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Hydrocarbon oxidation products (HOPs) formed from crude oil and diesel were generated from laboratory simulated spills at four different periods (1, 4, 7, and 10 days) under environmental conditions that mimicked those in Cook Inlet, Alaska.

The microbial carbon pump (MCP) hypothesis suggests that successive transformation of labile dissolved organic carbon (DOC) by prokaryotes produces refractory DOC (RDOC) and contributes to the long-term stability of the deep ocean DOC reservoir. We tested the MCP by exposing surface water from a deep convective region of the ocean to epipelagic, mesopelagic, and bathypelagic prokaryotic communities and tracked changes in dissolved organic matter concentration, composition, and prokaryotic taxa over time. Prokaryotic taxa from the deep ocean were more efficient at consuming DOC and producing RDOC as evidenced by greater abundance of highly oxygenated molecules and fluorescent components associated with recalcitrant molecules. This first empirical evidence of the MCP in natural waters shows that carbon sequestration is more efficient in deeper waters and suggests that the higher diversity of prokaryotes from the rare biosphere holds a greater metabolic potential in creating these stable dissolved organic compounds.

Glaciers and ice sheets cover over 10 % of Earth's land surface area and store a globally significant amount of dissolved organic matter (DOM), which is highly bioavailable when exported to proglacial environments. Recent rapid glacier mass loss is hypothesized to have increased fluxes of DOM from these environments, yet the molecular composition of glacially derived DOM has only been studied for a handful of glaciers. We determine DOM composition using ultrahigh resolution mass spectrometry from a diverse suite of Arctic glacial environments, including time series sampling from an ice sheet catchment in Greenland (Russell Glacier) and outflow from valley glaciers in catchments with varying degrees of glacial cover in Svalbard. Samples from the Greenland outflow time series exhibited a higher degree of similarity than glacier outflow between glaciers in Svalbard; however, supraglacial meltwater samples from Greenland and Svalbard were more similar to each other than corresponding glacial outflow. Outflow from Russell Glacier was enriched in polyphenolic formulae, potentially reflecting upstream inputs from plants and soils, or inputs from paleosols overridden by the ice sheet, whereas Svalbard rivers exhibited a high level of molecular richness and dissimilarity between sites. When comparing DOM compositional analyses from other aquatic systems, aliphatic, and peptide-like formulae appear particularly abundant in supraglacial meltwater, suggesting the DOM quickly metabolized in previous incubations of glacial water originates from energy-rich supraglacial sources. Therefore, as glaciers lose mass across the region, higher-quality fuel for microbial degradation will increase heterotrophy in coastal systems with ramifications for carbon cycling.

Permafrost degradation is delivering bioavailable dissolved organic matter (DOM) and inorganic nutrients to surface water networks. While these permafrost subsidies represent a small portion of total fluvial DOM and nutrient fluxes, they could influence food webs and net ecosystem carbon balance via priming or nutrient effects that destabilize background DOM. We investigated how addition of biolabile carbon (acetate) and inorganic nutrients (nitrogen and phosphorus) affected DOM decomposition with 28‐day incubations. We incubated late‐summer stream water from 23 locations nested in seven northern or high‐altitude regions in Asia, Europe, and North America. DOM loss ranged from 3% to 52%, showing a variety of longitudinal patterns within stream networks. DOM optical properties varied widely, but DOM showed compositional similarity based on Fourier transform ion cyclotron resonance mass spectrometry (FT‐ICR MS) analysis. Addition of acetate and nutrients decreased bulk DOM mineralization (i.e., negative priming), with more negative effects on biodegradable DOM but neutral or positive effects on stable DOM. Unexpectedly, acetate and nutrients triggered breakdown of colored DOM (CDOM), with median decreases of 1.6% in the control and 22% in the amended treatment. Additionally, the uptake of added acetate was strongly limited by nutrient availability across sites. These findings suggest that biolabile DOM and nutrients released from degrading permafrost may decrease background DOM mineralization but alter stoichiometry and light conditions in receiving waterbodies. We conclude that priming and nutrient effects are coupled in northern aquatic ecosystems and that quantifying two‐way interactions between DOM properties and environmental conditions could resolve conflicting observations about the drivers of DOM in permafrost zone waterways., Key Points Dissolved organic matter (DOM) from diverse circumpolar regions showed compositional and optical commonalitiesAdded acetate and nutrients suppressed background DOM degradation but accelerated colored DOM breakdownDisconnect between DOM composition and function indicates intrinsic and extrinsic conditions interact to regulate DOM dynamics

Interlaboratory comparison on the determination of the molecular composition of humic substances (HS) was undertaken in the framework of IUPAC project 2016-015-2-600. The analysis was conducted using high resolution mass spectrometry, nominally, Fourier transform ion cyclotron resonance mass spectrometry (FTICR MS) with electrospray ionization. Six samples of HS from freshwater, soil, and leonardite were used for this study, including one sample of humic acids (HA) from coal (leonardite), two samples of soil HA (the sod-podzolic soil and chernozem), two samples of soil fulvic acids (FA) (the sod-podzolic soil and chernozem), and one sample of freshwater humic acids (the Suwannee River). The samples were analyzed on five different FTICR MS instruments using the routine conditions applied in each participating laboratory. The results were collected as mass lists, which were further assigned formulae for the determination of molecular composition. The similarity of the obtained data was evaluated using appropriate statistical metrics. The results have shown that direct comparison of discrete stoichiometries assigned to the mass lists obtained by the different laboratories yielded poor results with low values of the Jaccard similarity score – not exceeding 0.56 (not more than 56 % of the similar peaks). The least similarity was observed for the aromatics-rich HA samples from leonardite (coal) and the chernozem soil, which might be connected to difficulties in their ionization. The reliable similarity among the data obtained in this intercomparison study was achieved only by transforming a singular point (stoichiometry) in van Krevelen diagram into a sizeable pixel (a number of closely located stoichiometries), which can be calculated from the population density distribution. The conclusion was made that, so far, these are descriptors of occupation density distribution, which provide the metrics compliant with the data quality requirements, such as the reproducibility of the data measurements on different instruments.

Spilled oil is highly susceptible to sunlight-induced transformations, both as films on the surface of water and material dissolved or dispersed in the water column. We utilized ultrahigh-resolutio...

Landcover changes have altered the natural carbon cycle; however, most landcover studies focus on either forest conversion to agriculture or urban, rarely both. We present differences in dissolved organic carbon (DOC) concentrations and dissolved organic matter (DOM) molecular composition within Upper Mississippi River Basin low order streams and rivers draining one of three dominant landcovers (forest, agriculture, and urban). Streams draining forest and urban landcovers have greater DOC concentrations, likely driven by differences in carbon sourcing, microbial processing, and soil disturbance. Using Fourier transform-ion cyclotron resonance mass spectrometry, 24% of assigned molecular formulae are common across all landcovers. Relative abundances of N-,S- heteroatomic formulae (CHON, CHOS, CHONS) are higher for agricultural and urban streams, with agricultural stream DOM having more N-containing formulae compared to urban stream DOM, which has more S-containing formulae. Higher N-,S- heteroatomic formulae abundance, along with enrichment in aliphatic, N-aliphatic, and highly unsaturated and phenolic (low O/C) compound categories within agricultural and urban stream DOM are likely to result from increased anthropogenic inputs, autochthonous production, and microbial processing associated with agricultural and urban impacts. Reduced N-,S- heteroatomic formulae abundances in forested stream DOM, along with enrichments in condensed aromatics, polyphenolics, and highly unsaturated phenolic (high O/C) compound categories, likely reflect greater contributions from surrounding organic-rich forest soil and vegetation. Overall, landcover change from forested to agriculture lowers DOC concentrations and changes from forested to agriculture or urban increases autochthonous, and presumably more biolabile, DOM contributions with ramifications for stream biogeochemical cycling.

Large rivers are the main arteries for transportation of carbon to the ocean; yet, how hydrology and anthropogenic disturbances may change the composition and export of dissolved organic matter along large river continuums is largely unknown. The Yangtze River has a watershed area of 1.80 × 106 km2. It originates from the Qinghai-Tibet Plateau and flows 6300 km eastward through the center of China. We collected samples (n = 271) along the river continuum and analyzed weekly samples at the most downstream situated gauging station in 2017–2018 and gathered long-term (2006–2018) water quality data. We found higher gross domestic product, population density, and urban and agricultural land use downstream than upstream of the Three Gorges Dam, coinciding with higher dissolved organic carbon (DOC), UV absorption (a254), specific ultraviolet absorbance (SUVA254), parallel factor analysis-derived C1–C5, aliphatic compounds, and lower a250:a365 and spectral slope (S275–295). Chemical oxygen demand, humic-like C1–C2 and C6, and protein-like C4 and C7 increased, while dissolved oxygen and ammonium decreased with increasing discharge at most of the sites studied, including the intensively monitored downstream site. The annual DOC fluxes were ca. 1.5–1.8 Tg yr−1, and 12–18% was biodegradable in a 28-d bio-incubation. Our results highlight that urbanization and stormwater periods enhanced the export of both terrestrial organic-rich substances and household effluents from nearshore residential areas. Our study emphasizes the continued need to protect the Yangtze River watershed as increased organic carbon loading or altered composition and bio-lability may change the ecosystem function and carbon cycling.

Natural organic matter (NOM) is a complex mixture of biogenic molecules resulting from the deposition and transformation of plant and animal matter. It has long been recognized that NOM plays an important role in many geological, geochemical, and environmental processes. Of particular concern is the fate of NOM in response to a warming climate in environments that have historically sequestered carbon (e.g., peatlands and swamps) but may transition to net carbon emitters. In this review, we will highlight developments in the application of high-field Fourier transform ion cyclotron resonance mass spectrometry (FTICR MS) in identifying the individual components of complex NOM mixtures, focusing primarily on the fraction that is dissolved in natural waters (dissolved organic matter or DOM). We will first provide some historical perspective on developments in FTICR technology that made molecular-level characterizations of DOM possible. A variety of applications of the technique will then be described, followed by our view of the future of high-field FTICR MS in carbon cycling research, including a particularly exciting metabolomic approach.

Permafrost is an extreme habitat yet it hosts microbial populations that remain active over millennia. Using permafrost collected from a Pleistocene chronosequence (19 ka to 33 ka), we hypothesized that the functional genetic potential of microbial communities in permafrost would reflect microbial strategies to metabolize permafrost soluble organic matter (OM) in situ over geologic time. We also hypothesized that changes in the metagenome across the chronosequence would correlate with shifts in carbon chemistry, permafrost age, and paleoclimate at the time of permafrost formation. We combined high-resolution characterization of water-soluble OM by Fourier-transform ion-cyclotron-resonance mass spectrometry (FT-ICR MS), quantification of organic anions in permafrost water extracts, and metagenomic sequencing to better understand the relationships between the molecular-level composition of potentially bioavailable OM, the microbial community, and permafrost age. Both age and paleoclimate had marked effects on both the molecular composition of dissolved OM and the microbial community. The relative abundance of genes associated with hydrogenotrophic methanogenesis, carbohydrate active enzyme families, nominal oxidation state of carbon (NOSC), and number of identifiable molecular formulae significantly decreased with increasing age. In contrast, genes associated with fermentation of short chain fatty acids (SCFAs), the concentration of SCFAs and ammonium all significantly increased with age. We present a conceptual model of microbial metabolism in permafrost based on fermentation of OM and the buildup of organic acids that helps to explain the unique chemistry of ancient permafrost soils. These findings imply long-term in situ microbial turnover of ancient permafrost OM and that this pooled biolabile OM could prime ancient permafrost soils for a larger and more rapid microbial response to thaw compared to younger permafrost soils.

Relationships between dissolved organic matter (DOM) reactivity and chemical composition in a groundwater plume containing petroleum-derived DOM (DOMHC) were examined by quantitative and qualitative measurements to determine the source and chemical composition of the compounds that persist downgradient. Samples were collected from a transect down the core of the plume in the direction of groundwater flow. An exponential decrease in dissolved organic carbon concentration resulting from biodegradation along the transect correlated with a continuous shift in fluorescent DOMHC from shorter to longer wavelengths. Moreover, ultrahigh resolution mass spectrometry showed a shift from low molecular weight (MW) aliphatic, reduced compounds to high MW, unsaturated (alicyclic/aromatic), high oxygen compounds that are consistent with carboxyl-rich alicyclic molecules. The degree of condensed aromaticity increased downgradient, indicating that compounds with larger, conjugated aromatic core structures were less susceptible to biodegradation. Nuclear magnetic resonance spectroscopy showed a decrease in alkyl (particularly methyl) and an increase in aromatic/olefinic structural motifs. Collectively, data obtained from the combination of these complementary analytical techniques indicated that changes in the DOMHC composition of a groundwater plume are gradual, as relatively low molecular weight (MW), reduced, aliphatic compounds from the oil source were selectively degraded and high MW, alicyclic/aromatic, oxidized compounds persisted.

Chemical herders and in-situ burning (ISB) are designed to mitigate the effects that oil spills may have on the high latitude marine environment. Little information exists on the water solubilization of petroleum residues stemming from chemically herded ISB and whether these bioavailable compounds have measurable impacts on marine biota. In this experiment, we investigated the effects of Siltech OP40 and crude oil ISB on a) petroleum-derived dissolved organic matter (DOMHC) composition and b) seawater microbial community diversity over 28 days at 4 °C in aquarium-scale mesocosms. Ultra-high resolution mass spectrometry and fluorescence spectroscopy revealed increases in aromaticity over time, with ISB and ISB+OP40 samples having higher % aromatic classes in the initial incubation periods. ISB+OP40 contained a nearly 12-fold increase in the number of DOMHC formulae relative to those before ISB. 16S rRNA gene sequencing identified differences in microbial alpha diversity between seawater, ISB, OP40, and ISB+OP40. Microbial betadiversity shifts were observed that correlated strongly with aromatic/condensed relative abundance and incubation time. Proteobacteria, specifically from the genera Marinomonas and Perlucidibaca experienced −22 and +24 log2-fold changes in ISB+OP40 vs. seawater, respectively. These findings provide an important opportunity to advance our understanding of chemical herders and ISB in the high latitude marine environment.

The Qinghai–Tibet Plateau (QTP) accounts for approximately 70 % of global alpine permafrost and is an area sensitive to climate change. The thawing and mobilization of ice-rich and organic-carbon-rich permafrost impact hydrologic conditions and biogeochemical processes on the QTP. Despite numerous studies of Arctic permafrost, there are no reports to date for the molecular-level in-stream processing of permafrost-derived dissolved organic matter (DOM) on the QTP. In this study, we examine temporal and spatial changes of DOM along an alpine stream (3850–3207 m above sea level) by Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS), accelerator mass spectrometry (AMS) and UV–visible spectroscopy. Compared to downstream sites, dissolved organic matter (DOM) at the headstream site exhibited older radiocarbon age, higher mean molecular weight, higher aromaticity and fewer highly unsaturated compounds. At the molecular level, 6409 and 1345 formulas were identified as unique to the active layer (AL) leachate and permafrost layer (PL) leachate, respectively. Comparing permafrost leachates to the downstream site, 59 % of AL-specific formulas and 90 % of PL-specific formulas were degraded, likely a result of rapid in-stream degradation of permafrost-derived DOM. From peak discharge in the summer to low flow in late autumn, the DOC concentration at the headstream site decreased from 13.9 to 10.2 mg L−1, while the 14C age increased from 745 to 1560 years before present (BP), reflecting an increase in the relative contribution of deep permafrost carbon due to the effect of changing hydrological conditions over the course of the summer on the DOM source (AL vs. PL). Our study thus demonstrates that hydrological conditions impact the mobilization of permafrost carbon in an alpine fluvial network, the signature of which is quickly lost through in-stream mineralization and transformation.

Inland waters play an important role for the storage of chromophoric dissolved organic matter (CDOM) and outgassing of methane (CH4). However, to date, linkages between the optical dynamics of CDOM and dissolved CH4 levels remain largely unknown. We used multi-year (2012-2014) seasonal data series collected from Lake Taihu and 51 connecting channels to investigate how CDOM optical dynamics may impact dissolved CH4 levels in the lake. High dissolved CH4 in the northwestern inflowing river mouths coincided with high underwater UV-vis light availability, dissolved organic carbon (DOC), chemical oxygen demand (COD), DOM aromaticity, terrestrial humic-rich fluorescence, in situ measured terrestrial CDOM, depleted dissolved oxygen (DO), stable isotopic delta H-2, and delta O-18 compared with other lake regions. Our results further revealed positive relationships between dissolved CH4 and CDOM absorption at 350 nm, i.e. a(350), COD, DOC, terrestrial humic-rich fluorophores, and DOM aromaticity, and negative relationships between dissolved CH4 and DO, delta H-2, and delta O-18. The central lake samples showed a major contribution of terrestrial-sourced molecular formulas to the ultrahigh resolution mass spectrometry data, suggesting the presence of allochthonous DOM sources even here. We conclude that an elevated terrestrial CDOM input likely enhances dissolved CH4 levels in Lake Taihu.

Groundwater samples containing petroleum-derived dissolved organic matter (DOMHC) originating from the north oil body within the National Crude Oil Spill Fate and Natural Attenuation Research Site near Bemidji, MN, USA were analyzed by optical spectroscopic techniques (i.e., absorbance and fluorescence) to assess relationships that can be used to examine natural attenuation and toxicity of DOMHC in contaminated groundwater. A strong correlation between the concentration of dissolved organic carbon (DOC) and absorbance at 254 nm (a254) along a transect of the DOMHC plume indicates that a254 can be used to quantitatively assess natural attenuation of DOMHC. Fluorescence components, identified by parallel factor (PARAFAC) analysis, show that the composition of the DOMHC beneath and adjacent to the oil body is dominated by aliphatic, low O/C compounds (“protein-like” fluorescence) and that the composition gradually evolves to aromatic, high O/C compounds (“humic-/fulvic-like” fluorescence) as a function of di...

The link between composition and reactivity of dissolved organic matter (DOM) is central to understanding the role aquatic systems play in the global carbon cycle; yet, unifying concepts driving molecular composition have yet to be established. We characterized 37 DOM isolates from diverse aquatic ecosystems, including their stable and radiocarbon isotopes (δ

We describe complex organic mixture analysis by 21 tesla (T) Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS). Ultrahigh mass-resolving power (m/Δm50% > 2 700 000 at m/z 400) and mass accuracy (80 ppb rms) enable resolution and confident identification of tens of thousands of unique elemental compositions. We demonstrate 2.2-fold higher mass-resolving power, 2.6-fold better mass measurement accuracy, and 1.3-fold more assigned molecular formulas compared to our custom-built, state-of-the-art 9.4 T FT-ICR mass spectrometer for petroleum and dissolved organic matter (DOM) analyses. Analysis of a heavy petroleum distillate exemplifies the need for ultrahigh-performance mass spectrometry (49 040 assigned molecular formulas for 21 T versus 29 012 for 9.4 T) and extends the identification of previously unresolved Oo, SsOo, and NOo classes. Mass selective ion accumulation (20 Thompson isolation) of an asphalt volcano sample yields 462 resolved mass spectral peaks at m/z 677 and reveals pre...

The herein described High Performance Liquid Chromatography (HPLC) platform (termed HPLC-3) combines a complex solvent gradient with two electron acceptor columns to provide aromatic ring class (ARC) separation for heavy oils. The separation yields seven major fractions: saturates, monoaromatics (1 ring), diaromatics (2 rings), triaromatics (3 rings), tetra-aromatics (4 rings), polyaromatics and polars (5+ polars), and aliphatic sulfides. The system utilizes a photodiode array detector (PDA) for online measurements of aromaticity in series with an evaporative light scattering detector (ELSD) to provide improved quantitative mass determination across the entire solvent gradient. A new postcolumn dilution strategy was successfully utilized to compensate for solvent effects on the ELSD signal. The method allows for calibration across the entire HPLC-3 solvent gradient and simultaneously diverts ∼90% of the sample effluent for fraction collection and further characterization. In addition to the major ARC frac...

This study investigates the effect of photodissolution on the production of dissolved black carbon (DBC) from particulate charcoal and a fire-impacted soil. A soil sample and a char sample were collected within the burn vicinity of the 2012 Cache La Poudre River wildfire and irradiated in deionized water with artificial sunlight. Photoexposure of the suspended char and soil significantly enhanced production of DBC after 7 days continuous exposure to the simulated sunlight. The increase was coupled with an increase in the DBC polycondensed character. In agreement with this, characterization using Fourier transform-ion cyclotron resonance-mass spectrometry (FT-ICR-MS) showed an increase in the number of BC molecular formulae detected and in their average molecular weight, suggesting that increasing photoexposure is required for dissolution of larger, more polycondenced DBC compounds. An increase in molecular signatures with lower H/C ratio and higher O/C ratio after 7 days photoexposure suggested increasing functionality of newly produced DBC with irradiation time, and therefore photooxidation as a potential mechanism for the photodissolution of BC. The photoproduced DBC was also strongly coupled with the photoproduced bulk dissolved organic carbon (DOC). The results suggest that photodissolution may be a significant and previously unrecognized mechanism of DBC translocation to aquatic systems.

Dissolved organic nitrogen (DON) represents a large percentage of the total nitrogen in rivers and estuaries, and can contribute to coastal eutrophication and hypoxia. This study reports on the composition and bioavailability of DON along the Caloosahatchee River (Florida), a heavily managed system receiving inputs from Lake Okeechobee as well as agricultural and urban runoff from the surrounding watershed. Water samples were collected bimonthly for 1 year beginning December 2014 at three stations along the river. Treatments included 28-day dark incubations with and without prior photo-irradiation. Concentrations of DON, ammonium, nitrate–nitrite, total hydrolyzable amino acids (THAA), and urea, as well as bacterial numbers, leucine aminopeptidase activity, and fluorescent optical properties were measured. Ultra-high resolution Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) was used to characterize the molecular composition of DON before and after incubation for selective samples. The total dissolved N pool was dominated by DON (61–99%), with low inorganic N (1–39%), and small amounts of THAA-N (0.1–23%) and urea-N (0.6–3.2%). The mean percentage of biologically available DON (BDON) for the study was 15% (−12–61% range) with highest values occurring when water inputs from Lake Okeechobee were the most dominant freshwater source. FT-ICR MS analysis revealed the presence of a wide range of N-containing formulas and the generation of aliphatic and ‘peptide-like’ structures likely due to microbial alteration of the carbon skeleton of DON compounds. Effects of light exposure prior to incubation did not have a measurable effect on %BDON but did affect bacterial biomass and DON composition. These findings may help predict nutrient loading effects to the Caloosahatchee River estuary and may aid in understanding wetland potential as a treatment technology for removing N in this and other freshwater systems sensitive to N loading.

The Central Siberian Plateau is undergoing rapid climate change that has resulted in increased frequency of forest fires and subsequent alteration of watershed carbon and nutrient dynamics. Across a watershed chronosequence (3 to >100 years since wildfire) we quantified the effects of fire on quantity and composition of dissolved organic matter (DOM), stream water nutrient concentrations, as well as in-stream nutrient uptake. Wildfires increased concentrations of nitrate for a decade, while decreasing concentrations of dissolved organic carbon and nitrogen (DOC and DON) and aliphatic DOM contribution for five decades. These post-wildfire changes in stream DOM result in lower uptake efficiency of in-stream nitrate in recently burned watersheds. Nitrate uptake (as uptake velocity) is strongly dependent on DOM composition (e.g. polyphenolics), ambient dissolved inorganic nitrogen (DIN), and DOC to DIN ratios. Our observations and experiments suggest that a decade-long pulse of inorganic nitrogen and a reduction of DOC export occur following wildfires in streams draining the Central Siberian Plateau. Increased fire frequency in the region is thus likely to both decrease DOM and increase nitrate delivery to the main stem Yenisei River, and ultimately the Arctic Ocean, in the coming decades.

To examine the molecular-level composition and acute toxicity per unit carbon of the petroleum-derived dissolved organic matter (DOMHC) produced via photo-oxidation, heavy and light oils were irradiated over seawater with simulated sunlight. Increases in dissolved organic carbon concentrations as a function of time were associated with changes in the DOMHC composition and acute toxicity per unit carbon. Parallel factor analysis showed that the fluorescent dissolved organic matter (FDOM) composition produced from the heavy oil became more blue-shifted over time, while the light oil produced a mixture of blue- and red-shifted components similar to FDOM signatures. Ultrahigh-resolution mass spectrometry reveals that the composition of the DOMHC produced from both heavy and light oils was initially relatively reduced, with low O/C. With time, the composition of the DOMHC produced from the heavy oil shifted to unsaturated, high-oxygen compounds, while that produced from the light oil comprised a range of high O/C aliphatic, unsaturated, and aromatic compounds. Microtox assays suggest that the DOMHC initially produced is the most toxic (62% inhibition); however, after 24 h, a rapid decrease in toxicity decreased linearly to 0% inhibition for the heavy DOMHC and 12% inhibition for the light DOMHC at extended exposure periods.

The flux and composition of carbon (C) from land to rivers represents a critical component of the global C cycle as well as a powerful integrator of landscape-level processes. In the Congo Basin, an expansive network of streams and rivers transport and cycle terrigenous C sourced from the largest swathe of pristine tropical forest on Earth. Increasing rates of deforestation and conversion to agriculture in the Basin are altering the current regime of terrestrial-to-aquatic biogeochemical cycling of C. To investigate the role of deforestation on dissolved organic and inorganic C (DOC and DIC, respectively) biogeochemistry in the Congo Basin, six lowland streams that drain catchments of varying forest proportion (12%-77%) were sampled monthly for 1 year. Annual mean concentrations of DOC exhibited an asymptotic response to forest loss, while DIC concentrations increased continuously with forest loss. The isotopic signature of DIC became significantly more enriched with deforestation, indicating a shift in source and processes controlling DIC production. The composition of dissolved organic matter (DOM), as revealed by ultra-high-resolution mass spectrometry, indicated that deforested catchments export relatively more aliphatic and heteroatomic DOM sourced from microbial biomass in soils. The DOM compositional results imply that DOM from the deforested sites is more biolabile than DOM from the forest, consistent with the corresponding elevated stream CO2 concentrations. In short, forest loss results in significant and comprehensive shifts in the C biogeochemistry of the associated streams. It is apparent that land-use conversion has the potential to dramatically affect the C cycle in the Congo Basin by reducing the downstream flux of stable, vascular-plant derived DOC while increasing the transfer of biolabile soil C to the atmosphere.

Introductory Paragraph In the mostly pristine Congo Basin, agricultural land-use change has intensified in recent years. One potential and understudied consequence of this deforestation and conversion to agriculture is the mobilization and loss of organic matter from soils to rivers as dissolved organic matter. Here, we quantify and characterize dissolved organic matter sampled from 19 catchments of varying deforestation extent near Lake Kivu over a two-week period during the wet season. Dissolved organic carbon from deforested, agriculturally-dominated catchments was older (14C age: ~1.5kyr) and more biolabile than from pristine forest catchments. Ultrahigh-resolution mass spectrometry revealed that this aged organic matter from deforested catchments was energy-rich and chemodiverse, with higher proportions of nitrogen- and sulfur-containing formulae. Given the molecular composition and biolability, we suggest that organic matter from deforested landscapes is preferentially respired upon disturbance, resulting in elevated in-stream concentrations of carbon dioxide. We estimate that while deforestation reduces the overall flux of dissolved organic carbon by ~56%, it does not significantly change the yield of biolabile dissolved organic carbon. Ultimately, the exposure of deeper soil horizons through deforestation and agricultural expansion releases old, previously stable, and biolabile soil organic carbon into the modern carbon cycle via the aquatic pathway.

Photochemically-released dissolved organic matter (PR-DOM) from resuspended sediments is an understudied flux of dissolved organic carbon (DOC) and nutrients with the potential to influence estuarine microbial food webs. There is currently limited knowledge on the composition, lability and biological alterations of this material once released into the water column. This study addresses the composition and fate of PR-DOM from resuspended sediments of the Cape Fear River Estuary (CFRE) in southeastern North Carolina. Six-hour irradiation released 22–44% more DOC, and PR-DOM was of a different composition and enhanced lability, relative to dark controls. Irradiation led to release of humic-like DOM, indicated by increased chromophoric and fluorescent dissolved organic matter, substantial increases in the humification index, and production of oxidized higher molecular weight compounds with higher aromaticity, relative to dark controls. However, DOM of lower molecular weight and reduced aromaticity was produced as well. This was indicated by increased spectral slope (S275–295) and decreased specific ultraviolet absorbance at 254 nm (SUVA254), relative to dark controls. This latter pool of DOM may be linked to nitrogen-(N-) and sulfur-(S-)containing compounds that were photodegraded or biologically altered during irradiation experiments. In subsequent lability incubation experiments, degradation of PR-DOM was more rapid than DOM released from dark controls, especially for marine humic-like fluorophores. Incubation of PR-DOM led to an 8-fold increase in compounds with molecular formulas that were unique to light-exposed DOM relative to unexposed DOM, the majority of which were N- and S-containing compounds. Given that coastal sediments are typically enriched in these nutrients, N- and S-containing compounds appear to influence the lability of PR-DOM from estuarine resuspended sediments. Estimated lability of photoreleased DOC from resuspension events in the CFRE is comparable to previous bioavailable DOC estimates and suggests that episodic photochemical interactions with sediments may act as a previously unrecognized source of labile DOC to bacteria and plankton in these coastal waters.

The boreal region stores large amounts of organic carbon (C) in organic-soil horizons, which are vulnerable to destabilization via warming and disturbance. Decomposition of soil organic matter (SOM) contributes to the production and turnover of dissolved organic matter (DOM). While temperature is a primary control on rates of SOM and DOM cycling, little is known about temperature effects on DOM composition in soil leachate. Here, we conducted a 30-day incubation to examine the effects of temperature (20 vs. 5 °C) and SOM decomposition state (moss vs. fibric vs. amorphous horizons) on DOM composition in organic soils of interior Alaska. We characterized DOM using bulk dissolved organic C (DOC) concentration, chemical fractionation, optical properties, and ultrahigh-resolution mass spectrometry. We observed an increase in DOC concentration and DOM aromaticity in the 20 °C treatment compared to the 5 °C treatment. Leachate from fibric horizons had higher DOC concentration than shallow moss or deep amorphous horizons. We also observed chemical shifts in DOM leachate over time, including increases in hydrophobic organic acids, polyphenols, and condensed aromatics, and decreases in low-molecular weight hydrophilic compounds and aliphatics. We compared ultrahigh-resolution mass spectrometry and optical data, and observed strong correlations between polyphenols, condensed aromatics, SUVA254, and humic-like fluorescence intensities. These findings suggest that bio-labile DOM was preferentially mineralized, and the magnitude of this transformation was determined by kinetics (i.e. temperature) and substrate quality (i.e. soil horizon). With future warming, our findings indicate that organic soils may release higher concentrations of aromatic DOM to aquatic ecosystems.

The fate of carbon stored in permafrost-zone peatlands represents a significant uncertainty in global climate modeling. Given that the breakdown of dissolved organic matter (DOM) is often a major p ...

Estuaries support the livelihood of ~75% of the world's population and maintain high primary production in coastal waters, which are often subjected to strong tides and anthropogenic disturbances. There is a paucity of information on how the optical composition and bioavailability of chromophoric dissolved organic matter (CDOM) are influenced by tidal oscillations in estuaries with highly urbanized surrounding areas. We examined the semi-diurnal Qiantang Bore, one of the Earth's three most predominant tide bores, and found that dissolved organic carbon (DOC), CDOM absorption a(254) and terrestrial humic-like C1, tryptophan-like C2 and C5, fulvic-like C3, and microbial humic-like C4 decreased markedly with increasing salinity. This suggests that physical mixing of riverine freshwater and saltwater can shape the optical composition of CDOM in the estuary. This was supported by the semi-diurnally and hourly observations at Zhijiang (salinity ~0.1‰ upstream of the estuary) that DOC, bioavailable DOC (BDOC), C1–C2, and C4–C5 increased markedly with decreasing tidal level, while DOC and C1–C5 increased notably with increasing salinity. We further found δ 18 O was enriched with increasing tidal level, while tryptophan-like C2 and C5, and fulvic-like C3 decreased significantly with increasing tidal level at Zhapu (salinity ~7‰ downstream of the estuary). Furthermore, DOC, BDOC, C1, and C4 decreased, while δ 18 O and C3 increased markedly with increasing salinity. Further evidences come from the notably lower mean first principal component (PC1) scores at Zhijiang and Zhapu, both positively associated with anthropogenic tryptophan-like inputs, were observed during ebb than during flood tides, and PC1 at Zhijiang increased notably with increasing salinity. We conclude that anthropogenic inputs contributed primarily to the CDOM pool in the estuary and are mediated by the physical mixing of riverine freshwater and seawater, and ebb tides are often associated with enhanced anthropogenic CDOM with relatively high bioavailability.

Atmospheric nitrogen (N) deposition is an important determinant of N availability for natural ecosystems worldwide. Increased anthropogenic N deposition shifts the stoichiometric equilibrium of ecosystems, with direct and indirect impacts on ecosystem functioning and biogeochemical cycles. Current simulation data suggest that remote tropical forests still receive low atmospheric N deposition due to a lack of proximate industry, low rates of fossil fuel combustion, and absence of intensive agriculture. We present field-based N deposition data for forests of the central Congo Basin, and use ultrahigh-resolution mass spectrometry to characterize the organic N fraction. Additionally, we use satellite data and modeling for atmospheric N source apportionment. Our results indicate that these forests receive 18.2 kg N hectare-1 years-1 as wet deposition, with dry deposition via canopy interception adding considerably to this flux. We also show that roughly half of the N deposition is organic, which is often ignored in N deposition measurements and simulations. The source of atmospheric N is predominantly derived from intensive seasonal burning of biomass on the continent. This high N deposition has important implications for the ecology of the Congo Basin and for global biogeochemical cycles more broadly.

Fluvial plain lake watersheds are usually highly urbanized and have high concentrations of chromophoric dissolved organic matter (CDOM). CDOM derived from the connecting urban channels usually share strong terrestrial and anthropogenic signals and net inflow runoff (Qnet) to the lake serves as a proxy of residential household sewage input. We investigate how Qnet controls the optical characteristics of CDOM in fluvial plain Lake Taihu and the connecting channels. CDOM absorption coefficient a(350), dissolved organic carbon (DOC), the fluorescence intensity (Fmax) of seven PARAFAC components C1-C7, and δ15N-TDN were higher in the northwestern relative to the other lake regions, and a(250)/a(365), spectral slope S275–295, and δ13C-DOM relative low in the northwestern lake, all indicating strong terrestrial and anthropogenic effects. Conversely, the urban land cover (%Cities), gross domestic product (GDP), and population density were relatively low in the western sub-watersheds and high in the eastern sub-watersheds. This apparent paradox reflects variations in Qnet from different sub-watersheds. Thus, significant positive relationships were found between Qnet and a(350), DOC, chemical oxygen demand (COD), chlorophyll-a (Chl-a), Fmax of C1-C3 and C6-C7, and %C2-%C3 in the five hydraulic sub-watersheds. We revealed significant positive relationships between mean a(350), DOC, COD, Chl-a, C1-C3 and C6, %C2-%C3, and the products of Qnet × %Cities, Qnet × GDP, and Qnet × population density. We further found dominant contribution of lignin to the total number of assigned formulas for the samples collected from the channels in the Huxi watershed and the central lake using high resolution mass spectroscopy. We conclude that Qnet is of key importance for the optical properties of CDOM molecules in the various regions of Lake Taihu and the connecting channels.