Aquatic Dissolved Organic Matter Research Articles

Characterization of Low-Molecular-Weight Dissolved Organic Matter Using Optional Dialysis and Orbitrap Mass Spectrometry.

Low-molecular-weight (LMW, <1000 Da) dissolved organic matter (DOM) plays a significant role in metal/organic pollutant complexation, as well as photochemical/microbiological processes in freshwater ecosystems. The micro size and high reactivity of LMW-DOM hinder its precise characterization. In this study, Suwannee River fulvic acid (SRFA), a commonly used reference material for aquatic DOM, was applied to examine the optical features and molecular composition of LMW-DOM by combining membrane separation, ultraviolet-visible absorption and Orbitrap mass spectrometry (MS) characterization. The 100-500 Da molecular weight cut-off (MWCO) membrane had a better performance in regard to separating the tested LMW-DOM relative to the 500-1000 Da MWCO membrane. The ultraviolet-visible absorbance decreased dramatically for the retentates, whereas it increased for the dialysates. Specifically, carbohydrates, lipids and peptides exhibited high selectivity to the 100-500 Da MWCO membrane in early dialysis. Lignins, tannins and condensed aromatic molecules displayed high permeability to the 500-1000 Da MWCO membrane in late dialysis. Overall, the retentates were dominated by aromatic rings and phenolic hydroxyls with high O/Cwa (weighted average of O/C) and low H/Cwa. Conversely, such dialysates had numerous aliphatic chains with high H/Cwa and low O/Cwa compared to SRFA. In particular, LMW-DOM below 200 Da was identified by Orbitrap MS. This work provides an operational program for identifying LMW-DOM based on the SRFA standard and MS analysis.

Dynamic Changes of Dissolved Organic Matter Derived from Algal Decomposition and the Environmental Effects in Eutrophic Lakes

The global occurrences of lake eutrophication have led to algal bloom and the subsequent algal decomposition, releasing high amounts of algae-derived dissolved organic matter (DOM) into the lake water. Algae-derived DOM could regulate the quantity and composition of DOM in lake water and further impact the biogeochemical cycles of multiple elements. In this study, the dynamic changes in the quantity and quality of DOM during algal decomposition under different eutrophic scenarios (e.g., from oligotrophication to severe eutrophication) were monitored, and the corresponding environmental effects (e.g., microbial responses and greenhouse gas emissions) caused by algal decomposition were further explored. The results showed that algal decomposition significantly increased the DOM levels, bioavailability, and intensities of fluorescent components in the water. The total DOM levels gradually decreased, whereas the average molecular weight increased along the decomposition process. Furthermore, unsaturated hydrocarbon and aliphatic compounds were preferentially utilized by microorganisms during algal decomposition, and some refractory molecules (e.g., lignin, condensed hydrocarbons, and tannin with high O/C values) were synchronously generated, as evidenced by the results from ultra-high-resolution mass spectrometry. The dominant bacterial species during algal decomposition shifted from Proteobacteria (46%) to Bacteroidetes (42%). In addition, algae addition resulted in 1.2-5 times the emissions of CO2 and CH4 from water, and the emission rates could be well predicted by the optical index of a254 in water. This study provides comprehensive perspectives for understanding the environmental behaviors of aquatic DOM and further paves the ways for the mitigation of lake eutrophication.

Photochemical processes transform dissolved organic matter differently depending on its initial composition

Dissolved organic matter (DOM) is one of the most important fluxes in the global carbon cycle but its response to light exposure remains unclear at a molecular-level. The chemical response of DOM to light should vary with its molecular composition and environmental conditions while some basic hypotheses are still unclear, such as the balance between photobleaching and photo-humification and the question of oxidative properties. Here we exposed aquatic DOM from diverse freshwaters impacted by different levels of anthropogenic activity and algal exudates to environmentally-realistic light conditions. We found that photobleaching occurred in DOM with relatively high initial humic content producing low H/C molecules, whereas DOM with low initial humic content was humified. DOM pools with relatively high initial saturation and low aromaticity were prone to transform towards more unsaturated molecular formulae and high H/C molecules with a distinct decrease of bioavailability. Photo-transformation was mainly influenced by reactive intermediates, with reactive oxygen species (ROS) playing a dominant role in humification when the initial humus content of DOM was high. In contrast, for algal DOM with high protein content, it was likely that the autoxidation of excited state DOM was more important than indirect oxidation involving ROS. Our results reveal how photo-transformation patterns depend on the initial composition of DOM and provide new insights into the role of photochemical processes in biogeochemical cycling of DOM.

Rethinking terrestrial dissolved organic matter in dam reservoirs before mixing: Linking photodegradation and biodegradation and the phenanthrene binding behavior

With the increased construction of dam reservoirs and the demand for water security, terrestrial dissolved organic matter (DOM) has received attention because of its role in regulating water quality, ecological functions, and the fate and transport of pollutants in dam reservoirs. This study investigated the transformations of soil DOM and vegetation DOM of dam reservoirs following photodegradation and biodegradation before conservative mixing, as well as the resultant effects on phenanthrene binding. Based on the results, terrestrial DOM could undergo transformation via photodegradation and biodegradation before conservative mixing in dam reservoirs. Although both processes resulted in substantial decreases in DOM concentrations, the changes in chromophoric DOM and fluorescent DOM depended on the original DOM sources. Furthermore, the photodegradation of terrestrial DOM resulted in more pronounced photobleaching than photomineralization. In addition, photodegradation of terrestrial DOM resulted in the generation of DOM-derived by-products with low molecular weight and low aromaticity, whereas the biodegradation of terrestrial DOM resulted in DOM-derived by-products with low molecular weight and high aromaticity. Subsequently, the photodegradation and biodegradation of terrestrial DOM substantially enhanced the binding affinity of phenanthrene. Soil DOM is prior to vegetation DOM when predicting the ecological risk of HOCs. These results indicate that the terrestrial DOM in dam reservoirs should be reconsidered before conservative mixing. Further studies on the coupling effects of both biogeochemical processes, as well as on the relative contributions of soil DOM and vegetation DOM after transformation to the aquatic DOM in dam reservoirs, are required. This study provides information on the environmental effects of dam construction from the perspective of biogeochemical processes.

Improved Predictions of Dissolved Organic Carbon–Water Partitioning and Unveiling the Chemodiversity of Dissolved Organic Matter

Dissolved organic matter (DOM) is a complex mixture of organic compounds with chemical heterogeneity in natural soils, sediments, and waters. Predicting the dissolved organic carbon (DOC)–water partition coefficients (KDOC) of organic pollutants to DOMs from various sources is important for assessing their fate and bioavailability. However, the accuracy of the recently developed polyparameter linear free energy relationship (pp-LFER) KDOC models is generally restricted by the small data set, inclusion of experimental data from unreliable measurement methods, or undefined selection standards. The aim of this study was to establish pp-LFER models for predicting the KDOC of nonionic organic chemicals to a variety of sources of DOMs and to get an understanding of DOM chemodiversity. A reliable and expanded experimental KDOC data set was compiled. Improved pp-LFER models were developed and assessed for All DOM (DOM from all sources), Aldrich humic acid (HA), Roth HA, soil porewater DOM, sediment porewater DOM, natural aquatic DOM, natural terrestrial DOM, natural DOM, and commercial DOM. The models developed in this study were reasonably robust and accurate with a root mean square error (RMSE) of 0.538 for the All DOM model and RMSE from 0.196 to 0.860 for the specific DOMs. Also, the models generally performed better than previously published ones. Moreover, the system parameters of the models well described the chemical variabilities between soil porewater DOM and sediment porewater DOM, between natural aquatic DOM and natural terrestrial DOM, and between natural DOM and commercial DOM regarding polarizability, dipolarity, H-bond-accepting and -donating ability, and cavity formation energy. This study provides effective tools to assess the tendencies of organic chemicals to DOMs and improves our understanding of the chemical heterogeneity of DOMs from different sources.

High Voltage: The Molecular Properties of Redox-Active Dissolved Organic Matter in Northern High-Latitude Lakes.

Redox-active functional groups in dissolved organic matter (DOM) are crucial for microbial electron transfer and methane emissions. However, the extent of aquatic DOM redox properties across northern high-latitude lakes and their relationships with DOM composition have not been thoroughly described. We quantified electron donating capacity (EDC) and electron accepting capacity (EAC) in lake DOM from Canada to Alaska and assessed their relationships with parameters from absorbance, fluorescence, and ultrahigh resolution mass spectrometry (FT-ICR MS) analyses. EDC and EAC are strongly tied to aromaticity and negatively related to aliphaticity and protein-like content. Redox-active formulae spanned a range of aromaticity, including highly unsaturated phenolic formulae, and correlated negatively with many aliphatic N and S-containing formulae. This distribution illustrates the compositional diversity of redox-sensitive functional groups and their sensitivity to ecosystem properties such as local hydrology and residence time. Finally, we developed a reducing index (RI) to predict EDC in aquatic DOM from FT-ICR MS spectra and assessed its robustness using riverine DOM. As the hydrology of the northern high-latitudes continues to change, we expect differences in the quantity and partitioning of EDC and EAC within these lakes, which have implications for local water quality and methane emissions.

Molecular-level insights into the heterogeneous variations and dynamic formation mechanism of leached dissolved organic matter during the photoaging of polystyrene microplastics

Microplastics (MPs) and their derivatives have received worldwide attention owing to their adverse effects on ecosystems. However, molecular diversity and dynamic formation of dissolved organic matter (DOM) during the photoaging of MPs remain unclear. Herein, we explored a molecular‒level formation mechanism for polystyrene MP (MPPS)‒derived DOM (PSDOM) during the photoaging of MPs to explain the evolution, heterogeneity, and sequential response of molecules to irradiation. Two‒dimensional correlation spectroscopy was applied to correlate the variations of PSDOM molecules detected by Fourier transform–ion cyclotron resonance mass spectrometry with those of MPPS functional groups detected by Fourier transform infrared spectroscopy. Irradiation‒induced PSDOM contained the most highly unsaturated structures with oxygen, but showed fewer aromatic structures than natural aquatic DOM. Photochemical transformations occurred between saturated‒reduced and oxidized molecules during PSDOM leaching, with the low‒oxidized and high‒oxidized molecules undergoing considerable changes in the normal carbon oxidation state and molecular number, respectively. The primary sequential response of PSDOM molecules to increasing irradiation time [low‒oxidized/high‒weight (450<m/z<800) → high‒oxidized → saturated/low‒weight molecules (m/z<450)] corresponded to the response of MPPS functional groups (aromatic C‒H → carbonyl → aromatic ring, CH2 bend → C‒H groups), demonstrating well synergistic relationships between them. These novel findings will contribute to the understanding of underappreciated behaviors or risks of MPDOM in aquatic ecosystems.

Impact of light-aged microplastic on microalgal production of dissolved organic matter

Microplastics (MPs) can affect phytoplankton and its photosynthetic performance in many but often in negative ways. Phytoplankton is an important source of dissolved organic matter (DOM) in aquatic ecosystems, but the impact of MPs on the algal production of DOM is poorly known. We investigated the impacts of polyvinyl chloride MPs on the growth and DOM production by Chlamydomonas reinhardtii microalgae in a 28-day-long experiment. During the exponential growth phase of C. reinhardtii, MPs slightly affected algal growth and DOM production. At the end of experiment, MPs decreased the biomass of C. reinhardtii by 43 % in the treatment with MPs exposed to simulated solar radiation prior the experiment (light-aged) and more than in the treatment with virgin MPs. The light-aged MPs decreased algal DOM production by 38 % and modified the chemical composition of DOM. According to spectroscopic analyses, the light-aged MPs increased aromaticity, average molecular weight and fluorescence of DOM produced by C. reinhardtii. The elevated fluorescence was associated with humic-like components identified by a 5-component parallel factor analysis (PARAFAC) from the excitation-emission matrices. We conclude that although MPs can leach DOM to aquatic ecosystems, they potentially modify the aquatic DOM more by interfering with the algal production of DOM and changing the composition of produced DOM.

Effects of UV-based oxidation processes on the degradation of microplastic: Fragmentation, organic matter release, toxicity and disinfection byproduct formation

The occurrence and transformation of microplastics (MPs) remaining in the water treatment plants has recently attracted considerable attention. However, few efforts have been made to investigate the behavior of dissolved organic matter (DOM) derived from MPs during oxidation processes. In this study, the characteristics of DOM leached from MPs during typical ultraviolet (UV)-based oxidation was focused on. The toxicity and disinfection byproduct (DBP) formation potentials of MP-derived DOM were further investigated. Overall, UV-based oxidation significantly enhanced the aging and fragmentation of highly hydroscopic MPs. The mass scales of leachates to MPs increased from 0.03% - 0.18% at initial stage to 0.09% - 0.71% after oxidation, which were significantly higher than those leached by natural light exposure. Combined fluorescence analysis with high resolution mass spectrometer scan confirmed that the dominant MP-derived DOM are chemical additives. PET-derived DOM and PA6-derived DOM showed inhibition of Vibrio fischeri activity with corresponding EC50 of 2.84 mg/L and 4.58 mg/L of DOC. Bioassay testing with Chlorella vulgaris and Microcystis aeruginosa showed that high concentrations of MP-derived DOM inhibited algal growth by disrupting the cell membrane permeability and integrity. MP-derived DOM had a similar chlorine consumption (1.63 ± 0.41 mg/DOC) as surface water (1.0 - 2.0 mg/DOC), and MP-derived DOM mainly served as precursors for the investigated DBPs. Contrary to the results of previous studies, the DBP yields from MP-derived DOM were relatively lower than those of aquatic DOM under simulated distribution system conditions. This suggests that MP-derived DOM itself rather than serving as DBP precursor might be potential toxic concern.

Complementary Elucidation of the Molecular Characteristics of Groundwater Dissolved Organic Matter Using Ultrahigh-Resolution Mass Spectrometry Coupled with Negative- and Positive-Ion Electrospray Ionization.

The formula assignment of the Fourier transform ion cyclotron resonance mass spectrometry coupled with positive-ion electrospray ionization [ESI(+)-FT-ICR MS] is challenging because of the extensive occurrence of adducts. However, there is a paucity of automated formula assignment methods for ESI(+)-FT-ICR MS spectra. The novel automated formula assignment algorithm for ESI(+)-FT-ICR MS spectra developed herein has been applied to elucidate the composition of dissolved organic matter (DOM) in groundwater during air-induced ferrous [Fe(II)] oxidation. The ESI(+)-FT-ICR MS spectra of groundwater DOM were profoundly impacted by [M + Na]+ adducts and, to a lesser extent, [M + K]+ adducts. Oxygen-poor and N-containing compounds were frequently detected when the FT-ICR MS was operated in the ESI(+) mode, while the components with higher carbon oxidation states were preferentially ionized in the negative-ion electrospray ionization [ESI(-)] mode. Values for the difference between double-bond equivalents and the number of oxygen atoms from -13 to 13 are proposed for the formula assignment of the ESI(+)-FT-ICR MS spectra of aquatic DOM. Furthermore, for the first time, the Fe(II)-mediated formation of highly toxic organic iodine species was reported in groundwater rich in Fe(II), iodide, and DOM. The results of this study not only shed light on the further algorithm development for comprehensive characterization of DOM by ESI(-)-FT-ICR MS and ESI(+)-FT-ICR MS but also highlight the importance of appropriate treatment of specific groundwater prior to use.

Assessment of sample freezing as a preservation technique for analysing the molecular composition of dissolved organic matter in aquatic systems.

Dissolved organic matter (DOM) is widely studied in environmental and biogeochemical sciences, but is susceptible to chemical and biological degradation during sample transport and storage. Samples taken in remote regions, aboard ships, or in large numbers need to be preserved for later analysis without changing DOM composition. Here we compare high-resolution mass spectra of solid phase extractable DOM before and after freezing at -20 °C. We found that freezing increases compositional dissimilarity in DOM by between 0 to 18.2% (median = 2.7% across 7 sites) when comparing replicates that were frozen versus unfrozen, i.e., processed immediately after sampling, as compared with differences between unfrozen replicates. The effects of freezing primarily consisted of a poorer detection limit, but were smaller than other sample preparation and analysis steps, such as solid phase extraction and variable ionisation efficiency. Freezing samples for either 21 or 95 days led to similar and only slight changes in DOM composition, albeit with more variation for the latter. Therefore, we conclude that sample freezing on these time scales should not impede scientific study of aquatic DOM and can be used where it makes logistical sense, such as for large spatial surveys or study of archived samples.

Dissolved Organic Matter Component and Source Characteristics of the Metropolitan Lakes and Reservoirs in a Typical Karst Region

In order to explore dissolved organic matter (DOM) components and their origins in metropolitan lakes and reservoirs in the karst region, the typical Hongfeng Lake, Baihua Lake, Songbaishan Reservoir, and Aha Reservoir were investigated in Guiyang City. Surface water parameters, including dissolved organic carbon (DOC), chlorophyll a (Chla), and optical parameters (a254, a280, a350, E2:E3, S275-295, FI, β:α, BIX, and HIX) were analyzed. Fluorescence peaks (B, T, A, M, C, D, and N) and three-dimensional matrix fluorescence with parallel factor analysis (EEM-PARAFAC) were employed to explain distinct DOM abundances and proportions. Meanwhile, Spearman's correlation coefficients and principal component analysis (PCA) were used to decipher parameter types and primary environmental processes. The results showed that aquatic ρ(DOC) and ρ(Chla) ranged between 4.24-11.9 mg·L-1 and 0.32-19.7 μg·L-1, respectively. High humic-like (a254) and protein DOM (a280) were observed in the Songbaishan Reservoir, resulting in higher DOM molecular weight when compared to that in other lakes and reservoirs. Surface water DOM mainly contained visible-light humic-like (23.8%-46.9%) and terrestrial fulvic-like components (17.6%-28.4%). High FI, β:α, and BIX but low HIX values in this study suggested that endogenous inputs largely contributed to aquatic DOM. Aquatic DOM component and source characteristics were significantly correlated with each other. Furthermore, inputs of humic-like DOM and microbial metabolism, as well as coupled carbonate dissolution and photosynthesis, drove dynamic DOM behaviors in the karst lakes and reservoirs.

Dissolved organic matters with low molecular weight fractions exhibit high photochemical potential for reactive oxygen formation

The photochemical properties of dissolved organic matter (DOM) were highly related to the molecular weight (MW) and organic compositions. In this study, the bulk algae- and macrophyte-derived DOM (ADOM and MDOM, respectively) and Suwannee River humic acid (SRHA) were applied and fractionated into low MW- (LMW, <1 kDa) and high MW-(HMW-, 1 kDã0.45 μm) fractions. The formation and mechanisms of photochemically produced reactive intermediates (e.g., HO•, 1O2, and 3CDOM*) for these bulk and MW-fractionated samples were compared via the irradiation experiment, fluorescence and Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS). Results showed that humic-/fulvic-like substances were mainly distributed in the LMW fraction which occupied about 44–60% of total organic carbon for ADOM and MDOM and 13% for SRHA. Photochemical experiments showed that the autochthonous DOMs (e.g., ADOM and MDOM) were characterized with comparable formation rates and quantum yields of reactive oxygens with the allochthonous SRHA, suggesting the high photochemical formation potential. Further analysis showed obvious MW-dependent heterogeneities that, irrespective of DOM types, the LMW-fraction exhibited higher formation rates and quantum yields, followed by the bulk- and then the HMW-fractions. The fluorescence and FT-ICR-MS results indicated that the unique biochemical classes, i.e., humic-/fulvic-like moieties and protein-/lipid-derived compounds in the LMW fractions may be responsible for the high apparent quantum yields. This study highlighted the importance of simultaneous characterization of MW and organic compositions for evaluating the photochemical potential and other behaviors and effects of aquatic DOMs.

Organic Molecular Signatures of the Congo River and Comparison to the Amazon

AbstractThe Congo and Amazon are the two largest rivers on Earth and serve as major sources of dissolved organic carbon to the ocean. We compared the dissolved organic matter (DOM) composition of both rivers using Fourier‐transform ion cyclotron resonance mass spectrometry to investigate seasonal and regional differences in DOM composition exported to the ocean. We found that over a 15‐month observational period in the Congo River, molecular aromaticity and oxygenation between the wet and dry periods varied slightly, but most of the relative abundance of DOM formulae (∼90%) were present in all samples, suggesting that Congo River DOM quality is stable across different hydrological conditions. In contrast, the multi‐year DOM composition in the Amazon River was highly susceptible to changes in hydrology, with clear differences in molecular aromaticity, oxygenation, and heteroatom (N, S, P) content between the wet and dry seasons. Overall, the DOM composition of the Congo River was more terrestrial than Amazon River DOM, which was more characteristic of aquatic DOM. Finally, we compared the relative contribution of island of stability (IOS) formulae between the rivers and found that both rivers export similar amounts of these formulae annually, more than several major rivers combined, and that the Congo is more than twice as efficient in exporting these IOS formulae. With changing precipitation and land use, the quantity and composition of exported DOM will likely reflect the mobilization of additional terrestrial and anthropogenic sources that will also be subjected to downstream land‐to‐ocean cycling.

DOM in the long arc of environmental science: looking back and thinking ahead

Dissolved organic matter (DOM) is a heterogeneous mixture of organic compounds that is produced through both microbial degradation and abiotic leaching of solid phase organic matter, and by a wide range of metabolic processes in algae and higher plants. DOM is ubiquitous throughout the hydrologic cycle and plays an important role in watershed management for drinking water supply as well as many aspects of aquatic ecology and geochemistry. Due to its wide-ranging effects in natural waters and analytical challenges, the focal research questions regarding DOM have varied since the 1920s. A standard catchment-scale model has emerged to describe the environmental controls on DOM concentrations. Modest concentrations of DOM are found in atmospheric deposition, large increases occur in throughfall and shallow soil flow paths, and variable concentrations in surface waters occur largely as a result of the extent to which hydrologic flow paths encounter deeper mineral soils, wetlands or shallow organic-rich riparian soils. Both production and consumption of DOM occur in surface waters but appear to frequently balance, resulting in relatively constant concentrations with distance downstream in most streams and rivers. Across biomes the concentration and composition of DOM in flowing waters is driven largely by soil processes or direct inputs to channels, but high levels can be found in streams and rivers from the tropics to the poles. Seven central challenges and opportunities in the study of DOM should frame ongoing research. These include maintaining or establishing long-term records of changes in concentrations and fluxes over time, capitalizing on the use of sensors to describe short-term DOM dynamics in aquatic systems, integrating the full carbon cycle into understanding of watershed and aquatic DOM dynamics, understanding the role of DOM in evasion of greenhouse gases from inland waters, unraveling the enigma of dissolved organic nitrogen, documenting gross versus net DOM fluxes, and moving beyond an emphasis on functional ecological significance to understanding the evolutionary significance of DOM in a wide range of environments.

Temperature effects on sorption of dissolved organic matter on ferrihydrite under dynamic flow and batch conditions

AbstractAccurately predicting the effect of temperature on soil C storage remains a crucial objective in the effort to understand, mitigate, and adapt to climate change. Associations between soil organic C and short‐range order minerals like the iron hydroxide ferrihydrite contribute substantially to C sequestration, but little is known about how these associations respond to changes in temperature. We investigated the effects of temperature (7, 25, and 45 °C) and dissolved organic matter (DOM) source and fraction on DOM sorption to ferrihydrite‐coated sand in continuous flow and batch systems at circumneutral pH. Our findings demonstrate a positive relationship between temperature and adsorption, especially between 25 and 45 °C. For aquatic DOM, desorption also increased appreciably with temperature, whereas desorption of peat and soil DOM was less sensitive. More aquatic DOM adsorbed compared with soil DOM at all temperatures, but flow studies revealed that aquatic DOM also desorbed at higher rates. Modeling of DOM breakthrough curves using the advection‐diffusion equation with a modified Freundlich isotherm suggested the partition coefficient increased over time. Specific ultraviolet absorbance values of initial column effluents were low, suggesting that aromatic‐rich compounds preferentially adsorbed to the mineral surface. Our results indicate that some circumstances may favor the accumulation of DOM on iron mineral surfaces as temperature increases, potentially removing organic substrates from the accessible dissolved C pool. However, the stability of new associations likely depends on the chemical characteristics of DOM and the conditions under which it adsorbed.

Relationships between the Physicochemical Properties of Dissolved Organic Matter and Its Reaction with Sodium Borohydride.

The reaction of dissolved organic matter (DOM) with sodium borohydride has been used to understand the geographic origin of DOM and investigate the photophysical model underlying DOM's optical properties. However, the physicochemical properties of DOM (e.g., molecular size and charge) that influence the kinetics and ultimate reducibility of DOM by borohydride remain poorly characterized. Herein, we studied the kinetics of DOM-borohydride reactions by recording absorbance and fluorescence spectra at a high temporal frequency (every ∼10 min for 24 h) for a diverse set of DOM isolates of aquatic and soil origin. The reducibility of DOM by sodium borohydride (as judged by relative removal of initial absorbance) varied appreciably among the DOM samples studied, with soil humic substances being less reducible than aquatic humic substances and natural organic matter. While statistically significant correlations were found between the reducibility of DOM and descriptors of molecular size, these descriptors were not able to differentiate the reducibility of soil versus aquatic DOM isolates that had similar bulk properties. Thus, it appears that the extent of absorbance removal by borohydride is largely driven by the origin of the humic substance isolate (aquatic vs soil) instead of molecular size or charge. Borohydride reduction resulted in increased fluorescence emission across UV and visible excitation wavelengths. However, the enhanced emission at visible excitation decreased over a time period of hours to days, suggesting that reduction of an important subset of DOM chromophores is reversible. This reversibility in fluorescence emission is consistent with the small role of quinones in the absorbance of DOM but suggests a more important role for quinone-containing charge-transfer contacts in the fluorescence of DOM, particularly at visible excitation wavelengths.

Dissolved Organic Matter Quality and Biofilm Composition Affect Microbial Organic Matter Uptake in Stream Flumes

Agriculture delivers significant amounts of dissolved organic matter (DOM) to streams, thereby changing the composition and biodegradability of the aquatic DOM. This study focuses on the interactive effects of DOM quality and biofilm composition on the degradation of DOM in a laboratory flume experiment. Half of the flumes were exposed to light to stimulate algal growth, the other half was shaded. Leachates of deciduous leaves, maize leaves, and cow dung were added to the flumes in a single pulse and changes of DOC (dissolved organic carbon) and nutrient concentrations, DOM composition (absorbance and fluorescence data), chlorophyll-a concentrations, bacterial abundances, and enzymatic activities were recorded over a week. DOM was taken up with rates of 50, 109, and 136 µg DOC L−1 h−1 for dung, leaf, and maize leachates, respectively, in the light flumes and 37, 80, and 170 µg DOC L−1 h−1 in the dark flumes. DOC uptake correlated strongly with initial SRP (soluble reactive phosphorus) and DOC concentrations, but barely with DOM components and indices. Algae mostly stimulated the microbial DOC uptake, but the effects differed among differently aged biofilms. We developed a conceptual model of intrinsic (DOM quality) and external (environmental) controlling factors on DOM degradation, with the microbial community acting as biotic filter.

Impacts of fish farming on elemental stoichiometry, fluorescence components, and stable isotopes of dissolved organic matter in a tropical reservoir.

Aquaculture impacts on aquatic organic matter and ecosystem integrity are poorly understood, especially in tropical regions. Here, we investigated the impacts of Nile tilapia net cage farming on the elemental stoichiometry, fluorescence components, and stable isotopes of dissolved organic matter (DOM) of the large, tropical Furnas Reservoir (SE Brazil). Early-stage fish farming, i.e., relatively small and recently implemented farms, had detectable incipient effects on DOM characteristics, and these effects differed between reservoir branches. In the less eutrophic Rio Grande branch of the reservoir, we found a reduction in natural humic-like DOM components and an increase in a protein-like DOM component as far as 100m away from fish farms. Further, we observed a decrease in δ15N-TDN due to fish farming. In the more eutrophic Rio Sapucaí branch, there were only local decreases in C:N ratios, as well as rises in C:P and N:P of DOM due to fish farming. These results suggest that early-stage fish farming had local but detectable effects on aquatic DOM that depended on previous eutrophication levels and highlight the need to assess the early impacts of fish farming on tropical reservoirs by combining different monitoring strategies.

Investigating the Ionization of Dissolved Organic Matter by Electrospray.

Electrospray ionization (ESI) operating in the negative mode coupled to high-resolution mass spectrometry is the most popular technique for the characterization of dissolved organic matter (DOM). The vast molecular heterogeneity and the functional group diversity of this complex mixture prevents the efficient ionization of the organic material by a single ionization source, so the presence of uncharacterized material is unavoidable. The extent of this poorly ionizable pool of carbon is unknown, is presumably variable between samples, and can only be assessed by the combination of analysis with a uniform detection method. Charged aerosol detection (CAD), whose response is proportional to the amount of nonvolatile material and is independent from the physicochemical properties of the analytes, is a suitable candidate. In this study, a fulvic acid mixture was fractionated and analyzed by high-pressure liquid chromatography–mass spectrometry in order to investigate the polarity and size distributions of highly and poorly ionizable material in the sample. Additionally, DOM samples of terrestrial and marine origins were analyzed to evaluate the variability of these pools across the land–sea aquatic continuum. The relative response factor values indicated that highly ionizable components of aquatic DOM mixtures are more hydrophilic and have lower molecular weight than poorly ionizable components. Additionally, a discrepancy between the samples of terrestrial and marine origins was found, indicating that marine samples are better represented by ESI than terrestrial samples, which have an abundant portion of hydrophobic poorly ionizable material.