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Dissolved organic matter (DOM) is a vast and complex chemical mixture that plays a key role in the mediation of the global carbon cycle. Fundamental understanding of the source and fate of oceanic organic matter is obscured due to poor definition of the key molecular contributors to DOM, which limits accurate sample analysis and prediction of the Earth's carbon cycle. Previous work has attempted to define the components of the DOM through a variety of chromatographic and spectral techniques. However, modern preparative and analytical methods have not isolated or unambiguously identified molecules from DOM. Therefore, previously proposed structures are based solely on the mixture's aggregate properties and do not accurately describe any true individual molecular component. In addition to this, there is a lack of appropriate analogues of the individual chemical classes within DOM, limiting the scope of experiments that probe the physical, chemical, and biological contributions from each class. To address these problems, we synthesized a series of analogues of carboxylate-rich alicyclic molecules (CRAM), a molecular class hypothesized to exist as a major contributor to DOM. Key analytical features of the synthetic CRAMs were consistent with marine DOM, supporting their suitability as chemical substitutes for CRAM. This new approach provides access to a molecular toolkit that will enable previously inaccessible experiments to test many unproven hypotheses surrounding the ever-enigmatic DOM.

Photochemical degradation of dissolved organic matter (DOM) has been the subject of numerous studies; however, its regulation along the inland water continuum is still unclear. We aimed to unravel the DOM photoreactivity and concurrent DOM compositional changes across 30 boreal aquatic ecosystems including peat waters, streams, rivers, and lakes distributed along a water residence time (WRT) gradient. Samples were subjected to a standardized exposure of simulated sunlight. We measured the apparent quantum yield (AQY), which corresponds to DOM photomineralization per photon absorbed, and the compositional change in DOM at bulk and individual compound levels in the original samples and after irradiation. AQY increased with the abundance of terrestrially derived DOM and decreased at higher WRT. Additionally, the photochemical changes in both DOM optical properties and molecular composition resembled changes along the natural boreal WRT gradient at low WRT (<3 years). Accordingly, mass spectrometry revealed that the abundance of photolabile and photoproduced molecules decreased with WRT along the boreal aquatic continuum. Our study highlights the tight link between DOM composition and DOM photodegradation. We suggest that photodegradation is an important driver of DOM composition change in waters with low WRT, where DOM is highly photoreactive.

Aquatic dissolved organic matter (DOM) is a crucial component of the global carbon cycle, and the extent to which DOM escapes mineralization is important for the transport of organic carbon from the continents to the ocean. DOM persistence strongly depends on its molecular properties, but little is known about which specific properties cause the continuum in reactivity among different dissolved molecules. We investigated how DOM fractions, separated according to their hydrophobicity, differ in biodegradability across three different inland water systems. We found a strong negative relationship between hydrophobicity and biodegradability, consistent for the three systems. The most hydrophilic fraction was poorly recovered by solid-phase extraction (SPE) (3-28% DOC recovery) and was thus selectively missed by mass spectrometry analysis during SPE. The change in DOM composition after incubation was very low according to SPE-ESI (electrospray ionization)-mass spectrometry (14% change, while replicates had 11% change), revealing that this method is sub-optimal to assess DOM biodegradability, regardless of fraction hydrophobicity. Our results demonstrate that SPE-ESI mass spectrometry does not detect the most hydrophilic and most biodegradable species. Hence, they question our current understanding of the relationships between DOM biodegradability and its molecular composition, which is built on the use of this method.

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.

Earth's lakes at northern latitudes are mostly ice-covered in winter. When lake water freezes, some organic matter dissolved in the water is excluded from the ice. We performed complementary field sampling and laboratory freeze-up experiments to explore how freeze-up may impact the partitioning and composition of dissolved organic matter (DOM) in boreal lakes. We found that 16.2 ± 4.7% of dissolved organic carbon (DOC) was retained in the overlying ice, 81.3 ± 5.7% of DOC was expelled to underlying unfrozen water, and 1.3 ± 0.7% was expelled as flocs. During ice formation, nitrogen (TDN, total dissolved nitrogen), ions (specific conductance), and oxidized and aromatic DOM were preferentially expelled to the underlying water column. The apparent retention factor DOCIce: DOCBefore decreased from clearwater to brownwater lakes, that is, with increasing allochthonous DOC lost from lake ice, indicating that DOM exclusion from the ice cover will become more prevalent as lakes experience browning.

Small synthetic mimics of cationic antimicrobial peptides represent a promising class of compounds with leads in clinical development for the treatment of persistent microbial infections. The activity and selectivity of these compounds rely on a balance between hydrophobic and cationic components, and here, we explore the activity of 19 linear cationic tripeptides against five different pathogenic bacteria and fungi, including clinical isolates. The compounds incorporated modified hydrophobic amino acids inspired by motifs often found in bioactive marine secondary metabolites in combination with different cationic residues to probe the possibility of generating active compounds with improved safety profiles. Several of the compounds displayed high activity (low mu M concentrations), comparable with the positive controls AMC-109, amoxicillin, and amphotericin B. A higher activity was observed against the fungal strains, and a low in vitro off-target toxicity was observed against erythrocytes and HeLa cells, thereby illustrating effective means for tuning the activity and selectivity of short antimicrobial peptides.

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.

Sea spray aerosol is the largest natural source of aerosol to Earth's atmosphere with significant impacts on climate. Despite this, estimates of the impact of sea spray aerosol on Earth's radiation budget are highly uncertain due to an overall lack of understanding of the physical and chemical factors controlling its composition. Critically, results from studies probing the importance of oceanic biological activity on the amount and type of organic matter present in nascent sea spray aerosol have been ambiguous. Some field studies have shown a relationship between the organic fraction of sea spray aerosol and oceanic primary productivity while others have reported no such relationships. Given this, we have probed the composition of seawater and nascent sea spray aerosol during a phytoplankton bloom in the North Atlantic using a novel liquid chromatography-mass spectrometry method. We observed that the composition of dissolved organic matter present in seawater changed as the phytoplankton bloom progressed over an 18 day period. Further, we observed changes to both the chemical composition of the organic matter present in seawater and the chemical composition of the organic matter present in the sea spray aerosol despite the organic matter mass fraction of the aerosol remaining unchanged. More specifically, we observed that the nascent sea spray aerosol became progressively more enriched in surface-active organic substances as the bloom progressed and that the sea spray aerosol had a distinct organic matter composition compared to the seawater. Thus, our work provides additional insight into the biological dependence of nascent sea spray aerosol composition.

Oil sands process waters can release toxic naphthenic acids (NAs) into aquatic environments. Analytical techniques for NAs are challenged by sample complexity and interference from naturally occurring dissolved organic matter (DOM). Herein, we report the use of a poly(dimethylsiloxane) (PDMS) polymer membrane for the on-line separation of NAs from DOM and use direct infusion electrospray ionization mass spectrometry to yield meaningful qualitative and quantitative information with minimal sample cleanup. We compare the composition of membrane-permeable species from natural waters fortified with a commercial NA mixture to those derived from weak anion exchange solid-phase extraction (SPE) using high-resolution mass spectrometry. The results show that SPE retains a wide range of carboxylic acids, including biogenic DOM, while permeation through PDMS was selective for petrogenic classically defined NAs (CnH2n+zO2). A series of model compounds (log K-ow similar to 1-7) were used to characterize the perm-selectivity and reveal the separation is based on hydrophobicity. This convenient sample cleanup method is selective for the O-2 class of NAs and can be used prior to conventional analysis or as an on-line analytical strategy when coupled directly to mass spectrometry.

Neurotoxic methylmercury (MeHg) is formed by microbial methylation of inorganic divalent Hg (HgII) and constitutes severe environmental and human health risks. The methylation is enabled by hgcA and hgcB genes, but it is not known if the associated molecular-level processes are rate-limiting or enable accurate prediction of MeHg formation in nature. In this study, we investigated the relationships between hgc genes and MeHg across redox-stratified water columns in the brackish Baltic Sea. We showed, for the first time, that hgc transcript abundance and the concentration of dissolved HgII-sulfide species were strong predictors of both the HgII methylation rate and MeHg concentration, implying their roles as principal joint drivers of MeHg formation in these systems. Additionally, we characterized the metabolic capacities of hgc+ microorganisms by reconstructing their genomes from metagenomes (i.e., hgc+ MAGs), which highlighted the versatility of putative HgII methylators in the water column of the Baltic Sea. In establishing relationships between hgc transcripts and the HgII methylation rate, we advance the fundamental understanding of mechanistic principles governing MeHg formation in nature and enable refined predictions of MeHg levels in coastal seas in response to the accelerating spread of oxygen-deficient zones.

During a research program to identify new cholinesterase inhibitors of natural origin, two new 7,8-didehy-droprotoberberine alkaloids (1 and 2) and nine known compounds (3-11) were isolated from the capsules of the common ornamental poppy, Papaver setiferum (previously P. pseudo-orientale). Despite their reported instability, the 7,8-didehydroprotoberberines isolated herein appeared relatively stable, particularly as their trifluoroacetic acid salts. The spatial distributions of the isolated alkaloids were also analyzed using desorption electrospray ionization imaging mass spectrometry. The alkaloids were localized predominantly within the walls and vascular bundles of the capsules, with the highest relative abundances occurring in the lower half of the capsules toward the peduncle. The relative abundances of the alkaloids were also compared across plant development stages. Although most alkaloids did not show clear patterns in their concentration across development stages, the concentration of suspected oxidation products clearly spiked upon plant death. Finally, all isolated natural products were screened for inhibitory activities against a panel of cholinesterases, from both human and animal sources. These studies identified several competitive inhibitors of cholinesterases with potency in the low micromolar range (1-4, 6, 7), offering new lead compounds for the development of cholinesterase inhibitory drugs.

Neurotoxic methylmercury (MeHg) is formed by microbial methylation of inorganic divalent Hg (HgII) and constitutes severe environmental and human health risks. The methylation is enabled by hgcA and hgcB genes, but it is not known if the associated molecular-level processes are rate-limiting or enable accurate prediction of MeHg formation in nature. In this study, we investigated the relationships between hgc genes and MeHg across redox-stratified water columns in the brackish Baltic Sea. We showed, for the first time, that hgc transcript abundance and the concentration of dissolved HgII-sulfide species were strong predictors of both the HgII methylation rate and MeHg concentration, implying their roles as principal joint drivers of MeHg formation in these systems. Additionally, we characterized the metabolic capacities of hgc+ microorganisms by reconstructing their genomes from metagenomes (i.e., hgc+ MAGs), which highlighted the versatility of putative HgII methylators in the water column of the Baltic Sea. In establishing relationships between hgc transcripts and the HgII methylation rate, we advance the fundamental understanding of mechanistic principles governing MeHg formation in nature and enable refined predictions of MeHg levels in coastal seas in response to the accelerating spread of oxygen-deficient zones