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To examine the impact of heterotrophic bacteria on microalgal physiology, we co-cultured the diatom Phaeodactylum tricornutum with six bacterial strains to quantify bacteria-mediated differences in algal biomass, total intracellular lipids, and for a subset, extracellular metabolite accumulation. A Marinobacter isolate significantly increased algal cell concentrations, dry biomass, and lipid content compared to axenic algal cultures. Two other bacterial strains from the Bacteroidetes order, of the genera Algoriphagus and Muricauda, significantly lowered P. tricornutum biomass, leading to overall decreased lipid accumulation. These three bacterial co-cultures (one mutualistic, two competitive) were analyzed for extracellular metabolites via untargeted liquid chromatography mass spectrometry to compare against bacteria-free cultures. Over 80% of the extracellular metabolites differentially abundant in at least one treatment were in higher concentrations in the axenic cultures, in agreement with the hypothesis that the co-cultured bacteria incorporated algal-derived organic compounds for growth. Furthermore, the extracellular metabolite profiles of the two growth-inhibiting cultures were more similar to one another than the growth-promoting co-culture, linking metabolite patterns to ecological role. Our results show that algal-bacterial interactions can influence the accumulation of intracellular lipids and extracellular metabolites, and suggest that utilization and accumulation of compounds outside the cell play a role in regulating microbial interactions.

The Laguna Madre-Tamaulipas is the world’s largest hypersaline lagoon and is equally located in south Texas, USA, and Tamaulipas, Mexico. Over 40% of its American surface area is covered by wind-ti...

The transport of methane from deep sediments towards the seafloor is widespread in ocean margins and has important biogeochemical implications for the deep ocean [1]. A significant portion (>80%) o...

Iningainema is a recently described genus of heterocytous, false-branching cyanobacteria originally described from Australia. In this work, we present Iningainema tapete sp. nov., isolated from subaerial and terrestrial environments in central Florida (USA). In comparison to the sister species, our novel cyanobacterium produces nodularin-R (NOD-R) and a methylated isoform [MeAdda3] NOD previously not reported within this genus; in addition to possessing the biosynthetic gene clusters for microcystin and anabaenopeptins production. Nodularin accumulation by this cyanobacterium exceeded 500 µg g−1 dry weight in cultures grown in nitrogen-depleted media. Such elevated toxin concentrations are alarming as the cyanobacterium was isolated from a food production greenhouse and poses a potential risk for food products and for workforce exposure. Using morphology, 16S rRNA gene phylogeny, and 16S-23S rRNA internal transcribed spacer (ITS) secondary structure, coupled with toxin detection and toxin gene presence, we provide evidence for the establishment of a novel toxic species of cyanobacteria, Iningainema tapete.

Aside from two samples collected nearly 50 years ago, little is known about the microbial composition of wind tidal flats in the hypersaline Laguna Madre, Texas. These mats account for ~42% of the lagoon&rsquo, s area. These microbial communities were sampled at four locations that historically had mats in the Laguna Madre, including Laguna Madre Field Station (LMFS), Nighthawk Bay (NH), and two locations in Kenedy Ranch (KRN and KRS). Amplicon sequencing of 16S genes determined the presence of 51 prokaryotic phyla dominated by Bacteroidota, Chloroflexi, Cyanobacteria, Desulfobacteria, Firmicutes, Halobacteria, and Proteobacteria. The microbial community structure of NH and KR is significantly different to LMFS, in which Bacteroidota and Proteobacteria were most abundant. Twenty-three cyanobacterial taxa were identified via genomic analysis, whereas 45 cyanobacterial taxa were identified using morphological analysis, containing large filamentous forms on the surface, and smaller, motile filamentous and coccoid forms in subsurface mat layers. Sample sites were dominated by species in Oscillatoriaceae (i.e., Lyngbya) and Coleofasciculaceae (i.e., Coleofasciculus). Most cyanobacterial sequences (~35%) could not be assigned to any established taxa at the family/genus level, given the limited knowledge of hypersaline cyanobacteria. A total of 73 cyanobacterial bioactive metabolites were identified using ultra performance liquid chromatography-Orbitrap MS analysis from these commu nities. Laguna Madre seems unique compared to other sabkhas in terms of its microbiology.

Methane transport from subsurface reservoirs to shallow marine sediment is characterized by unique biogeochemical interactions significant for ocean chemistry. Sulfate-Methane Transition Zone (SMTZ) is an important diagenetic front in the sediment column that quantitatively consumes the diffusive methane fluxes from deep methanogenic sources toward shallow marine sediments via sulfate-driven anaerobic oxidation of methane (AOM). Recent global compilation from diffusion-controlled marine settings suggests methane from below and sulfate from above fluxing into the SMTZ at an estimated rate of 3.8 and 5.3 Tmol year–1, respectively, and wider estimate for methane flux ranges from 1 to 19 Tmol year–1. AOM converts the methane carbon to dissolved inorganic carbon (DIC) at the SMTZ. Organoclastic sulfate reduction (OSR) and deep-DIC fluxes from methanogenic zones contribute additional DIC to the shallow sediments. Here, we provide a quantification of 8.7 Tmol year–1 DIC entering the methane-charged shallow sediments due to AOM, OSR, and the deep-DIC flux (range 6.4–10.2 Tmol year–1). Of this total DIC pool, an estimated 6.5 Tmol year–1 flows toward the water column (range: 3.2–9.2 Tmol year–1), and 1.7 Tmol year–1 enters the authigenic carbonate phases (range: 0.6–3.6 Tmol year–1). This summary highlights that carbonate authigenesis in settings dominated by diffusive methane fluxes is a significant component of marine carbon burial, comparable to ∼15% of carbonate accumulation on continental shelves and in the abyssal ocean, respectively. Further, the DIC outflux through the SMTZ is comparable to ∼20% of global riverine DIC flux to oceans. This DIC outflux will contribute alkalinity or CO2 in different proportions to the water column, depending on the rates of authigenic carbonate precipitation and sulfide oxidation and will significantly impact ocean chemistry and potentially atmospheric CO2. Settings with substantial carbonate precipitation and sulfide oxidation at present are contributing CO2 and thus to ocean acidification. Our synthesis emphasizes the importance of SMTZ as not only a methane sink but also an important diagenetic front for global DIC cycling. We further underscore the need to incorporate a DIC pump in methane-charged shallow marine sediments to models for coastal and geologic carbon cycling.

Proteins represent the most abundant class of biomolecules in marine sinking particles and microbial biomass, yet their cycling in marine sediments is not fully understood. To investigate whether some portion of hydrolyzed proteins escapes complete remineralization and accumulate in the pore waters, we analyzed dissolved organic matter from the anoxic sediments of Santa Barbara Basin, California, by Fourier Transform Ion Cyclotron Resonance Mass Spectrometry (FTICR-MS). The results showed an increase in the molecular diversity and abundance of dissolved organic nitrogen (DON) formulas with depth. A comparison of the detected DON formulas to a database of small peptides (2–4 amino acid sequences) returned 119 matches, and these formulas were most abundant near the sediment surface. When we compared our detected formulas to all possible structures that would result from deamination of peptides in the database, we found 680 formula matches. However, these molecular formulas can represent hundreds of different structural isomers (in the present case as many as 3257 different deaminated peptide structures), which cannot be distinguished by the FTICR-MS settings that were used. Analysis of amino acid sequences suggests that these deaminated peptides may be the products of selective degradation of source proteins in marine sediments. We hypothesize that these deaminated peptides accumulate in the pore waters due to extracellular proteinases being inhibited from completely hydrolyzing specific peptides to free amino acids. We suggest that anaerobic microbes deaminate peptides largely to produce H2, which is ultimately used as a reducing agent by other sediment microbes (e.g. CO2 reduction by methanogens). Simple calculations suggest that deaminated peptides may represent ∼25–45% of DOC accumulating in these sediment pore waters. Unlike rapid remineralization of free amino acids, peptide deamination leaves behind the peptide carbon skeleton. Molecular structures of these remnant carbon skeletons may hold important clues about specific microbial processes influencing organic matter remineralization and accumulation.

Global climate change and anthropogenic nutrient inputs are responsible for increased frequency of cyanobacterial blooms that potentially contain 55 classes of bioactive metabolites. This study investigated the effects of CO2 availability and concomittant pH levels on two cyanobacteria that produce microcystins: a marine cf. Synechocystis sp. and a freshwater Microcystis aeruginosa. Cyanobacterial strains were semi-continuously cultured in mesotrophic growth media at pH 7.5, 7.8, 8.2, and 8.5 via a combination of CO2 addition and control of alkalinity. The cell concentration between treatments was not significantly different and nutrient availability was not limited. Concentration of most known cyanobacterial bioactive metabolites in both cyanobacterial strains increased as CO2 increased. At pH 7.8, bioactive metabolite intracellular concentration in M. aeruginosa and Synechocystis was 1.5 and 1.2 times greater than the other three treatments, respectively. Intracellular concentration of microginin in M. aeruginosa at pH 7.5 was reduced by 90% compared to the other three treatments. Intracellular concentration of microcyclamide-bistratamide B was lower in M. aeruginosa and higher in Synechocystis at elevated CO2 concentration. M. aeruginosa products were more diverse metabolites than Synechocystis. The diversity of accumulated metabolites in M. aeruginosa increased as CO2 increased, whereas the metabolite diversity in Synechocystis decreased as pH decreased. Overall, intracellular concentration of bioactive metabolites was higher at greater CO2 concentrations; marine and freshwater cyanobacteria had different allocation products when exposed to differing CO2 environments.

Hydroclimatic disturbances, like flooding, may greatly impact dissolved organic matter (DOM) composition in coastal waters by altering hydraulic gradients, groundwater residence times, and seafloor recirculation. This study provides new evidence regarding seasonal molecular DOM changes, in a submarine groundwater discharge influenced semi-arid estuary , across different hydroclimatic conditions: from flood peak (summer) to flood recession (fall), to typical dry (winter) to semi-wet (spring) conditions. DOM molecular characterization of seasonal surface- and pore- water samples was conducted using PPL solid phase extraction and UPLC-Orbitrap Fusion mass spectrometry, in positive mode. The proportion of CHO compounds present was lowest during flooding (34%), increased during fall flood recession (39%), and was highest under semi-wet baseflow (spring) conditions (42%). While CHON compounds increased from the flood and flood recession events (27% and 22%, respectively) to dry and semi-wet conditions (35% and 34%, respectively), sulfur and phosphorous containing compounds decreased (flood ~34% and flood recession ~6%; dry DOC and DON showed porewater influence. Baseflow characteristics were highly similar, with low saturation and high likelihood of rings or double bonds. It was evident that the influence of riverine inputs decreased within six months from the flood peak, which also showed the limited fresh riverine inputs outside extreme wet precipitation events when benthic fluxes became one of the major drivers of DOM characteristics. Thus, surface water DOM molecular characteristics showed significant responses to hydrologic changes , due to surface runoff inputs and benthic fluxes, which reflect changes in source and processing of OM within the estuary.

Submarine groundwater discharge (SGD) is often an overlooked component of the solute budgets in coastal embayments and is not considered in oyster restoration, conservation, and management plans. A combination of spatial and temporal geochemistry (nutrients, trace metals, alkalinity components, stable isotopes, and major ions) of porewater and surface water combined with SGD-derived solute fluxes and turnover times was used to examine the significance of SGD in delivering nutrients to paleovalley systems in coastal embayments, thus sustaining the health and productivity of oyster reefs. A 1-km2 area encompassing a paleovalley system, in Copano Bay, Texas, exhibited significant differences in the spatial and temporal hydrogeochemical characteristics (major ions, stable isotopes and nutrients) along the reef when compared to the other environments (i.e., paleovalley, estuary-wide). Solute fluxes (i.e., dissolved organic carbon (DOC), dissolved inorganic nitrogen (DIN), total alkalinity, DIC, etc.) are slightly larger at the reef, followed by the margin and shoreline. During dry conditions, SGD from the 1-km2 area was estimated to supply anywhere between two-fold to one order of magnitude more nitrogen (in the form of DIN) than the riverine inputs to Copano Bay. During a wet year SGD equates the river input in the form of DIN. In addition, SGD-based turnover times, averaging

Sulfurization has been found to enhance organic matter preservation and petroleum formation in marine sediments. However, we do not yet have a comprehensive understanding of sulfurization mechanisms. In this study, we investigated several possible mechanisms of dissolved organic sulfur (DOS) formation in the top 4.5 m of anoxic sediments of Santa Barbara Basin (SBB), California Borderland. Using Fourier Transform Ion Cyclotron Resonance Mass Spectrometry (FTICR-MS), we identified chemical formulas of potential dissolved organic matter (DOM) precursors to these DOS compounds. We also examined how the formulas of abiotically formed DOS changed as a function of depth across a major redox gradient. Results show that abiotic nucleophilic addition reactions involving bisulfide (HS−) and polysulfide (HSx−) are the major sulfurization pathways that form DOS in anoxic pore waters of SBB sediments. We identified 2124 unique DOS formulas that could be generated from the addition of HS− and HSx− to 2203 DOM formulas, and this accounted for ∼70% of all DOS formulas detected in these pore waters. Examining the DOM formulas that served as reactants in the abiotic sulfurization reactions, we found that 64% contained only carbon, hydrogen, and oxygen (CHO formulas) while the remainder (34%) included nitrogen (DON formulas). Our results revealed high reactivity toward sulfurization among many of the CHO and DON formulas that have H/C and O/C elemental ratios that overlap with those of carboxyl-rich alicyclic molecules (CRAM). This specific class of formulas could play an important role in the formation of organic sulfur compounds in sulfidic marine ecosystems, and in the formation of sulfur-containing protokerogen in marine sediments. Our results further suggest that anoxic sediments are a source of DOS compounds to the oceans.

Marine sediments are globally significant sources of dissolved organic matter (DOM) to the oceans, but the biogeochemical role of pore-water DOM in the benthic and marine carbon cycles remains unclear due to a lack of understanding about its molecular composition. To help fill this knowledge gap, we used 1H nuclear magnetic resonance (NMR) spectroscopy to examine depth variability in the composition of pore-water DOM in anoxic sediments of Santa Barbara Basin, California Borderland. Proton detected spectra were acquired on whole samples without pre-concentration to avoid preclusion of any DOM components from the analytical window. Broad unresolved resonance (operationally assigned to carboxyl-rich alicyclic molecules, or CRAM) dominated all spectra. Most of the relatively well-resolved peaks (attributed to biomolecules or their derivatives) appeared at chemical shifts similar to those previously reported for marine DOM in the literature, but at different relative intensities. DOM composition changed significantly within the top 50 cm of the sediment column, where the relative intensity of CRAM increased, and the relative intensity of resolved resonances decreased. The composition of CRAM itself also changed throughout the entire length of the 4.5-m profile, as CRAM protons became increasingly aliphatic at the expense of functionalized protons. Given that pore-water DOM is generated from sedimentary organic matter that includes pre-aged and degraded material, and that DOM could theoretically be subjected to microbial reworking in the pore waters for centuries to millennia, these data suggest that marine sediments may be sources of CRAM that are compositionally unique from CRAM generated in the upper ocean.

Dissolved iron (dFe) and organic dFe-binding ligands were determined in San Francisco Bay, California by competitive ligand exchange adsorptive cathodic stripping voltammetry (CLE-ACSV) along a salinity gradient from the freshwater endmember of the Sacramento River (salinity 26). A range of dFe-binding ligand classes was simultaneously determined using multiple analytical window analysis, involving titrations with multiple concentrations of the added ligand, salicylaldoxime. The highest dFe and ligand concentrations were determined in the low salinity end of the estuary, with dFe equal to 131.5 nmol L− 1 and strong ligand (log K F e L , F e ′ cond ≥ 12.0) concentrations equal to 139.5 nmol L− 1. The weakest ligands (log K F e L , F e ′ cond K F e L , F e ′ cond > 11.0) were tightly coupled to dFe throughout the estuary, with average excess ligand concentrations ([L]–[dFe]) equal to 0.5 nmol L− 1. Humic-like substances analyzed via both CLE-ACSV and proton nuclear magnetic resonance in several samples were found to be a significant portion of the dFe-binding ligand pool in San Francisco Bay, with concentrations ranging from 559.5 μg L− 1 to 67.5 μg L− 1 in the lowest and highest salinity samples, respectively. DFe-binding ligands and humic-like substances were also found in benthic boundary layer samples taken from the shelf near the mouths of San Francisco Bay and Eel River, suggesting estuaries are an important source of dFe-binding ligands to California coastal shelf waters.

Photochemical processing of dissolved organic matter (DOM) in natural waters can alter its composition and structure, supply particulate organic matter (POM) to sediments, and deliver modified terrestrial DOM to the ocean. Our studies show that terrestrial DOM exposed to simulated sunlight is altered to produce POM with a markedly different molecular composition enriched with newly formed aliphatic and condensed aromatic molecules. This process is closely tied to the chemistry of iron, which primarily exists as dissolved Fe(II) and Fe(III)–organic complexes in initial DOM and photochemically matures to Fe(III) oxyhydroxides before coprecipitating out with POM. The newly formed condensed aromatic compounds resemble black carbon, which until now was thought to be produced by only combustion. These new molecules contribute a pool of Fe-rich, aliphatic, and black carbon-like organic matter to sediments as the terrestrial DOM is transported through rivers. We estimate that the annual global flux of this photop...

The bioreactivity or susceptibility of dissolved organic matter (DOM) to microbial degradation in streams and rivers is of critical importance to global change studies, but a comprehensive understanding of DOM bioreactivity has been elusive due, in part, to the stunningly diverse assemblages of organic molecules within DOM. We approach this problem by employing a range of techniques to characterize DOM as it flows through biofilm reactors: dissolved organic carbon (DOC) concentrations, excitation emission matrix spectroscopy (EEMs), and ultrahigh resolution mass spectrometry. The EEMs and mass spectral data were analyzed using a combination of multivariate statistical approaches. We found that 45% of stream water DOC was biodegraded by microorganisms, including 31–45% of the humic DOC. This bioreactive DOM separated into two different groups: (1) H/C centered at 1.5 with O/C 0.1–0.5 or (2) low H/C of 0.5–1.0 spanning O/C 0.2–0.7 that were positively correlated (Spearman ranking) with chromophoric and fluorescent DOM (CDOM and FDOM, respectively). DOM that was more recalcitrant and resistant to microbial degradation aligned tightly in the center of the van Krevelen space (H/C 1.0–1.5, O/C 0.25–0.6) and negatively correlated (Spearman ranking) with CDOM and FDOM. These findings were supported further by principal component analysis and 2-D correlation analysis of the relative magnitudes of the mass spectral peaks assigned to molecular formulas. This study demonstrates that our approach of processing stream water through bioreactors followed by EEMs and FTICR-MS analyses, in combination with multivariate statistical analysis, allows for precise, robust characterization of compound bioreactivity and associated molecular level composition.

Dissolved organic matter (DOM) is the most reactive organic carbon pool in earth. However, the heterogeneity of this organic mixture makes it difficult to investigate its dynamics under different external perturbations. In this review, we present the potential of using the two dimensional correlation spectroscopy analysis (2D correlations) as a tool to study the dynamic of DOM. We demonstrate the application of the 2D correlation analysis on high molecular weight DOM (HMW-DOM) with the salinity as perturbation parameter. We used four different chemical probes: Carbon nuclear magnetic resonance spectroscopy (13C NMR), Fourier transform infrared spectroscopy (FTIR), proton nuclear magnetic resonance spectroscopy (1H NMR) and Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS).

This study investigated the concentration and isotopic composition of different size fractions of organic matter (OM) in Lake Superior and in one of its many tributary streams and rivers (Amity Creek, Duluth, Minnesota, USA). Structural compositional drivers of the Δ14C of high molecular weight (HMW, >1 kDa) dissolved organic carbon (DOC) in the lake were also evaluated. Low molecular weight (LMW, 0.7 μm) was generally 13C-depleted (−29 ± 1.2‰) relative to “bulk” (

In a study of chemical transformations of estuarine high-molecular-weight (HMW, >1000 Da) dissolved organic matter (DOM) collected over a period of two years along a transect through the Elizabeth River/Chesapeake Bay system to the coastal Atlantic Ocean off Virginia, USA, δ 13 C values, N/C ratios, and principal component analysis (PCA) of the solid-state 13 C NMR (nuclear magnetic resonance) spectra of HMW-DOM show an abrupt change in both its sources and chemical structural composition occurring around salinity 20. HMW-DOM in the lower salinity region had lighter isotopic values, higher aromatic and lower carbohydrate contents relative to that in the higher salinity region. These changes around a salinity of 20 are possibly due to introduction of a significant amount of new carbon (autotrophic DOM) to the transect. PC-1 loadings plot shows that spatially differing DOM components are similar to previously reported 13 C NMR spectra of heteropolysaccharides (HPS) and carboxyl-rich alicyclic molecules (CRAM). Applying two dimensional correlation spectroscopy techniques to 1 H NMR spectra from the same samples reveals increases in the contribution of N -acetyl amino sugars, 6-deoxy sugars, and sulfated polysaccharides to HPS components along the salinity transect, which suggests a transition from plant derived carbohydrates to marine produced carbohydrates within the HMW-DOM pool. In contrast to what has been suggested previously, our combined results from 13 C NMR, 1 H NMR, and FTIR indicate that CRAM consists of at least two different classes of compounds (aliphatic polycarboxyl compounds and lignin-like compounds).

The atmospheric delivery of soluble and bioavailable iron (Fe) is essential for the biogeochemical functioning of many oceanic ecosystems where Fe is a limiting micronutrient for biological production. Aerosol samples associated with air masses characterized as European-influenced, primarily marine (no continental influence within 5 day back trajectories), or North African-influenced were collected along a cruise track in the eastern North Atlantic Ocean during a 2010 US GEOTRACES cruise. Aerosols were analyzed for total and soluble Fe and aluminum (Al) and organic matter (OM) loadings and OM chemical characteristics, to explore potential relationships between aerosol OM and Fe and Al that contribute to higher Fe and Al solubilities in combustion-influenced aerosols. Similar to the results from previous studies, North African-influenced air masses contained higher aerosol Fe (4.7–86 nmol m − 3 ) and Al (13–240 nmol m − 3 ) total loadings than European-influenced air masses (Fe: 0.63–2.7 nmol m − 3 ; Al: 2.5–5.9 nmol m − 3 ), but Fe and Al relative solubilities were much higher for European (Fe: 2.1–4.6%; Al: 1.9–3.2%) versus North African-influenced aerosols (Fe: 0.22–0.70%; Al: 0.39–1.1%). Water soluble organic carbon (WSOC) to trace metal ratios correlated positively with this trend in Fe and Al relative solubilities, as European-influenced WSOC/trace metal ratios ranged from ~ 2 to 32 while North African-influenced aerosol WSOC/trace metal ratios ranged from 0.04 to 0.51. Aerosols from primarily marine air masses showed the lowest Fe, Al, and OM loadings of all samples and Fe (0.71–2.5%) and Al (0.36–9.2%) solubilities that were variable and did not fit the patterns described for the continentally-influenced samples. Principal component analysis was employed on aerosol water soluble OM (WSOM) solution state 1 H nuclear magnetic resonance spectra and revealed the European-influenced aerosol WSOM to be characterized by higher contributions from acetic acid (a common photoproduct of atmospheric OM) and aliphatic hydrogens, while North African-influenced aerosol WSOM was characterized by carbohydrate-like compounds and compounds with unsaturations. The abundance of the acetic acid photoproduct in European-influenced aerosol WSOM suggests this WSOM to be rich in carboxyl groups that are thought to be strong Fe-binding ligands and provides evidence for the potential role of WSOM in maintaining aerosol Fe and Al solubilities.

Glacier-derived dissolved organic matter represents a quantitatively significant source of ancient, but bioavailable, carbon to downstream ecosystems. Anthropogenic aerosols supply glaciers with aged organic matter, according to an analysis of organic matter from glaciers in Alaska.

In this work, we use Fourier transform infrared spectroscopy (FTIR) and nuclear magnetic resonance spectroscopy ( 13 C NMR) data to quantify the changes of major chemical compound classes (carboxylic acid, amide, ester, aliphatic, aromatic and carbohydrate) in high molecular weight (HMW, >1 kDa) dissolved organic matter (DOM) isolated along a transect through the Elizabeth River/Chesapeake Bay system to the coastal Atlantic Ocean off Virginia, USA. Results show that carboxylic acids and aromatic compounds are lost along the transect, while HMW DOC becomes enriched in carbohydrate moieties that could have a mid-transect source, perhaps the intensive red tide bloom ( Choclodinium polykrikoides ) which occurred during our sampling period. Taking the second derivative of the FTIR spectra resolved three pools of de-protonated carboxylic acids at our Dismal Swamp site (used to represent terrestrial organic matter in this area): one carboxylic acid pool, complexed with iron, seems to be lost between the Dismal Swamp and river sites; the second appears biogeochemically active throughout the riverine transect, disappearing in the coastal ocean sample; the third seems refractory, with the potential to be transported to and to accumulate within the open ocean. Five-member ring esters (γ-lactones) were the major ester form in the Dismal Swamp; aliphatic and acetate esters were the dominant esters in the estuary/marine DOM. No amide groups were detectable in Dismal Swamp DOM; secondary amides were present at the estuarine/marine sites. Coupling FTIR with 13 C NMR provides new insights into the biogeochemical roles of carboxylic acid, amide and ester compounds in aquatic ecosystems.

We present a new stable isotope mass balance method for measuring the enhanced aqueous solubility of specific organic compounds in the presence of natural dissolved organic matter (DOM). It involves interfacing a standard dissolved organic carbon (DOC) analyzer with a stable isotope ratio monitoring system, is applicable to a wide range of model organic compounds and can be tuned to provide maximum precision for a given range of compound solubility and initial natural DOC concentration. Using 13 C-labeled styrene as a model compound, we applied the method to investigate the reactivity of Dismal Swamp DOM as a function of season, nominal molecular size and chemical composition as determined using Fourier Transform Infrared Spectroscopy (FTIR). The solubility enhancement of styrene ranged from 23% to 118% relative to deionized water, while DOC-normalized enhancements varied from about 0.04 to 0.35 μM styrene/μM DOC as a function of season and nominal molecular weight. Statistical analysis of FTIR spectra reveals a strong positive correlation between the styrene concentration and the carboxyl content of the natural DOM. Reactivity differences between high molecular weight (HMW), low molecular weight (LMW) and total DOM samples are consistent with potential variations in their higher order structures.

We performed laboratory studies to determine the effects of salinity on the photodegradation of dissolved organic matter (DOM) from the Great Dismal Swamp, Virginia, an important source of terrestrial DOM to the lower Chesapeake Bay. Samples were created by mixing Great Dismal Swamp water (ionic strength < 0 mol L 21 ) with modified artificial seawater solutions of differing salinities while keeping the final dissolved organic carbon (DOC) concentration constant. These samples were then irradiated for 24 h in a light box providing ultraviolet (UV) light similar to that of natural sunlight. Light absorbance and DOC concentrations decreased after photoexposure, whereas dissolved inorganic carbon (DIC) concentrations increased. Variations in salinity affected both DIC production and UV absorption, with the higher salinity samples showing lower DIC production and less photobleaching. Addition of an iron chelator eliminated the relationship between photochemistry and salinity by reducing both photobleaching and DIC production at low salinities. As terrigenous DOM transits through an estuary, its photochemical reactivity and optical properties may change significantly as a function of salinity, probably as a result of changes in DOM conformation or changes in iron– DOM photochemistry, or both.

In the following study, we addressed the effects of photoirradiation on the turnover of dissolved organic nitrogen (DON) from both natural and anthropogenic sources at the molecular level. Analysis of long-term photoirradiated samples via Fourier-transform ion cyclotron resonance mass spectrometry (FT-ICR-MS) identified both the photolabile and the photoproduced DON from both natural and anthropogenic sources. Although photoproduction of DON was prominent with natural dissolved organic matter (DOM) sources, even in a low nitrogen environment, the anthropogenic source shows a shift from photobleaching to photohumification denoted by an increase in the average molecular weight (MW) and the double bound equivalent (DBE) after 25 days of a continuous exposure to UV light, implying condensation of low MW molecules (LMW) to form high MW (HMW) molecules. Furthermore, the sharp increase in N/C molar ratio, in the anthropogenic source, substantiates the photoinduced dissolved inorganic nitrogen (DIN) incorporation hypothesis. Hence, our findings suggest that anthropogenic input will drive substantial variation in riverine DOM and, thus, estuarine optics and photochemistry and bioavailability. Furthermore, we validate that photochemistry is one of the main processes that shapes the DON quality in aquatic systems regardless of its original source.

In this study it was observed that, during long-term irradiations (>1 day) of natural waters, the methods for measuring hydroxyl radical (˙OH) formation rates based upon sequentially determined cumulative concentrations of photoproducts from probes significantly underestimate actual ˙OH formation rates. Performing a correction using the photodegradation rates of the probe products improves the ˙OH estimation for short term irradiations (

Two-dimensional (2D) correlation analysis was applied to 20 Fourier transform ion cyclotron resonance mass spectra (FTICR-MS) of ultrafiltered dissolved organic matter samples from a salinity transect of the lower Chesapeake Bay. We were able to investigate the chemical changes in the dissolved organic matter pool at the molecular level and classify the individual peaks based on their biogeochemical reactivity. The power of this technique is its ability to be used on either the presence/absence of the individual peaks or their normalized magnitudes. The presence or absence of the peaks are utilized to identify the reactivity and correlation between peaks that plot in different regions of the van Krevelen diagram, whereas the normalized magnitudes are used to correlate the changes among individual peaks. One of the promising advantages of 2D correlation of FTICR-MS data is the ability to associate the variations of the individual peaks with the changes in the functional groups that are measured by other spectroscopic techniques. This approach takes us one step further from identifying molecular formulas to proposing chemical structures.