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Dissolved organic matter (DOM) is a complex mixture of thousands of molecular formulas comprised of an unknown number of chemical compounds, the concentration and composition of which are critical to ecosystem function and biogeochemical cycling. Despite its importance, our understanding of the DOM composition is lacking. This is principally due to its molecular complexity, which means that no single method is capable of describing DOM in its entirety. Quantification is typically done by proxy (e.g., relative to carbon content) and does not necessarily match well to compositional data, due to incomplete analytical windows and selectivity of different analytical methods. We present an integrated liquid chromatography (LC)-diode array detector (DAD)-charged aerosol detector (CAD)-mass spectrometry (MS) pipeline designed to both characterize and quantify solid-phase extractable DOM (SPE-DOM) in a single analysis. We applied this method to a set of eight Swedish water bodies sampled in the summer and winter. Chromophoric SPE-DOM was proportionally higher in samples with higher SPE-DOM concentrations but remained relatively consistent between sampling occasions. Ionizable SPE-DOM was relatively consistent across sites but was proportionally higher in summer. Overall, the carbon content of DOM was very consistently similar to 40% across sites in both summer and winter. These findings suggest that SPE-DOM concentration at these sites is driven by (presumably allochthonous) chromophoric inputs, with an increased relative contribution in summer of material that is more ionizable and less chromophoric and may be either autochthonous or selectively enriched from allochthonous sources. Thus, with minimal additional effort, this method provided further compositional insights not attained by any single analysis in isolation.

Dissolved organic matter (DOM) is widely studied in environmental and biogeochemical sciences, but is susceptible to chemical and biological degradation during sample transport and storage. Samples taken in remote regions, aboard ships, or in large numbers need to be preserved for later analysis without changing DOM composition. Here we compare high-resolution mass spectra of solid phase extractable DOM before and after freezing at -20 & DEG;C. We found that freezing increases compositional dissimilarity in DOM by between 0 to 18.2% (median = 2.7% across 7 sites) when comparing replicates that were frozen versus unfrozen, i.e., processed immediately after sampling, as compared with differences between unfrozen replicates. The effects of freezing primarily consisted of a poorer detection limit, but were smaller than other sample preparation and analysis steps, such as solid phase extraction and variable ionisation efficiency. Freezing samples for either 21 or 95 days led to similar and only slight changes in DOM composition, albeit with more variation for the latter. Therefore, we conclude that sample freezing on these time scales should not impede scientific study of aquatic DOM and can be used where it makes logistical sense, such as for large spatial surveys or study of archived samples.

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.

Estuaries receive and process a large amount of particulate organic carbon (POC) prior to its export into coastal waters. Studying the origin of this POC is key to understanding the fate of POC and the role of estuaries in the global carbon cycle. Here, we evaluated the concentrations of POC, as well as particulate organic nitrogen (PON), and used stable carbon and nitrogen isotopes to assess their sources across 13 contrasting British estuaries during five different sampling campaigns over 1 year. We found a high variability in POC and PON concentrations across the salinity gradient, reflecting inputs, and losses of organic material within the estuaries. Catchment land cover appeared to influence the contribution of POC to the total organic carbon flux from the estuary to coastal waters, with POC contributions >36% in estuaries draining catchments with a high percentage of urban/suburban land, and <11% in estuaries draining catchments with a high peatland cover. There was no seasonal pattern in the isotopic composition of POC and PON, suggesting similar sources for each estuary over time. Carbon isotopic ratios were depleted (-26.7 +/- 0.42 parts per thousand, average +/- sd) at the lowest salinity waters, indicating mainly terrigenous POC (TPOC). Applying a two-source mixing model, we observed high variability in the contribution of TPOC at the highest salinity waters between estuaries, with a median value of 57%. Our results indicate a large transport of terrigenous organic carbon into coastal waters, where it may be buried, remineralized, or transported offshore. Plain Language Summary Estuaries transport and process a large amount terrigenous particulate organic matter (i.e., carbon and nitrogen) prior to its export to coastal waters. In order to understand the fate of organic carbon and the role of estuaries in the global carbon cycle it is essential to improve our knowledge on its composition, origin, and amount of carbon transported. We quantified the elemental concentrations and stable isotopes composition of carbon and nitrogen to quantify the amount of terrigenous particulate organic matter transported by 13 British estuaries, which drain catchments of diverse land cover under different hydrological conditions. We found a great variability in particulate organic carbon (POC) and particulate organic nitrogen concentrations across the salinity gradient, implying inputs, and losses of material within the estuaries. Each estuary had similar sources of particulate material throughout the year. In most of the estuaries, the POC had a terrigenous origin at the lowest salinity waters. The terrigenous organic carbon contribution decreased toward coastal waters with an average contribution of 57% at the highest salinity waters, indicating a large transport of terrigenous organic carbon into coastal waters.

Dissolved inorganic carbon (DIC) fluxes from the land to ocean have been quantified for many rivers globally. However, CO₂ fluxes to the atmosphere from inland waters are quantitatively significant components of the global carbon cycle that are currently poorly constrained. Understanding, the relative contributions of natural and human-impacted processes on the DIC cycle within catchments may provide a basis for developing improved management strategies to mitigate free CO₂ concentrations in rivers and subsequent evasion to the atmosphere. Here, a large, internally consistent dataset collected from 41 catchments across Great Britain (GB), accounting for ∼36% of land area (∼83,997 km²) and representative of national land cover, was used to investigate catchment controls on riverine dissolved inorganic carbon (DIC), bicarbonate (HCO₃⁻) and free CO₂ concentrations, fluxes to the coastal sea and annual yields per unit area of catchment. Estimated DIC flux to sea for the survey catchments was 647 kt DIC yr⁻¹ which represented 69% of the total dissolved carbon flux from these catchments. Generally, those catchments with large proportions of carbonate and sedimentary sandstone were found to deliver greater DIC and HCO₃⁻ to the ocean. The calculated mean free CO₂ yield for survey catchments (i.e. potential CO₂ emission to the atmosphere) was 0.56 t C km⁻² yr⁻¹. Regression models demonstrated that whilst river DIC (R² = 0.77) and HCO₃⁻ (R² = 0.77) concentrations are largely explained by the geology of the landmass, along with a negative correlation to annual precipitation, free CO₂ concentrations were strongly linked to catchment macronutrient status. Overall, DIC dominates dissolved C inputs to coastal waters, meaning that estuarine carbon dynamics are sensitive to underlying geology and therefore are likely to be reasonably constant. In contrast, potential losses of carbon to the atmosphere via dissolved CO₂, which likely constitute a significant fraction of net terrestrial ecosystem production and hence the national carbon budget, may be amenable to greater direct management via altering patterns of land use.