High Dissolved Organic Matter Concentrations Research Articles

Biogas slurry-derived dissolved organic matter inhibited oxytetracycline adsorption by tropical agricultural soils

The increasing presence of oxytetracycline (OTC) in agricultural soils has raised global environmental concerns. We investigated the environmental behavior and fate of OTC in two types of tropical agricultural soils, focusing on the impact of dissolved organic matter (DOM) from biogas slurry. Techniques such as three-dimensional excitation-emission matrix fluorescence spectroscopy (3D-EEM), Fourier Transform Infrared (FTIR), X-ray photoelectron spectroscopy (XPS), and Ultraviolet-visible spectrophotometer (UV–vis) were used to explore the adsorption mechanisms. Our findings revealed that biogas slurry-derived DOM decreased the OTC adsorption on soils and extended the time to reach adsorption equilibrium. Specifically, the equilibrium adsorption of OTC by the two soils decreased by 19.41 and 15.32 %, respectively. These adsorption processes were effectively modelled by Elovich, intraparticle diffusion, linear, and Freundlich thermodynamic models. Thermodynamic parameters suggested that OTC adsorption onto soils was spontaneous and endothermic, with competitive interactions between biogas slurry-derived DOM and OTC molecules intensifying at higher DOM concentrations. The adsorption mechanisms were governed by both physical and chemical processes. Furthermore, the presence of Ca2+ and Na+ ions significantly inhibited OTC adsorption. These insights advanced our understanding of the fate and risk of OTC in soil environments influenced by DOM, contributing to more informed agricultural and environmental management practices.

Groundwater solutes influence the adsorption of short-chain perfluoroalkyl acids (PFAA) to colloidal activated carbon and impact performance for in situ groundwater remediation

Subsurface injection of colloidal activated carbon (CAC) is an in situ remediation strategy for perfluoroalkyl acids (PFAA), but the influence of groundwater solutes on longevity is uncertain, particularly for short-chain PFAA. We quantify the impact of inorganic anions, dissolved organic matter (DOM), and stabilizing polymer on PFAA adsorption to a commercial CAC. Surface characterization supported PFAA chain-length dependent adsorption results and mechanisms are provided. Inorganic anions decreased adsorption for short-chain PFAA (<7 perfluorinated carbons) due to competitive effects, while long-chain PFAA (≥ 7 perfluorinated carbons) were less impacted. DOM decreased adsorption of all PFAA in a chain-length dependent manner. High DOM concentrations (10 mg/L, ∼5 mg OC/L) decreased PFOA adsorption by a factor of 2, PFPeA by one order of magnitude, and completely hindered PFBA adsorption. High MW DOM has less impact on short-chain PFAA than low MW DOM, possibly due to differences in the ability to access CAC micropores. Low DOM concentrations (1 mg/L, ∼0.5 mg OC/L) did not impact adsorption. CMC (90 kDa average MW) had negligible impact on PFAA adsorption likely due to minimal CAC surface coverage. Longevity modeling demonstrated that groundwater solutes limit the capacity for PFAA in a CAC barrier, particularly for short-chain PFAA.

Binding of Dissolved Organic Matter to RNA and Protection from Nuclease-Mediated Degradation.

The persistence of RNA in environmental systems is an important parameter for emerging applications, including ecological surveys, wastewater-based epidemiology, and RNA interference biopesticides. RNA persistence is controlled by its rate of biodegradation, particularly by extracellular enzymes, although the specific factors determining this rate have not been characterized. Due to prior work suggesting that nucleic acids-specifically DNA-interact with dissolved organic matter (DOM), we hypothesized that DOM may bind RNA and impede its biodegradation in natural systems. We first adapted a technique previously used to assess RNA-protein binding to differentiate RNA that is bound at all sites by DOM from RNA that is unbound or partially bound by DOM. Results from this technique suggested that humic acids bound RNA more extensively than fulvic acids. At concentrations of 8-10 mgC/L, humic acids were also found to be more effective than fulvic acids at suppressing enzymatic degradation of RNA. In surface water and soil extract containing DOM, RNA degradation was suppressed by 39-46% relative to pH-adjusted controls. Due to the ability of DOM to both bind and suppress the enzymatic degradation of RNA, RNA biodegradation may be slowed in environmental systems with high DOM concentrations, which may increase its persistence.

Mercury Sources and Fate in a Large Brackish Ecosystem (the Baltic Sea) Depicted by Stable Isotopes.

Identifying Hg sources to aquatic ecosystems and processes controlling the levels of monomethylmercury (MMHg) is critical for developing efficient policies of Hg emissions reduction. Here we measured Hg concentrations and stable isotopes in sediment, seston, and fishes from the various basins of the Baltic Sea, a large brackish ecosystem presenting extensive gradients in salinity, redox conditions, dissolved organic matter (DOM) composition, and biological activities. We found that Hg mass dependent fractionation (Hg-MDF) values in sediments mostly reflect a mixing between light terrestrial Hg and heavier industrial sources, whereas odd Hg isotope mass independent fractionation (odd Hg-MIF) reveals atmospheric inputs. Seston presents intermediate Hg-MDF and odd Hg-MIF values falling between sediments and fish, but in northern basins, high even Hg-MIF values suggest the preferential accumulation of wet-deposited Hg. Odd Hg-MIF values in fish indicate an overall low extent of MMHg photodegradation due to limited sunlight exposure and penetration but also reveal large spatial differences. The photodegradation extent is lowest in the central basin with recurrent algal blooms due to their shading effect and is highest in the northern, least saline basin with high concentrations of terrestrial DOM. As increased loads of terrestrial DOM are expected in many coastal areas due to global changes, its impact on MMHg photodegradation needs to be better understood and accounted for when predicting future MMHg concentrations in aquatic ecosystems.

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.

Effects of dissolved organic matter derived from two herbs on the growth, physiology, and physico-chemical characteristics of four bloom-forming algae species

While algal blooms occur frequently in lakes and reservoirs worldwide, the effects of dissolved organic matter (DOM) from lakeside and riparian zones on bloom formation are not well understood. In this study, we characterized the molecular composition of DOM from Cynodon dactylon (L.) Pers. (CD-DOM) and Xanthium sibiricum Patrin ex Widder (XS-DOM) and assessed their effects on the growth, physiology, volatile organic compounds (VOCs), and stable carbon isotope in four bloom-forming algae species (Microcystis aeruginosa, Anabaena sp., Chlamydomonas sp., and Peridiniopsis sp.). Stable carbon isotope analysis showed that the four species were affected by DOM. Both DOM types increased the cell biomass, polysaccharide and protein contents, chlorophyll fluorescence parameter values, and VOCs release of Anabaena sp., Chlamydomonas sp. and Microcystis aeruginosa, suggesting that DOM stimulated algal growth by increasing nutrient sources, photosynthetic efficiency, and stress tolerance. And in general, these three strains exhibited better growth at higher DOM concentrations. However, DOM treatment inhibited the growth of Peridiniopsis sp., as indicated by the increases in reactive oxygen species, damage in photosystem II reaction centers, and blockage in electron transport. Fluorescence analysis showed that tryptophan-like compounds were the main DOM components that affected algal growth. Molecular-level analysis suggested that unsaturated aliphatic compounds may be the most important DOM components. The findings indicate that CD-DOM and XS-DOM promote the blue-green algal blooms formation and thus should be considered in the management of natural water quality.

The Composition of Dissolved Organic Matter in Arable Lands: Does Soil Management Practice Matter?

Dissolved organic matter (DOM) is a key soil quality property, indicative of the organic matter stored in the soil, which may also be a function of temporal variation. This study examines whether DOM is a robust property of the soil, controlling fertility, or if it may change with time. Altogether eight sets of soil samples were collected in 2018 and 2019 from the cultivated topsoil (0–10 cm) of cropland and from a nearby grassland near Martonvásár, Hungary. The study sites were characterized by Chernozem soil and were part of a long-term experimental project comparing the effects of manure application and fertilization to the control under maize and wheat monocultures. DOM was extracted from the samples with distilled water. The dissolved organic carbon (DOC), total dissolved nitrogen (DN), biological index (BIX), fluorescence index (FI), humification index (HIX), carbon nitrogen (C/N) ratio and specific ultraviolet absorbance at 254 nm (SUVA254) index were studied in the arable soils, and the results showed that all the DOM samples were humified, suggesting relevant microbiological contributions to the decomposition of OM and its conversion into more complex molecules (FI = 1.2–1.5, BIX = ~0.5, and HIX = ~0.9). Temporal variations were detected only for the permanent grassland where higher DOM concentration was found in spring. This increased DOM content mainly originated from humified, solid phase associated, recalcitrant OM. In contrast, there were no differences among fertilization treatments and sampling dates under cropfield conditions. Moreover, climatic conditions were not proven as a general ruler of DOM properties. Therefore, momentary DOM alone is not necessarily the direct property of soil organic matter under cropfield conditions. The application of this measure needs further details of sampling conditions to achieve adequate comparability.

Spatial Complexity in Dissolved Organic Matter and Trace Elements Driven by Hydrography and Freshwater Input Across the Arctic Ocean During 2015 Arctic GEOTRACES Expeditions

AbstractThis study traces dissolved organic matter (DOM) in different water masses of the Arctic Ocean and its effect on the distributions of trace elements (TEs; Fe, Cu, Mn, Ni, Zn, Cd) using fluorescent properties of DOM and the terrigenous biomarker lignin. The Nansen, Amundsen, and Makarov Basins were characterized by the influence of Atlantic water and the fluvial discharge of the Siberian Rivers with high concentrations of terrigenous DOM (tDOM). The Canada Basin and the Chukchi Sea were characterized by Pacific water, modified through contact with productive shelf sediments with elevated levels of marine DOM. Within the surface layer of the Beaufort Gyre, meteoric water (river water and precipitation) was characterized by low concentrations of lignin and tDOM fluorescence proxies as DOM is removed during freezing. High‐resolution in situ fluorescence profiles revealed that DOM distribution closely followed isopycnals, indicating the strong influence of sea‐ice formation and melt, which was also reflected in strong correlations between DOM fluorescence and brine contributions. The relationship of DOM and hydrography to TEs showed that terrigenous and marine DOM were likely carriers of dissolved Fe, Ni, Cu from the Eurasian shelves into the central Arctic Ocean. Chukchi shelf sediments were important sources of dCd, dZn, and dNi, as well as marine ligands that bind and carry these TEs offshore within the upper halocline in the Canada Basin. Our data suggest that tDOM components represent stronger ligands relative to marine DOM components, potentially facilitating the long‐range transport of TE to the North Atlantic.

Comparing the influence of humic/fulvic acid and tannic acid on Cr(VI) adsorption onto polystyrene microplastics: Evidence for the formation of Cr(OH)3 colloids

Microplastics (MPs) can act as vectors for various contaminants in the aquatic environment. Although some research has investigated the adsorption characteristics and influencing factors of metals/organic molecules on MPs, the effects of dissolved organic matter (DOM) (which are ubiquitous active species in ecosystems) on metal oxyanions such as Cr(VI) capture by MPs are largely unknown. This study explored the adsorption behaviors and mechanisms of Cr(VI) oxyanions onto polystyrene (PS) MPs using batch adsorption experiments and multiple spectroscopic methods. The effects of representative DOM components (i.e., humic acid (HA), fulvic acid (FA) and tannic acid (TA)) on Cr(VI) capture by PS were particularly studied. Results revealed a significantly enhanced adsorption of Cr(VI) on PS in the presence of TA. The Cr(VI) adsorption capacity was increased from 2876 μg g−1 to 4259 μg g−1 and 5135 μg g−1 when the TA concentrations raised from 0 to 10 and 20 mg L−1, respectively. Combined microscopic and spectroscopic investigations revealed that Cr(VI) was reduced to Cr(III) by TA and formed stable Cr(OH)3 colloids on PS surfaces. Contrarily, HA and FA inhibited Cr(VI) adsorption onto PS, especially at pH > 2.0 and higher DOM concentrations, due to site competition and electrostatic repulsion. Increase in pH was found to reduce zeta potentials of MPs, resulting in inhibited Cr(VI) adsorption. The adsorbed Cr(VI) declined with increasing ionic strength, implying that outer-sphere surface complexation affected the adsorption process in the presence of DOM. These new findings improved our fundamental understanding of the fate of Cr(VI) and MPs in DOM-rich environmental matrices.

Drought Reduces Release of Plant Matter Into Dissolved Organic Matter Potentially Restraining Ecosystem Recovery

Future climate scenarios indicate increasing drought intensity that threatens ecosystem functioning. However, the behavior of ecosystems during intense drought, such as the 2018 drought in Northern Europe, and their respective response following rewetting is not fully understood. We investigated the effect of drought on four different vegetation types in a temperate climate by analyzing dissolved organic matter (DOM) concentration and composition present in soil leachate, and compared it to two accompanying years. DOM is known to play an important role in ecosystem recovery and holds information on matter flows between plants, soil microorganisms and soil organic matter. Knowledge about DOM opens the possibility to better disentangle the role of plants and microorganisms in ecosystem recovery. We found that the average annual DOM concentration significantly decreased during the 2018 drought year compared to the normal year. This suggests a stimulation of DOM release under normal conditions, which include a summer drought followed by a rewetting period. The rewetting period, which holds high DOM concentrations, was suppressed under more intense drought. Our detailed molecular analysis of DOM using ultrahigh resolution mass spectrometry showed that DOM present at the beginning of the rewetting period resembles plant matter, whereas in later phases the DOM molecular composition was modified by microorganisms. We observed this pattern in all four vegetation types analyzed, although vegetation types differed in DOM concentration and composition. Our results suggest that plant matter drives ecosystem recovery and that increasing drought intensity may lower the potential for ecosystem recovery.

Multiproxy probing of anthropogenic influences on the different components of dissolved organic matter in coastal rainwater

In an environment that is tightly linked to humankind, how anthropogenic activity affects the quality and quantity of dissolved organic matter (DOM) in atmospheric depositions is not well understood. In this study, dissolved organic carbon (DOC), UV–vis spectra combined with molecular markers, including formic acid (FA), acetic acid (AA) and dissolved black carbon (DBC), were applied to track the temporal variation and influential factors of rainwater DOM at a coastal site. The ranges of DOC, light absorption at 254 nm (a254), FA, AA and DBC were 23.2–471 μmol L−1, 0.16–10.6 m−1, 0.12–23.5 μmol L−1, 0.44–37.8 μmol L−1 and 0.02–4.8 μmol L−1, respectively. The negative correlations between DOC, a254, AA and precipitation amount revealed a dilution effect. The concentrations of all measured DOM components were statistically different among different seasons with the highest value in spring. Higher DOM concentrations also occurred in the rain with backward trajectories influenced by the land. Compared to the nearby riverine DOM, the DOC-specific UV absorbance (SUVA254) of rainwater was lower, suggesting lower aromaticity of rainwater DOM. Significant correlations among different DOM components suggest that they shared similar sources or were affected by the same processes, while the significant correlations with anions (SO42−, F− and NO3−) and the ratio of FA to AA all suggested that the direct emission and secondary production from anthropogenic emissions (fossil fuel burning, biomass and biofuel burning) played important roles in regulating the level of DOM concentration in rainwater. Correlations with environmental variables (PM2.5, CO and NO2) further confirmed the input from anthropogenic activities. Furthermore, the monthly wet atmospheric deposition fluxes of DOM components (except DBC) can be successfully simulated by monthly precipitation and monthly average values of PM2.5 and NO2. Future studies should examine how atmospheric deposition affects the biogeochemical cycles in coastal regions.

Review on the interactions of arsenic, iron (oxy)(hydr)oxides, and dissolved organic matter in soils, sediments, and groundwater in a ternary system

High concentrations of arsenic (As) in groundwater threaten the environment and public health. Geogenically, groundwater As contamination predominantly occurs via its mobilization from underground As-rich sediments. In an aquatic ecosystem, As is typically driven by several underlying processes, such as redox transitions, microbially driven reduction of iron (Fe) oxide minerals, and release of associated As. Notably, dissolved As mobilized from soils and sediments exhibits high affinity for dissolved organic matter (DOM). Thus, high DOM concentrations can increase As mobility. Therefore, it is crucial to understand the complex interactions and biogeochemical cycling of As, DOM, and Fe oxides. This review collates knowledge regarding the fate of As in multicomponent As–DOM–Fe systems, including ternary complexes involving both Fe and DOM. Additionally, the release mechanisms of As from sediments into groundwater in the presence of both Fe and DOM have been discussed. The mechanisms of As mobilization/sorption at the solid–water interface can be affected by negatively charged DOM competing for sorption sites with As on Fe (oxy)(hydr)oxides and may be further modified by other anionic ubiquitous species such as phosphate, silicic acid, or sulfur. This review emphasizes the need for a comprehensive understanding of the impact of DOM, Fe oxides, and related biogeochemical processes on As mobilization to aquifers. The review identifies important knowledge gaps that may aid in developing applicable practices for preventing the spread of As contamination in aquatic resources and traditional soil management practices.

Succession of marine bacteria in response to Ulva prolifera-derived dissolved organic matter

Increasing macroalgal blooms as a consequence of climate warming and coastal eutrophication have profound effects on the marine environment. The outbreaks of Ulva prolifera in the Yellow Sea of China occurring every summer since 2007 to present have formed the world’s largest green tide. The green tide releases huge amounts of dissolved organic matter (DOM) to the seawater, causing an organic overload. However, how marine bacteria respond to this issue and the potential impact on the marine environment are still unclear. Here, we monitored the highly temporally resolved dynamics of marine bacterial community that occur in response to Ulva prolifera-derived DOM by performing a 168-h microcosm incubation experiment. DOM inputs significantly increased bacterial abundances within 6 h, decreased bacterial diversity and triggered clear community successions during the whole period of incubation. Vibrio of Gammaproteobacteria robustly and rapidly grew over short timescales (6–24 h), with its relative abundance accounting for up to 52.5% of active bacteria. From 24 to 48 h, some genera of Flavobacteriia grew rapidly, which was more conspicuous at a higher DOM concentration than at a lower concentration. The genus Donghicola of Alphaproteobacteria was predominant at later time points (>48 h). This bacterial community succession was accompanied by significant variations in the activity of 12 different extracellular enzymes, resulting in a rapid reduction of dissolved organic carbon by 74.5% within the first 36 h. In summary, our study demonstrates rapid successions of bacterial community and extracellular enzyme activity after DOM inputs, suggesting that the bacterial response to Ulva prolifera-derived organic matter may contribute to environmental restoration and may pose a health threat due to the bloom of potential pathogenic Vibrio.

Plant diversity enhances production and downward transport of biodegradable dissolved organic matter

Abstract Plant diversity is an important driver of below‐ground ecosystem functions, such as root growth, soil organic matter (SOM) storage and microbial metabolism, mainly by influencing the interactions between plant roots and soil. Dissolved organic matter (DOM), as the most mobile form of SOM, plays a crucial role for a multitude of soil processes that are central for ecosystem functioning. Thus, DOM is likely to be an important mediator of plant diversity effects on soil processes. However, the relationships between plant diversity and DOM have not been studied so far. We investigated the mechanisms underlying plant diversity effects on concentrations of DOM using continuous soil water sampling across 6 years and 62 plant communities in a long‐term grassland biodiversity experiment in Jena, Germany. Furthermore, we investigated plant diversity effects on the molecular properties of DOM in a subset of the samples. Although DOM concentrations were highly variable over the course of the year with highest concentrations in summer and autumn, we found that DOM concentrations consistently increased with plant diversity across seasons. The positive plant diversity effect on DOM concentrations was mainly mediated by increased microbial activity and newly sequestered carbon in topsoil. However, the effect of soil microbial activity on DOM concentrations differed between seasons, indicating DOM consumption in winter and spring, and DOM production in summer and autumn. Furthermore, we found increased contents of small and easily decomposable DOM molecules reaching deeper soil layers with high plant diversity. Synthesis. Our findings suggest that plant diversity enhances the continuous downward transport of DOM in multiple ways. On the one hand, higher plant diversity results in higher DOM concentrations, on the other hand, this DOM is less degraded. This study indicates, for the first time, that higher plant diversity enhances the downward transport of dissolved molecules that likely stimulate soil development in deeper layers and therefore increase soil fertility.

Origin and fate of dissolved organic matter in four shallow Baltic Sea estuaries

Coastal waters have strong gradients in dissolved organic matter (DOM) quantity and characteristics, originating from terrestrial inputs and autochthonous production. Enclosed seas with high freshwater input therefore experience high DOM concentrations and gradients from freshwater sources to more saline waters. The brackish Baltic Sea experiences such salinity gradients from east to west and from river mouths to the open sea. Furthermore, the catchment areas of the Baltic Sea are very diverse and vary from sparsely populated northern areas to densely populated southern zones. Coastal systems vary from enclosed or open bays, estuaries, fjords, archipelagos and lagoons where the residence time of DOM at these sites varies and may control the extent to which organic matter is biologically, chemically or physically modified or simply diluted with transport off-shore. Data of DOM with simultaneous measurements of dissolved organic (DO) nitrogen (N), carbon (C) and phosphorus (P) across a range of contrasting coastal systems are scarce. Here we present data from the Roskilde Fjord, Vistula and Öre estuaries and Curonian Lagoon; four coastal systems with large differences in salinity, nutrient concentrations, freshwater inflow and catchment characteristics. The C:N:P ratios of DOM of our data, despite high variability, show site specific significant differences resulting largely from differences residence time. Microbial processes seemed to have minor effects, and only in spring did uptake of DON in the Vistula and Öre estuaries take place and not at the other sites or seasons. Resuspension from sediments impacts bottom waters and the entire shallow water column in the Curonian Lagoon. Finally, our data combined with published data show that land use in the catchments seems to impact the DOC:DON and DOC:DOP ratios of the tributaries most.

Motile phytoplankton species such as Gonyostomum semen can significantly reduce CO2 emissions from boreal lakes

Boreal lakes typically have high levels of allochthonous dissolved organic matter (DOM), causing light limitation of photosynthetic CO2 consumption while stimulating CO2 production. They are therefore considered as important sources of atmospheric CO2. However, boreal lakes are also experiencing a marked expansion of bloom-forming motile phytoplankton organisms that can circumvent the shading effect of DOM by performing phototaxis and that thus might have an impact on the lakes’ CO2 balance. We tested this idea in a DOM-rich lake using the widespread raphidophyte flagellate Gonyostomum semen as model organism. Employing continuous field measurements, we found that G. semen can reduce the partial pressure of CO2 even at low algal densities. Periods with high algal densities were associated with CO2 undersaturation and invasion of atmospheric CO2. The mean daily net losses of CO2 to the atmosphere during and after a G. semen bloom were estimated at 12.9 and 70.4 mmol C m–2 day–1, respectively. G. semen caused steep pCO2 gradients in space and time, which make it difficult to unveil the species’ impact without employing continuous pCO2 vertical profiling. This suggests that the effect of G. semen on the CO2 balance of boreal lakes might have been overlooked in the past. Taken together, our data suggest that G. semen can significantly reduce the CO2 emissions from boreal lakes despite high concentrations of allochthonous DOM. G. semen and other motile phytoplankton species should therefore be considered when estimating CO2 emissions from boreal lakes, especially if these organisms continue their expansion.

Origin of dissolved organic matter in the Harz Mountains (Germany): A thermally assisted hydrolysis and methylation (THM-GC–MS) study

Environmental change is increasing the concentration of dissolved organic matter (DOM) in catchments of the Northern Hemisphere. This study aims to assess the causes of high DOM concentrations in streams and reservoirs of the Harz National Park (Germany), by means of molecular characterization using thermally assisted hydrolysis and methylation (THM-GC–MS). In order to formulate proxies of the prevailing origin of the numerous THM products of polyphenols, carbohydrates, proteins, aliphatic macromolecules, resins and other DOM precursors, we created a reference sample set of potential sources (spruce, birch, blueberry, heather, peat moss, soils) from the area. Besides solid-state reference samples (bulk organic matter; BOM) we obtained and analyzed their leachates (water-extractable OM; WEOM). Finally, an existing THM-GC–MS dataset of the DOM from the Oder river, which crosses the boundary between peat and forest biomes in the Harz, was extended and explored chemometrically using Principal Component Analysis (PCA) to test the proxies for stream DOM assessment. The results show large differences between BOM and WEOM, which suggests that the solid-to-leachate transition is highly selective or significantly alters the major biomolecular constituents. THM compounds that tend to be more abundant in WEOM than in BOM are G-type phenolic compounds (1,2-dimethoxybenzenes, from lignin and tannin), nitrogen-containing moieties and benzene carboxylic acids, whereas WEOM is depleted in products of polysaccharides, syringyl lignin and aliphatic macromolecules (cutin and suberin). The lignin fingerprint of the WEOM also differs significantly from that of BOM, being depleted in the vast majority of the typical products of macromolecular lignin (G7, G8, G14, G15) and enriched in the acid moiety (G6, predominantly from vanillic acid), especially for spruce wood. THM chromatograms of DOM from the forest section of the Oder show an extraordinary abundance of G6, most probably from spruce-derived lignin. This may indicate a major role of DOM released from decaying spruce logs and forest soils. The results highlight both the potential and the pitfalls associated with source identification of DOM using THM-GC–MS.

Dissolved organic matter composition and reactivity in Lake Victoria, the world’s largest tropical lake

We report a data set of dissolved organic carbon (DOC) concentration and dissolved organic matter (DOM) composition (stable carbon isotope signatures, absorption and fluorescence properties) obtained from samples collected in Lake Victoria, a large lake in East Africa. Samples were collected in 2018–2019 along a bathymetric gradient (bays to open waters), during three contrasting seasons: long rainy, short rainy and dry, which corresponded to distinctly water column mixing regimes, respectively, stratified, semi-stratified and mixed regimes. Eight DOM components from parallel factor analysis (PARAFAC) were identified based on three-dimensional excitation–emission matrices (EEMs), which were aggregated into three main groups of components (microbial humic-like, terrestrial humic-like, protein-like). Spatially, the more productive bays were characterized by higher DOM concentration than deeper more offshore waters (fluorescence intensity and DOC were ~ 80% and ~ 30% higher in bays, respectively). Seasonally, the DOM pool shifted from protein-like components during the mixed regime to microbial humic-like components during the semi-stratified regime and to terrestrial humic-like components during the stratified regime. This indicates that pulses of autochthonous DOM derived from phytoplankton occurred when the lake was mixing, which increased the availability of dissolved inorganic nutrients. Subsequently, this freshly produced autochthonous DOM was microbially processed during the following semi-stratified regime. In the open waters, during the stratified regime, only terrestrial refractory DOM components remained because the labile and fresh stock of DOM created during the preceding mixed season was consumed. In the bays, the high terrestrial refractory DOM during the stratified regime may be additionally due to the allochthonous DOM input from the runoff. At the scale of the whole lake, the background refractory DOM probably comes mainly from precipitation and followed by river inputs.

From canals to the coast: dissolved organic matter and trace metal composition in rivers draining degraded tropical peatlands in Indonesia

Abstract. Worldwide, peatlands are important sources of dissolved organic matter (DOM) and trace metals (TMs) to surface waters, and these fluxes may increase with peatland degradation. In Southeast Asia, tropical peatlands are being rapidly deforested and drained. The blackwater rivers draining these peatland areas have high concentrations of DOM and the potential to be hotspots for CO2 release. However, the fate of this fluvial carbon export is uncertain, and its role as a trace metal carrier has never been investigated. This work aims to address these gaps in our understanding of tropical peatland DOM and associated elements in the context of degraded tropical peatlands in Indonesian Borneo. We quantified dissolved organic carbon and trace metal concentrations in the dissolved and fine colloidal (&lt;0.22 µm) and coarse colloidal (0.22–2.7 µm) fractions and determined the characteristics (δ13C, absorbance, fluorescence: excitation-emission matrix and parallel factor – PARAFAC – analysis) of the peatland-derived DOM as it drains from peatland canals, flows along the Ambawang River (blackwater river) and eventually mixes with the Kapuas Kecil River (whitewater river) before meeting the ocean near the city of Pontianak in West Kalimantan, Indonesia. We observe downstream shifts in indicators of in-stream processing. An increase in the δ13C of dissolved organic carbon (DOC), along with an increase in the C1∕C2 ratio of PARAFAC fluorophores, and a decrease in SUVA (specific UV absorbance) along the continuum suggest the predominance of photo-oxidation. However, very low dissolved oxygen concentrations also suggest that oxygen is quickly consumed by microbial degradation of DOM in the shallow layers of water. Blackwater rivers draining degraded peatlands show significantly higher concentrations of Al, Fe, Pb, As, Ni and Cd compared to the whitewater river. A strong association is observed between DOM, Fe, As, Cd and Zn in the dissolved and fine colloid fraction, while Al is associated with Pb and Ni and present in a higher proportion in the coarse colloidal fraction. We additionally measured the isotopic composition of lead released from degraded tropical peatlands for the first time and show that Pb originates from anthropogenic atmospheric deposition. Degraded tropical peatlands are important sources of DOM and trace metals to rivers and a secondary source of atmospherically deposited contaminants.

Formation of calcite in the presence of dissolved organic matter: Partitioning, fabrics and fluorescence

Dissolved organic matter (DOM) is omnipresent in natural waters and is commonly incorporated into carbonates. Records of DOM from speleothems (secondary carbonates found in caves) have often been interpreted to reflect groundwater DOM concentrations. However, the fidelity of these records is largely untested. An understanding of the relationship between dripwater and speleothem DOM is thus required to allow speleothems to be reliably used as archives of DOM concentration.We precipitated calcite (CaCO3) crystals from weak solutions of (NH4)2CO3, CaCl2 and NH4Cl. These solutions also contained peat DOM (from 0 to 15 mgC/L). Fluorescence 3D excitation-emission matrix (3D EEM) analysis showed a strong, positive correlation between [DOM] in the parent-solution, and [DOM] in the calcite. Calcite precipitation was reduced at high DOM concentrations, potentially indicating inhibition of crystallisation. Partition coefficient values showed that DOMaq was subtly preferentially incorporated into calcite.Scanning electron microscope images indicated that the crystal structures were heavily influenced by DOM adsorption with finer, smooth-faced, rhombohedral crystals forming in growth solutions with low aqueous [DOM] (0–5 mgC/L), and prismatic, ‘impure’ crystals produced at high aqueous [DOM] (10 and 15 mgC/L).Overall, our results indicate that authigenic carbonates are likely to faithfully record variations in aqueous [DOM] within the natural range of DOM concentrations in representative freshwater systems (caves, soil water), and that crystal habits are altered by aqueous [DOM] within their growth solutions.We also applied our findings to three flowstones collected from three New Zealand caves which vary in climatic, vegetation and hydrological regimes. We conclude that differences in initial aqueous [DOM] do indeed control incorporation of DOM into calcite, and thus 3D EEM fluorescence can be used to reconstruct original aqueous [DOM] from authigenic carbonates.