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TIMS-FT-ICR MS is an important alternative to study the isomeric diversity and elemental composition of complex mixtures. While the chemical structure of many compounds in the dissolved organic matter (DOM) remains largely unknown, the high structural diversity has been described at the molecular level using chemical formulas. In this study, we further push the boundaries of TIMS-FT-ICR MS by performing chemical formula-based ion mobility and tandem MS analysis for the structural characterization of DOM. The workflow described is capable to mobility select (R ∼ 100) and isolate molecular ion signals (Δm/z = 0.036) in the ICR cell, using single-shot ejections after broadband ejections and MS/MS based on sustained off-resonance irradiation collision-induced dissociation (SORI-CID). The workflow results are compared to alternative TIMS-q-FT-ICR MS/MS experiments with quadrupole isolation at nominal mass (∼1 Da). The technology is demonstrated with isomeric and isobaric mixtures (e.g., 4-methoxy-1-naphthoic acid, 2-methoxy-1-naphthoic acid, decanedioic acid) and applied to the characterization of DOM. The application of this new methodology to the analysis of a DOM is illustrated by the isolation of the molecular ion [C18H18O10-H]- in the presence of other isobars at nominal mass 393. Five IMS bands were assigned to the heterogeneous ion mobility profile of [C18H18O10-H]-, and candidate structures from the PubChem database were screened based on their ion mobility and the MS/MS matching score. This approach overcomes traditional challenges associated with the similarity of fragmentation patterns of DOM samples (e.g., common neutral losses of H2O, CO2, and CH2-H2O) by narrowing down the isomeric candidate structures using the mobility domain.

Reconstructing past responses of coastal wetlands to climate change contextualizes ongoing and future developments in these globally important ecosystems. The molecular distributions and stable isotope ratios (δ2H and δ13C) of sedimentary plant wax n-alkanes are frequently used to infer past vegetation and hydroclimate changes in wetland systems. However, there is limited modern information available about these compounds in subtropical wetlands. Here we analyzed mature leaves from 30 typical plant species and roots from 6 plant species collected in the Florida Everglades, including tree island plants, freshwater wetland plants, mangroves, and seagrass. The n-alkane abundance (2 to 884 µg/g dry weight), percent of aquatic plants ratio (Paq, 0 to 1), average chain length (ACL23-33, 24.0–30.7), concentration weighted average (CWA) δ2H (−231 to −78‰) and δ13C values (−38.9 to −14.4‰) spanned wide ranges with plant growth habit. Significant differences in n-alkane abundances, Paq, ACL23-33, CWA δ2H and δ13C values were found to exist between the leaves and roots of some emergent aquatic plants. Simple mass balance calculations of wetland aquatic plants suggest that long chain n-alkanes (e.g., C29 n-alkanes) are predominantly derived from leaves rather than roots in wetland surface sediments/soils. However, the contribution from mid-chain n-alkanes (e.g., C23 n-alkane) from roots may be equal to or greater than those from leaves. This implies that the differences in the isotopic compositions between root and leaf derived material need to be taken into account when interpreting down core changes in mid-chain n-alkane δ2H and δ13C values, which may be derived from variable contributions from leaves and roots rather than a change in hydroclimate or vegetation. Considering the large variation in both n-alkane distribution proxies and isotopic composition, no single molecular index or stable isotope ratio can capture multivariate changes of wetland ecosystems in the past. Nevertheless, principal component analysis shows promising potential to resolve different plant functional types. Paleo-reconstruction of subtropical aquatic ecosystems using n-alkanes will be most useful if the full molecular and isotopic distribution information of plant waxes are used.

The temporal evolution of molecular compositions and changes in structural features of Hillsboro Canal (Florida, USA) dissolved organic matter (DOM) was studied with an emphasis on nitrogen and sulfur containing molecules, after a 13 day time-series exposure to simulated sunlight. The Hillsboro Canal drains from the ridge and slough wetland environment underlain by peat soils from the northern extent of the Greater Everglades Ecosystem. The Hillsboro Canal-DOM was characterized by combining ultrahigh-resolution mass spectrometry (FT-ICR-MS), high-field nuclear magnetic resonance spectroscopy (

Dissolved organic matter (DOM) is considered an essential component of the Earth's ecological and biogeochemical processes. Structural information of DOM components at the molecular level remains one of the most extraordinary analytical challenges. Advances in determination of chemical formulas from the molecular studies of DOM have provided limited indications on structural signatures and potential reaction pathways. In this work, we extend the structural characterization of a wetland DOM sample using precursor and fragment molecular ions obtained by a sequential electrospray ionization-Fourier transform-ion cyclotron resonance tandem mass spectrometry (ESI-FT-ICR CASI-CID MS/MS) approach. The DOM chemical complexity resulted in near 900 precursors (P) and 24 000 fragment (F) molecular ions over a small

Agricultural land use leads to significant changes in both the quality (e.g., sources and compositions) and quantity of dissolved organic matter (DOM) exported from terrestrial to aquatic ecosystems. However, the effect of agricultural activities often interacts with those of hydroclimatic drivers, making it difficult to delineate agriculture-induced changes and identify associated mechanisms. Using partial least square path modeling (PLS-PM), we examined the relative importance of agricultural land use, stream order, precipitation, and temperature in mediating allochthonous versus autochthonous sources and pathways that influenced stream DOM quality and quantity. We analyzed stream water DOM from 15 small streams draining watersheds across a gradient of agricultural land use in Southeast USA for about one year. For DOM quantity, agricultural land use increased the export of DOC and various DOM pools (terrestrial humic, microbial humic, and protein-like DOM) from land to streams, and for DOM quality, agricultural streams showed greater proportions of microbial humic compounds than forested streams. The PLS-PM model for DOM quantity accounted for 75.5% of total variance and identified that agricultural land use increased stream water DOM quantity primarily through increasing allochthonous inputs, which can be attributed to shallower flow paths in agricultural watersheds that enabled the export of organic materials from the upper, organic-rich soil horizon. PLS-PM models for DOM quality only explained ~13% of the total variance, highlighting the complex dynamics between environmental drivers and stream water DOM. Relative to commonly used multivariate statistic modeling (e.g., redundancy analysis (RDA)), PLS-PM models offer the advantages of identifying the primary pathway by which agricultural lands alter freshwater DOM and quantifying the relative importance of interactive effects of agriculture and hydroclimatic drivers. Therefore, structural equation modeling is a powerful tool that should be more widely adopted to distinguish among multiple drivers and mechanisms regulating freshwater biogeochemistry.

Leaves from three mangrove species, and surface and deeper soils along salinity gradients in the Shark River estuary, USA, were analyzed to determine numerous diagenetic degradation products and pathways for mangrove derived triterpenoids. The dehydration of pentacyclic triterpenols was observed in mangrove leaves, leading to pentacyclic triterpadienes with Δ2,12 and Δ2,14 unsaturations. Surprisingly, various mono-unsaturated triterpenes (with Δ12 and Δ14), nor-, bisnor- (24,25-bisnortaraxer-14-ene), trisnor-triterpenes (1,2,3-trisnortaraxera-5(10),14-diene and 1,2,3-trisnortaraxer-14-ene) and tetrakisnor- and pentakisnor-triterpenes were detected in Rhizophora mangle leaves, suggesting that reduction and later demethylation of triterpadienes can occur prior to mangrove leaf abscission or senescence/death. Most of the unsaturated and nortriterpenes were also found in mangrove stand soils (>100 years old), suggesting their relative stability. In addition, a high diversity of aliphatic and aromatic des-A-triterpenes from the taraxerane, oleanane, ursane, and lupane precursors were present in the surface and deeper soils of mangrove stands, suggesting that isomerization, rapid diagenetic loss of ring-A and further aromatization of triterpenoids occurred early during litter decay. The overall diagenetic transformations could be caused by a combination of photodegradation, microbial alteration (bacteria/fungi), anaerobic alteration (reduction), oxidation and secondary processes. Possible mechanisms of the early diagenesis of triterpenoids were proposed using taraxerol, a triterpenol, highly enriched in R. mangle, as an example. These results, coupled with the detection of various intermediate compounds, provide a better understanding of the diagenetic fate of mangrove derived triterpenoids.

The incomplete combustion of organic molecules produces a chemically diverse suite of pyrogenic residues termed black carbon (BC). The significance of BC cycling on land has long been recognized, and the recognition of dissolved BC (DBC) as a major component of the aquatic carbon cycle is developing rapidly. As we seek a greater understanding of DBC cycling, our interpretation of environmental DBC concentrations and molecular composition should take into account both the formation conditions of charred residues, and the physico‐chemical transformation of DBC that occurs during transit within aquatic systems. We present the current state of knowledge concerning sources, processing, and sinks of DBC in inland, coastal/estuarine, and ocean waters. We feature studies and new methodologies which focus specifically on the aquatic cycling of DBC, explore the relationship between particulate and dissolved BC, and highlight research gaps which should be targeted to advance our current knowledge of DBC biogeochemistry.

Interactions between dissolved organic matter (DOM) and different physical-chemical forms of iron (Fe) represent important biogeochemical processes in the organic carbon cycle. Due to the effect of climate change and anthropogenic activities such as land-use change, the loading of terrestrial DOM into aquatic systems is increasing, and thus, enhancing the organic matter-based acidity in aquatic ecosystems. While complexation of Fe with DOM and the sorption of DOM on iron oxides and (oxy)hydroxides have been reported, less is known about how co-precipitation processes might affect by DOM composition. Here the co-precipitation of two DOM standards, namely the Suwannee River Standard Humic Acid Standard II (SRHA) and Nordic Aquatic Fulvic Acid Reference (NAFA), with Fe was investigated in a pH range of 4.0–8.0. The DOM remaining after co-precipitating with Fe was systematically characterized by various analytical methods to reveal the molecular fractionation of DOM. The co-precipitation of SRHA or NAFA with Fe was enhanced by decreasing the pH, where at pH 4.0, about 70~80% DOC of SRHA or NAFA was removed at Fe(III)/C ratios higher than 0.12. The decrease in SUVA254 and the humification index (HIX) during the co-precipitation process suggests that DOM with high aromatic character was preferentially co-precipitated with Fe. DOM molecular weight influenced the selectivity to co-precipitation, with high molecular weight (HMW) DOM showing a stronger affinity. DOM co-precipitation with Fe was clearly dependent on DOM composition, showing an affinity order of terrestrial humic-like> ubiquitous humic-like> microbial humic-like components. The difference in the reactivity and the relative abundances of excitation emission matrix fluorescence combined with parallel factor analysis (EEM-PARAFAC) components explained the difference in DOC removal efficiency between SRHA and NAFA. This study provides direct insights into the effects of DOM composition on its fractionation specifically through co-precipitation with Fe, and suggests that for aquatic systems rich in iron-based (oxy)hydroxides, and for environmental redox interfaces, co-precipitation of DOM with iron might affect optical properties of the aqueous phase, and represent an important sink for terrestrially-derived organic matter.

Human land use has led to significant changes in the character of dissolved organic matter (DOM) in lotic ecosystems. These changes are expected to have important environmental and ecological consequences. However, high spatiotemporal variability has been reported in previous studies, and the underlying mechanisms remain inadequately understood. This study assessed variation in the properties of stream water DOM within watersheds across a gradient of agricultural land use with grazing pasture lands as the dominant agricultural type in the southeastern United States. We collected water samples under baseflow conditions five times over eight months from a regional group of first- to fourth-order streams. Samples were analyzed for dissolved organic carbon (DOC) concentration, DOM quality based on absorbance and fluorescence properties, as well as DOM biodegradability. We found that air temperature and antecedent hydrological conditions (indicated by antecedent precipitation index and stream water sodium concentrations) positively influenced stream water DOC concentration, DOM fluorescence index, and the proportion of soil-derived, microbial humic fluorescence. This observation suggests that elevated production and release of microbial DOM in soils facilitated by high temperature, in conjunction with strong soil-stream hydrological connectivity, were important drivers for changes in the concentration and composition of stream water DOM. By comparison, watersheds with a high percentage of agricultural land use showed higher DOC concentration, larger proportion of soil-derived, humic-like DOM compounds, and higher DOC biodegradability. These observations reflect preferential mobilization of humic DOM compounds from shallow organic matter-rich soils in agricultural watersheds, likely due to enhanced soil erosion, organic matter oxidation and relatively shallow soil-to-stream flow paths.

Litter decomposition in wetlands is an important component of ecosystem function in these detrital systems. In oligotrophic wetlands, such as the Florida Everglades, litter decomposition processes are dependent on nutrient availability and litter quality. The aim of this study was to assess the differences and changes in chemical composition of above- and belowground plant tissues at different stages of decomposition, and to compare them to organic matter accumulating in wetland surface soils. To understand the chemical changes occurring during the early stages of litter decomposition in wetlands, short-term subaqueous decomposition patterns of above- and belowground tissues from Cladium jamaicense and Eleocharis cellulosa were investigated at two freshwater marsh sites in the Florida Everglades. The composition of litter at different stages of decomposition was compared to that of the two end-members, namely fresh plant tissues and soil organic matter (SOM), in an effort to assess both the gradual transformation of this organic matter (OM) and the incorporation of above- vs. belowground biomass to wetland soils. The chemical composition of the litter and of surface soils was assessed using solid-state 13C nuclear magnetic resonance spectroscopy. Decomposition indices (alkyl/O-alkyl ratio, Aromaticity index) of Cladium and Eleocharis leaves varied during incubation likely reflecting physical leaching processes followed by a shift to microbial decomposition. Overall, Eleocharis leaves were more labile compared to Cladium leaves. Relative to aboveground litter, the belowground biomass of both species was more resistant to degradation, and roots were more resistant than rhizomes. Compared to the observed early diagenetic transformations of the plant litter, the SOM is at a more advanced stage of degradation, suggesting that the decomposition of litter and belowground biomass prior to its incorporation into wetland soils requires longer degradation times than those applied in this study. Litter decomposition in Everglades’ freshwater marshes is driven by a combination of tissue quality and site characteristics such as hydroperiod and nutrient availability, ultimately leading to the accumulation of peat.

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.

The effect of salinity on hydrogen isotope fractionation during the production of leaf wax n-alkanes was assessed for Laguncularia racemosa (white mangrove), Rhizophora mangle (red mangrove), and Avicennia germinans (black mangrove) along a 31 ppt (parts per thousand) salinity gradient in the Shark River estuary, Florida, USA. Significant variation in hydrogen isotope ratios was observed among these three Atlantic-East Pacific (AEP) species, with increasing leaf wax n-alkane 2H/1H fractionation with increasing salinity. Net 2H/1H fractionation for hentriacontane (n-C31) increased by 0.8, 1.4 and 1.8‰/ppt in R. mangle, A. germinans and L. racemosa, respectively. The observations are consistent with published δ2HnC31 data from 5 species of Indo-West Pacific (IWP) mangroves, which increased with salinity by 0.7–1.5‰/ppt. Although all measured species from both the AEP and IWP regions have more 2H/1H fractionation at high salinity, differences in slope and intercepts of these relationships are observed among genera. The differences may result from variation in the composition of compatible solutes, reliance on storage carbohydrates, and/or physiological response to salt. However, no statistically significant difference in the sensitivity of δ2HnC31 to salinity was observed in four Rhizophora species from both Indo-West Pacific and Americas-East Atlantic regions, which makes sedimentary Rhizophora lipids a promising target for paleohydroclimatic reconstruction.

Black carbon (BC) is derived from the incomplete combustion of biomass and fossil fuels and can enhance glacial recession when deposited on snow and ice surfaces. Here we explore the influence of environmental conditions and the proximity to anthropogenic sources on the concentration and composition of dissolved black carbon (DBC), as measured by benzenepolycaroxylic acid (BPCA) markers, across snow, lakes, and streams from the global cryosphere. Data are presented from Antarctica, the Arctic, and high alpine regions of the Himalayas, Rockies, Andes, and Alps. DBC concentrations spanned from 0.62 µg/L to 170 µg/L. The median and (2.5, 97.5) quantiles in the pristine samples were 1.8 µg/L (0.62, 12), and non-pristine samples were 21 µg/L (1.6, 170). DBC is susceptible to photodegradation when exposed to solar radiation. This process leads to a less condensed BPCA signature. In general, DBC across the dataset was comprised of less-polycondensed DBC. However, DBC from the Greenland Ice Sheet (GRIS) had a highly-condensed BPCA molecular signature. This could be due to recent deposition of BC from Canadian wildfires. Variation in DBC appears to be driven by a combination of photochemical processing and the source combustion conditions under which the DBC was formed. Overall, DBC was found to persist across the global cryosphere in both pristine and non-pristine snow and surface waters. The high concentration of DBC measured in supra-glacial melt on the GRIS suggests DBC can be mobilized across ice surfaces. This is significant because these processes may jointly exacerbate surface albedo reduction in the cryosphere.

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.

About 250 Tg of dissolved organic carbon are annually transported from inland waters to coastal systems making rivers a critical link between terrestrial and ocean carbon pools. During transport through fluvial systems, various biogeochemical processes selectively remove or transform labile material, effectively altering the composition of dissolved organic matter (DOM) exported to the ocean. The river continuum concept (RCC) has been historically used as a model to predict the fate and quality of organic matter along a river continuum. However, the conversion of natural landscapes for urban and agricultural practices can also alter the sources and quality of DOM exported from fluvial systems, and the RCC may be significantly limited in predicting DOM quality in anthropogenically impacted watersheds. Here, we studied DOM dynamics in the Altamaha River watershed in Georgia, USA, a fluvial system where headwater streams are highly impacted by anthropogenic activities. The primary goal of this study was to quantitatively assess the importance of both the RCC and land use as environmental drivers controlling DOM composition. Land use was a stronger predictor of spatial variation (∼50%) in DOM composition defined by both excitation–emission matrix–parallel factor analysis (EEM–PARAFAC) and ultrahigh-resolution mass spectrometry. This is compared to an 8% explained variability that can be attributed to the RCC. This study highlights the importance of incorporating land use among other controls into the RCC to better predict the fate and quality of DOM exported from terrestrial to coastal systems.

In the present work, the advantages of ESI-TIMS-FT-ICR MS to address the isomeric content of dissolved organic matter are studied. While the MS spectra allowed the observation of a high number of peaks (e.g., PAN-L: 5004 and PAN-S: 4660), over 4× features were observed in the IMS-MS domain (e.g., PAN-L: 22 015 and PAN-S: 20 954). Assuming a total general formula of CxHyN0–3O0–19S0–1, 3066 and 2830 chemical assignments were made in a single infusion experiment for PAN-L and PAN-S, respectively. Most of the identified chemical compounds (∼80%) corresponded to highly conjugated oxygen compounds (O1–O20). ESI-TIMS-FT-ICR MS provided a lower estimate of the number of structural and conformational isomers (e.g., an average of 6–10 isomers per chemical formula were observed). Moreover, ESI-q-FT-ICR MS/MS at the level of nominal mass (i.e., 1 Da isolation) allowed for further estimation of the number of isomers based on unique fragmentation patterns and core fragments; the later suggested that multiple structural isomers could have very closely related CCS. These studies demonstrate the need for ultrahigh resolution TIMS mobility scan functions (e.g., R = 200–500) in addition to tandem MS/MS isolation strategies.

Mangrove ecotypes are distinct monospecific or mix-species assemblages and used as classification criteria to evaluate coastal biogeochemical cycles at the local, regional, and global scales. However, it is not clear how plant nitrogen and carbon content, including bulk δ13C and δ15N and n-alkane δ13C values, vary across species and within species when plants are exposed to the interaction between nutrient (nitrogen-N, phosphorus-P) availability and stressors (i.e., salinity). Here we present significant differences in green leaves wax n-alkane δ13C (δ13Cn-alkane) values and brown-senescent leaves C:N atomic ratios and total phosphorus (TP) concentrations of three mangrove species (Rhizophora mangle, Laguncularia racemosa, and Avicennia germinans) that reflect ecophysiological adaptations to nutrient availability and salinity along the Shark River estuary (SRE), South Florida, USA. Linear models between leaf wax δ13Cn-alkane values and species location along TP fertility and salinity gradients showed distinct differences, particularly between the species A. germinans and R. mangle. Our analyses showed that leaf wax δ13Cn-alkane properly represented major differences in ecophysiological responses by each mangrove species. We also found that both R. mangle and L. racemosa showed different isotopic footprints among the SRE upper, middle and lower estuarine salinity regions. Further, the green leaves bulk δ13C values in R. mangle (−32.3‰ to −27.6‰) were positively correlated with distance from the mouth of the estuary. In contrast, L. racemosa showed a negative relationship with distance and a narrower bulk δ13C range (−29.8‰ to −28.1‰) in comparison to the other two species. A. germinans, a species found only in the brackish (salinity: 18.8 ± 1.2) and saline (30.3 ± 0.53) estuarine regions, also showed a positive bulk δ13C relationship with distance. Because of the well-defined species-specific leaf wax n-alkane δ13C values along both water column/soil pore water salinity and TP gradients, we propose these values as a potential salinity proxy for paleoclimate reconstruction.

Human activities can alter dissolved organic matter (DOM) in lakes through both direct (i.e., exporting DOM of anthropogenic sources) and indirect effects (i.e., enhancing the autochthonous production of DOM via nutrient loading). Distinguishing between the direct and indirect effects is important to better understand human impacts on aquatic systems, but it remains highly challenging due to the interdependence of associated environmental variables. Here, we demonstrated that disentangling the direct and indirect effects can be achieved through combining large-scale environmental monitoring with the Partial Least Squares Path Modeling (PLS-PM). We presented DOM data from 61 lakes within the floodplain of the Yangtze River (Lakes-YR), China, a region that has been subjected to intense anthropogenic disturbances. We analyzed the amount and composition of DOM through dissolved organic carbon (DOC), chromophoric DOM (CDOM), and fluorescent DOM (FDOM). Four fluorescence components were identified, including one tyrosine-like component, one tryptophan-like component, and two humic-like components. Most of the lakes were dominated by freshly produced DOM with small molecular weights and low humification. Results from the PLS-PM models showed that the autochthonous production was more important than anthropogenic inputs in mediating DOC and CDOM. In contrast, FDOM parameters in lakes were more sensitive to the direct, anthropogenic sources, including treated domestic, industrial wastewater, and the effluents of aquaculture. These sources can be identified by elevated FDOM content per DOC (FDOM: DOC ratio) relative to autochthonous DOM, suggesting the potential of using FDOM as a tracer to identify and monitor the contribution of anthropogenic organic matter to inland waters.

Urban and agricultural development of the South Florida peninsula has disrupted historic freshwater flow in the Everglades, a hydrologically connected ecosystem stretching from central Florida to the Gulf of Mexico, USA. Current system-scale restoration efforts aim to restore natural hydrologic regimes to reestablish pre-drainage ecosystem functioning through increased water availability, quality and timing. Aquatic transport of carbon in this ecosystem, primarily as dissolved organic carbon (DOC), plays a critical role in biogeochemical cycling and food-web dynamics, and will be affected both by water management policies and climate change. To better understand DOC dynamics in South Florida estuaries and how hydrology, climate and water management may affect them, 14 years of monthly data collected in the Shark River estuary were used to examine DOC flux dynamics in a broader environmental context. Multivariate statistical methods were applied to long-term datasets for hydrology, water quality and climate to untangle the interconnected environmental drivers that control DOC export at monthly and annual scales. DOC fluxes were determined to be primarily controlled by hydrology but also by seasonality and long-term climate patterns and episodic weather events. A four-component model (salinity, rainfall, inflow, Atlantic Multidecadal Oscillation) capable of predicting DOC fluxes (R 2 = 0.84, p

Dissolved organic matter (DOM) reactivity plays a central role in ecosystem function and the global carbon cycle. In this study, a suite of biomass and soil leachates together with surface water samples from the Florida coastal Everglades (FCE) were investigated to quantitatively assess the photo- and bio-reactivity of DOM via dissolved organic carbon (DOC), ultraviolet–visible absorbance (UV–Vis) measurements, and excitation-emission matrix (EEM) fluorescence combined with parallel factor analysis (PARAFAC). The decomposition patterns observed were diverse, but dominated by first order decay for most of the samples studied. The reactivity rate constants obtained based on a first order multi-pool kinetic model, suggest that the DOM in the Everglades is largely refractory on time scales relevant to this ecosystem (2 months). The relative reactivity of different fluorescent DOM pools determined as labile, semi-labile and refractory were in the order of biomass leachate > soil leachate > surface water. Photo-reactivity was found to be a more important process in controlling the fate of FDOM in this system, while FDOM was mainly refractory to bio-degradation. Degradation patterns and rate constants for samples of different origin displayed vast differences for the same PARAFAC component, suggesting a complex and heterogeneous composition of fluorophores for each component, most likely the result of different structures, speciation and conformation, and molecular weight distribution. In addition, a terrestrial humic-like and two protein-like components were found to have the potential to serve as indicators of photo-degradable and bioavailable DOM.

The perennially ice-covered, closed-basin lakes in the McMurdo Dry Valleys, Antarctica, serve as sentinels for understanding the fate of dissolved black carbon from glacial sources in aquatic ecosystems. Here we show that dissolved black carbon can persist in freshwater and saline surface waters for thousands of years, while preserving the chemical signature of the original source materials. The ancient brines of the lake bottom waters have retained dissolved black carbon with a woody chemical signature, representing long-range transport of black carbon from wildfires. In contrast, the surface waters are enriched in contemporary black carbon from fossil fuel combustion. Comparison of samples collected 25 years apart from the same lake suggests that the enrichment in anthropogenic black carbon is recent. Differences in the chemical composition of dissolved black carbon among the lakes are likely due to biogeochemical processing such as photochemical degradation and sorption on metal oxides.

This study aimed to assess the molecular properties of dissolved organic matter (DOM) and dissolved black carbon (DBC) using analytical pyrolysis (Py-GC-MS). The sample set was comprised of ultrafiltered DOM (UDOM) from North American headwater streams associated with Long Term Ecological Research network sites. Pyrolysis products for each UDOM sample were categorized as being sourced from non-pyrogenic sources and DBC. Major non-pyrogenic components of the headwater stream UDOM were comprised of phenolic compounds derived from lignin and chitin markers from microbial biomass, and their relative contributions indicated differences in organic matter dynamics of these ecosystems. The DBC pyrolyzates included benzene, PAHs and benzonitriles, which accounted for 12.5 ± 4.5% of total quantified peak area (TPQA), and decreased in the order Alaskan boreal forest (19%), Alaskan tundra (17%), Appalachian deciduous forest (11%), Colorado alpine tundra (9%), Puerto Rican mountainous tropical rainforest (9%) and Kansas tallgrass prairie (7%). Pyrolysis products were compared to DBC content as determined by the benzenepolycarboxylic acid (BPCA) method. Although Py-GC-MS has quantitative limitations, this technique can detect weakly condensed and other DBC structures which fall outside of the BPCA analytical window., This study was in part funded by NSF through the Florida Coastal Everglades long Term Ecological Research program (DEB-1237517). R.J. acknowledges additional funding through the George Barley Endowment.

Eight C25 highly branched isoprenoid (HBI) alkenes were detected in the freshwater wetland of the Florida Everglades and tentatively assigned as a C25 diene, three C25 trienes, two C25 tetraenes and two C25 pentaenes based on their mass spectra, retention index and literature reports. One diene and one triene were observed more frequently than the others. The HBIs were present in varying amount of up to 1000, 19,000, 780 and 150 ng/g dry weight in the periphyton, floc, surface soils and deeper soils (ca. 1900 AD), respectively. Compound specific carbon isotope analysis of the two most dominant HBIs (one diene and one triene) showed them to be highly depleted in 13C (δ13C −40.0‰ to −38.5‰) in freshwater floc, suggesting recycled CO2 produced from the decomposition of organic matter as an important C source in the biosynthesis of these compounds. HBIs were present across this freshwater wetland in greater diversity and abundance at locations with higher surface water N concentration and longer hydroperiod (inundation). Historical variation in the occurrence of the HBIs in soil cores from multiple slough and ridge environments was assessed. Their increased abundance after ca. 1960 AD in almost all cores suggests proliferation of their precursor biota (freshwater diatoms) over the past five decades.

Compound specific carbon and deuterium stable isotope values (δ13C and δD) and the relative abundance of mid-chain n-alkanes (Paq) were determined for a series of dominant wetland plants, a surface slough-to-ridge soil transect, and slough and ridge soil cores, to assess historical vegetation successions induced by hydrological modification in an anthropogenically impacted, subtropical wetland, the Florida Everglades, USA. A difference of as much as 3.6 and 130 ‰ in their δ13C and δD values was observed between the two most abundant emergent macrophyte species (Cladium and Eleocharis), respectively. A clear n-alkane δD value depletion (−130 to −167 ‰) and decreasing Paq was observed along the slough-to-ridge soil transect, likely the result of an eco-hydrological transition from slough-to-ridge dominated vegetation (Eleocharis to Cladium). In agreement with the relatively constant Paq values, the lack of significant changes in the δD depth profile for the slough core, suggest a consistent slough type of vegetation composition over time at that location. In contrast, changes of both n-alkane δ13C and δD values for the ridge core, especially after ~1960 AD, coincide with the expected plant successions from historically long hydroperiod (>8 months), slough type plants (Eleocharis, Utricularia, Nymphaea) to present day, shorter hydroperiod (

Rivers export roughly 250 Pg of dissolved organic carbon (DOC) to coastal oceans. DOC exported from rivers can be a reflection of watershed dynamics, and changes in land use can lead to shifts in the molecular composition and reactivity of riverine DOC. About 10% of DOC exported from rivers is dissolved black carbon (DBC), a collection of polycondensed aromatic compounds derived from the incomplete combustion of biomass and fossil fuels. While DOC and DBC export are generally coupled, the effects of watershed land use on DBC quality are not well understood. In this study, DBC samples were collected throughout the Altamaha River watershed in Georgia, USA. DBC was characterized using the benzenepoly(carboxylic acid) method and Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS). DBC had a more polycondensed character in areas of the watershed with less anthropogenic disturbance. Furthermore, FTICR-MS revealed that DBC became enriched with a lower molecular weight, heteroatomic signature in response to higher anthropogenic activity. As global land cover continues to change, this study demonstrates on a localized scale that watershed land use can influence the export and composition of DBC, which may have further implications for global carbon and nutrient cycling.

RATIONALE There is a need for fast, post-ionization separation during the analysis of complex mixtures. In this study, we evaluate the use of a high-resolution mobility analyzer with high-resolution and ultrahigh-resolution mass spectrometry for unsupervised molecular feature detection. Goals include the study of the reproducibility of trapped ion mobility spectrometry (TIMS) across platforms, applicability range, and potential challenges during routine analysis. METHODS A TIMS analyzer was coupled to time-of-flight mass spectrometry (TOF MS) and Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) instruments for the analysis of singly charged species in the m/z 150-800 range of a complex mixture (Suwannee River Fulvic Acid Standard). Molecular features were detected using an unsupervised algorithm based on chemical formula and IMS profiles. RESULTS TIMS-TOF MS and TIMS-FT-ICR MS analysis provided 4950 and 7760 m/z signals, 1430 and 3050 formulas using the general Cx Hy N0-3 O0-19 S0-1 composition, and 7600 and 22 350 [m/z; chemical formula; K; CCS] features, respectively. CONCLUSIONS TIMS coupled to TOF MS and FT-ICR MS showed similar performance and high reproducibility. For the analysis of complex mixtures, both platforms were able to capture the major trends and characteristics; however, as the chemical complexity at the level of nominal mass increases with m/z (m/z >300-350), only TIMS-FT-ICR MS was able to report the lower abundance compositional trends.

Here we report the molecular biomarker co-occurrence of three different races of Botryococcus braunii (B. braunii) in the freshwater wetland ecosystem of the Florida Everglades, USA. Thespecific biomarkers include C32–C34 botryococcenes for race B, C27–C32n-alkadienes and n-alkatrienes for race A, and lycopadiene for race L. The n-alkadienes and n-alkatrienes were present up to 3.1 and 69.5 µg/g dry weight (dw), while lycopadiene was detected in lower amounts up to 3.0 and 1.5 µg/g dw in periphyton and floc samples, respectively. Nutrient concentrations (P and N) did not significantly correlate with the abundances of these compounds. In contrast, n-alkadienes and n-alkatrienes were present in wider diversity and higher abundance in the floc from slough (deeper water and longer hydroperiod) than ridge (shallower water and shorter hydroperiod) locations. n-Alkadienes, n-alkatrienes, and lycopadiene, showed lower δ13C values from −40.0 to −35.5‰, suggesting that the source organisms B. braunii at least partially utilize recycled CO2 (13C depleted) produced from OM respiration rather than atmospheric CO2 (13C enriched) as the major carbon sources.

Free radicals are produced in aquatic environments through photochemical reactions. They can affect the concentration and composition of organic matter and have negative effects on aquatic organisms. Free radical scavengers (antioxidants) can remove these highly reactive species from the media. Some dissolved organic matter (DOM) constituents are widely known to present antioxidant properties (e.g. phenols and hydroquinones). However, little is known about the free radical scavenger capacity of DOM. Here we applied two simple, analytical assays (ABST and DPPH) to assess the antioxidant capacity of aquatic DOM, after their validation against a more complex electrochemical technique. These assays were applied to DOM from various environmental settings, including freshwater marshes, fringe mangrove estuaries and a coastal bay in Everglades National Park, Florida. All the samples presented different degrees of antioxidant activity depending on their origin and thus DOM quality. Samples associated with mangrove areas presented the highest antioxidant activity, possibly due to the presence of tannins, which are known to be powerful antioxidants. The free radical scavenging capacity or antioxidant properties of DOM may have important implications in aquatic photochemistry as well as in microbial processes.

Small rivers and streams are ecologically important because they contribute to the export of organic carbon to coastal environments, likely influencing the global carbon cycle. While organic matter (OM) dynamics in large rivers has been studied in quite some detail, less is known about small streams. Sources of OM in streams ultimately determine its availability to the food web and downstream transport. In this study, sediment samples were collected from the King’s Creek watershed in Konza Prairie (Kansas, USA) and analyzed using molecular biomarkers and bulk 13C stable isotopes with the objective to comparatively assess OM inputs between riparian forest vegetation and watershed grassland to small, intermittent streams. We are interested in the potential influence of woody riparian expansion that has been ongoing at the site. Biomarkers typical of the local C4 grasses (branched n-alkanes, phytadienes) were more abundant in some of the sediments of the upper reaches. The sediments of the lower reaches contained biomarkers of algae (short-chain aliphatic compounds, C25:5 highly branched isoprenoid, brassicasterol) and vascular plant-derived material (triterpenols). Degraded OM (triterpene/triterpenol ratio) was found throughout the watershed with no pattern between the upper and lower reaches. Bulk 13C isotope analysis showed that the upper reaches of the watershed receive significant OM inputs from the C4 grasses (74–99 %) while the lower reaches are more strongly influenced by riparian trees (26–27 %) and algae (21–22 %). These results suggest that the environmental dynamics of bulk OM and the biomarker composition of small prairie streams are highly complex and likely a function of several factors such as light availability, riparian vegetative composition and density, and varying degrees of OM storage, retention and transport along the river continuum.

Several long-chain n-alkyl coumarates and ferulates were identified in cattails (Typha domingensis and Typha latifolia) from the Florida Everglades. Characterization of these compounds was achieved based on the interpretation of mass spectra obtained by GCMS as their trimethylsilyl ether derivatives, comparison with published mass spectra and available standards. Both n-alkyl p-coumarates and n-alkyl ferulates were identified in roots and leaves of both Typha species, featuring unique distribution patterns and differences between leaf and root biomass. For both Typha species, roots have higher concentrations and a much greater diversity of n-alkyl p-coumarates and ferulates but with different side chain carbon numbers ranging from C14 to C28. Typha domingensis leaves only contained n-alkyl ferulates with traces of n-alkyl p-coumarates, while both types of compounds were present in Typha latifolia leaf material. These chemicals were not found in the other dominant wetland vegetation, which suggests their potential for application as phytochemical tracers of fresh cattail-derived organic matter in the Everglades ecosystem.

The effects of photodegradation on the molecular size distribution and composition of dissolved black carbon (DBC) were explored using a surface water dissolved organic matter (DOM) sample from a terrigenous-influenced, fire-impacted Everglades area canal. The original and photodegraded DOM samples were fractionated using size exclusion chromatography and DBC was quantified via benzene polycarboxylic acid (BPCA) analysis. Size fractionation revealed that DBC was unequally distributed along the DOM molecular weight (MW) continuum and was preferentially associated with high MW (HMW) fractions. The photo-decomposition of HMW DBC generated less condensed DBC photo-products that preferentially re-associated with, and became enriched in, low MW (LMW) DOM size fractions. DBC composition in whole and size-fractionated DOM, as determined from relative BPCA distributions, was not considerably altered with short term photodegradation. This indicated that the size of the conjugated aromatic ring structure may drive the association of DBC compounds with different DOM MW fractions. HMW DBC was also more photo-labile than LMW DBC, which suggests that DBC associated with DOM over a range of size fractions may not exhibit the same degree of photo-reactivity, thereby resulting in different environmental fates for pyrogenic OM.

Annually, rivers and inland water systems deliver a significant amount of terrestrial organic matter (OM) to the adjacent coastal ocean in both particulate and dissolved forms; however, the metabolic and biogeochemical transformations of OM during its seaward transport remains one of the least understood components of the global carbon cycle. This transfer of terrestrial carbon to marine ecosystems is crucial in maintaining trophic dynamics in coastal areas and critical in global carbon cycling. Although coastal regions have been proposed as important sinks for exported terrestrial materials, most of the global carbon cycling data, have not included fjords in their budgets. Here we present distributional patterns on the quantity and quality of dissolved OM in Fiordland National Park, New Zealand. Specifically, we describe carbon dynamics under diverse environmental settings based on dissolved organic carbon (DOC) depth profiles, oxygen concentrations, optical properties (fluorescence) and stable carbon isotopes. We illustrate a distinct change in the character of DOC in deep waters compared to surface and mid-depth waters. Our results suggest that, both, microbial reworking of terrestrially derived plant detritus and subsequent desorption of DOC from its particulate counterpart (as verified in a desorption experiment) are the main sources of the humic-like enriched DOC in the deep basins of the studied fjords. While it has been suggested that short transit times and protection of OM by mineral sorption may ultimately result in significant terrestrial carbon burial and preservation in fjords, our data suggests the existence of an additional source of terrestrial OM in the form of DOC generated in deep, fjord water.

In this study, we contrast the fluorescent properties of dissolved organic matter (DOM) in fens and bogs in a Northern Minnesota peatland using excitation emission matrix fluorescence spectroscopy with parallel factor analysis (EEM-PARAFAC). EEM-PARAFAC identified four humic-like components and one protein-like component and the dynamics of each were evaluated based on their distribution with depth as well as across sites differing in hydrology and major biological species. The PARAFAC-EEM experiments were supported by dissolved organic carbon measurements (DOC), optical spectroscopy (UV-Vis), and compositional characterization by ultrahigh resolution Fourier transform ion cyclotron resonance mass spectroscopy (FT-ICR MS). The FT-ICR MS data indicate that metabolism in peatlands reduces the molecular weights of individual components of DOM, and oxygen-rich less aromatic molecules are selectively biodegraded. Our data suggest that different hydrologic and biological conditions within the larger peat ecosystem drive molecular changes in DOM, resulting in distinctly different chemical compositions and unique fluorescent fingerprints. PARAFAC modeling of EEM data coupled with ultrahigh resolution FT-ICR MS has the potential to provide significant molecular-based information on DOM composition that will support efforts to better understand the composition, sources, and diagenetic status of DOM from different terrestrial and aquatic systems.

Most transboundary rivers and their wetlands are subject to considerable anthropogenic pressures associated with multiple and often conflicting uses. In the Eastern Mediterranean such systems are also particularly vulnerable to climate change, posing additional challenges for integrated water resources management. Comprehensive measurements of the optical signature of colored dissolved organic matter (CDOM) were combined with measurements of river discharges and water physicochemical and biogeochemical properties, to assess carbon dynamics, water quality, and anthropogenic influences in a major transboundary system of the Eastern Mediterranean, the Evros (or, Марица or, Meriç) river and its Ramsar protected coastal wetland. Measurements were performed over three years, in seasons characterized by different hydrologic conditions and along transects extending more than 70 km from the freshwater end‐member to two kilometers offshore in the Aegean Sea. Changes in precipitation, anthropogenic dissolved organic matter (DOM) inputs from the polluted Ergene tributary, and the irregular operation of a dam were key factors driving water quality, salinity regimes, and biogeochemical properties in the Evros delta and coastal waters. Marsh outwelling affected coastal carbon quality, but the influence of wetlands was often masked by anthropogenic DOM contributions. A distinctive five‐peak CDOM fluorescence signature was characteristic of upstream anthropogenic inputs and clearly tracked the influence of freshwater discharges on water quality. Monitoring of this CDOM fluorescence footprint could have direct applications to programs focusing on water quality and environmental assessment in this and other transboundary rivers where management of water resources remains largely ineffective.

The occurrence of wildfires is expected to increase with the progression of climate change. These natural burn events can drastically alter the geomorphology and hydrology of affected areas and are one of the primary sources of black carbon (BC) in the environment. BC can be mobilized from soils and charcoal in fire-affected watersheds, potentially impacting downstream water quality. In June of 2012, the High Park Fire burned a large portion of the Cache La Poudre River watershed located in the Colorado Rocky Mountains. Seasonal riverine export of BC in both the dissolved (DBC) and particulate (PBC) phase was compared between burned and unburned sections of the watershed during the year following the High Park Fire. There was little difference in overall DBC concentration between sites, however seasonal changes in DBC quality reflected a shift in hydrology and associated DBC source between peak and base flow conditions. PBC export was substantially larger in fire-affected areas of the watershed during periods of overland flow. Our findings suggest that export processes of BC in the particulate and dissolved phase are decoupled in burned watersheds and that, in addition to DBC, the export of PBC could be a significant contributor to the cycling of charcoal in freshwater ecosystems.

The aerobic respiration of flocculent detrital organic material (floc) from Everglades National Park was found to be dependent on phosphorus limitation and carbon quality and is likely influenced by substrate age, hydrology, and local biomass productivity. Floc was collected at four sites along the Shark River and Taylor Sloughs of Everglades National Park and incubated for up to one week at room temperature in the dark. Floc respiration was determined by measuring the total amount of CO2 evolved and CO2 generation rates. To investigate the effect of hydrological conditions, samples were collected in a typical dry (April) and wet (October) season and from short- and long-hydroperiod sites. Floc from the short-hydroperiod freshwater site generated more CO2 compared to the long-hydroperiod site due to the labile nature of the periphyton-derived organic matter at the former and the presence of more degraded and aged material at the latter. The tidally-influenced Shark River Slough mangrove site generated more CO2 compared to the Taylor Slough mangrove site, likely as a result of phosphorus inputs from the adjacent Gulf of Mexico at the former and reduced phosphorus inputs and prolonged inundation at the latter. Generally, more CO2 was generated during the dry season. Floc respiration rates were faster in the wet season, suggesting that fresh vegetation inputs to the floc can influence this process. Phosphorus and glucose additions enhanced CO2 generation suggesting that phosphorus limitation and carbon quality are important factors regulating floc decomposition.

Combustion produces a complex mixture of polycondensed aromatic compounds known as black carbon (BC). Such products can become remobilized from char and soil in the form of dissolved BC (DBC). Ultra-high resolution Fourier transform ion cyclotron resonance mass spectrometry (ESI–FT-ICRMS) analysis of a variety of soil and char leachates showed that a significant proportion of DBC compounds contained one or more nitrogen atoms. While the presence of black nitrogen (DBN) in dissolved organic matter (DOM) has been reported, its molecular features were uncharacterized. Here we present results of FT-ICRMS characterization of DBN, where assigned formulae were validated on the basis on their 13C isotope signatures and fragmentation patterns obtained via collision induced dissociation. Possible chemical structures were assigned for several DBN formulae and suggest that nitrogen was incorporated into the core ring system as a pyrrole-type moiety. Most DBN compounds existed as part of homologous series where homologs differed by a mass corresponding to CO2, suggesting that they were polysubstituted with carboxylic acid groups. The environmental contribution of such novel, aromatic, combustion-derived nitrogen compounds with respect to global nitrogen cycling remains elusive. The biogeochemical implications of the input of such fire-derived products to aquatic ecosystems as part of climate change therefore need to be assessed.

The dynamics of dissolved organic matter (DOM) in subtropical coastal bays are complex. For example, variations in DOM characteristics and sources in Florida Bay are believed to be mainly driven by both hydrology and associated runoff of terrestrial DOM, and by primary productivity mostly from seagrass sources. However, confirmation and quantification of different DOM sources are still incomplete and needed for carbon budget assessments. Optical parameters based on excitation emission matrix fluorescence coupled with parallel factor analysis (EEM–PARAFAC) that had previously been tentatively assigned to both terrestrial and seasgrass sources. These correlated linearly with determined δ13C values, confirming an allochthonous, hydrologically-driven terrestrial source for the humic-like fluorescent components, while autochthonous DOM reflected by the protein-like fluorescence is mainly derived through primary productivity of seagrass communities. This study demonstrated the feasibility of combining optical signatures and stable isotopes in advancing the understanding of DOM dynamics in estuarine systems. Using stable carbon isotopic signatures of DOM, and applying a simple two end-member mixing model, the relative contributions of these two sources to the DOM pool in the bay were estimated. Results indicate that the highest proportion of DOM (ca. 72%) during the dry season was seagrass-derived, but clear variations were observed on both spatial and temporal scales. Limitations to the application of optical properties for the quantitative estimation of DOM sources in such coastal systems are discussed.