Dissolved Organic Matter Compounds Research Articles

Environmental Drivers of Dissolved Organic Matter Molecular Composition in the Delaware Estuary

Estuaries as connectors of freshwater and marine aquatic systems are hotspots of biogeochemical element cycling. In one of the best studied temperate estuaries, the Delaware Estuary (USA), we investigated the variability of dissolved organic matter (DOM) over five sampling cruises along the salinity gradient in August and November of 3 consecutive years. Dissolved organic carbon (DOC) concentrations were more variable in the upper reaches of the estuary (245±49 µmol L-1) than at the mouth of the estuary (129±14 µmol L-1). Bulk DOC decreased conservatively along the transect in November but was non-conservative with increased DOC concentrations mid-estuary in August. Detailed analysis of the solid-phase extractable DOM pool via ultrahigh resolution mass spectrometry (Fourier-transform ion cyclotron resonance mass spectrometry, FT-ICR-MS) revealed compositional differences at the molecular level that were not reflected in changes in concentration. Besides the mixing of terrestrial and marine endmember signatures, river discharge levels and biological activity were found to impact DOM molecular composition. DOM composition changed less between August and November than along the salinity gradient. Relative contributions of presumed photolabile DOM compounds did not reveal non-conservative behavior indicative of photochemical processing; suggesting that on the timescales of estuarine mixing photochemical removal of molecules plays a minor role in the turbid Delaware Bay. Overall, a large portion of molecular formulae overlapped between sampling campaigns and persisted during estuarine passage. Extending the analysis to the structural level via the fragmentation of molecular masses in the FT-ICR-MS cell, we found that the relative abundance of isomers along the salinity gradient did not change, indicating a high structural similarity of aquatic DOM independent of the origin. These results point towards a recalcitrant character of the DOM supplied by the Delaware River. We demonstrate that in addition to bulk DOC quantification, detailed information on molecular composition is essential for constraining sources of DOM and to identify the processes that impact estuarine DOM, thereby controlling amount and composition of DOM eventually discharged to the ocean through estuaries.

Solid-phase extraction-stepwise elution (SPE-SE) procedure for isolation of dissolved organic matter prior to ESI-FT-ICR-MS analysis

Characterization of dissolved organic matter (DOM) at the molecular level will greatly improve our understanding of its bio-geochemical role in controlling the fate of contaminants in the environment, and Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS) is the most powerful analytical technique for this purpose. Before FT-ICR-MS analysis, isolation, desalination and concentration of DOM are necessary, and solid-phase extraction (SPE) is the most widely applied pretreatment procedure. However, some molecular information is lost using conventional SPE methods. Here, we propose a novel strategy of SPE enrichment using stepwise elution (SPE-SE). Compounds in DOM were divided into three fractions by this SPE-SE procedure according to their polarity and ionization efficiency. The diversity of DOM molecules identified by ESI-FT-ICR-MS using SPE-SE exceeded those using conventional SPE methods by more than 50%. This method is feasible and has the potential to be used as a pretreatment strategy for complex DOM matrixes prior to ESI-FT-ICR-MS analysis, especially for those rich in nitrogenous molecules, carbohydrates, lipids and/or aromatic compounds.

Optical properties of dissolved organic matter relate to different depth-specific patterns of archaeal and bacterial community structure in the North Atlantic Ocean.

Prokaryotic abundance, activity and community composition were studied in the euphotic, intermediate and deep waters off the Galician coast (NW Iberian margin) in relation to the optical characterization of dissolved organic matter (DOM). Microbial (archaeal and bacterial) community structure was vertically stratified. Among the Archaea, Euryarchaeota, especially Thermoplasmata, was dominant in the intermediate waters and decreased with depth, whereas marine Thaumarchaeota, especially Marine Group I, was the most abundant archaeal phylum in the deeper layers. The bacterial community was dominated by Proteobacteria through the whole water column. However, Cyanobacteria and Bacteroidetes occurrence was considerable in the upper layer and SAR202 was dominant in deep waters. Microbial composition and abundance were not shaped by the quantity of dissolved organic carbon, but instead they revealed a strong connection with the DOM quality. Archaeal communities were mainly related to the fluorescence of DOM (which indicates respiration of labile DOM and generation of refractory subproducts), while bacterial communities were mainly linked to the aromaticity/age of the DOM produced along the water column. Taken together, our results indicate that the microbial community composition is associated with the DOM composition of the water masses, suggesting that distinct microbial taxa have the potential to use and/or produce specific DOM compounds.

Comprehensive structure-selective characterization of dissolved organic matter by reducing molecular complexity and increasing analytical dimensions

Deciphering the molecular codes of dissolved organic matter (DOM) improves our understanding of its role in the global element cycles and its active involvement in ecosystem services. This study demonstrates comprehensive characterization of DOM by an initial polarity-based stepwise solid phase extraction (SPE) with single methanol elution of the cartridges, but separate collection of equal aliquots of eluate. The reduction of molecular complexity in the individual DOM fractions attenuates intermolecular interactions and substantially increases the disposable resolution of any structure selective characterization. Suwannee River DOM (SR DOM) was used to collect five distinct SPE fractions with overall 91% DOC recovery. Optical spectroscopy (UV and fluorescence spectroscopy), high-field Fourier transform ion cyclotron mass spectrometry (FTICR MS) and nuclear magnetic resonance (NMR) spectroscopy showed analogous hierarchical clustering among the five eluates corroborating the robustness of this approach. Two abundant moderately hydrophobic fractions contained most of the SR DOM compounds, with substantial proportions of aliphatics, carboxylic-rich alicyclic molecules, carbohydrates and aromatics. A minor early eluting hydrophilic fraction was highly aliphatic and presented a large diversity of alicyclic carboxylic acids, whereas the two late eluting, minor hydrophobic fractions appeared as a largely defunctionalized mixture of aliphatic molecules. Comparative mass analysis showed that fractionation of SR DOM was governed by multiple molecular interactions depending on O/C ratio, molecular weight and aromaticity. The traditional optical indices SUVA254 and fluorescence index (FI) indicated the relative aromaticity in agreement with FTICR mass and NMR spectra; the classical fluorescent peaks A and C were observed in all four latter eluates. This versatile approach can be easily expanded to preparative scale under field conditions, and transferred to different DOM sources and SPE conditions.

Sorption of DOM and hydrophobic organic compounds onto sewage-based activated carbon.

Treatment of stormwater via sorption has the potential to remove both colloidal and dissolved pollutants. Previous research shows that activated carbon produced from sewage sludge is very efficient in sorbing hydrophobic organic compounds (HOCs), frequently detected in stormwater. The aim of this research was to determine whether the presence of dissolved organic matter (DOM) has a negative effect on the adsorption of HOCs onto sludge-based activated carbon (SBAC) in batch adsorption tests. Batch adsorption tests were used to investigate the influence of two types of DOM - soil organic matter and humic acid (HA) technical standard - on the sorption of HOCs onto SBAC, and whether preloading adsorbent and adsorbates with DOM affects HOC sorption. The results indicate that soil DOM and HAs do not have a significant negative effect on the adsorption of HOCs under tested experimental conditions, except for a highly hydrophobic compound. In addition, preloading SBAC or HOCs with DOM did not lead to lower adsorption of HOCs. Batch adsorption tests appear to be inefficient for investigating DOM effects on HOC adsorption, as saturating the carbon is difficult because of high SBAC adsorption capacity and low HOC solubility, so that limited competition occurs on the sorbent.

Effects of dissolved organic matter (DOM) sources and nature of solid extraction sorbent on recoverable DOM composition: Implication into potential lability of different compound groups.

Noting the source-dependent properties of dissolved organic matter (DOM), this study explored the recoverable compounds by solid phase extraction (SPE) of two common sorbents (C18 and PPL) eluted with methanol solvent for contrasting DOM sources via fluorescence excitation-emission matrix coupled with parallel factor analysis (EEM-PARAFAC) and Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS). Fresh algae and leaf litter extracts DOM, one riverine DOM, and one upstream lacustrine DOM were selected for the comparison. C18 sorbent was generally found to extract more diverse molecular formula, relatively higher molecular weight, and more heteroatomic DOM compounds within the studied mass range than PPL sorbent except for the leaf litter extract. Even with the same sorbent, the main molecular features of the two end member DOM were distributed on different sides of the axes of a multivariate ordination, indicating the source-dependent characteristics of the recoverable compounds by the sorbents. In addition, further examination of the molecular formula uniquely present in the two end members and the upstream lake DOM suggested that proteinaceous, tannin-like, and heteroatomic DOM constituents might be potential compound groups which are labile and easily degraded during their mobilization into downstream watershed. This study provides new insights into the sorbent selectivity of DOM from diverse sources and potential lability of various compound groups.

Dissolved organic matter in pore water of Arctic Ocean sediments: Environmental influence on molecular composition

Marine organic matter (OM) sinks from surface water to the seafloor via the biological pump. Benthic communities, which use this sedimented OM as an energy and carbon source, produce dissolved OM (DOM) in the process of degradation, enriching the sediment pore water with fresh DOM compounds. In the oligotrophic deep Arctic basin, particle flux is low but highly seasonal. We hypothesized that the molecular signal of freshly deposited, primary produced OM would be detectable in surface sediment pore water, which should differ in DOM composition from bottom water and deeper sediment pore water. The study focused on (i) the molecular composition of the DOM in sediment pore water of the deep Eurasian Arctic basins, (ii) the signal of marine vs. terrigenous DOM represented by different compounds preserved in the pore water and (iii) the relationship between Arctic Ocean ice cover and DOM composition. Composition based on mass spectrometric information, obtained via 15T Fourier transform ion cyclotron resonance mass spectrometry, was correlated with environmental parameters with partial least square analysis. The fresh marine detrital OM signal from surface water was limited to pore water from <5cm sediment depth. The productive ice margin stations showed a higher abundance of peptide, unsaturated aliphatic and saturated fatty acid molecular formulae, indicative of recent phytodetritus deposition, than the multiyear ice-covered stations, which had a stronger aromatic signal. The study contributes to the understanding of the coupling between Arctic Ocean productivity and its depositional regime, and how it may be altered in response to sea ice retreat and increasing river runoff.

Deciphering ocean carbon in a changing world

Dissolved organic matter (DOM) in the oceans is one of the largest pools of reduced carbon on Earth, comparable in size to the atmospheric CO2 reservoir. A vast number of compounds are present in DOM, and they play important roles in all major element cycles, contribute to the storage of atmospheric CO2 in the ocean, support marine ecosystems, and facilitate interactions between organisms. At the heart of the DOM cycle lie molecular-level relationships between the individual compounds in DOM and the members of the ocean microbiome that produce and consume them. In the past, these connections have eluded clear definition because of the sheer numerical complexity of both DOM molecules and microorganisms. Emerging tools in analytical chemistry, microbiology, and informatics are breaking down the barriers to a fuller appreciation of these connections. Here we highlight questions being addressed using recent methodological and technological developments in those fields and consider how these advances are transforming our understanding of some of the most important reactions of the marine carbon cycle.

Characterization of water dissolved organic matter under woody vegetation patches in semi-arid Mediterranean soils

Woody patches in semiarid environments favor the establishment of other plants. Facilitation may be favored by an increase in soil fertility. Dissolved organic matter (DOM), is the most active fraction of soil organic matter and may contain compounds affecting plant establishment, as allelochemicals, hormone-like substances and metal carriers. However, information on DOM contents and composition in these environments is scarce. In this paper, we study the impact of woody patches on DOM in Stipa tenacissima L. steppes and discuss its implications for community dynamics. DOM under patch- and inter-patch areas, was analyzed for elemental composition, UV–Vis indices and organic acid content. Element concentration and composition in DOM, and organic acid concentration were similar in patch- and inter-patch areas. Yet, soils under patches were richer in DOC, aromatic species and organic acids (particularly fumaric acid) than soils in inter-patch areas. Dominant species affected organic matter concentration and quality in complex ways. Thus, patches dominated by Ephedra fragilis showed higher concentrations of TOC and aromatics than those dominated by other species. Rhamnus lycioides patches showed the highest accumulation of fumaric acid, which may contribute to its successful recruitment rate and expansion in the area. Our results show substantial differences in the amount and composition of DOM and specific compounds affecting soil functionality and plant dynamics. Further studies on the effects of such changes on seedling performance are needed to increase our understanding of plant–plant interactions in semiarid environments.

Interaction between iron and dissolved organic matter in a marine shallow hydrothermal system off Dominica Island (Lesser Antilles)

Shallow submarine hydrothermal systems are extreme environments with unique biogeochemical conditions, originating from the interaction of hot, reduced fluids and cold, oxygenated seawater. Hydrothermal fluids represent one of the marine sources of essential trace elements like iron, the flux of which is controlled by dissolved organic matter (DOM) in and between terrestrial and marine ecosystems. However, the selectivity of the DOM with iron in marine environments is not well understood. Here we characterized at a molecular level the marine hydrothermal iron–DOM interaction using Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS). Our study site was a shallow-water hydrothermal system off Dominica Island (Lesser Antilles, Caribbean Sea), where reduced fluids were strongly enriched in dissolved Fe and Si as compared to surface seawater. The dissolved organic carbon (DOC) concentration was lower in the hydrothermal fluids, most likely due to low-DOC meteoric water influence, but also suggesting biotic or abiotic processes consuming or depleting DOC when seawater is re-circulated through the sediment. The formation of hydrous ferric oxides upon aeration of the hydrothermal fluids for 10h leads to an 8% decrease in DOC, indicating co-precipitation of iron and DOM. Re-solubilization of iron precipitates revealed increased relative abundance of aromatic compounds in co-precipitated DOM, which is in accordance with iron-coagulation observed in terrestrial environments. In conclusion, we provide evidence of co-precipitation of DOM with iron at hydrothermal systems as a selective process, which characteristically alters the molecular composition of DOM released with hydrothermal fluids.

Photodegradation of dissolved organic matter in ice under solar irradiation.

The photodegradation behavior of dissolved organic matter (DOM) with different origins in ice under solar irradiation was investigated. Exposure to sunlight at 2.7 × 10(5) J m(-2) resulted in dissolved organic carbon (DOC) reductions of 22.1-36.5% in ice. The naturally occurring DOM had higher photodegradation potentials than the wastewater-derived DOM in ice. Ultraviolet (UV)-absorbing compounds in DOM, regardless of DOM origin, had much higher photodegradation potentials than gross DOC in ice. The susceptibility of UV-absorbing compounds with natural origin to sunlight exposure in ice was higher than those derived from wastewater. Trihalomethane (THM) precursors were more susceptible to photochemical reactions than gross DOC and haloacetic acid (HAA) precursors in ice. THM precursors in naturally occurring DOM were more photoreactive than those in wastewater-derived DOM in ice, while the photoreactivity of HAA precursors in ice was independent of DOM origin. In ice, the photoreactivity of humic-like fluorescent materials, regardless of DOM origin, was higher than that of gross DOC and protein-like fluorescent materials. DOC reductions caused by sunlight irradiation were found to be negatively correlated to DOC levels, and positively correlated to the aromaticity of DOM. The photodegradation of both wastewater-derived and naturally occurring DOM in ice was significantly facilitated at both acid and alkaline pH, as compared to neutral pH. The photodegradation of DOM in ice, regardless of the origin, was facilitated by nitrate ion [Formula: see text] , nitrite ion [Formula: see text] , ferric ion (Fe(3+)) and ferrous ion (Fe(2+)), and on the other hand, was inhibited by chloridion ion (Cl(-)) and copper ion (Cu(2+)).

Experimental insights into the importance of aquatic bacterial community composition to the degradation of dissolved organic matter.

Bacteria play a central role in the cycling of carbon, yet our understanding of the relationship between the taxonomic composition and the degradation of dissolved organic matter (DOM) is still poor. In this experimental study, we were able to demonstrate a direct link between community composition and ecosystem functioning in that differently structured aquatic bacterial communities differed in their degradation of terrestrially derived DOM. Although the same amount of carbon was processed, both the temporal pattern of degradation and the compounds degraded differed among communities. We, moreover, uncovered that low-molecular-weight carbon was available to all communities for utilisation, whereas the ability to degrade carbon of greater molecular weight was a trait less widely distributed. Finally, whereas the degradation of either low- or high-molecular-weight carbon was not restricted to a single phylogenetic clade, our results illustrate that bacterial taxa of similar phylogenetic classification differed substantially in their association with the degradation of DOM compounds. Applying techniques that capture the diversity and complexity of both bacterial communities and DOM, our study provides new insight into how the structure of bacterial communities may affect processes of biogeochemical significance.

Molecular-level changes of dissolved organic matter along the Amazon River-to-ocean continuum

Coastal oceans link terrestrial and marine carbon cycles. Yet, carbon sources and sinks in these biomes remain poorly understood. Here, we explore the dynamics of dissolved organic matter (DOM) along the Amazon River-to-ocean continuum from the lower mainstem at Óbidos to the open ocean of the western tropical North Atlantic. We molecularly characterized DOM via ultrahigh-resolution Fourier-transform ion cyclotron resonance mass spectrometry (FT-ICR-MS), determined DOM stable carbon isotopes, and interpreted the data in the context of bacterial abundance and production, phytoplankton biomass and composition. Multivariate analysis revealed that the DOM molecular variability in the plume was mainly influenced by the input of terrigenous DOM. Incubation experiments with water from close to the river mouth showed that photo- and bio-degradation preferentially removed 13C-depleted and 13C-enriched terrigenous DOM, respectively. However, there was no significant quantitative change in the total amount of dissolved organic carbon (DOC) over five days. This result suggests that most of the reactive DOM had already been bio-degraded upstream within the river and that photo-degradation was diminished in the turbid plume close to the river mouth. Terrigenous DOM therefore appeared to be relatively non-reactive nearshore. In the less turbid offshore plume, enhanced light penetration stimulated growth of phytoplankton and increased bacterial production. Although marine DOM compounds became relatively enriched, bulk DOC concentrations were 9 to 30% below levels expected from conservative mixing of river and ocean endmembers suggesting that quantitative removal of terrigenous DOM was not compensated by marine DOM production. We propose that removal of terrigenous DOM in the outer plume may be enhanced by (i) bio-degradation primed by reactive algal DOM, (ii) photo-degradation, which may further break down DOM into more bio-available forms, and possibly (iii) sorption of DOM to sinking particles.

Dissolved organic matter composition drives the marine production of brominated very short-lived substances.

Brominated very short-lived substances (BrVSLS), such as bromoform, are important trace gases for stratospheric ozone chemistry. These naturally derived trace gases are formed via bromoperoxidase-mediated halogenation of dissolved organic matter (DOM) in seawater. Information on DOM type in relation to the observed BrVSLS concentrations in seawater, however, is scarce. We examined the sensitivity of BrVSLS production in relation to the presence of specific DOM moieties. A total of 28 model DOM compounds in artificial seawater were treated with vanadium bromoperoxidase (V-BrPO). Our results show a clear dependence of BrVSLS production on DOM type. In general, molecules that comprise a large fraction of the bulk DOM pool did not noticeably affect BrVSLS production. Only specific cell metabolites and humic acid appeared to significantly enhance BrVSLS production. Amino acids and lignin phenols suppressed enzyme-mediated BrVSLS production and may instead have formed halogenated nonvolatile molecules. Dibromomethane production was not observed in any experiments, suggesting it is not produced by the same pathway as the other BrVSLS. Our results suggest that regional differences in DOM composition may explain the observed BrVSLS concentration variability in the global ocean. Ultimately, BrVSLS production and concentrations are likely affected by DOM composition, reactivity, and cycling in the ocean.

Novel insights into the molecular structure of non-volatile marine dissolved organic sulfur

Abiotic sulfurization likely contributes to the preservation of organic matter in fossil deposits. It is unknown whether this mechanism also stabilizes dissolved organic matter (DOM) in the oceanic water column. Knowledge of the structure of the sulfur-containing compounds in DOM could help to understand the observed stability of at least a fraction of refractory DOM in the ocean. Structural analysis of dissolved organic sulfur (DOS) is complicated by it's great molecular diversity and the low concentration of each compound. Two contrasting marine DOM samples, one deep-sea sample from the North Pacific Ocean and one surface sample from the marginal North Sea (Germany), were examined in this study. Selective alteration experiments targeting different sulfur-containing functional groups were applied prior to Fourier-transform ion cyclotron resonance mass spectrometry (FT-ICR-MS). All treatments were also carried out with corresponding model compounds, in order to test for the applicability of the chosen reactions and for matrix effects, and to confirm the types of changes caused by the treatments. Alteration experiments were composed of harsh hydrolysis, selective derivatization of thiols, oxidation, and deoxygenation. None of these treatments induced detectable changes to DOS, indicating the absence of thioesters, sulfonic acid esters, alkylsulfates, thiols, non-aromatic thioethers, and sulfoxides in solid-phase-extractable DOM (SPE-DOM). Collision-induced fragmentation of isolated nominal masses in the FT-ICR-MS confirmed these findings and revealed the presence of sulfonic acids in both samples. Additionally, the presence of thiophenes and possibly also sulfones is likely, while the presence of any other form of sulfur in SPE-DOM can be ruled out based on our results. In conclusion, only unreactive (fully oxidized and hydrolyzed) sulfur compounds resist in the water column as part of refractory DOM. There was no detectable difference in molecular structure between DOS of the marginal North Sea and the deep North Pacific, indicating that the chemical inertness and the presence of sulfonic acids are global features of DOS residing in the oxic water column.

Investigating the potential of solid-phase extraction and Fourier-transform ion cyclotron resonance mass spectrometry (FT-ICR-MS) for the isolation and identification of dissolved metal–organic complexes from natural waters

In aquatic environments, iron and copper often occur at low concentrations, and are bound to dissolved organic matter (DOM). The detection and chemical characterization of such iron- and copper-complexes are only slowly progressing due to the high diversity of natural DOM. Recent developments of sample preparation and measurement techniques have opened up new opportunities to selectively isolate and identify metal–organic compound groups from natural water samples. In this study, the isolation of the model complex desferrioxamine–iron (DFO–Fe) and naturally occurring iron- and copper–organic complexes from a groundwater and a seawater sample was investigated with a variety of solid-phase extraction (SPE) sorbents (polar to nonpolar) and extraction/elution (low and neutral pH) setups. Natural DOM, the model complex desferrioxamine–iron (DFO–Fe), and natural Cu-binding ligands were recovered in a range of 60–100% at low pH by the majority of the sorbents. In contrast, extraction efficiencies for solid-phase extractable iron–DOM and copper–DOM compounds (SPE-Fe–DOM and SPE-Cu–DOM) were overall lower and highly influenced by pH settings, sample type, and sorbent type. Especially, the SPE techniques preferentially isolated SPE-metal–DOM with neutral/weak acidic to basic characteristics, fractions which made up a relatively small amount (~10–15%) of the total natural SPE-DOM from the two water samples. Furthermore, our data indicate that solid-phase extractable small Fe–DOM colloids and acid-stable Fe- and Cu-organic compounds occur in natural DOM. A series of desferrioxamine–copper (DFO–Cu) and desferrioxamine–iron (DFO–Fe) calibration solutions were measured by ultrahigh-resolution Fourier-transform ion cyclotron resonance mass spectrometry (FT-ICR-MS), and both complexes were detectable in positive ion mode at concentrations as low as 150nM (DFO–Cu) and 2nM (DFO–Fe). DFO–Fe and DFO–Cu in the nM range were also detectable when added to a groundwater DOM sample to evaluate matrix effects by the natural DOM background. Our study demonstrates that SPE combined with high-resolution FT-ICR-MS is currently the most promising technique to isolate and unambiguously identify dissolved metal–organic complexes in highly diverse natural water samples.

Identification and characterization of dissolved organic matter sources in Kushiro river impacted by a wetland

The characterization of dissolved organic matter (DOM) is an important parameter for the management of water resources. In this study, physical and chemical characteristics of DOM in Kushiro river, and its territory (Eastern Hokkaido, Japan) were analyzed using multiple analytical tools. Multiple samples were collected from diverse locations (Kushiro river, Kushiro wetland, compost fertilizer, forest and treated sewage) and compared them against their DOM characteristics. Among the samples, Kushiro wetland samples presented higher specific ultraviolet absorbance (SUVA) values demonstrating DOM derived from vascular plants which are rich in aromatic-components. The SUVA values of the two samples of the Kushiro river were relatively close to those of the wetland samples implying the fact that the river contains high amount of plant derived aromatic DOM compounds, originating from the wetland. The excitation–emission matrix (EEM) fluorescence results showed that generally all water samples have two peaks namely, A and C. These two peaks are related to humic-like substance typically derived from the breakdown of organic matters. The excitation–emission matrix (EEM) fluorescence results of the river samples were also similar to those of the wetland samples, characterized by no appearance of protein, amino acid, polysaccharide, and fluvic like matter, but more pronounced to the aromatic component rich humic acid. Principal component analysis revealed that approximately 88% of the variance in the DOM characteristics might be explained by the type of different sources. From the loadings on PC1 and PC2 in the scores plot, the properties of the DOM of the wetland appeared to be similar to those of the river DOM. Combined results exhibited that the quality of the Kushiro river water is fundamentally inherited from the Kushiro wetland, and the main structure of the river water is characterized by poly-aromatic humic like matter and higher molecular weight.

Photochemical production of polyols arising from significant photo-transformation of dissolved organic matter in the oligotrophic surface ocean

Ultrahigh resolution mass spectrometry of marine dissolved organic matter (DOM) has suggested the presence of many common molecular compositions throughout the open ocean. The majority of these supposedly ubiquitous molecules was concluded to represent the refractory marine DOM pool. This study demonstrates that 24h of exposure of Atlantic and Pacific surface DOM to simulated sunlight causes phototransformation of about half of these supposedly refractory molecular compositions. It is suggested that these transformations are related to indirect photobleaching possibly involving reactive oxygen species (e.g. hydroxyl radicals), because very little change in the fluorescent component of the DOM (FDOM) was observed during the photo-degradation experiments. A significant decline in average mass with distinct decrease of average O/C ratios and concomitant increase of H/C ratios was observed. NMR spectra revealed a decrease in aromatic and olefinic unsaturation and the formation of a limited and near identical suite of oxygenated aliphatic compounds in both Atlantic and Pacific surface DOM. Their NMR characteristics indicated a mixture of about 10 polyols that are plausible products of convergent pathways of photochemical carbohydrate decomposition and oxidation of functionalized, branched aliphatic compounds. These prominent photochemical signature molecules amounted to ~2% of total proton NMR integral and are expected to be quickly consumed by various microorganisms in the open ocean. These results may suggest a fast photo-induced large-scale cycling of DOM within the surface ocean dynamic equilibrium of photo- and bio-transformations.

Evidence for key enzymatic controls on metabolism of Arctic river organic matter

Permafrost thaw in the Arctic driven by climate change is mobilizing ancient terrigenous organic carbon (OC) into fluvial networks. Understanding the controls on metabolism of this OC is imperative for assessing its role with respect to climate feedbacks. In this study, we examined the effect of inorganic nutrient supply and dissolved organic matter (DOM) composition on aquatic extracellular enzyme activities (EEAs) in waters draining the Kolyma River Basin (Siberia), including permafrost-derived OC. Reducing the phenolic content of the DOM pool resulted in dramatic increases in hydrolase EEAs (e.g., phosphatase activity increased >28-fold) supporting the idea that high concentrations of polyphenolic compounds in DOM (e.g., plant structural tissues) inhibit enzyme synthesis or activity, limiting OC degradation. EEAs were significantly more responsive to inorganic nutrient additions only after phenolic inhibition was experimentally removed. In controlled mixtures of modern OC and thawed permafrost endmember OC sources, respiration rates per unit dissolved OC were 1.3-1.6 times higher in waters containing ancient carbon, suggesting that permafrost-derived OC was more available for microbial mineralization. In addition, waters containing ancient permafrost-derived OC supported elevated phosphatase and glucosidase activities. Based on these combined results, we propose that both composition and nutrient availability regulate DOM metabolism in Arctic aquatic ecosystems. Our empirical findings are incorporated into a mechanistic conceptual model highlighting two key enzymatic processes in the mineralization of riverine OM: (i) the role of phenol oxidase activity in reducing inhibitory phenolic compounds and (ii) the role of phosphatase in mobilizing organic P. Permafrost-derived DOM degradation was less constrained by this initial 'phenolic-OM' inhibition; thus, informing reports of high biological availability of ancient, permafrost-derived DOM with clear ramifications for its metabolism in fluvial networks and feedbacks to climate.

Fluorescence spectroscopic characterization of dissolved organic matter fractions in soils in soil aquifer treatment

This work investigated the effect of soil aquifer treatment (SAT) operation on the fluorescence characteristics of dissolved organic matter (DOM) fractions in soils through laboratory-scale soil columns with a 2-year operation. The resin adsorption technique (with XAD-8 and XAD-4 resins) was employed to characterize the dissolved organic matter in soils into five fractions, i.e., hydrophobic acid (HPO-A), hydrophobic neutral (HPO-N), transphilic acid (TPI-A), transphilic neutral (TPI-N), and hydrophilic fraction (HPI). The synchronous fluorescence spectra revealed the presence of soluble microbial byproduct- and humic acid-like components and polycyclic aromatic compounds in DOM in soils, and SAT operation resulted in the enrichment of these fluorescent materials in all DOM fractions in the surface soil (0-12.5 cm). More importantly, the quantitative method of fluorescence regional integration was used in the analysis of excitation-emission matrix (EEM) spectra of DOM fractions in soils. The cumulative EEM volume (Φ T, n ) results showed that SAT operation led to the enrichment of more fluorescent components in HPO-A and TPI-A, as well as the dominance of less fluorescent components in HPO-N, TPI-N, and HPI in the bottom soil (75-150 cm). Total Φ T, n values, which were calculated as [Formula: see text], suggested an accumulation of fluorescent organic matter in the upper 75 cm of soil as a consequence of SAT operation. The distribution of volumetric fluorescence among five regions (i.e., P i, n ) results revealed that SAT caused the increased content of humic-like fluorophores as well as the decreased content of protein-like fluorophores in both HPO-A and TPI-A in soils.