Transport Of Dissolved Organic Matter Research Articles

Linking Dissolved Organic Matter Composition to Landscape Properties in Wetlands Across the United States of America

AbstractWetlands are integral to the global carbon cycle, serving as both a source and a sink for organic carbon. Their potential for carbon storage will likely change in the coming decades in response to higher temperatures and variable precipitation patterns. We characterized the dissolved organic carbon (DOC) and dissolved organic matter (DOM) composition from 12 different wetland sites across the USA spanning gradients in climate, landcover, sampling depth, and hydroperiod for comparison to DOM in other inland waters. Using absorption spectroscopy, parallel factor analysis modeling, and ultra‐high resolution mass spectroscopy, we identified differences in DOM sourcing and processing by geographic site. Wetland DOM composition was driven primarily by differences in landcover where forested sites contained greater aromatic and oxygenated DOM content compared to grassland/herbaceous sites which were more aliphatic and enriched in N and S molecular formulae. Furthermore, surface and porewater DOM was also influenced by properties such as soil type, organic matter content, and precipitation. Surface water DOM was relatively enriched in oxygenated higher molecular weight formulae representing HUPHigh O/C compounds than porewaters, whose DOM composition suggests abiotic sulfurization from dissolved inorganic sulfide. Finally, we identified a group of persistent molecular formulae (3,489) present across all sites and sampling depths (i.e., the signature of wetland DOM) that are likely important for riverine‐to‐coastal DOM transport. As anthropogenic disturbances continue to impact temperate wetlands, this study highlights drivers of DOM composition fundamental for understanding how wetland organic carbon will change, and thus its role in biogeochemical cycling.

Outwelling of reduced porewater drives the biogeochemistry of dissolved organic matter and trace metals in a major mangrove‐fringed estuary in Amazonia

AbstractMangrove‐fringed estuaries are intertidal ecosystems discharging significant amounts of dissolved organic matter (DOM) into coastal oceans. DOM in these ecosystems is derived from autochthonous production, fluvial input, and mangrove porewater outwelling; however, differentiating between these sources remains challenging. Our incomplete understanding of the biogeochemical factors controlling DOM dynamics and its relationship with nutrient and trace metal cycling still hinders the formulation of elemental budgets in coastal environments. Here, we relate the DOM composition in a mangrove‐fringed estuary in North Brazil (Amazonia) to the redox conditions at the formation sites. We combined molecular DOM analyses via ultrahigh‐resolution mass spectrometry (FT‐ICR‐MS) with parallel factor analysis of excitation–emission fluorescence matrices (EEM‐PARAFAC), nutrient and redox‐sensitive trace metal analyses. During low tide, the influx of oxygen‐depleted porewater carried terrigenous DOM, inorganic nutrients, and trace metals into the mangrove‐fringed creeks. Precipitation of metal(hydr)oxides and microbial turnover controlled nutrient and trace metal dynamics in the estuary. The highest inorganic nitrogen concentrations within the upper mangrove‐fringed estuary indicated outwelling from mangrove sediments as an essential source. Phosphate concentrations were highest within the lower mangrove‐fringed estuary, where available phosphate likely exceeded precipitation with iron(hydr)oxides. We tracked the DOM transport to the coastal ocean using a novel molecular index derived from sulfidic porewater (ISuP). Outwelling of recalcitrant DOM from mangrove habitats is relevant in the context of blue carbon storage. Therefore, applying our molecular proxy (ISuP), together with trace‐metal and optical DOM analyses, is a powerful approach for differentiating contributions of diverse DOM sources in highly complex coastal ecosystems.

Hypoxia diversifies molecular composition of dissolved organic matter and enhances preservation of terrestrial organic carbon in the Yangtze River Estuary

Dissolved organic matter (DOM) is an essential component of the global carbon cycle, and estuaries link the rivers and the oceans, thus playing important roles in land-ocean DOM transformation and transport. However, the effects of hypoxia on DOM transport and fate in estuaries and coastal oceans remains poorly understood. To address this gap, we characterized the molecular composition of DOM in bottom water (BW) and sediment porewater (PW) at hypoxic and non-hypoxic sites in the Yangtze River Estuary (YRE) using ultra-high-resolution Fourier transform ion cyclotron resonance mass spectrometry. Our results showed significant differences in DOM molecular composition between hypoxic and non-hypoxic areas for both BW and PW. Specifically, DOM in hypoxic sites was more recalcitrant than that in non-hypoxic areas for both BW and PW, with lower H/C, and higher O/C, double bond equivalent, and modified aromaticity index. The presence of higher polyphenols, and black carbon in hypoxic areas suggested that hypoxic conditions could facilitate the preservation of terrestrial organic matter. Furthermore, we identified a much higher number of hypoxia-unique formulas than ocean-non-hypoxia-unique formulas, indicating that hypoxia could diversify the DOM pool. Within hypoxia-unique formulas for PW, both biologically labile (unsaturated aliphatic compounds and peptides) and recalcitrant formulas (carboxyl-rich alicyclic molecules) were found, suggesting that hypoxia could facilitate the preservation of labile formulas and the production of recalcitrant formulas. In addition, we formulated that the sulfurization is more important in PW than BW in hypoxic areas based on the higher dissolved organic sulfur (DOS) abundance and larger number of hypoxia-only formulas in hypoxic PW, and also the precursor analysis results. Overall, our study provides insights into the effect of hypoxia on the molecular characteristics and preservation of DOM in estuaries and coastal oceans, highlighting the importance of considering hypoxia in understanding the biogeochemical processes of these ecosystems.

Autochthonous sources and biogeochemical processes drive the spatiotemporal variation of DOM composition and optical indicators in a karst river

Dissolved organic matter (DOM), as a large carbon pool, is key to biogeochemical cycles, especially in some unique areas. Karst rivers typically exhibit unique biogeochemical characteristics and different human inputs; whether and how these special differences affect DOM distribution, transport and composition are not clear. Here, 134 samples were obtained from the Daning River, a typical karst river located in the mountain landscapes of the Yangtze River, during both the dry and wet seasons. Multiple methods including UV–visible absorption, three-dimensional fluorescence spectroscopy parallel factor analysis (PARAFAC), principal component analysis (PCA) and correlation analysis were used to research the molecular compositions, optical properties and origins of DOM. During the wet season, there was higher aromaticity and intensity of UV absorbing functional groups in DOM. The higher Fmax of the protein-like component in the wet season suggested more biological sources in DOM. PCA indicated that autochthonous sources and biodegradation were the main sources of DOM during the two seasons. During the dry season, forest showed the opposite effect on DOM quality when compared to farmland and urban. The findings demonstrated that monsoonal climate and biogeochemical processes were the primary reasons for the differences in DOM components and sources, which benefits the understanding of carbon biogeochemical processes in the karst rivers. More importantly, the analysis of DOM composition and sources can provide valuable insights into identifying potential contaminants and understanding water quality variations, which is beneficial to the concrete implementation of water protection.

How does anthropogenic activity influence the spatial distribution of dissolved organic matter in rivers of a typical basin located in the Loess Plateau, China

River ecosystems interact strongly with adjacent terrestrial environments and receive dissolved organic matter (DOM) from a variety of sources, all of which are vulnerable to human activities and natural processes. However, it is unclear how and to what extent human and natural factors drive DOM quantity and quality changes in river ecosystems. Here, three fluorescence components were identified via optical techniques, including two humic-like substances and one protein-like component. The protein-like DOM was mainly accumulated in anthropogenically impacted regions, while humic-like components exhibit the opposite trend. Furthermore, the driving mechanisms of both natural and anthropogenic factors on the variations in DOM composition were investigated using partial least squares structural equation modelling (PLS-SEM). Human activities, especially agriculture, positively influence the protein-like DOM directly by enhancing anthropogenic discharge with protein signals and also indirectly by affecting water quality. Water quality directly influences the DOM composition by stimulating in-situ production through a high nutrient load from anthropogenic discharge and inhibiting the microbial humification processes of DOM due to higher salinity levels. The microbial humification processes can also be restricted directly by a shorter water residence time during the DOM transport processes. Furthermore, protein-like DOM was more sensitive to direct anthropogenic discharge than indirect in-situ production (0.34 vs. 0.25), especially from non-point source input (39.1%), implying that agricultural industry optimization may be an efficient way to improve water quality and reduce protein-like DOM accumulation.

Dissolved organic matter in peat and marl marshes varies with nutrient enrichment and restored hydrology

Dissolved organic matter (DOM) drives biogeochemical processes in aquatic ecosystems. Yet, how hydrologic restoration in nutrient‐enriched ecosystems changes DOM and the consequences of those changes for the carbon cycle remain unclear. To predict the consequences of hydrologic restoration on carbon cycling in restored wetlands, we need to understand how local environmental factors influence production, processing, and transport of DOM. We collected surface water samples along transects in restored peat (organic‐rich, macrophyte‐dominated) and marl (carbonate, periphyton‐dominated) freshwater marshes in the Everglades (Florida, U.S.A.) that varied in environmental factors (water depth, phosphorus [P] concentrations [water, macrophytes, periphyton, and soil], and primary producer biomass) to understand drivers of dissolved organic carbon (DOC) concentrations and DOM composition. Higher water depths led to a “greening” of DOM, due to increasing algal contributions, with decreasing concentrations of DOC in peat wetlands, and a “browning” of DOM, due to increasing humic contributions, with increasing DOC concentrations in marl wetlands. Soil total P was positively correlated with DOC concentrations and microbial contributions to DOM in peat wetlands, and periphyton total P was positively correlated with algal contributions to DOM in marl wetlands. Despite large variations in both vegetation biomass and periphyton biovolume across transects and sites, neither were predictors of DOC concentrations or DOM composition. Hydrologic restoration differentially alters DOM in peat and marl marshes and interacts with nutrient enrichment to shift proportions of green and brown contributions to surface water chemistry, which has the potential to modify wetland food webs, as well as the processing of carbon by micro‐organisms.

Optical properties of dissolved organic matter in throughfall and stemflow vary across tree species and season in a temperate headwater forest

Tree-derived dissolved organic matter (DOM) comprises a significant carbon flux within forested watersheds. Few studies have assessed the optical properties of tree-derived DOM. To increase understanding of the factors controlling tree-derived DOM quality, we measured DOM optical properties, dissolved organic carbon (DOC) and calcium concentrations in throughfall and stemflow for 17 individual rain events during summer and fall in a temperate deciduous forest in Vermont, United States. DOC and calcium fluxes in throughfall and stemflow were enriched on average 4 to 70 times incident fluxes in rain. A multiway model was developed using absorbance and fluorescence spectroscopy to further characterize DOM optical properties. Throughfall contained a higher percentage of protein-like DOM fluorescence than stemflow while stemflow was characterized by a higher percentage of humic-like DOM fluorescence. DOM absorbance spectral slopes in yellow birch (Betula alleghaniensis) stemflow were significantly higher than in sugar maple (Acer saccharum) stemflow. DOM optical metrics were not influenced by rainfall volume, but percent protein-like fluorescence increased in throughfall during autumn when leaves senesced. Given the potential influence of tree-derived DOM fluxes on receiving soils and downstream ecosystems, future modeling of DOM transport and soil biogeochemistry should represent the influence of differing DOM quality in throughfall and stemflow across tree species and seasons.

Climate warming-driven changes in the flux of dissolved organic matter and its effects on bacterial communities in the Arctic Ocean: A review

The warming of the Arctic Ocean impacts the dissolved organic matter (DOM) imports into the Arctic region, which affects the local bacterial communities. This review addressed the current status of DOM inputs and their potential influences on bacteria data (e.g., population, production, and metabolic activity of bacteria), as well as the projected changes of DOM inputs and bacterial communities as a result of climate warming. Microbial communities are likely affected by the warming climate and the transport of DOM to the Arctic Ocean. Imported DOM can alter Arctic bacterial abundance, cell size, metabolism, and composition. DOM fluxes from Arctic River runoff and adjacent oceans have been enhanced, with warming increasing the contribution of many emerging DOM sources, such as phytoplankton production, melted sea ice, thawed permafrost soil, thawed subsea permafrost, melted glaciers/ice sheets, atmospheric deposition, groundwater discharge, and sediment efflux. Imported DOM contains both allochthonous and autochthonous components; a large quantity of labile DOM comes from emerging sources. As a result, the Arctic sea water DOM composition is transformed to include a wider range of various organic constituents such as carbohydrates (i.e., glucose), proteinaceous compounds (i.e., amino acid and protein-like components) and those with terrigenous origins (i.e., humic-like components). Changes to DOM imports can alter Arctic bacterial abundance, cell size, metabolism, and composition. Under current global warming projections, increased inflow of DOM and more diverse DOM composition would eventually lead to enhanced CO2 emissions and frequent emergence of replacement bacterial communities in the Arctic Ocean. Understanding the changes in DOM fluxes and responses of bacteria in the Arctic broadens our current knowledge of the Arctic Ocean’s responses to global warming.

Water‐Soluble Organic Matter From Soils at the Terrestrial‐Aquatic Interface in Wetland‐Dominated Landscapes

AbstractHydrologic controls on carbon processing and export are a critical feature of wetland ecosystems. Hydrologic response to climate variability has important implications for carbon‐climate feedbacks, aquatic metabolism, and water quality. Little is known about how hydrologic processes along the terrestrial‐aquatic interface in low‐relief, depressional wetland catchments influence carbon dynamics, particularly regarding soil‐derived dissolved organic matter (DOM) transport and transformation. To understand the role of different soil horizons as potential sources of DOM to wetland systems, we measured water‐soluble organic matter (WSOM) concentration and composition in soils collected from upland to wetland transects at four Delmarva Bay wetlands in the eastern United States. Spectral metrics indicated that WSOM in shallow organic horizons had increased aromaticity, higher molecular weight, and plant‐like signatures. In contrast, WSOM from deeper, mineral horizons had lower aromaticity, lower molecular weights, and microbial‐like signatures. Organic soil horizons had the highest concentrations of WSOM, and WSOM decreased with increasing soil depth. WSOM concentrations also decreased from the upland to the wetland, suggesting that continuous soil saturation reduces WSOM concentrations. Despite wetland soils having lower WSOM, these horizons are thicker and continuously hydrologically connected to wetland surface and groundwater, leading to wetland soils representing the largest potential source of soil‐derived DOM to the Delmarva Bay wetland system. Knowledge of which soil horizons are most biogeochemically significant for DOM transport in wetland ecosystems will become increasingly important as climate change is expected to alter hydrologic regimes of wetland soils and their resulting carbon contributions from the landscape.

Spatiotemporal Controls on the Delivery of Dissolved Organic Matter to Streams Following a Wildfire

AbstractWarmer and drier climate has contributed to increased occurrence of large, high severity wildfires in the Pacific Northwest, drawing concerns for water quality and ecosystem recovery. While nutrient fluxes generally increase post‐fire, the composition of organic matter (OM) transported to streams immediately following a fire is poorly constrained, yet can play an integral role in downstream water quality and biogeochemistry. Here, we quantified the spatiotemporal patterns of dissolved OM (DOM) chemistry for five streams burned by wildfires in Oregon, USA in 2020. We sampled over a 24 hr storm event 1 month after the fire revealing DOM dynamics were temporally variable, but spatially linked with burn severity. Specifically, nitrogen and aromatic character of DOM increased in streams burned at greater severity. Our results suggest spatially distinct gradients of burn severity impact DOM dynamics immediately following fire activity and highlight a key gap in our knowledge of post‐fire DOM transport to streams.

Groundwater metabolome responds to recharge in fractured sedimentary strata

Understanding the sources, structure and fate of dissolved organic matter (DOM) in groundwater is paramount for the protection and sustainable use of this vital resource. On its passage through the Critical Zone, DOM is subject to biogeochemical conversions. Therefore, it carries valuable cross-habitat information for monitoring and predicting the stability of groundwater ecosystem services and assessing these ecosystems’ response to fluctuations caused by external impacts such as climatic extremes. Challenges arise from insufficient knowledge on groundwater metabolite composition and dynamics due to a lack of consistent analytical approaches for long-term monitoring. Our study establishes groundwater metabolomics to decipher the complex biogeochemical transport and conversion of DOM. We explore fractured sedimentary bedrock along a hillslope recharge area by a 5-year untargeted metabolomics monitoring of oxic perched and anoxic phreatic groundwater. A summer with extremely high temperatures and low precipitation was included in the monitoring. Water was accessed by a monitoring well-transect and regularly collected for liquid chromatography-mass spectrometry (LC-MS) investigation. Dimension reduction of the resulting complex data set by principal component analysis revealed that metabolome dissimilarities between distant wells coincide with transient cross-stratal flow indicated by groundwater levels. Time series of the groundwater metabolome data provides detailed insights into subsurface responses to recharge dynamics. We demonstrate that dissimilarity variability between groundwater bodies with contrasting aquifer properties coincides with recharge dynamics. This includes groundwater high- and lowstands as well as recharge and recession phases. Our monitoring approach allows to survey groundwater ecosystems even under extreme conditions. Notably, the metabolome was highly variable lacking seasonal patterns and did not segregate by geographical location of sampling wells, thus ruling out vegetation or (agricultural) land use as a primary driving factor. Patterns that emerge from metabolomics monitoring give insight into subsurface ecosystem functioning and water quality evolution, essential for sustainable groundwater use and climate change-adapted management.

Size and optical properties of dissolved organic matter in large boreal rivers during mixing: Implications for carbon transport and source discrimination

Study regionThe lower Athabasca River (LAR), Northern Alberta, Canada Study focusThe functionality of dissolved organic matter (DOM) in natural waters largely depends upon its size and composition. Identifying the sources, associated properties and transport behavior of DOM is vital to understand its effects on downstream ecosystems. River mixing has great potential to alter DOM quality and transport, but the extent of these impacts is largely unknown in large boreal rivers. New hydrological insights for the regionInputs of DOM from tributaries served as a major source and shifted DOM quantity and quality in the LAR towards higher concentrations of dissolved organic carbon (DOC), and greater degrees of humification and aromaticity. Seasonal variations in DOM quality were observed during spring freshet, including elevated molecular mass (i.e., size), and proportions of protein-like components (i.e., tryptophan-like). The conservative and delayed mixing of DOM was apparent at three large confluences, and contrasting mixing patterns for different tributaries suggested that these patterns were governed by both hydrological conditions and river geomorphology. Results suggest that DOM may be generally useful as a conservative tracer at large confluences in boreal rivers, thus highlighting its potential importance as a tracer for source discrimination in mixing zones.

Fractional-derivative model simulations of reach-scale uptake and transport dynamics of natural fluorescent dissolved organic matter in a temperate forested stream in southeastern U.S.

Dissolved organic matter (DOM) entering the river networks affects aquatic ecosystems, yet it remains difficult to quantify the strength of various environmental factors in controlling reach-scale uptake and transport of DOM. This study combined reach-scale field experiments and stochastic modeling to investigate the uptake and transport dynamics of natural fluorescent DOM (FDOM) in a forested coastal plain stream located in the southeastern U.S. FDOM from litter leachate and sodium chloride (NaCl) were injected into the stream under base flow conditions (with different flow rates) on three separate occasions over a 3-month period. Field measurements showed that FDOM and NaCl exhibited different anomalous dynamics characterized by the peak and tailing behaviors of concentration breakthrough curves (BTC), indicating that the transport of FDOM was regulated more by physical retention and/or biogeochemical recycling than that of NaCl. The preferential removal of humic fluorescence than protein fluorescence before the BTC peak suggests that physical sorption was more important than biological degradation in early FDOM removal at the field site. A tempered fractional advection–dispersion-reaction model (TFADRM) was proposed to describe the FDOM migration process and estimate the FDOM spiraling metrics, and the resultant metrics were compared to those from conventionally used BTC-integrated approach. Results revealed that solute retention can lower the peak concentration and enhance the late-time tail of the FDOM BTC, whereas irreversible biogeochemical reaction processes can consume FDOM and decrease the BTC peak. Relative to the commonly used OTIS model, TFADRM can better capture the observed BTC late-time tail by considering multiple rates for the mass exchange/uptake of FDOM in streams, and therefore, this study provided a more reasonable estimate of FDOM spiraling metrics and transport dynamics at the reach scale.

Characterizing Dissolved Organic Matter Across a Riparian Soil–Water Interface: Preliminary Insights from a Molecular Level Perspective

Riparian soils are an important source of dissolved organic matter (DOM) to their connected rivers. The transport of DOM from riparian soils to rivers exerts a significant impact on both terrestria...

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.

Spatial changes in molecular composition of dissolved organic matter in the Yangtze River Estuary: Implications for the seaward transport of estuarine DOM

The complexity of dissolved organic matter (DOM) limits our understanding of the estuarine carbon cycle. This study adopted a combination of bulk carbon isotope, optical techniques and ultra-high resolution mass spectrometry to study the spatial heterogeneity and compositional variations of DOM across a latitudinal transect of the Yangtze River Estuary (YRE). Results show that the whole section of YRE received high abundance of protein-like C4 fluorescent component (0.66 ± 0.08 R.U.) and high relative abundance of aliphatic compounds and peptides (8.28 ± 1.46%) from phytoplankton, which would contribute to the bioavailable DOM pool of the Eastern China Sea (ECS). However, multivariate analysis indicated that polycyclic aromatics and polyphenols from the Yangtze River experienced a significant decrease of 5% within the turbidity zone, creating a significant decrease of 0.08 in aromaticity index and modulating DOM content and compositions within the YRE. 1837 molecular formulae were identified to track dynamic behaviors of terrestrial DOM in the YRE. Molecular imprints showed the removal of terrestrial molecules in the turbidity zone indicated by the decrease of 753 in molecular quantity, when water masses mixing diluted the abundance of aromatic compounds. Adsorption and flocculation could serve important mechanisms to remove terrestrial DOM, promoting the burial of terrestrial DOM within estuarine sediments. Besides, some terrestrial molecular formulae were also detected in the ECS, suggesting the potential contribution of terrestrial DOM to the carbon stock of open seas after experiencing physical and photochemical transformations. This research provides a comprehensive insight into spatial variations of estuarine DOM composition, underlining the important role of estuaries in sorting and transporting DOM.

Acid-base properties of dissolved organic matter extracted from the marine environment

Marine dissolved organic matter (DOM) plays a key role in the current and future global carbon cycle, which supports life on Earth. Trace metals such as iron, an essential micronutrient, compete with protons and major ions for the binding to DOM. These competitive effects and the DOM binding capacity are related to the DOM acid-base properties, which also influence DOM transport and reactivity in marine waters. Here we present the results of a complete set of acid-base titration experiments of a pre-concentrated marine DOM sample in the range 0.01 ≤ I ≤ 0.7 M and 3 ≤ pH ≤ 10. We characterize the obtained proton binding curves using a combination of the non-ideal competitive adsorption (NICA) isotherm and Donnan electrostatic model. Within the main chemical groups of marine DOM, the carboxylic distribution was accurately characterized from the obtained data (QmaxH, 1=2.52 mol·kg−1, logk¯H,1 = 3.26, m1 = 0.69 and b = 0.70). This carboxylic mode was found to be less acidic and more homogeneous than a generic fulvic acid, but the differences are consistent with the reported variability of fulvic acids of freshwater and terrestrial origin. We find that changes in temperature (down to 5.5 °C), and the presence of calcium or magnesium (at 0.01 M) resulted in no significant modification of the proton ion binding curves obtained at 25 °C and 0.7 or 0.1 M ionic strength, respectively. We demonstrate the relevance of proton binding parameters for the modelling of the system iron/marine DOM throughout a wide range of salinity and acidity conditions in the context of different future ocean scenarios.

Agricultural Practices and Hydrologic Conditions Shape the Temporal Pattern of Soil and Stream Water Dissolved Organic Matter

This study investigates the combined effects of land management and hydrology on the temporal dynamics of dissolved organic matter (DOM) quantity and composition in stream water and groundwaters in an agricultural watershed. We assessed dissolved organic carbon (DOC) concentrations, DOM UV–Vis absorbance, and DOM fluorescence in groundwater under cultivated upland, riparian grassland, and riparian woodland land covers, as well as in the stream water at the watershed outlet and livestock-impacted runoff. During one year, stream water and groundwater were monitored weekly to biweekly, complemented by sub-hourly stream sampling during seven storm events. Results showed that: (1) groundwater DOC concentration was lower in cultivated upland (6.4 ± 5.6 mg l−1) than in riparian grassland and woodland (22.4 ± 13.7 mg l−1 and 17.2 ± 9.9 mg l−1, respectively). (2) The proportion of microbially processed compounds decreased in the order upland cropland > riparian grassland > riparian woodland. (3) Principal component analysis (PCA) of groundwater DOM revealed a change in composition indicating that low-aromaticity microbially processed compounds were preferentially exported to the stream. (4) PCA of stream DOM indicated that seasonal increases in groundwater elevation expanded the contributing source areas, thereby increasing the connectivity between upland croplands and the stream, which amplified the effects of cultivation on fluvial DOM during the winter. (5) Storm events occurring after manure application in spring produced hot moments of manure-derived protein-like DOM transport to streams. Together, these results suggest that cultivated uplands in agricultural lands using animal manure as fertilizer may leach more DOM than vegetative buffers.

Anthropogenic influences on dissolved organic matter transport in high arsenic groundwater: Insights from stable carbon isotope analysis and electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry

In East and Southeast Asia, the health of over 100 million people is threatened by the consumption of groundwater containing high concentrations of arsenic (>10 μg L−1), which is released from sediments through reductive dissolution of arsenic-bearing iron/manganese oxides. Dissolved organic matter (DOM) is known to play a crucial role in the process of arsenic mobilization in shallow aquifers, and its availability and reactivity are key factors controlling the variation of arsenic concentrations in groundwater. However, it is unclear how human activities influence the transport of DOM and how the transportation affects the DOM molecular properties in high arsenic groundwater. This study provides insights on the sources and molecular compositions of DOM in groundwater from the Jianghan Plain, central China, a newly discovered area with seasonal fluctuations in arsenic concentrations in shallow groundwater. Monitoring of water levels and stable carbon isotope compositions in groundwater from different depths and canal water over a year indicated that terrestrial DOM was the dominant source, accounting for 54.2%–85.5% of groundwater DOM. Electrospray ionization combined with ultrahigh-resolution Fourier transform ion cyclotron resonance mass spectrometry revealed that canal water infiltration transferred aliphatic, tannin-like and leached aromatic DOM from sediments into groundwater. Therefore, groundwater recharge through irrigation using canal water not only inputs terrestrial DOM, but also accelerates the release of sedimentary DOM. Furthermore, carboxylic-rich alicyclic molecule (CRAM)-like DOM that is derived from biomolecules has the highest proportion (60.1%–65.5%) among the identified DOM structures. And, it might be reused in biochemical processes during arsenic mobilization, suggesting a third source of groundwater DOM in addition to canal water and sediments. The findings in this study advance the understanding on transport processes and molecular properties of DOM in high arsenic groundwater under extensive anthropogenic influences.

Assessing inter-annual and seasonal patterns of DOC and DOM quality across a complex alpine watershed underlain by discontinuous permafrost in Yukon, Canada

Abstract. High-latitude environments store approximately half of the global organic carbon pool in peatlands, organic soils and permafrost, while large Arctic rivers convey an estimated 18–50 Tg C a−1 to the Arctic Ocean. Warming trends associated with climate change affect dissolved organic carbon (DOC) export from terrestrial to riverine environments. However, there is limited consensus as to whether exports will increase or decrease due to complex interactions between climate, soils, vegetation, and associated production, mobilization and transport processes. A large body of research has focused on large river system DOC and dissolved organic matter (DOM) lability and observed trends conserved across years, whereas investigation at smaller watershed scales show that thermokarst and fire have a transient impact on hydrologically mediated solute transport. This study, located in the Wolf Creek Research Basin situated ∼20 km south of Whitehorse, YT, Canada, utilizes a nested design to assess seasonal and annual patterns of DOC and DOM composition across diverse landscape types (headwater, wetland and lake) and watershed scales. Peak DOC concentration and export occurred during freshet, as is the case in most northern watersheds; however, peaks were lower than a decade ago at the headwater site Granger Creek. DOM composition was most variable during freshet with high A254 and SUVA254 and low FI and BIX. DOM composition was relatively insensitive to flow variation during summer and fall. The influence of increasing watershed scale and downstream mixing of landscape contributions was an overall dampening of DOC concentrations and optical indices with increasing groundwater contribution. Forecasted vegetation shifts, enhanced permafrost and seasonal thaw, earlier snowmelt, increased rainfall and other projected climate-driven changes will alter DOM sources and transport pathways. The results from this study support a projected shift from predominantly organic soils (high aromaticity and less fresh) to decomposing vegetation (more fresh and lower aromaticity). These changes may also facilitate flow and transport via deeper flow pathways and enhance groundwater contributions to runoff.