Dissolved Organic Matter Pool Research Articles

Anthropogenic dissolved organic matter accumulation fuels greenhouse gas diffusive emissions in urban lakes along trophic state levels

Lakes are an important reservoir of dissolved organic matter (DOM) and also emit large amounts of greenhouse gases (GHGs), such as carbon dioxide (CO2), methane (CH4), and nitrous oxide (N2O). Yet, the linkages between quantity and quality of DOM and GHGs emissions are still not well understood. Hence, we investigated how DOM optical properties mediated dissolved GHGs levels and diffusive fluxes along a trophic state level in subtropical urban lakes, China. Our study showed that anthropogenic protein-like DOM (tryptophan- and tyrosine-like components) dominated the DOM pools, comprising 62% of total fluorescence DOM (FDOM). Partial least squares path modeling (PLS-PM) showed that the direct contribution of relative abundance of DOM to CO2 and CH4 diffusion in the highly-eutrophic state was higher than in the mesotrophic and lightly/moderately-eutrophic states. In particular, protein-like DOM primarily accounted for CO2 variations (44%-49%), while humic- and protein-like DOM contributed comparably to CH4 variations (38%-40% vs. 36%-40%). Furthermore, in the lightly/moderately- and highly-eutrophic states, nutrients contributed to DOM, CO2 and CH4 in both direct and indirect ways, while phytoplankton (chlorophyll a, Chl-a) negatively and directly affected carbon emissions. However, only nitrogen content directly contributed to N2O production and diffusion in the mesotrophic and lightly/moderately-eutrophic states. We concluded that protein-like DOM enrichment had the potential to trigger CO2 and CH4 diffusion and this process was largely mediated by nutrient levels. N2O diffusion was found to be mainly influenced by nitrogen loadings and forms. Our findings highlight the urgency for effective strategies to reduce anthropogenic DOM inputs and control nutrient levels to reduce GHGs diffusion in highly human-impacted aquatic systems.

Naturalization of treated wastewater by a constructed wetland in a water-scarce Mediterranean region

The effluents from conventional wastewater treatment plants (WWTP), even if accomplishing quality regulations, substantially differ in their characteristics with those of waters in natural environments. Constructed wetlands (CWs) serve as transitional ecosystems within WWTPs, mitigating these differences and restoring natural features before water is poured into the natural environment. Our study focused on an experimental surface-flow CW naturalizing the WWTP effluent in a semiarid area in Eastern Spain. Despite relatively low pollutant concentrations entering the CW, it effectively further reduced settled organic matter and nitrogen. Dissolved organic matter (DOM) reaching the CW was mainly protein-like, yet optical property changes in the DOM indicated increased humification, aromaticity, and stabilization as it flowed through the CW. Flow cytometry analysis revealed that the CW released less abundant but more active bacterial populations than those received. MiSeq Illumina sequencing highlighted changes in the prokaryotic community composition, with phyla Proteobacteria, Bacteroidetes, Firmicutes, and Actinobacteria dominating the CW outflow. Functional prediction tools (FaproTax and PICRUSt2) demonstrated a shift towards microbial guilds aligned with those of the natural aquatic environments, increased aerobic chemoheterotrophs, photoautotrophs, and metabolic reactions at higher redox potentials. Enhanced capabilities for degrading plant material correlated well with changes in the DOM pool. Our findings emphasize the role of CWs in releasing biochemically stable DOM and functionally suited microbial populations for natural receiving environments. Consequently, we propose CWs as a naturalization nature-based solution (NBS) in water-scarce regions like the Mediterranean, where reclaimed discharged water can significantly contribute to ecosystem's water resources compared to natural flows.

Photochemical processes transform dissolved organic matter differently depending on its initial composition

Dissolved organic matter (DOM) is one of the most important fluxes in the global carbon cycle but its response to light exposure remains unclear at a molecular-level. The chemical response of DOM to light should vary with its molecular composition and environmental conditions while some basic hypotheses are still unclear, such as the balance between photobleaching and photo-humification and the question of oxidative properties. Here we exposed aquatic DOM from diverse freshwaters impacted by different levels of anthropogenic activity and algal exudates to environmentally-realistic light conditions. We found that photobleaching occurred in DOM with relatively high initial humic content producing low H/C molecules, whereas DOM with low initial humic content was humified. DOM pools with relatively high initial saturation and low aromaticity were prone to transform towards more unsaturated molecular formulae and high H/C molecules with a distinct decrease of bioavailability. Photo-transformation was mainly influenced by reactive intermediates, with reactive oxygen species (ROS) playing a dominant role in humification when the initial humus content of DOM was high. In contrast, for algal DOM with high protein content, it was likely that the autoxidation of excited state DOM was more important than indirect oxidation involving ROS. Our results reveal how photo-transformation patterns depend on the initial composition of DOM and provide new insights into the role of photochemical processes in biogeochemical cycling of DOM.

The chemical succession in anoxic lake waters as source of molecular diversity of organic matter

The aquatic networks that connect soils with oceans receive each year 5.1 Pg of terrestrial carbon to transport, bury and process. Stagnant sections of aquatic networks often become anoxic. Mineral surfaces attract specific components of organic carbon, which are released under anoxic conditions to the pool of dissolved organic matter (DOM). The impact of the anoxic release on DOM molecular composition and reactivity in inland waters is unknown. Here, we report concurrent release of iron and DOM in anoxic bottom waters of northern lakes, removing DOM from the protection of iron oxides and remobilizing previously buried carbon to the water column. The deprotected DOM appears to be highly reactive, terrestrially derived and molecularly distinct, generating an ambient DOM pool that relieves energetic constraints that are often assumed to limit carbon turnover in anoxic waters. The Fe-to-C stoichiometry during anoxic mobilization differs from that after oxic precipitation, suggesting that up to 21% of buried OM escapes a lake-internal release-precipitation cycle, and can instead be exported downstream. Although anoxic habitats are transient and comprise relatively small volumes of water on the landscape scale, our results show that they may play a major role in structuring the reactivity and molecular composition of DOM transiting through aquatic networks and reaching the oceans.

Dissolved organic matter promoted hydroxyl radical formation and phenanthrene attenuation during oxygenation of iron-pillared montmorillonites

The oxygenation of Fe(II)-bearing minerals for hydroxyl radicals (HO•) formation and contaminant attenuation receives increasing attentions. However, information on dissolved organic matter (DOM) with different types, concentrations, and molecular weights (MWs) in manipulating HO• formation and contaminant attenuation during mineral oxygenation remain unclear. In this study, four iron-pillared montmorillonites (IPMs) and two DOM samples [e.g., humic acids (HA) and fulvic acids (FA)] were prepared to explore the HO• formation and phenanthrene attenuation during the oxygenation of IPMs in the presence or absence of DOMs. Results showed that iron-pillared and high-temperature calcination procedures extended the interlayer domain of IPMs, which provided favorable conditions for a high HO• production from 1293 to 14537 μmol kg−1. The surface-absorbed/low crystalline Fe(Ⅱ) was the predominant Fe(Ⅱ) fractionations for HO• production, and presence of DOMs significantly enhanced the HO• production and phenanthrene attenuation. Moreover, regardless of the types and concentrations, the low MW (LMW, <1 kDa) fraction within DOM pool contributed highest to HO• production and phenanthrene attenuation, followed by the bulk and high MW (HMW-, 1 kDa∼0.45 μm) fractions, and FA exhibited more efficient effects in promoting HO• production and phenanthrene attenuation than HA. The fluorescent spectral analysis further revealed that phenolic-like fluorophores in LMW-fraction were the main substances responsible for the enhanced HO• production and phenanthrene attenuation. The results deepen our understandings toward the behaviors and fate of aquatic HO• and contaminants, and also provide technical guidance for the remediation of contaminated environments.

Regulation of Precipitation on Soil Dissolved Organic Matter in Perturbed Mangrove Ecosystems

Carbon sinks in mangrove soils play a critical role in climate change mitigation globally. Soil dissolved organic matter (DOM) is a major form of labile organic matter and influences carbon cycling in wetland ecosystems. However, the factors regulating DOM pools in mangrove soils on a regional scale are not well understood. Here, we used a novel approach to assess soil DOM dynamics and its environmental drivers in mangrove wetlands on a national scale in China. Soil samples were collected from 43 sampling sites and distributed in mangroves across the coastline of China. DOM extracted from mangrove soils was characterized by fluorescence spectroscopy. We estimated that dissolved organic carbon (DOC) content ranged from 0.20 ± 0.02 g/kg to 3.85 ± 0.09 g/kg and nationally averaged 0.73 ± 0.07 g/kg in mangrove soils. Soil DOM was composed of humic-like substances, including humic acid-like (53.46 ± 8.74%) and fulvic acid-like (46.54 ± 8.74%). DOM pools in mangrove soils were identified to be perturbed by terrestrial inputs. Besides, the coupling interactions of environmental controls on the soil DOM pool were validated by establishing the structural equation modeling (SEM). We found that precipitation is the most important driver, which controlled directly the inputs and outputs of DOM pools. It also indirectly influenced DOM pools by regulating soil parameters through the cascade reactions. Cu, salinity, and clay are key mediators among soil parameters for precipitation affecting DOM pools. Precipitation influences soil DOC negatively and CDOM and FDOM positively markedly. The results provide novel insights into the labile carbon pool in mangrove soils and are beneficial for improving the assessment frameworks in the blue carbon ecosystems.

Urbanization-Driven Anthropogenic and Environmental Factors Shape Soil Dissolved Organic Matter in Mangrove Ecosystems

Mangrove ecosystems play a critical role in supporting ecological service values and regulating the global carbon cycle. They have become one of the most highly vulnerable ecosystems in the Anthropocene under the long-term influence of diverse human perturbations. Soil dissolved organic matter (DOM) is an active fraction within the carbon cycle in mangrove ecosystems. However, it remains unclear how human perturbations regulate DOM dynamics. Here, we used the fluorescence method and structural equation modeling to quantify the anthropogenic and environmental influence on soil DOM across the urban development gradient on a national scale in China. Anthropogenic activities (urban construction and sewage discharge) and environmental factors (salinity, metals, pH, and soil organic carbon) were striking forces that shaped DOM quality in mangrove soils. Both indirect and direct effects played critical roles in the soil DOM heterogeneity across the gradient of urbanization. Environmental factors can act as cofactors mediating human impact on DOM pools and as promoters transforming soil DOM in mangroves. Our study provided novel insights into the relationship between coastal developments and mangrove soil DOM heterogeneity and improved knowledge of coastal ecosystems as blue carbon sinks.

Insights into priming effects of dissolved organic matter degradation in urban lakes with different trophic states

Priming effect (PE) is recognized as an important potential mechanism for dissolved organic matter (DOM) degradation in aquatic ecosystems. However, the priming effects (PEs) of various priming substances on the degradation of DOM pools in urban lakes along diverse trophic states remain unknown. To address this knowledge gap, the PEs and drivers of glucose and plant leachate of lake water with three trophic states were investigated. We reveal differences in the bioavailability of DOM in lake water, glucose, and plant leachate. The PE of the same priming substance was significantly higher in highly-eutrophic lake water than in mesotrophic lake. The priming intensity induced by glucose was significantly higher when compared to plant leachate. Regarding the addition of glucose, humic-like components (C1 and C3) showed slight PE, while the tyrosine-like component C2 showed negative PE. However, the positive PEs were observed on three components after adding plant leachate. The driver of PE by glucose shifted from nutrients to DOM components with increasing trophic levels. The PEs induced by plant leachate were affected by nutrients, chlorophyll-a (Chl-a), water chemistry, and DOM components in lightly/moderately-eutrophic lake water. This study revealed the intensities, directions, and drivers of PEs, providing essential insights into uncovering the DOM biogeochemical process in urban lakes.

Solar radiation stimulates release of semi-labile dissolved organic matter from microplastics

Microplastics can release dissolved organic matter (DOM) into seawater under solar radiation exposure. However, the molecular composition and bioavailability of this DOM remain to be investigated. Here, two popular microplastics, low-density polyethylene (LDPE) and polystyrene (PS), were exposed to solar radiation in an artificial seawater for 10 days. The solar-induced LDPE-DOM and PS-DOM were molecularly characterized using ultra-high-resolution mass spectrometry, and were further incubated in a coastal microbial assemblage to examine their bioavailability. Results showed that solar radiation stimulated release of DOM from the microplastics. Dissolved organic carbon concentration analysis indicated that approximately 19.03 µg C L–1 and 3.85 µg C L–1 were released from each gram of LDPE and PS per day, respectively. Molecular composition analysis showed that both the LDPE-DOM and PS-DOM comprised a proportion of nitrogen- and sulfur-bearing molecules, and that the LDPE-DOM molecules were associated with lower molecular abundance and values of double-equivalent-bond and aromatic-index, but higher average hydrogen-to-carbon ratio than that in the PS-DOM. In addition, a proportion of the assigned formulas in LDPE-DOM (22.3%) and PS-DOM (55.8%) could be found in a coastal-DOM sample, suggesting their potential contribution to coastal DOM pool. The further incubation experiment showed that nearly 18.7% of LDPE-DOM and 9.5% of PS-DOM were utilized or transformed within 30 days. Still, a fraction of the solar-induced LDPE-DOM and PS-DOM resisted rapid microbial utilization, remained as semi-labile DOM. These results underlined unaccounted consequences of microplastic-derived DOM in coastal DOM pool.

Contrasting optical properties of dissolved organic matter between oceanic regions near the Getz and Dotson ice shelves in the Amundsen Sea, West Antarctica

The Amundsen Sea, located in West Antarctica, is experiencing rapid melting due to the intrusion of Circumpolar Deep Water, which is causing ice sheet thinning and basal melting. The resulting changes can affect the biogeochemical cycle of dissolved organic matter (DOM) by supplying iron from sea ice and/or glacier, thereby influencing primary production and ocean circulation. Therefore, it is crucial to understand the dynamics of the DOM in this region. In this study, our primary focus was to examine the optical properties of DOM in the oceanic regions adjacent to the West Getz Ice Shelf (WGIS) and the Dotson Ice Shelf (DIS). Significant differences in DOM optical properties, including the chromophoric DOM (CDOM) absorption coefficient at 350 nm (a350), spectral slope coefficient (S275–295), and specific UV absorbance at 254 nm (SUVA254), were observed between the WGIS and DIS regions (t-test, p < 0.05). Notably, the WGIS regions exhibited high a350 values. Additionally, the S275–295 and SUVA254 values, which serve as indices of molecular weight, indicated that the DOM pool in the WGIS regions was dominated by high molecular weight compounds with a substantial proportion of aromatic compounds. In contrast, the low values of a350 and SUVA254 along with the high S275–295 values in the DIS region suggested the dominance of low molecular weight CDOM associated with compounds of lower aromaticity. Furthermore, significant negative correlations were found between biomass of Phaeocystis antarctica (P. antarctica) and phosphate (PO4) in the WGIS regions (r2 = 0.82, p < 0.01 for WGIS 1 and r2 = 0.73, p < 0.01 for WGIS 2). However, no significant relationship was observed in the DIS region. These findings suggest that the high value and molecular weight of a350, extending from the surface layer to the deep layer, in the WGIS regions were associated with autochthonous sources, primarily driven by the colony-forming bloom of P. antarctica. These findings demonstrate that the quantity and quality of DOM in the Amundsen Sea are strongly affected by bloom conditions. The results emphasize that a combination of physical and biological processes interacts in complex ways to determine the characteristics of DOM in the Amundsen Sea.

Quantifying Stochastic Processes in Shaping Dissolved Organic Matter Pool with High-Resolution Mass Spectrometry.

Natural dissolved organic matter (DOM) represents a ubiquitous molecular mixture, progressively characterized by spatiotemporal resolution. However, an inadequate comprehension of DOM molecular dynamics, especially the stochastic processes involved, hinders carbon cycling predictions. This study employs ecological principles to introduce a neutral theory to elucidate the fundamental processes involving molecular generation, degradation, and migration. A neutral model is thus formulated to assess the probability distribution of DOM molecules, whose frequencies and abundances follow a β-distribution relationship. The neutral model is subsequently validated with high-resolution mass spectrometry (HRMS) data from various waterbodies, including lakes, rivers, and seas. The model fitting highlights the prevalence of molecular neutral distribution and quantifies the stochasticity within DOM molecular dynamics. Furthermore, the model identifies deviations of HRMS observations from neutral expectations in photochemical and microbial experiments, revealing nonrandom molecular transformations. The ecological null model further validates the neutral modeling results, demonstrating that photodegradation reduces molecular stochastic dynamics at the surface of an acidic pit lake, while random distribution intensifies at the river surface compared with the porewater. Taken together, the DOM molecular neutral model emphasizes the significance of stochastic processes in shaping a natural DOM pool, offering a potential theoretical framework for DOM molecular dynamics in aquatic and other 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.

Molecular characterization of dissolved organic matter in urban stormwater pond and municipal wastewater discharges transformed by the Florida red tide dinoflagellate Karenia brevis

Karenia brevis blooms occur almost annually in southwest Florida, imposing significant ecological and human health impacts. Currently, 13 nutrient sources have been identified supporting blooms, including nearshore anthropogenic inputs such as stormwater and wastewater outflows. A 21-day bioassay was performed, where K. brevis cultures were inoculated with water sourced from three stormwater ponds along an age gradient (14, 18, and 34 yrs.) and one municipal wastewater effluent sample, with the aim of identifying biomolecular classes and transformations of dissolved organic matter (DOM) compounds used by K. brevis. All sample types supported K. brevis growth and showed compositional changes in their respective DOM pools. Fourier-transform ion cyclotron resonance mass spectrometry (FT-ICR MS) catalogued the molecular composition of DOM and identified specific compound classes that were biodegraded. Results showed that K. brevis utilized species across a wide range of compositions that correspond to amino sugars, humic, and lignin-like biomolecular classes. The municipal wastewater and the youngest stormwater pond (SWP 14) effluent contained the largest pools of labile DOM compounds which were bioavailable to K. brevis, which indicates younger stormwater pond effluents may be as ecologically important as wastewater effluents to blooms. Conversely, generation of DOM compounds of greater complexity and a wide range of aromaticity was observed with the older (SWP 18 and SWP 34) stormwater pond treatments. These data confirm the potential for stormwater ponds and/or wastewater to contribute nutrients which can potentially support K. brevis blooms, revealing the need for improved nutrient retention strategies to protect coastal waters from the potential ill effects of urban effluent.

Controls on the composition of dissolved organic matter in treatment wetland source waters of South Florida, USA

Dissolved organic matter (DOM) plays an important role in the phosphorus (P) and nitrogen (N) cycle, but the examination of coupled biogeochemical cycling in treatment wetlands, like the Everglades Stormwater Treatment Areas (STAs), has been limited. Here, we studied eight STA inflow waters to gain insights into the production and potential photo- and biolability of DOM in surface waters flowing into these treatment wetlands. A suite of optical and fluorometric indices was coupled with amino acid and bulk elemental analyses to evaluate differences in inflow water quality for particulate organic matter (POM), DOM (<0.2 μm), and high and low molecular weight DOM (HMW-DOM and LMW-DOM). A photochemical experiment was conducted with these inflow waters to assess how solar exposure alters DOM turnover and its relationship with nutrient concentrations, and to evaluate the influence of photochemistry on potential STA performance. The DOM of STA inflow water was predominantly composed of allochthonous terrestrial sources, and the LMW-DOM fraction represented 70 to 94% of the total DOM pool. Inflow waters separated along the biophysical dimension of our PCA based on their photolability and bioavailability, driven by differences in the inflow water's DOM composition. UV exposure decreased humic and aromaticity proxies with concomitant photo-production of LMW compounds and increases in bioavailability proxies. Photo-exposure significantly decreased nitrate and dissolved organic carbon (DOC) concentrations for most of the sites and dissolved organic N (DON) for three of the eight sites, but no significant changes were noted for ammonia. One site exhibited an increase in nitrate with UV exposure and had DOM primarily from terrestrial origins. Spectroscopic indices, PARAFAC components, and amino acids provided corroborating evidence that further supported the differences in photo- and biolability at each inflow site, which is likely driven by their original DOM characteristics. PARAFAC components were correlated with dissolved organic P (DOP) and suggest that there may be adsorption of DOP with humic components in the LMW fraction. This work highlights the importance of photochemistry in the STAs, the complexity of DOM turnover in STA source waters, and the potential interactions between dissolved P and other DOM components, which may further influence the treatment efficiency of the STAs.

Molecular insights into the impacts of acid mine drainage on dissolved organic matter dynamics in pit lakes

Pit lakes are artificial hydrological features created by mining operations that typically suffer from acid mine drainage (AMD), which not only endangers water quality but also exacerbates carbon loss. However, the impacts of AMD on the fate and role of dissolved organic matter (DOM) in pit lakes remain unclear. This study employed negative electrospray ionization Fourier-transform ion cyclotron resonance mass spectrometry (FT-ICR-MS) combined with biogeochemical analysis to examine DOM molecular variations and environmental controls across the AMD-induced acidic and metalliferous gradients in five pit lakes. The results demonstrated distinct DOM pools in pit lakes characterized by the prevalence of smaller aliphatic compounds compared to other waterbodies. AMD-induced geochemical gradients promoted DOM heterogeneity among pit lakes, with acidic pit lakes containing more lipid-like compounds. Acidity and metals enhanced DOM photodegradation, reducing the content, chemo-diversity and aromaticity. Organic sulfur was detected in high abundance, potentially from sulfate photo-esterification and mineral flotation agent. Furthermore, microbial involvements in carbon cycling were revealed by DOM-microbe correlation network, but microbial contributions to the DOM pools decreased under acidic and metal stresses. These findings highlight abnormal carbon dynamics caused by AMD pollution and integrate DOM fate into pit lake biogeochemistry, thereby contributing to management and remediation.

Seasonal variations of dissolved organic matter chemistry in a semi-enclosed and eutrophic coastal bay in southeastern China: Implications for carbon cycling

As the widely distributed transition zones connecting the terrestrial and marine ecosystems, coastal bays have long water retention times to reconstruct the DOM pool affecting global carbon cycling. However, we still have a limited understanding of mechanisms shaping the carbon cycling of coastal bays at regional scales. To address this issue, we combined stable carbon isotopes, ultraviolet–visible absorption, fluorescence spectroscopy, and ultrahigh-resolution mass spectrometry to investigate the spatiotemporal chemistry of dissolved organic matter (DOM) in Xiangshan Bay, a semi-enclosed, eutrophic bay in southeastern China. The DOM in Xiangshan Bay was characterized by a higher degree of humification and aromaticity during winter, whereas the inverse signature during summer. Results showed that the significant seasonal variation of DOM chemistry was mainly modulated by intense primary productivity stimulated by nutrients during summer, and other factors including sediment pore water DOM release and photochemical reactions. Additionally, based on the microbial carbon pump (MCP) hypothesis, marine microorganisms may synthesize biologically recalcitrant DOM with millennia turnover time. The efficient MCP associated with reduced nutrients probably acted as a critical factor in Xiangshan Bay, leading to the formation of additional refractory molecular formulae (carboxyl-rich alicyclic molecules) and a more recalcitrant signature of DOM during winter. Incorporated with seven other coastal bays across China, it is revealed that anthropogenic inputs substantially contributed to Chinese coastal bays. Further studies need to better constrain the biogeochemical implications of these anthropogenic inputs. More importantly, decreasing the anthropogenic input of nutrients to coastal bays may enhance their functions in long-term carbon sequestration.

A Tropical Cocktail of Organic Matter Sources: Variability in Supraglacial and Glacier Outflow Dissolved Organic Matter Composition and Age Across the Ecuadorian Andes

AbstractThe biogeochemistry of rapidly retreating Andean glaciers is poorly understood, and Ecuadorian glacier dissolved organic matter (DOM) composition is unknown. This study examined molecular composition and carbon isotopes of DOM from supraglacial and outflow streams (n = 5 and 14, respectively) across five ice capped volcanoes in Ecuador. Compositional metrics were paired with streamwater isotope analyses (δ18O) to assess if outflow DOM composition was associated with regional precipitation gradients and thus an atmospheric origin of glacier DOM. Ecuadorian glacier outflows exported ancient, biolabile dissolved organic carbon (DOC), and DOM contained a high relative abundance (RA) of aliphatic and peptide‐like compounds (≥27%RA). Outflows were consistently more depleted in Δ14C‐DOC (i.e., older) compared to supraglacial streams (mean −195.2 and −61.3‰ respectively), perhaps due to integration of spatially heterogenous and variably aged DOM pools across the supraglacial environment, or incorporation of aged subglacial OM as runoff was routed to the outflow. Across Ecuador, Δ14C‐DOC enrichment was associated with decreased aromaticity of DOM, due to increased contributions of organic matter (OM) from microbial processes or atmospheric deposition of recently fixed and subsequently degraded OM (e.g., biomass burning byproducts). There was a regional gradient between glacier outflow DOM composition and streamwater δ18O, suggesting covariation between regional precipitation gradients and the DOM exported from glacier outflows. Ultimately, this highlights that atmospheric deposition may exert a control on glacier outflow DOM composition, suggesting regional air circulation patterns and precipitation sources in part determine the origins and quality of OM exported from glacier environments.

Solid phase extraction of ocean dissolved organic matter with PPL cartridges: efficiency and selectivity

Our current knowledge of the chemical composition of ocean dissolved organic matter (DOM) is limited, mainly because of its extreme molecular diversity, low concentration of individual compounds and the elevated ionic strength of ocean waters. As a result, many analytical methods require a previous extraction step. The efficiency and selectivity of the extraction method defines the representativeness of the extracted DOM fraction. Nowadays, the most widespread procedure for concentrating DOM is solid phase extraction (SPE) using styrene divinyl benzene polymer cartridges (PPL). Here, we investigate the effect of SPE-PPL on DOM elemental and optical properties to assess the efficiency and selectivity of this extraction method on water samples from the main intermediate and deep water masses of Arctic, Mediterranean and Antarctic origin present in the Cape Vert Frontal Zone (CVFZ, NW Africa). Furthermore, North and South Atlantic Central waters converge in this area and coastal DOM is injected by the giant upwelling filament of Cape Blanc. On one side, the colored fraction of DOM (CDOM) presented extraction efficiencies comparable to that of the bulk dissolved organic carbon (DOC), but decreased significantly with increasing wavelength, suggesting an affinity of PPL cartridges for low molecular weight organic compounds. While the protein-like fluorescent fraction of DOM (FDOM) was also extracted with the same efficiency than DOC, the extraction efficiency of the humic-like fraction was comparatively much higher. On the other side, dissolved organic nitrogen (DON) extraction efficiencies were about half that of DOC. These contrasting extraction efficiencies of the different DOM pools indicated that the extracts were enriched in N-poor, low molecular weight and recalcitrant DOM, therefore showing less variability than the corresponding bulk DOM. Furthermore, DOC, DON, CDOM and FDOM extracted were not homogeneous through the water column but displayed certain significant differences among water masses in both efficiency and selectivity.

Characterization of a Newly Available Coastal Marine Dissolved Organic Matter Reference Material (TRM-0522).

Recent methodological advances have greatly increased our ability to characterize aquatic dissolved organic matter (DOM) using high-resolution instrumentation, including nuclear magnetic resonance (NMR) and mass spectrometry (HRMS). Reliable DOM reference materials are required for further method development and data set alignment but do not currently exist for the marine environment. This presents a major limitation for marine biogeochemistry and related fields, including natural product discovery. To fill this resource gap, we have prepared a coastal marine DOM reference material (TRM-0522) from 45 m deep seawater obtained ∼1 km offshore of Sweden's west coast. Over 3000 molecular formulas were assigned by direct infusion HRMS, confirming sample diversity, and the distribution of formulas in van Krevelen space was typical for a marine sample, with the majority of formulas in the region H/C 1-1.5 and O/C 0.3-0.7. The extracted DOM pool was more nitrogen (N)- and sulfur (S)-rich than a typical terrestrial reference material (SRFA). MZmine3 processing of ultrahigh-performance liquid chromatography (UPLC)-HRMS/MS data revealed 494 resolvable features (233 in negative mode; 261 in positive mode) over a wide range of retention times and masses. NMR data indicated low contributions from aromatic protons and, generally speaking, low lignin, humic, and fulvic substances associated with terrestrial samples. Instead, carboxylic-rich aliphatic molecules were the most abundant components, followed by carbohydrates and aliphatic functionalities. This is consistent with a very low specific UV absorbance SUVA254 value of 1.52 L mg C-1 m-1. When combined with comparisons with existing terrestrial reference materials (Suwannee River fulvic acid and Pony Lake fulvic acid), these results suggest that TRM-0522 is a useful and otherwise unavailable reference material for use in marine DOM biogeochemistry.

Dissolved organic matter defines microbial communities during initial soil formation after deglaciation

Ecosystem succession and pedogenesis reshuffle the composition and turnover of dissolved organic matter (DOM) and its interactions with soil microbiome. The changes of these connections are especially intensive during initial pedogenesis, e.g. in young post-glacial areas. The temporal succession and vertical development of DOM effects on microbial community structure remains elusive. Using Fourier Transform Ion Cyclotron Resonance Mass Spectrometry (FT-ICR MS), high-throughput sequencing, and molecular ecological networks, we characterized the molecular diversity of water-extractable DOM and identified its links to microbial communities in soil profiles along deglaciation chronosequence (12, 30, 40, 52, 80, and 120 years) in the southeastern Tibetan Plateau. Low-molecular-weight compound content decreased, whereas the mid- and high-molecular-weight compounds increased with succession age and soil depth. This was confirmed by the increase in double bond equivalents and averaged oxygen-to‑carbon ratios (O/C), and decrease in hydrogen-to‑carbon ratios (H/C), which reflect DOM accumulation and stabilization. Microbial community succession shifted towards the dominance of oligotrophic Acidobacteria and saprophytic Mortierellomycota, reflecting the increase of stable DOM components (H/C < 1.5 and wider O/C). Less DOM-bacterial positive networks during the succession reduced specialization of labile DOM production (such as lipid- and protein-like compounds), whereas more DOM-fungal negative networks increased specialization of stable DOM decomposition (such as tannin- and condensed aromatic-like compounds). Consequently, DOM stability is not intrinsic during initial pedogenesis: stable DOM compounds remain after fast bacterial utilization of labile DOM compounds, whereas fungi decompose slowly the remaining DOM pools.