Dissolved Organic Matter In Summer Research Articles

Role of molecular weight-dependent spectral properties in regulating Cu(II) binding by dissolved organic matter from different sources

The complexation of metals with dissolved organic matter (DOM) under different compositions and molecular weights (MWs) will result in different environmental fate and toxicity, but the specific role and impact of DOM MWs remain less well understood. This study explored the metal binding characteristics by DOM with different MWs from different sources, including sea, river, and wetland waters. The results of fluorescence characterization showed that the >1 kDa high-molecular-weight (HMW)-DOM were mainly from terrestrial sources while the low-molecular-weight (LMW)-DOM fractions were mostly from microbial sources. Based on UV–Vis spectroscopic characterization, the LMW-DOM contained more unsaturated bonds than its HMW counterpart, and the substituents are generally dominated by polar functional groups. Summer DOM had more unsaturated bonds and a higher metal binding capacity than winter DOM. Furthermore, DOM with different MWs had significantly different Cu binding properties. In addition, Cu binding with microbially derived LMW-DOM mainly caused the change in the peak at 280 nm, while binding with terrigenous HMW-DOM resulted in the change of the 210 nm peak. Compared with the HMW-DOM, most of the LMW-DOM had stronger Cu-binding ability. Correlation analysis indicates that metal binding ability of DOM mainly depends on its concentration, number of unsaturated bonds and benzene rings, and types of substituents during interactions. This work provides an improved understanding of the metal-DOM binding mechanism, the role of composition- and MW-dependent DOM from different sources, and thus the transformation and environmental/ecological role of metals in aquatic systems.

Seasonal variations in dissolved organic matter concentration and composition in an outdoor system for bank filtration simulation

Dissolved organic matter (DOM) in surface waters can vary markedly in character depending on seasonal variations such as rainfall intensity, UV radiations and temperature. Changes in DOM as well as temperature and rainfall intensity over the year can affect the biochemical processes occurring in bank filtration (BF). Identification and characterization of DOM in the surface water could help to optimize the water treatment and provide stable and safe drinking water. This study investigated year-long variations of DOM concentrations and compositions in a surface water of a circulated outdoor pond (research facility) connected to a BF passage. DOM was dominated by humic substances and a changing pattern of DOM in surface water was observed throughout the year. A significant increase of DOM (∼ 38%) in surface water was noted in August compared to November. The fluorescent DOM showed that DOM in summer was enriched with the degradable fraction whilst non-degradable fraction was dominated in winter. A constant (1.7 ± 0.1 mg/L) effluent DOM was recirculated in the system throughout the year. DOM removal through BF varied between 4% to 39% and was achieved within a few meters after infiltration and significantly correlated with influent DOM concentration (R2 = 0.82, p < 0.05). However, no significant (p > 0.05) change in the removal of DOM was observed in two subsurface layers (upper and lower). This study highlights the presence of a constant non-degradable DOM in the bank filtrate, which was not affected by temperature, redox conditions and UV radiations.

Composition of dissolved organic matter (DOM) in lakes responds to the trophic state and phytoplankton community succession

Dissolved organic matter (DOM), a heterogeneous mixture of diverse compounds with different molecular weights, is crucial for the lake carbon cycle. The properties and concentration of DOM in lakes are closely related to anthropogenic activities, terrigenous input, and phytoplankton growth. Thus, the lake's trophic state, along with the above factors, has an important effect on DOM. We determined the DOM sources and molecular composition in six lakes along a trophic gradient during and after phytoplankton bloom by combining optical techniques and the Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS). CDOM pools in eutrophic lakes may be more biologically refractory than in oligotrophic and mesotrophic lakes. Molecular formulas of DOM were positively correlated with the TSI (trophic state index) value (R2 = 0.73), with the nitrogen-containing compounds (CHON) being the most abundant formulas in all studied lakes. Eutrophication modified the molecular formulas of DOM to have less CHO% and more heteroatom S-containing compounds (CHOS% and CHNOS%), and this was the synactic result of the anthropogenic perturbation and phytoplankton proliferation. In eutrophic lakes, summer DOM showed higher molecular lability than in autumn, which was related to the seasonal phytoplankton community succession. Although the phytoplankton-derived DOM is highly bioavailable, we detected a simpler and more fragile phytoplankton community ecosystem in autumn, which may be accompanied by a lower phytoplankton production and metabolic activity. Therefore, we concluded that the lake eutrophication increased the allochthonous DOM accumulation along with sewage and nutrient input, and subsequently increased its release with phytoplankton bloom. Eutrophication and phytoplankton growth are accompanied by more highly unsaturated compounds, O3S+O5S compounds, and carboxylic-rich alicyclic compounds (CRAMs), which are the biotransformation product of phytoplankton-derived DOM. Eutrophication may be a potential source of refractory DOM compounds for biodegradation and photodegradation. Our results can clarify the potential role of water organic matter in the future global carbon cycle processes, considering the increasing worldwide eutrophication of inland waters.

Spectral Characteristics Change in Dissolved Organic Matter in Urban River Under the Influences of Different Intensities of Non-point Source Pollution

With the method of ultraviolet-visible absorption spectroscopy (UV-vis) and excitation-emission matrix spectroscopy combined with parallel factor analysis (EEMs-PARAFAC), this study analyzed the change in dissolved organic matter (DOM) content and composition in spring and summer of two non-point source urban rivers which had different input intensities. The results indicated that the level of humification and molecular weight of DOM in summer was significantly higher than that in spring in these two rivers (P<0.01). The PARAFAC model was used to analyze four chemical compositions, including C1 (UVC fulvic-like), C2 (tryptophan-like), C3 (humic-like), and C4 (UVA fulvic-like); furthermore, C1[(31±6)%] and C2[(31±4)%] were the main fluorescent contents of the water. The high non-point source input river had a higher fluorescence intensity of all four PARAFAC components in spring than in summer, contrary to the low non-point source input river. The random forest regression model showed that C3% had the highest sensitivity to the changes in water parameters (R2=0.75, P<0.001) and could be an effective indicator. Additionally, the coverage level of the water surface (Cover) had an essential effect on the prediction of C4% (P<0.001), and C4% was susceptible to photochemical oxidation. According to the principal component analysis (PCA) and Adonis test, nitrogen and phosphorus were the essential impetuses for the biological process of the river; non-point source inputs and seasonal changes had a significant impact on the urban river (R2=0.775, P<0.001). The contents and compositions of urban river DOM were affected by many essential factors. Non-point source inputs improved the input level of terrestrial humus in the water and promoted the biological process at the same time, dynamically contributing to the changes in the DOM of the water body.

Travel Time and Source Variation Explain the Molecular Transformation of Dissolved Organic Matter in an Alpine Stream Network

AbstractStreams and rivers are important components of the carbon cycle as they transport and transform dissolved organic matter (DOM). Using high‐resolution Fourier‐transform ion cyclotron resonance mass spectrometry, we studied the spatial distribution of DOM at the molecular level at more than 100 sites across a stream network during summer and winter baseflow. We developed a model approximating the time DOM spent in the fluvial network, a key constraint on the biogeochemical processing of DOM. Discharge‐weighted travel time explained the compositional changes of DOM, which differed markedly in summer and winter. We attribute these seasonal differences to variation in source material, putatively reflecting the dynamics of freshly produced DOM in summer and DOM with an imprint of leaf litter in winter. Hydrological mixing was an important driver of the spatial dynamics of DOM. From the convergence rate of DOM compound intensities to the network‐wide average, we inferred the spatial distribution of sources within the catchment. Finally, we estimated network‐wide apparent mass transfer coefficients (vf app) of individual DOM compounds, which describe the vertical velocity at which DOM compounds are removed by biotic and abiotic processes. We identified the oxidative state of carbon as an important factor explaining vf app, which we consequently attribute to biological uptake of thermodynamically favorable DOM compounds. This work contributes to our understanding of the spatial processes, temporal constraints, and chemical properties of DOM that regulate the transformation and diagenesis of DOM at the fluvial network scale.

Measuring the influence of environmental conditions on dissolved organic matter biodegradability and optical properties: a combined field and laboratory study

Fluorescence spectroscopy is a common tool to assess optical dissolved organic matter (DOM) and a number of characteristics, including DOM biodegradability, have been inferred from these analyses. However, recent findings on soil and DOM dynamics emphasize the importance of ecosystem-scale factors, such as physical separation of substrate from soil microbial communities and soil physiochemical cycles driving DOM stability. We apply this principle to soil derived DOM and hypothesize that optical properties can only supply information on biodegradability when evaluated in the larger ecosystem because substrate composition and the activity/abundance of the microbial community ultimately drive DOM degradation. To evaluate biodegradability in this context, we assessed aqueous soil extracts for water extractable organic carbon (WEOC) content, biodegradability, microbial biomass and DOM characteristics using fluorescence spectroscopy across a range of environmental conditions (covariant with season and land use) in northern Vermont, USA. Our results indicate that changes in environmental conditions affect composition, quantity, and biodegradability of DOM. WEOC concentrations were highest in the fall and lowest in the summer, while no significant differences were found between land covers; however, DOM biodegradability was significantly higher in the agricultural site across seasons. Despite a shift in utilized substrate from less aromatic DOM in summer to more aromatic DOM in winter, biodegradability was similar for all seasons. The only exception was cold temperature incubations where microbial activity was depressed, and processing was slowed. These results provide examples on how fluorescence based metrics can be combined with context relevant environmental parameters to evaluate bioavailability in the context of the larger ecosystem.

Transformation of dissolved organic matter and related trace elements in the mouth zone of the largest European Arctic river: experimental modeling

The relationship between dissolved organic matter (DOM) and heterotrophic bacterioplankton controls the ecological status of freshwater ecosystems and the fate of metals in aquatic environments. To improve our understanding of physicochemical and biological processes controlling the DOC and related trace elements in the Arctic estuary, we conducted experiments of the biodegradation and physicochemical coagulation of DOM and associated trace elements. For the experiments, water from the estuarine zone of the Severnaya Dvina River in Russia, the largest pristine European Arctic river, was mixed with sterile river water from the freshwater zone, sampled during spring flood in June and summer base flow in August. We revealed a lack of transformation of allochthonous organic matter in spring and measurable degradation of more autochthonous DOM in summer. According to their behavior during incubation experiments, several groups of trace metals were distinguished, comprising (1) nonconservative Fe, Mn, Al, trivalent (Ga, Y, rare earth elements) and tetravalent (Ti, Zr, Hf, Th) hydrolysates, subjected to significant removal from solution, especially at low salinities (0.5–2.5‰); and (2) divalent metals such as Ba, Cd, and Pb, subjected to desorption from suspended particulate matter. The trace elements present in the form of oxyanions and neutral molecules (B, Si, As, Sb, Mo) and alkalis (Rb) exhibited highly conservative behavior with negligible removal from the freshwater–seawater mixtures. The spring flood, providing the largest contribution to the annual riverine flux to the ocean, demonstrated high stability of freshwater dissolved organic carbon (DOC) and divalent metals (Cu, Zn, Ni, Cd) to both physicochemical coagulation and biodegradation. This may imply a less significant transformation of the riverine DOC and metal micronutrients delivery to the Arctic Ocean compared to a traditional estuarine removal scheme.

Carbon dynamics in highly heterotrophic subarctic thaw ponds

Abstract. Global warming has accelerated the formation of permafrost thaw ponds in several subarctic and arctic regions. These ponds are net heterotrophic as evidenced by their greenhouse gas (GHG) supersaturation levels (CO2 and CH4), and generally receive large terrestrial carbon inputs from the thawing and eroding permafrost. We measured seasonal and vertical variations in the concentration and type of dissolved organic matter (DOM) in five subarctic thaw (thermokarst) ponds in northern Quebec, and explored how environmental gradients influenced heterotrophic and phototrophic biomass and productivity. Late winter DOM had low aromaticity indicating reduced inputs of terrestrial carbon, while the high concentration of dissolved organic carbon (DOC) suggests that some production of non-chromophoric dissolved compounds by the microbial food web took place under the ice cover. Summer DOM had a strong terrestrial signature, but was also characterized with significant inputs of algal-derived carbon, especially at the pond surface. During late winter, bacterial production was low (maximum of 0.8 mg C m−3 d−1) and was largely based on free-living bacterioplankton (58 %). Bacterial production in summer was high (up to 58 mg C m−3 d−1), dominated by particle-attached bacteria (67 %), and strongly correlated with the amount of terrestrial carbon. Primary production was restricted to summer surface waters due to strong light limitation deeper in the water column or in winter. The phototrophic biomass was equal to the heterotrophic biomass, but as the algae were mostly composed of mixotrophic species, most probably they used bacteria rather than solar energy in such shaded ponds. Our results point to a strong heterotrophic energy pathway in these thaw pond ecosystems, where bacterioplankton dominates the production of new carbon biomass in both summer and winter.

Molecular and structural characterization of dissolved organic matter during and post cyanobacterial bloom in Taihu by combination of NMR spectroscopy and FTICR mass spectrometry

Seasonal molecular changes in dissolved organic matter (DOM) isolated from Tai Lake (Taihu) both during (June) and following (November) an algal bloom event in 2007 were characterized by nuclear magnetic resonance spectroscopy (NMR) and Fourier transform ion cyclotron resonance (FTICR) mass spectrometry. Considerable biosignatures were present in summer DOM, yet with a near absence of algal extract compounds. Extensive molecular alteration resulting from multistep and massively parallel biotic and subordinated abiotic transformations of algal biomass to DOM included loss and synthesis of carbohydrates, fundamental changes of aromatic compounds and progressive formation of carboxyl-rich alicyclic compounds (CRAM). The DOM transformation from summer to fall resulted in smaller molecules, increased abundance of CHNO continuous molecular series and overall molecular diversity. Analysis of MS-derived compositional networks placed summer DOM in-between the algal extract and fall DOM. Metabolic pathway annotation by means of high-resolution mass analysis provided a wide range of pathways associated with secondary metabolites in DOM and more basic ones like carbohydrate metabolism characteristic of algal extract compounds. Overall, the time-dependent molecular signature of Taihu DOM was likely dominated by microbial metabolism rather than abiotic chemical transformations. Results from this study indicate that high-resolution organic structural spectroscopy resolves meaningful structural detail out of complex environmental mixtures and has the potential to contribute significantly to future functional biodiversity studies.

Depth-dependent molecular composition and photo-reactivity of dissolved organic matter in a boreal lake under winter and summer conditions

Abstract. Transformations of dissolved organic matter (DOM) in boreal lakes lead to large greenhouse gas emissions as well as substantial carbon storage in sediments. Using novel molecular characterization approaches and photochemical degradation experiments we studied how seasonal patterns in water column stratification affected the DOM in a Swedish lake under early spring and summer conditions. Dissolved organic carbon (DOC) concentrations were consistently higher above the sediment when compared to surface waters throughout the sampling periods. Photobleaching alone could not explain this difference in DOC because the lake was covered by 40 cm-thick ice during late winter sampling and still showed the same DOC trend. The differences in the molecular diversity between surface DOM in winter and summer were consistent with ongoing photobleaching/decarboxylation and a possible bacterial consumption of photo-products. Additional photo-degradation experiments using simulated sunlight showed a production of highly oxidized organic molecules and low molecular weight compounds in all late winter samples and also in the deep water sample in summer. In the surface summer DOM sample, few such molecules were produced during the photo-degradation experiments, confirming that DOM was already photobleached prior to the experiments. This study suggests that photobleaching, and therefore also the ice cover during winter, plays a central role in surface DOM transformation, with important differences in the molecular composition of DOM between surface and deep boreal lake waters. The release of DOC from boreal lake sediments also contribute to this pattern. Photochemical degradation of DOM may be more extensive following ice-out and water column turnover when non-light exposed and thereby photosensitive DOM is photo-mineralized. Hence, the yearly DOM photo-mineralization may be greater than inferred from studies of recently light-exposed DOM.

Lakes as buffers of stream dissolved organic matter (DOM) variability: Temporal patterns of DOM characteristics in mountain stream-lake systems

[1] Lakes within fluvial networks may affect dissolved organic matter (DOM) dynamics in streams by dampening spring DOM snowmelt flushing responses and/or by increasing summer DOM production. We assessed the temporal variability of dissolved organic carbon (DOC) concentration and DOM characteristics (specific ultraviolet absorbance (SUVA254); DOC:dissolved organic nitrogen (DOC:DON)), as well as DOC export in seven paired lake inflows and outflows in the Sawtooth Mountain lake district, Idaho. We hypothesized that lakes would decrease stream DOM temporal variability and increase DOM export as a result of autotrophic production. We correlated DOM variability with landscape factors to evaluate potential drivers of DOM temporal patterns (measured as coefficient of variation). Coefficients of variation were 40–90% higher in lake inflows than outflows for DOC concentrations, characteristics, and DOC:DON. Increases in DOC concentrations on the ascending limb of the snowmelt hydrograph were greater in lake inflows than outflows, and on average mean DOC flux occurred 5.4 days earlier in the inflows than for the outflows. During base flow, mean outflow DOC concentrations were 1.7 times greater than inflows, and six outflows had higher annual export than inflows. Combined, these results illustrate that lakes alter the magnitude, timing and temporal variation of DOM concentration and characteristics exported from subalpine watersheds. This buffering effect results from a seasonal shift in the balance between hydrological versus biological controls on DOC dynamics, where lakes act as a sink during the spring when hydrologic controls dominate watershed DOM transport and act as a DOM source during summer.

Characterization of dissolved organic matter across the Subtropical Convergence off the South Island, New Zealand

Dissolved organic matter (DOM) was investigated along a gradient across the Subtropical Convergence (STC) off the South Island, New Zealand. Ultrahigh resolution electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS), excitation emission matrix fluorescence (EEM) spectroscopy, and molecular lignin analysis techniques were used to study this DOM. The analysis revealed a group of compounds found only in the coastal DOM samples, which were also characterized by an elevated terrestrial DOM fluorescence pattern and elevated lignin content if compared to the offshore samples. This group exhibited a high degree of carbon unsaturation, as evident from high double bond equivalence minus oxygen values (DBE-O > 9) and maximum fluorescence intensity. Sulfur-containing molecular formulae for summer DOM samples were much more abundant across the entire transect of the STC compared to winter and exhibited distinctly different hydrogen:carbon and oxygen:carbon elemental ratios, suggesting a possible correlation between biological activity and sulfur compounds. The molecular formulae common to all STC samples were compared with those calculated for DOM extracted from freshwater collected from a stream discharging into Doubtful Sound (West Coast, New Zealand). ESI-FT-ICR-MS measurements undertaken in negative electrospray ionization (ESI−) mode indicated that 30% of the molecular formulae were present in both types of DOM, while in positive ESI mode (ESI+) over 90% of the formulae were present in all samples. Hence, a significant portion of the molecular formulae assigned to the solid-phase extractable DOM pool (SPE-DOM) appear to be identical in oceanic and freshwater samples.