components in DOM and two metals. Triplicate titration experiments showed good reproducibility when assessing the interactions between humic-like components with Cu(ll). Our data show clear differences in metal-DOM interaction for samples of different DOM composition and between two different metals. The results demonstrate that the combination of fluorescence quenching titrations with EEM-PARAFAC was reproducible and sensitive to determine the binding properties of humic-like components with trace metals. The enhancement in fluorescence intensity after its initial decrease for the protein-like components with addition of Cu(II) was observed at mangrove-dominated sites, suggesting changes in the molecular environments of protein-like components due to increased Cu(II) interaction. The application of EEM-PARAFAC in fluorescence quenching studies is a useful tool to evaluate intermolecular DOM and DOM-trace metals interactions.

Investigating interactions of phenanthrene with dissolved organic matter: Limitations of Stern–Volmer plot

Although linear binding isotherms of hydrophobic organic chemicals (HOCs) with dissolved organic matter (DOM) are widely reported, several studies showed nonlinear HOC–DOM interactions. This study pointed out that fluorescence static quenching modeling (FSQM), which often uses a Stern–Volmer type plot to process the data from fluorescence quenching experiments, is conceptually different from the classic Stern–Volmer equation. We also emphasized that although linear Stern–Volmer plots are generally observed in literature, it does not necessarily indicate a linear HOC–DOM interaction. According to both mathematical simulation and laboratory sorption experiments in this study, nonlinear interactions could be concealed by the use of Stern–Volmer plot. Moreover, this study tested the two assumptions for applying FSQM to process binding data. Our results showed that binding coefficient ( K DOC) for phenanthrene is neither independent of free solute concentration, nor DOM concentration, which is a critical limitation for using FSQM in a form of Stern–Volmer equation to examine HOC–DOM interactions. Therefore, the true characteristics of HOC–DOM interactions need to be examined using different ways of experimental design and data processing.

Investigating sorption-driven dissolved organic matter fractionation by multidimensional fluorescence spectroscopy and PARAFAC

Soil organic matter is involved in many ecosystem processes, such as nutrient supply, metal solubilization, and carbon sequestration. This study examined the ability of multidimensional fluorescence spectroscopy and parallel factor analysis (PARAFAC) to provide detailed chemical information on the preferential sorption of higher-molecular-weight components of natural organic matter onto mineral surfaces. Dissolved organic matter (DOM) from soil organic horizons and tree leaf tissues was obtained using water extracts. The suite of fluorescence spectra was modeled with PARAFAC and it was revealed that the DOM extracts contained five fluorescing components: tryptophan-like (peak location at excitation <255 nm:emission 342 nm), tyrosine-like (276 nm:312 nm), and three humic-substance-like components (<255 nm:456 nm, 309 nm:426 nm, <255 nm:401 nm). In general, adsorption onto goethite and gibbsite increased with increasing DOM molecular weight and humification. PARAFAC analysis of the pre- and post-sorption DOM indicated that the ordering of sorption extent was humic-like components (average 91% sorption) > tryptophan-like components (52% sorption) > tyrosine-like components (29% sorption). This differential sorption of the modeled DOM components in both the soil organic horizon and leaf tissue extracts led to the fractionation of DOM. The results of this study demonstrate that multidimensional fluorescence spectroscopy combined with PARAFAC can quantitatively describe the chemical fractionation process due to the interaction of DOM with mineral surfaces.

Dissolution of cinnabar (HgS) in the presence of natural organic matter

Cinnabar (HgS) dissolution rates were measured in the presence of 12 different natural dissolved organic matter (DOM) isolates including humic, fulvic, and hydrophobic acid fractions. Initial dissolution rates varied by 1.3 orders of magnitude, from 2.31 × 10 −13 to 7.16 × 10 −12 mol Hg (mg C) −1 m −2s −1. Rates correlate positively with three DOM characteristics: specific ultraviolet absorbance (R 2 = 0.88), aromaticity (R 2 = 0.80), and molecular weight (R 2 = 0.76). Three experimental observations demonstrate that dissolution was controlled by the interaction of DOM with the cinnabar surface: (1) linear rates of Hg release with time, (2) significantly reduced rates when DOM was physically separated from the surface by dialysis membranes, and (3) rates that approached constant values at a specific ratio of DOM concentration to cinnabar surface area, suggesting a maximum surface coverage by dissolution-reactive DOM. Dissolution rates for the hydrophobic acid fractions correlate negatively with sorbed DOM concentrations, indicating the presence of a DOM component that reduced the surface area of cinnabar that can be dissolved. When two hydrophobic acid isolates that enhanced dissolution to different extents were mixed equally, a 20% reduction in rate occurred compared to the rate with the more dissolution-enhancing isolate alone. Rates in the presence of the more dissolution-enhancing isolate were reduced by as much as 60% when cinnabar was prereacted with the isolate that enhanced dissolution to a lesser extent. The data, taken together, imply that the property of DOM that enhances cinnabar dissolution is distinct from the property that causes it to sorb irreversibly to the cinnabar surface.

Dissolved organic matter in small streams along a gradient from discontinuous to continuous permafrost

AbstractThe Yenisei river passes every type of permafrost regime, from south to north, being characterized by increasing continuity of the permafrost and by decreasing thickness of the active layer. We used that situation to test the hypothesis that amounts and properties of dissolved organic matter (DOM) in small streams draining forested catchments respond to different permafrost regimes. Water samples were taken from eight tributaries along the Yenisei between 67°30′N and 65°49′N latitude. The samples were analysed for dissolved organic carbon (DOC) and nitrogen (DON) and DOM was characterized by its chemical composition (XAD‐8 fractionation, sugars, lignin phenols, amino acids, protein, UV and fluorescence spectroscopy), and its biodegradability. Most properties of the tributary waters varied depending on latitude. The higher the latitude, the higher were DOC, DON and the proportion of the hydrophobic fraction of DOC. The contribution of hexoses and pentoses to DOC were higher in southern tributaries; on the other hand, phenolic compounds were more abundant in northern tributaries. Mineralizable DOC ranged between 4% and 28% of total DOC. DOM in northern tributaries was significantly (P&lt;0.05) less biodegradable than that in southern tributaries reflecting the differences in the chemical properties of DOM. Our results suggest that the differences in DOM properties are mainly attributed to differences of permafrost regime, affecting depth of active layer, soil organic matter accumulation and vegetation. Soil organic matter and vegetation determine the amount and composition of DOM produced in the catchments while the depth of the active layer likely controls the quantity and quality of DOM exported to streams. Sorptive interactions of DOM with the soil mineral phase typically increase with depth. The results imply that a northern shift of discontinuous permafrost likely will change in the long term the input of DOM into the Yenisei and thus probably into the Kara Sea.

Evidence for organically associated iron in nearshore pore fluids

The role of dissolved organic matter (DOM) in the speciation of trace metals in natural waters is poorly understood1–3. Although dissolved organic matter–iron associations have been observed in freshwater systems4–6, it has been thought that DOM–iron species are not significant in saline waters7. Yet recent studies have suggested that iron–DOM interactions in the pore waters of anoxic marine sediments may be important8,9. The possibility of organically associated trace metals in anoxic water has been used to explain why metal concentrations are higher than those predicted by sulphide-mineral equilibria10,11. We present here data that indicate that strong iron–DOM associations do occur in the anoxic pore waters of nearshore marine sediments and that both the total dissolved iron and organically associated iron change seasonally.