Dissolved Organic Matter Export Research Articles

Fluorescence characteristics of dissolved organic matter in relation to land use in the wetland waters of Poyang Lake, China

Dissolved organic matter (DOM) plays a fundamental role in regulating carbon cycling and mediating various biogeochemical processes in wetland ecosystems. In this paper, DOM absorption and fluorescence spectra, and other data from thirty representative sites of wetland waters in Poyang Lake were collected in 2021. The composition, spatial distribution, and source characteristics of DOM were analyzed by 3D fluorescence spectroscopy technique combined with parallel factor analysis (PARAFAC). The findings showed that: (1) Two humic-like constituents (C1, C2) and a tryptophan constituent (C3) were recognized in the PARAFAC model. (2) The fluorescent DOM (FDOM) constituents in the Poyang Lake wetlands showed spatial differences. The fluorescence intensity of C1 and C2 were higher in the south and north sections, and lower in the east and west sections. The fluorescent intensity of C3 in the northern wetland waters was higher than other areas. (3) DOM in the Poyang Lake wetlands was predominantly influenced by inputs from terrestrial sources. Land use type analysis showed that marshland and cultivated land have a great impact on DOM in Poyang Lake. Spatial differences of fluorescent components reveal the impacts of human-induced land use variations. The results enhance our understanding of the significant role of land use in biogeochemical processes, particularly in the export of DOM to aquatic environments. Furthermore, they provide guidance for the management and protection of water resources in the Poyang Lake wetland.

The role of nitrogen and iron biogeochemical cycles in the production and export of dissolved organic matter in agricultural headwater catchments

Abstract. To better understand the seasonal variations in environmental conditions regulating dissolved organic matter (DOM) export in agricultural headwater catchments, we combined the monitoring of nitrate, iron, soluble phosphorus, and DOM concentration (as dissolved organic carbon; DOC) and composition (3D fluorescence) in soil and stream waters at regular intervals during 1 hydrological year. We installed 17 zero-tension lysimeters in organic-rich top soil horizons (15 cm below the surface) in the riparian area of a well-monitored agricultural catchment in French Brittany and collected them at a fortnightly frequency from October 2022 to June 2023. We observed a large increase in DOC concentrations in soil waters during the high-flow period linked to the establishment of Fe-reducing conditions and the subsequent release of DOM. We also noted that the timing and the spatial variability in Fe(II) biodissolution in soils was regulated by nitrate from agricultural origin and the heterogeneity of water flow paths at the hillslope scale. Contrary to our current understanding of DOM export in headwater catchments, these results lead us to consider the winter high-flow period as an active phase of both DOM production and export.

Beyond Hydrology: Exploring the Factors Influencing the Seasonal Variation of the Molecular Composition of Riverine Dissolved Organic Matter

AbstractThe export of dissolved organic matter (DOM) from rivers is essential for linking terrestrial and marine carbon reservoirs in the global carbon cycle. However, there is limited knowledge regarding how the molecular composition of riverine DOM changes under different hydrological conditions, especially during extreme rainfall events. Moreover, the factors beyond hydrology that impact DOM composition have not been well defined. To address these gaps, samples were collected from a human‐impacted medium‐sized subtropical monsoonal river across various hydrological conditions throughout a complete hydrological cycle. Utilizing high‐resolution mass spectrometry, it was discovered that the solid‐phase extractable DOM (SPE‐DOM) during the high‐flow (1 < runoff (Q): annual mean runoff (Qm) < 3) and extreme‐rain (Q:Qm > 3) periods exhibited a higher number of molecular formulae, lower H/C, higher O/C, and a higher proportion of carboxylic‐rich alicyclic molecules compared to the low‐flow period (LFP) (Q:Qm < 1). These alterations were attributed to input from more diverse sources, particularly a greater input from soil organic matter with higher oxidation degrees. Additionally, the P‐containing formulae were more enriched during the extreme‐rain period, likely from agricultural lands and sediment release. Conversely, the fraction of S‐containing formulae was significantly higher during the LFP, possibly due to the amplified influence of anthropogenic input. Furthermore, the DOM aromaticity did not fluctuate with runoff but was significantly associated with temperature. In summary, the study indicated that the composition of DOM varied significantly under different hydrological conditions, with temperature and anthropogenic activities identified as crucial factors influencing riverine DOM export.

Chemodiversity of dissolved organic matter exports from subtropical humid catchment driven by hydrological connectivity

The quantity and quality of dissolved organic matter (DOM) exported from source areas are closely related to hydrological linkage between source areas and streams, that is hydrological connectivity. However, understanding of how hydrological connectivity regulates the export of catchment DOM components remains inadequate. In this study, high-frequency monitoring of groundwater and runoff from subtropical humid catchment was conducted for 20 months, and hydrological connectivity was quantitatively characterized by considering both surface and subsurface hydrological processes. Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) was utilized to investigate the DOM molecular composition. Results showed that over half of the areas in the catchment could not persistently establish hydrological connectivity with the stream during the rainfall. The average proportion of lignin was the highest in DOM components, followed by tannin and proteins. Additionally, both modified aromaticity index and double bond equivalence reached maximums at peak discharge, reflecting terrestrial materials could increase DOM aromaticity and unsaturated degree. Partial least square-structural equation modeling revealed significantly direct effects of rainfall, antecedent conditions, and hydrological connectivity on dissolved organic carbon (DOC) export. Furthermore, nonlinear relationships were observed between hydrological connectivity and DOC, tannin, and condensed aromatics. Specifically, the instantaneous DOC flux increased dramatically when the hydrological connectivity strength exceeded 0.14; tannin and condensed aromatics exhibited a rapid increase with rising connectivity strength, but remained stable at connectivity strength above 0.25. However, hydrological connectivity showed no significant correlation with unstable components (such as lipids, protein, amino sugars, and carbohydrates). These results provide new insights into hydrological controls on the quantity and quality of DOM export and contribute to developing appropriate catchment management strategies for carbon storage.

Storm-driven hydrological, seasonal, and land use/land cover impact on dissolved organic matter dynamics in a mid-Atlantic, USA coastal plain river system characterized by 21 T FT-ICR mass spectrometry

Introduction: Dissolved organic matter (DOM) as primary and secondary energy sources can be transported via rivers to estuaries and impact coastal biogeochemical cycles. Storm-induced high discharge events can alter the dominant river flow paths and enhance leaching of shallow organic-rich soil layers, leading to elevated terrestrial DOM export. Land use/land cover (LULC) and associated anthropogenic interventions (including artificial reservoirs and agricultural irrigation) can control sources and transformation processes of exported DOM along with hydrologic factors. The relative significance of LULC, hydrological factors, and temperature variations with seasons will differ depending on geographical locations and complicate their incorporation in biogeochemical models of DOM dynamics. This study investigates the role of LULC, seasonality, and storm events on DOM concentrations and molecular composition in the Murderkill River system.Method: Surface water samples were collected seasonally and before/after storm events from 6 sites representing forested, agricultural, and developed LULC units. The DOM was characterized via parallel factor analysis of excitation-emission matrix data and electrospray ionization 21 T Fourier-transform ion cyclotron resonance mass spectrometry to determine potential DOM sources and enable the development of a conceptual model for DOM dynamics in rivers impacted by anthropogenic reservoirs.Result and Discussion: Our results suggest that storm-induced shallow and overland flow paths can increase surface-vegetation/plant-litter derived DOM based on atomic ratios associated with specific biogenic precursors (i.e., lignin, tannins, and/or oxygenated aromatic DOM), particularly in winter when autochthonous production was suppressed due to reduced temperatures. We further demonstrate that the damming effects of artificial reservoirs enhance the role of seasonal patterns of autochthonous production, disrupting storm-shunt process and stimulating significantly more bio-produced DOM export during spring and summer (i.e., tryptophan/tyrosine-like. N- and S- containing, phytoplankton-derived compounds). Collectively, these results demonstrate how artificial reservoirs alter the characteristics of DOM exported from rivers with implications for understanding carbon export and fate at river-estuary interfaces.

Hydrobiogeochemical Controls on the Delivery of Dissolved Organic Matter to Boreal Headwater Streams

AbstractUnderstanding controls on the delivery of dissolved organic matter (DOM) from terrestrial to aquatic systems is key for constraining carbon balances and fluxes in boreal headwater catchments. The largest export of DOM generally occurs during intense periods of water delivery to the landscape (e.g., rain events); however, the timing and magnitude of DOM is complicated by geomorphological, hydrometeorological, and biogeochemical variability. To better assess mechanisms controlling the delivery of DOM to boreal streams, DOM was investigated in two morphologically distinct catchments of an experimental forest watershed in western Newfoundland, one dominated by low relief wetlands and the other by steep hillslopes. The DOM was compared during two fall storms of similar magnitude but contrasting moisture conditions during the autumn transition. Variable concentrations and optical character highlighted antecedent conditions are important for the delivery of DOM to boreal streams. Concentration‐discharge relationships with stream hydrograph separation analysis suggest preferential flowpaths through shallow mineral horizons as a key pathway for delivery of DOM in the hillslope dominated catchment compared to rapid input from near‐stream wetlands in the low relief catchment. Loss of DOM via preferential pathways suggests an additional mechanism for surface soil carbon loss not directly informed by lateral flow and soil hydrology, which has important implications for our conceptualization and modeling of carbon fluxes in boreal systems. These results suggest watershed scale responses of DOM in boreal headwater catchments are complex, and better linkages between catchment scale hydrology and landscape hydrobiogeochemistry are required to constrain terrestrial to aquatic carbon fluxes in boreal landscapes.

Surface microrelief induced by tillage management alters the pathway and composition of dissolved organic matter exports from soils to runoff during rainfall

Rainfall-runoff process mobilizes considerable dissolved organic matter (DOM) from soils to aquatic systems via surface and sub-surface flow pathways. Microrelief induced by tillage management can alter this flow partitioning and thus likely affect the associated pathway and composition of DOM exports during rainfall. This study conducted rainfall simulation experiments, combined with three-dimensional fluorescence spectra analysis and Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) technology, to explore the effects of different surface microreliefs treatments on the quantity and composition of DOM exports at a plot scale. Four typical microrelief treatments (i.e., contour tillage (CP), longitudinal tillage (LP), artificial digging tillage (AP), and flat tillage (CK, as control)) were selected. Results showed that ratios of surface to sub-surface flow volume under four treatments were in order of LP (193:1)>CK (73:1)>AP (4.5:1)>CP (0.5:1). DOM concentrations in sub-surface flow (13.37∼33.50 mg L-1) were 7∼18 times of that in surface flow (0.03∼4.56 mg L-1). The total export fluxes of DOM were 134, 139, 563, and 1214 mg m-2 at LP, CK, AP, and CP treatments, respectively, with proportions of 8%, 17%, 82%, and 98% via sub-surface flow. Compared to surface flow, DOM molecular composition in sub-surface flow showed a significant feature of higher oxygen to carbon ratio, higher molecular weight, and lower hydrogen to carbon ratio. The findings indicated that microrelief with higher surface storage capacity tends to favor a large flux of DOM export, primarily via sub-surface flow, which might significantly affect the DOM cycling in the receiving aquatic ecosystems.

Seasonal controls override forest harvesting effects on the composition of dissolved organic matter mobilized from boreal forest soil organic horizons

Abstract. Dissolved organic matter (DOM) mobilized from the organic (O) horizons of forest soils is a temporally dynamic flux of carbon (C) and nutrients, and the fate of this DOM in downstream pools is dependent on the rate and pathways of water flow as well as its chemical composition. Here, we present observations of the composition of DOM mobilized weekly to monthly from O horizons in mature forest and adjacent harvested treatment plots. The study site was experimentally harvested, without replanting, 10-years prior to this study. Thus, the treatments differ significantly in terms of forest stand and soil properties, and they interact differently with the regional hydrometeorological conditions. This presented an opportunity to investigate the role of forest structure relative to environmental variation on soil DOM mobilization. On an annual basis, fluxes of total dissolved nitrogen (TDN) and dissolved organic nitrogen (DON) were largest from the warmer and thinner O horizons of the harvested (H) treatment compared to the forest (F) treatment; however, neither phosphate nor ammonium fluxes differed by treatment type. On a short-term basis in both H and F treatments, all fluxes were positively correlated to water input, and all concentrations were positively correlated to soil temperature and negatively correlated to water input. Soil moisture was negatively correlated to the C : N of DOM. These results suggest common seasonal controls on DOM mobilization regardless of harvesting treatment. Optical characterization of seasonally representative samples additionally supported a stronger control of season over harvesting. The chemical character of DOM mobilized during winter and snowmelt: lower C : N, higher specific ultraviolet absorbance and lower molecular weight of chromophoric DOM (CDOM; higher spectral slope ratio) were representative of relatively more decomposed DOM compared to that mobilized in summer and autumn. This shows that the decomposition of soil organic matter underneath a consistently deep snowpack is a key determinant of the composition of DOM mobilized from O horizons during winter and the hydrologically significant snowmelt period regardless of harvesting impact. Despite the higher proportion of aromatic DOM in the snowmelt samples, its lower molecular weight and rapid delivery from O to mineral horizons suggests that the snowmelt period is not likely to be a significant period of DOM sequestration by mineral soil. Rather, the higher-molecular-weight, high-C : N DOM mobilized during slow and relatively infrequent delivery during summer and rapid, frequent delivery during autumn are more likely to support periods of mineral soil sequestration and increased export of fresher terrestrial DOM, respectively. These observed seasonal dynamics in O horizon DOM suggest the predicted decreases in winter and spring snowfall and increasing autumn and winter rainfall with climate warming in this region will enhance mobilization of DOM that is more reactive to mineral interactions in deeper soil, but also more biological and photoreactive in the aquatic environment. Understanding the downstream consequences of this mobilized DOM in response to these shifts in precipitation timing and form can improve our ability to predict and manage forest C balance but requires understanding the response of landscape hydrology to these changing precipitation regimes.

Groundwater Plays an Important Role in Controlling Riverine Dissolved Organic Matter in a Cold Alpine Catchment, the Qinghai–Tibet Plateau

AbstractIn cold alpine areas, the hydrological control on dissolved organic matter (DOM) export in relation to permafrost distribution remains uncertain on a catchment scale. To address this, the seasonal variations in DOM chemical features of groundwater and stream water were examined from 2013 to 2019 in a representative catchment on the northeastern Qinghai–Tibet Plateau, which is covered by both permafrost (at elevations higher than 3,500 m a.s.l.) and seasonally frozen areas. The results show that the highest dissolved organic carbon (DOC) concentration occurred during the thawing period (April–May), while the highest DOC flux occurred during the thawed period (June–early October). In the permafrost area, the freeze–thaw process significantly influenced the groundwater flow paths and DOM. During the thawing period, with shallow groundwater flow path through the organic soil layer, the stream water DOM recharged by suprapermafrost groundwater was characterized by high aromaticity and high DOC concentrations. During the thawed period, the deepening groundwater flow path through the mineral layer and dilution by overland flow, resulted in low DOC concentrations and DOM with lower aromaticity in stream water. When groundwater flowed from the permafrost area into the porous aquifers in the seasonally frozen area, the groundwater flow path also affected DOM dynamics. The stream water at the catchment outlet, which received groundwater discharge from the porous aquifer, showed a lower peak DOC concentration, a higher proportion of protein‐like DOM, and a higher contribution of cold season DOC flux to annual DOC flux when compared to the water flowing out from the permafrost area. Our work highlights the role of the thick, porous aquifer in the seasonally frozen area in regulating DOM export. The results suggest that the cold alpine area may exhibit a stronger positive feedback to climate warming than that in Arctic areas.

Determining patterns in the composition of dissolved organic matter in fresh waters according to land use and management

In fresh waters, the origins of dissolved organic matter (DOM) have been found to exert a fundamental control on its reactivity, and ultimately, its ecosystem functional role. A detailed understanding of landscape scale factors that control the export of DOM to aquatic ecosystems is, therefore, pivotal if the effects of DOM flux to fresh waters are to be fully understood. In this study we present data from a national sampling campaign across the United Kingdom in which we explore the variability in DOM composition in three broad landscape types defined by similar precipitation, geology, land use and management, hydrology, and nutrient enrichment status. We characterised samples from fifty-one sites, grouping them into one of three major underlying classifications: circumneutral streams underlain by clay and mudstone (referred to as ‘clay’), alkaline streams underlain by Cretaceous Chalk or by Carboniferous or Jurassic Limestone (‘limestone’), and acidic streams in peatland catchments underlain by a range of low permeability lithologies (‘peat’). DOM composition was assessed through organic matter stoichiometry (organic carbon: organic nitrogen; organic carbon: organic phosphorus; C/N(P)DOM) and metrics derived from ultra-violet (UV)/visible spectroscopic analysis of DOM such as specific UV absorption (a254 nm; SUVA254). We found similar SUVA254, C/NDOM and DOM/a254 relationships within classifications, demonstrating that despite a large degree of heterogeneity within environments, catchments with shared environmental character and anthropogenic disturbance export DOM with a similar composition and character. Improving our understanding of DOM characterisation is important to help predict shifts in stream ecosystem function, and ecological responses to enrichment or mitigation efforts and how these may result in species composition shifts and biodiversity loss in freshwater ecosystems.

Linkages Among Dissolved Organic Matter Export, Dissolved Metabolites, and Associated Microbial Community Structure Response in the Northwestern Sargasso Sea on a Seasonal Scale.

Deep convective mixing of dissolved and suspended organic matter from the surface to depth can represent an important export pathway of the biological carbon pump. The seasonally oligotrophic Sargasso Sea experiences annual winter convective mixing to as deep as 300 m, providing a unique model system to examine dissolved organic matter (DOM) export and its subsequent compositional transformation by microbial oxidation. We analyzed biogeochemical and microbial parameters collected from the northwestern Sargasso Sea, including bulk dissolved organic carbon (DOC), total dissolved amino acids (TDAA), dissolved metabolites, bacterial abundance and production, and bacterial community structure, to assess the fate and compositional transformation of DOM by microbes on a seasonal time-scale in 2016–2017. DOM dynamics at the Bermuda Atlantic Time-series Study site followed a general annual trend of DOC accumulation in the surface during stratified periods followed by downward flux during winter convective mixing. Changes in the amino acid concentrations and compositions provide useful indices of diagenetic alteration of DOM. TDAA concentrations and degradation indices increased in the mesopelagic zone during mixing, indicating the export of a relatively less diagenetically altered (i.e., more labile) DOM. During periods of deep mixing, a unique subset of dissolved metabolites, such as amino acids, vitamins, and benzoic acids, was produced or lost. DOM export and compositional change were accompanied by mesopelagic bacterial growth and response of specific bacterial lineages in the SAR11, SAR202, and SAR86 clades, Acidimicrobiales, and Flavobacteria, during and shortly following deep mixing. Complementary DOM biogeochemistry and microbial measurements revealed seasonal changes in DOM composition and diagenetic state, highlighting microbial alteration of the quantity and quality of DOM in the ocean.

Groundwater-surface water interactions and flux of organic matter and nutrients in an urban, Mediterranean stream

The chemical quality of dissolved organic matter (DOM) and the speciation of nitrogen exported from urban catchments is of great importance to biogeochemical cycling in riverine and coastal receiving waters. Many urban streams in Mediterranean climates have a flashy hydrologic regime, which would suggest a rapid pulsing and shunting of solutes downstream. However, the role of these systems both as passive pipes for solute transport or as reactors for DOM and nutrient transformation is still an open question for urban, Mediterranean streams. To address this question, we evaluated changes in concentrations of inorganic and organic solutes and DOM optical properties in Alvarado Creek, a perennially-flowing, urban, first-order tributary of the San Diego River in San Diego, CA, USA, during dry weather (baseflow) conditions and during four storm events in 2016–2018. Chloride and sulfate concentrations corroborate the supposed saline groundwater supply that maintains perennial flow and brackish nature in this urban stream. During dry weather, high proportions of protein-like fluorescent component (AC4) and downstream decreases in total dissolved nitrogen (TDN) and nitrate imply in-stream processing (nitrification and denitrification). By contrast, storm hysteresis curves indicate that the supply of DOM and TDN was not exhausted over the duration of a storm event, whereas nitrate was eventually depleted, presumably because nitrification could not keep up with the export of nitrate from source areas. Rapid decreases in chloride during the storm hydrograph coincided with a shift in specific ultraviolet absorbance (SUVA) and fluorescence index (FI) to more terrestrially-derived and aromatic carbon sources, most likely from interflow of stormwater through vadose zone soils. On an annual basis, the export of microbially-derived DOM during dry weather was higher than the export of terrestrially-derived DOM during storm events; both represent important carbon inputs to coastal waters.

Cleaner air reveals growing influence of climate on dissolved organic carbon trends in northern headwaters

Surface water browning, the result of increasing concentrations of dissolved organic matter (DOM), has been widespread in northern ecosystems in recent decades. Here, we assess a database of 426 undisturbed headwater lakes and streams in Europe and North America for evidence of trends in DOM between 1990 and 2016. We describe contrasting changes in DOM trends in Europe (decelerating) and North America (accelerating), which are consistent with organic matter solubility responses to declines in sulfate deposition. While earlier trends (1990–2004) were almost entirely related to changes in atmospheric chemistry, climatic and chemical drivers were equally important in explaining recent DOM trends (2002–2016). We estimate that riverine DOM export from northern ecosystems increased by 27% during the study period. Increased summer precipitation strengthened upward dissolved organic carbon trends while warming apparently damped browning. Our results suggest strong but changing influences of air quality and climate on the terrestrial carbon cycle, and on the magnitude of carbon export from land to water.

Dissolved Organic Matter Dynamics in the Epipelagic Northwest Pacific Low‐Latitude Western Boundary Current System: Insights From Optical Analyses

AbstractHigh‐resolution horizontal and vertical distribution of dissolved organic carbon (DOC), chromophoric, and fluorescent dissolved organic matter (CDOM and FDOM) were investigated in the western boundary current system of the tropical Northwest Pacific (<200 m) in autumn 2017. A strong correlation between DOC and stratification index indicated that the vertical DOC profile was primarily regulated by physical processes. The association of high aCDOM(254) with the maximum chlorophyll (Chl a) layer infers phytoplankton‐sourced dissolved organic matter (DOM). The aCDOM(325) and humic‐like FDOM (FDOMH) showed an accumulation in the deeper layer and positive correlations with apparent oxygen utilization and Chl a concentration at the maximum chlorophyll layer, suggesting that these components are related to microbial degradation of biogenic materials. Elevated Chl a at the frontal area between the North Equatorial Current (NEC) and cold Mindanao Eddy enhanced DOM production. Input waters from the NEC showed higher DOC, but lower FDOMH, than inflow waters from the New Guinea Coastal Current/Undercurrent (NGC(U)C). A mass balance model estimated a 6‐times higher lateral DOC flux from the NEC tropical‐gyre branch (12°N–7.5°N) than that from the subtropical‐gyre branch (12°N–17°N). Based on comparison with long‐term (1994–2015) average DOC fluxes for the same season, eddy and upstream processes contributed 38%, 46% and 40% of lateral DOC fluxes for the NEC tropical‐gyre branch, NGC(U)C and export North Equatorial Counter Current, respectively. These results demonstrated that the quasi‐permanent Mindanao and Halmahera eddies greatly enhance lateral export of DOM with altered properties throughout this large conjunction area.

Amount and reactivity of dissolved organic matter export are affected by land cover change from old‐growth to second‐growth forests in headwater ecosystems

AbstractHeadwater forest ecosystems of the western USA generate a large portion of the dissolved organic matter (DOM) transported in streams across North America. Land cover changes that alter forest structure and species composition affect the quantity and composition of DOM transferred to aquatic ecosystems. Clear‐cut harvesting affects ~1% of the forest area of North America annually, leaving most western forests in varying stages of regrowth and the total area of old‐growth forest is decreasing. The consequences of this widespread management practice on watershed carbon cycling remain unknown. We investigated the role of land cover change, because of clear‐cut harvesting, from mixed‐species old‐growth to lodgepole pine‐dominated second‐growth forest on the character and reactivity of hillslope DOM exports. We evaluated inputs of DOM from litter leachates and export of DOM collected at the base of trenched hillslopes during a 3‐year period (2016–2018) at the Fraser Experimental Forest in north‐central Colorado, USA. Dissolved organic carbon and total dissolved nitrogen were higher in lateral subsurface flow draining old‐ versus second‐growth forest. Fluorescence spectroscopy showed that the DOM exported from the old‐growth forest was more heterogeneous and aromatic and that proteinaceous, microbially processed DOM components were more prevalent in the second‐growth forest. Biological oxygen demand assays revealed much lower microbial metabolism of DOM in litter leachate and subsurface exports from the old‐growth forest relative to second growth. Old‐growth and second‐growth forests are co‐mingled in managed ecosystems, and our findings demonstrate that land cover change from a mixture of conifer species to lodgepole pine dominance influences DOM inputs that can increase the reactivity of DOM transferred from terrestrial to aquatic ecosystems.

Stormwater Runoff and Tidal Flooding Transform Dissolved Organic Matter Composition and Increase Bioavailability in Urban Coastal Ecosystems

AbstractCoastal drainages contain multiple sources of dissolved organic matter (DOM) that influence OM transformation and fate along inland‐to‐marine gradients. Anthropogenic activities have altered DOM composition in urban drainages, thereby influencing in‐stream breakdown rates, primary productivity, and downstream export. Yet, it is uncertain how hydrologic conditions (i.e., rainfall, tides, shallow groundwater) interact with different sources of DOM to regulate the transformation and export of DOM through urban coastal drainages. We characterized how seasonal changes in hydrologic conditions influence DOM composition and bioavailability in tidally influenced drainages in Miami, FL, USA. We estimated the quality and bioavailability of DOM using compositional proxies based on fluorescence spectroscopy, including parallel‐factor analysis, and measured dissolved organic carbon degradation during laboratory incubations containing a local bacterial community. Interactions between stormwater runoff and tidal amplitude increased the bioavailability of DOM and were positively correlated with predominantly humic‐like components in the wet season and protein‐like components in the dry season. Further, increases in tryptophan fluorescence intensity corresponded with elevated concentrations of Escherichia coli and enterococci—likely from waste‐impacted groundwater—and contributed substantially to overall DOM bioavailability. Our results provide new evidence of an urban priming effect in which labile autochthonous DOM from anthropogenic sources facilitates microbial degradation of DOM that is driven by seasonal differences in stormwater runoff and tides. As hydrologic conditions in near‐shore aquatic ecosystems shift with urbanization and climate‐driven changes in sea‐level rise, increases in autochthonous sources of bioavailable DOM may impact ecosystem metabolism and affect the quality of DOM exported downstream.

Impact of biochar-induced vertical mobilization of dissolved organic matter, sulfamethazine and antibiotic resistance genes variation in a soil-plant system

The migration risk of antibiotic and antibiotic resistance genes (ARGs) have attracted lots of attentions due to their potential threaten to public health. Strategies to reduce their vertical mobilization risk are urgently required for groundwater safety and human health. Biochar enjoys numerous interests due to its excellent sorption affinity. However, little was known about the efficacy of biochar amendment in impeding the vertical mobilization of antibiotic and ARGs. To fill this gap, a column study was carried out to investigate biochar-induced variations in the leaching behavior of dissolved organic matter (DOM), sulfamethazine (SMZ) and ARGs. Results showed that biochar addition enhanced DOM export from soil, changed its composition and impeded the vertical transport of SMZ. Biochar amendment could effectively decrease the occurrence of extracellular and intracellular sul2 in soil and impede its vertical transportation, however, it did not work out with sul1 gene. Structural equation modeling analysis demonstrated that the abundance of sul2 was significantly controlled by SMZ concentration, while the primary drivers of sul1 were SMZ concentration and DOM content. These results indicated the failure in inhibiting the vertical transfer of sul1 under biochar amendment and highlighted the important role of DOM in the leaching of soil ARGs.

Pan‐Arctic Riverine Dissolved Organic Matter: Synchronous Molecular Stability, Shifting Sources and Subsidies

AbstractClimate change is dramatically altering Arctic ecosystems, leading to shifts in the sources, composition, and eventual fate of riverine dissolved organic matter (DOM) in the Arctic Ocean. Here we examine a 6‐year DOM compositional record from the six major Arctic rivers using Fourier‐transform ion cyclotron resonance mass spectrometry paired with dissolved organic carbon isotope data (Δ14C, δ13C) to investigate how seasonality and permafrost influence DOM, and how DOM export may change with warming. Across the pan‐Arctic, DOM molecular composition demonstrates synchrony and stability. Spring freshet brings recently leached terrestrial DOM with a latent high‐energy and potentially bioavailable subsidy, reconciling the historical paradox between freshet DOM's terrestrial bulk signatures and high biolability. Winter features undiluted baseflow DOM sourced from old, microbially degraded groundwater DOM. A stable core Arctic riverine fingerprint (CARF) is present in all samples and may contribute to the potential carbon sink of persistent, aged DOM in the global ocean. Future warming may lead to shifting sources of DOM and export through: (1) flattening Arctic hydrographs and earlier melt modifying the timing and role of the spring high‐energy subsidy; (2) increasing groundwater discharge resulting in a greater fraction of DOM export to the ocean occurring as stable and aged molecules; and (3) increasing contribution of nitrogen/sulfur‐containing DOM from microbial degradation caused by increased connectivity between groundwater and surface waters due to permafrost thaw. Our findings suggest the ubiquitous CARF (which may contribute to oceanic carbon sequestration) underlies predictable variations in riverine DOM composition caused by seasonality and permafrost extent.

Seasonal Variations of Dissolved Organic Matter by Fluorescent Analysis in a Typical River Catchment in Northern China

Fluorescence (excitation-emission matrices, EEMs) spectroscopy coupled with PARAFAC (parallel factor) modelling and UV-Vis (ultraviolet visible) spectra were used to ascertain the sources, distribution and biogeochemical transformation of dissolved organic matter (DOM) in the Duliujian River catchment. Dissolved organic carbon (DOC), chromophoric dissolved organic matter (a335) (CDOM), and hydrophobic components (a260) were higher in summer than in other seasons with 53.3 m−1, while aromaticity (SUVA254) was higher in spring. Four fluorescent components, namely terrestrial humic acid (HA)-like (A/C), terrestrial fulvic acid (FA)-like (A/M), autochthonous fulvic acid (FA)-like (A/M), and protein-like substances (Tuv/T), were identified using EEM-PARAFAC modelling in this river catchment. The results demonstrated that terrestrial HA-like substances enhance its contents in summer ARE compared with BRE, whilst terrestrial FA-like substances were newly input in summer ARE, which was entirely absent upstream and downstream, suggesting that rain events could significantly input the terrestrial soil-derived DOM in the ambient downward catchments. Autochthonous FA-like substances in summer BRE could derive from phytoplankton in the downstream waters. The results also showed that DOM from wetland exhibited lower fluorescent intensity of humic-like peak A/C and fulvic-like peak A/M, molecular weight (SR) and humification index (HIX) during the low-flow season. Built-up land, cropland, and unused land displayed higher a335 (CDOM). A higher proportion of forest and industrial land in the SCs showed higher SUVA254 values. Humic-like moiety, molecular weight and aromaticity were more responsive to land use during stormflow in summer. Rainfall could increase the export of soil DOM from cropland and unused land, which influences the spatial variation of HIX. The results in this study highlighted that terrestrial DOM has a significant influence on the biogeochemical alterations of DOM compositions and thus water quality in the downward watershed catchments, which might significantly vary according to the land-use types and their alterations by human activities.

Total organic carbon concentrations in ecosystem solutions of a remote tropical montane forest respond to global environmental change

The response of organic carbon (C) concentrations in ecosystem solutions to environmental change affects the release of dissolved organic matter (DOM) from forests to surface and groundwaters. We determined the total organic C (TOC) concentrations (filtered <1-7µm) and the ratios of TOC/dissolved organic nitrogen (DON) concentrations, electrical conductivity (EC), and pH in all major ecosystem solutions of a tropical montane forest from 1998 to 2013. The forest was located on the rim of the Amazon basin in Ecuador and experienced increasing numbers of days with >25°C, decreasing soil moisture, and rising nitrogen (N) deposition from the atmosphere during the study period. In rainfall, throughfall, mineral soil solutions (at the 0.15- and 0.30-m depths), and streamflow, TOC concentrations and fluxes decreased significantly from 1998 to 2013, while they increased in stemflow. TOC/DON ratios decreased significantly in rainfall, throughfall, soil solution at the 0.15-m depth, and streamflow. Based on Δ14 C values, the TOC in rainfall and mineral soil solutions was 1year old and that of litter leachate was 10years old. The pH in litter leachate decreased with time, that in mineral soil solutions increased, while those in the other ecosystem solutions did not change. Thus, reduced TOC solubility because of lower pH values cannot explain the negative trends in TOC concentrations in most ecosystem solutions. The increasing TOC concentrations and EC in stemflow pointed at an increased leaching of TOC and other ions from the bark. Our results suggest an accelerated degradation of DOM, particularly of young DOM, associated with the production of N-rich compounds simultaneously to changing climatic conditions and increasing N availability. Thus, environmental change increased the CO2 release to the atmosphere but reduced DOM export to surface and groundwater.