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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.

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.

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.

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.

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.

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

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 (

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.

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.

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.

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 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.

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.

Paleoecological reconstructions of environmental changes provide important information for Everglades restoration targets. Traditionally this has been achieved using a combination of biological and physical indicators. However, as microfossils may be sporadically abundant in Everglades soils, organic geochemical methods can provide information at the molecular level. To reconstruct vegetation trends over the last century, soil cores from Shark to Taylor Sloughs, the primary flowpaths of the southern Everglades, were examined using several geochemical proxies. The n-alkane derived biomarker Paq effectively distinguished organic inputs from sawgrass and slough habitats. Other proxies examined include Kaurenes, cyclic diterpenoids unique to sawgrass roots; biomarkers of algae (highly branched isoprenoids (C20HBIs) and Botryococcenes); lignin phenols as vascular plant indicators; and macrofossils. At all sites, soil profiles from sawgrass marshes showed vegetation had shifted over the last 100 years, from sloughs to sawgrass-dominated marshes, reflecting decreased water levels (shorter hydroperiods) induced by water management. Paleo-assessments of modern sloughs, however, indicate these habitats remained deeper water habitats throughout the period of record, though shifts toward shorter hydroperiod vegetation were observed. In Taylor Slough, evidence of increasingly dry conditions in sloughs was confirmed by seed inputs from woody species. At 3 of the 5 sites, recent increases in C20HBIs and Botryococcene concentrations indicated greater periphyton abundance, coincidental with increased mineral concentrations observed in surface waters during the mid-20th Century. Bulk proxies such as organic content and carbon:nitrogen ratios also supported findings of changes in relative contributions of microbial and higher plants in this ecosystem.

Boreal forests are thought to be an important source and sink for pyrogenic carbon, or black carbon (BC), as fire is very common in this type of ecosystem. However, the reported soil BC content in boreal forests is low, suggesting active removal processes of soil BC possibly through transfer to the dissolved phase. In this study, dissolved black carbon (DBC) concentrations from samples collected from streams in Alaska boreal forest watersheds and in glacial rivers are reported. The DBC levels, as well as its degree of polycondensation, in glacial rivers are much lower than those from boreal forest streams. This suggests source differences (fossil fuel vs. forest fires) as a possible reason for these molecular variations. Our hypothesis is that DBC in boreal forest watersheds is mostly generated from forest fires, while glacial rivers will receive a higher relative contribution of BC from atmospheric deposition, resulting in a more fossil fuel like molecular signature of DBC in the latter. To test the source hypothesis, we compared the DBC molecular characteristics of samples from boreal rives and glacier-fed streams with additional samples from locations isolated from significant fire-derived inputs, where atmospheric deposition of anthropogenic soot may be important. Based on this comparative approach, we suggest that anthropogenic BC, associated with small soot particles, is the most prominent source of DBC in the glacial rivers. A linear positive correlation between dissolved organic carbon (DOC) and DBC concentrations was observed for both boreal forest and glacial samples, once again confirming that DOC and DBC dynamics are closely coupled. The ever increasing export of DOC associated DBC from high latitude boreal forests and glaciers as a result of global warming, may impact DOC quality and ultimately trophic dynamics in the receiving marine environment.

Assessing the sources and quantifying the contributions of particulate organic matter (POM) in estuaries is a challenge. Here we apply source-specific biomarkers to assess POM sources in an estuary receiving suspended material from freshwater wetlands, fringe mangroves and coastal environments. A three end-member mixing model, including terrestrial, estuarine and marine end-member contributions was developed and successfully validated to assess general OM dynamics and hydrologic processes that control POM distributions within the Shark River estuary in South Florida. Low tide and wet season conditions coincided with an enhanced signal of the freshwater end-member biomarker abundance, while high tide and dry season conditions resulted in enhanced POM input of marine origin. Incoming tide was observed to be an important factor in the re-suspension and tidal pumping of mangrove-derived POM, which seems to be the dominant source of particulate organic carbon (POC) in the estuary. The three end-member conceptual model was tested to obtain a rough estimate of POC source strength, with the ultimate goal of constraining carbon budgets in this sub-tropical estuary. Mangrove-derived POC flux of ca. 5.3 × 105 to 1.0 × 106 kg/yr POC from the Shark River to the Gulf of Mexico were estimated, but end-member values used in the assessment need to be better constrained to reduce the degree of variability.

As basic information for assessing reactivity and functionality of wetland-associated dissolved organic matter (DOM) based on their composition and structural properties, chemical characteristics of N in ultrafiltered DOM (UDON; > 1 kD) isolated from wetland-associated rivers in three climates (cool-temperate, Hokkaido, Japan; sub-tropical, Florida, USA; tropical, Sarawak, Malaysia) were investigated. The UDON was isolated during dry and wet seasons, or during spring, summer, and autumn. The proportion of UDON present as humic substances, which was estimated as the DAX-8 adsorbed fraction, ranged from 47 to 91%, with larger values in the Sarawak than at the other sites. The yield of hydrolyzable amino acid N ranged 1.24 to 7.01mg g − 1 , which correlated positively to the total N content of UDOM and tended to be larger in the order of Florida > Hokkaido > Sarawak samples. X-ray photoelectron N1s spectra of UDON showed a strong negative correlation between the relative abundances of amide/peptide N and primary amine N. The relative abundances of amide/peptide N and primary amine N in the Sarawak samples were smaller (70–76%) and larger (20–23%) respectively compared to those (80–88% and 4–9%) in the Florida and Hokkaido samples. Assuming terminal amino groups and amide N of peptides as major constituents of primary amine N and amide/peptide N, respectively, the average molecular weight of peptides was smaller in the Sarawak samples than that in the Florida and Hokkaido samples. Seasonal variations in UDON composition were scarce in the Sarawak and Florida samples, whereas the distribution of humic substance-N and nonhumic substance-N and compositions of amino acids and N functional groups showed a clear seasonality in the Hokkaido samples. While aromatic N increased from spring to autumn, contributions from fresh proteinaceous materials were also enhanced during autumn, resulting in the highest N content of UDOM for this season.

Wetlands are key components in the global carbon cycle and export significant amounts of terrestrial carbon to the coastal oceans in the form of dissolved organic carbon (DOC). Conservative behavior along the salinity gradient of DOC and chromophoric dissolved organic matter (CDOM) has often been observed in estuaries from their freshwater end-member (salinity = 0) to the ocean (salinity = 35). While the oligo/meso-haline (salinity A 254 ) and excitation–emission matrix (EEM) fluorescence coupled with parallel factor analysis (PARAFAC) along the lower salinity range (salinity A 254 was observed, while these parameters showed similar conservative behavior for the third. Three distinct EEM-PARAFAC models established for each of the rivers provided similar spectroscopic characteristics except for some unique fluorescence features observed for the Judan River. The distribution patterns of PARAFAC components suggested that the inputs from plankton and/or submerged aquatic vegetation can be important in the Bekanbeushi River. Further, DOM photo-products formed in the estuarine lake were also found to be transported upstream. In the Harney River, whereas upriver-derived terrestrial humic-like components were mostly distributed conservatively, some of these components were also derived from mangrove inputs in the oligo/meso-haline zone. Interestingly, fluorescence intensities of some terrestrial humic-like components increased with salinity for the Judan River possibly due to changes in the dissociation state of acidic functional groups and/or increase in the fluorescence quantum yield along the salinity gradient. The protein-like and microbial humic-like components were distributed differently between three wetland rivers, implying that interplay between loss to microbial degradation and inputs from diverse sources are different for the three wetland-influenced rivers. The results presented here indicate that upper estuarine oligo/meso-haline regions of coastal wetland rivers are highly dynamic with regard to the biogeochemical behavior of DOM.

Dissolved organic matter (DOM) source and composition are critical drivers of its reactivity, impact microbial food webs and influence ecosystem functions. It is believed that DOM composition and abundance represent an integrated signal derived from the surrounding watershed. Recent studies have shown that land-use may have a long-term effect on DOM composition. Methods for characterizing DOM, such as those that measure the optical properties and size of the molecules, are increasingly recognized as valuable tools for assessing DOM sources, cycling, and reactivity. In this study we measured DOM optical properties and molecular weight determinations to evaluate whether the legacy of forest disturbance alters the amount and composition of stream DOM. Differences in DOM quantity and composition due to vegetation type and to a greater extent, wetland influence, were more pronounced than effects due to disturbance. Our results suggest that excitation-emission matrix fluorescence with parallel factor analysis is a more sensitive metric of disturbance than the other methods evaluated. Analyses showed that streams draining watersheds that have been clearcut had lower dissolved organic carbon (DOC) concentrations and higher microbially-derived and protein-like fluorescence features compared to reference streams. DOM optical properties in a watershed amended with calcium, were not significantly different than reference watersheds, but had higher concentrations of DOC. Collectively these results improve our understanding of how the legacy of forest disturbances and natural landscape characteristics affect the quantity and chemical composition of DOM in headwater streams, having implications for stream water quality and carbon cycling.

The coastal zone of the Florida Keys features the only living coral reef in the continental United States and as such represents a unique regional environmental resource. Anthropogenic pressures combined with climate disturbances such as hurricanes can affect the biogeochemistry of the region and threaten the health of this unique ecosystem. As such, water quality monitoring has historically been implemented in the Florida Keys, and six spatially distinct zones have been identified. In these studies however, dissolved organic matter (DOM) has only been studied as a quantitative parameter, and DOM composition can be a valuable biogeochemical parameter in assessing environmental change in coastal regions. Here we report the first data of its kind on the application of optical properties of DOM, in particular excitation emission matrix fluorescence with parallel factor analysis (EEM-PARAFAC), throughout these six Florida Keys regions in an attempt to assess spatial differences in DOM sources. Our data suggests that while DOM in the Florida Keys can be influenced by distant terrestrial environments such as the Everglades, spatial differences in DOM distribution were also controlled in part by local surface runoff/fringe mangroves, contributions from seasgrass communities, as well as the reefs and waters from the Florida Current. Application of principal component analysis (PCA) of the relative abundance of EEM-PARAFAC components allowed for a clear distinction between the sources of DOM (allochthonous vs. autochthonous), between different autochthonous sources and/or the diagenetic status of DOM, and further clarified contribution of terrestrial DOM in zones where levels of DOM were low in abundance. The combination between EEM-PARAFAC and PCA proved to be ideally suited to discern DOM composition and source differences in coastal zones with complex hydrology and multiple DOM sources.

Dissolved organic carbon (DOC) concentration and dissolved organic matter (DOM) optical properties were analyzed along two estuarine river transects during the wet and dry seasons to better understand DOM dynamics and quantify mangrove inputs. A tidal study was performed to assess the impacts of tidal pumping on DOM transport. DOM in the estuaries showed non-conservative mixing indicative of mangrove-derived inputs. Similarly, fluorescence data suggest that some terrestrial humic-like components showed non-conservative behavior. An Everglades freshwater-derived fluorescent component, which is associated with soil inputs from the Northern Everglades, behaved conservatively. During the dry season, a protein-like component behaved conservatively until the mid-salinity range when non-conservative behavior due to degradation and/or loss was observed. The tidal study data suggests mangrove porewater inputs to the rivers following low tide. The differences in quantity of DOM exported by the Shark and Harney Rivers imply that geomorphology and tidal hydrology may be a dominant factor controlling the amount of DOM exported from the mangrove ecotone, where up to 21 % of the DOC is mangrove-derived. Additionally, nutrient concentrations and other temporal factors may control DOM export from the mangroves, particularly for the microbially derived fluorescent components, contributing to the seasonal differences. The wet and dry season fluxes of mangrove DOM from the Shark River is estimated as 0.27 × 109 mg C d−1 and 0.075 × 109 mg C d−1, respectively, and the Harney River is estimated as 1.9 × 109 mg C d−1 and 0.20 × 109 mg C d−1.

Herein, lipid biomarker analysis is applied to surface sediments from the southeastern Niger Delta region for the quantitative determination of aliphatic lipids, steroids and triterpenoids in order to differentiate between natural (autochthonous vs. allochthonous) and anthropogenic organic matter (OM) inputs to this deltaic environment. This ecosystem, composed of the Cross, Great Kwa and Calabar Rivers, is receiving new attention due to increased human and industrial development activities and the potential effects of these activities impacting its environmental health. While the presence of low molecular weight n -alkanes ( 22 ) and the fossil biomarkers pristane and phytane in all samples, are indicative of a minor petroleum related input, the total extractable organic component of the surface sediments of these rivers remains predominantly of a natural origin as characterized by the variety and predominance of lipid classes that are mainly derived from the epicuticular waxes of vascular plants and include n -alkanes, n -alkanols, n -alkan-2-ones, n -alkanoic acids, steroids and triterpenoids. In addition, recent OM inputs from microorganisms are indicated by the presence of lower molecular weight n -alkanoic acids (C max = 16), while the major triterpenoids of the sediments, taraxerol and friedelin, and the major sterol, sitosterol, indicate recent OM inputs from vascular plants. Plankton-derived sterols, such as fucosterol and dinosterol, are also found in sediments from the Cross and Great Kwa Rivers and likely originate from autochthonous primary productivity. Furthermore, the coprosterols coprostanol and 24-ethylcoprostanol are present in most samples and indicate measurable anthropogenic contributions from domestic untreated sewage inputs and agricultural run-off, respectively. Of the three rivers studied, the Cross River system was excessively influenced by human and industrial development activities, including drivers such as urbanization and population center growth, land-use change to support agricultural production and animal husbandry, and petroleum exploration and production. These influences were found to be regionally specific as controlled by point sources of pollution based on the relative distributions measured and on the fact that the molecular characteristics of sedimentary OM were not distributed smoothly along a gradient.

While the existence of black carbon as part of dissolved organic matter (DOM) has been confirmed, quantitative determinations of dissolved black carbon (DBC) in freshwater ecosystem and information on factors controlling its concentration are scarce. In this study, stream surface water samples from a series of watersheds subject to different burn frequencies in Konza Prairie (Kansas, USA) were collected in order to determine if recent fire history has a noticeable effect on DBC concentration. The DBC levels detected ranged from 0.04 to 0.11 mg L(-1), accounting for ca. 3.32±0.51% of dissolved organic carbon (DOC). No correlation was found between DBC concentration and neither fire frequency nor time since last burn. We suggest that limited DBC flux is related to high burning efficiency, possibly greater export during periods of high discharge and/or the continuous export of DBC over long time scales. A linear correlation between DOC and DBC concentrations was observed, suggesting the export mechanisms determining DOC and DBC concentrations are likely coupled. The potential influence of fire history was less than the influence of other factors controlling the DOC and DBC dynamics in this ecosystem. Assuming similar conditions and processes apply in grasslands elsewhere, extrapolation to a global scale would suggest a global grasslands flux of DBC on the order of 0.14 Mt carbon year(-1).

Dissolved organic matter (DOM) is an essential component of the carbon cycle and a critical driver in controlling variety of biogeochemical and ecological processes in wetlands. The quality of this DOM as it relates to composition and reactivity is directly related to its sources and may vary on temporal and spatial scales. However, large scale, long-term studies of DOM dynamics in wetlands are still scarce in the literature. Here we present a multi-year DOM characterization study for monthly surface water samples collected at 14 sampling stations along two transects within the greater Everglades, a subtropical, oligotrophic, coastal freshwater wetland-mangrove-estuarine ecosystem. In an attempt to assess quantitative and qualitative variations of DOM on both spatial and temporal scales, we determined dissolved organic carbon (DOC) values and DOM optical properties, respectively. DOM quality was assessed using, excitation emission matrix (EEM) fluorescence coupled with parallel factor analysis (PARAFAC). Variations of the PARAFAC components abundance and composition were clearly observed on spatial and seasonal scales. Dry versus wet season DOC concentrations were affected by dry-down and re-wetting processes in the freshwater marshes, while DOM compositional features were controlled by soil and higher plant versus periphyton sources respectively. Peat-soil based freshwater marsh sites could be clearly differentiated from marl-soil based sites based on EEM–PARAFAC data. Freshwater marsh DOM was enriched in higher plant and soil-derived humic-like compounds, compared to estuarine sites which were more controlled by algae- and microbial-derived inputs. DOM from fringe mangrove sites could be differentiated between tidally influenced sites and sites exposed to long inundation periods. As such coastal estuarine sites were significantly controlled by hydrology, while DOM dynamics in Florida Bay were seasonally driven by both primary productivity and hydrology. This study exemplifies the application of long term optical properties monitoring as an effective technique to investigate DOM dynamics in aquatic ecosystems. The work presented here also serves as a pre-restoration condition dataset for DOM in the context of the Comprehensive Everglades Restoration Plan (CERP).

Wetlands provide quintessential ecosystem services such as maintenance of water quality, water supply and biodiversity, among others; however, wetlands are also among the most threatened ecosystems worldwide. They are usually characterized by high levels of natural dissolved organic matter (DOM), representing a critical component in wetland biogeochemistry. This study describes the first detailed, comparative, molecular characterization of DOM in sub-tropical, pulsed, wetlands, namely the Everglades (USA), the Pantanal (Brazil) and the Okavango Delta (Botswana), using optical properties, high field nuclear magnetic resonance (NMR) and ultrahigh resolution mass spectrometry (FT-ICRMS), and compares compositional features to variations in organic matter sources and flooding characteristics (i.e. differences in hydroperiod). While optical properties showed both similarities and differences between these ecosystems, these differences were mainly based on the degree of aromaticity of the DOM. Analogies were such that an established excitation emission matrix fluorescence parallel factor analysis (EEM-PARAFAC) model for the Everglades was perfectly applicable to the other two wetlands. High-field (500 and 800 MHz) NMR spectra with cryogenic detection provided exceptional coverage and chemical description of wetland solid phase extracted (SPE) DOM. Area-normalized 1H NMR spectra of selected samples revealed clear distinctions of samples along with pronounced congruence within the three pairs of wetland DOM. Within sample pairs (long vs. short hydroperiod sites), internal differences mainly referred to intensity variations (denoting variable abundance) rather than to alterations of NMR resonances positioning (denoting diversity of molecules). The relative disparity was largest between the Everglades long and short hydroperiod samples, whereas Pantanal and Okavango samples were more alike among themselves. Otherwise, molecular divergence was most obvious in the case of unsaturated protons (δH > 5 ppm). The larger discrimination observed between 1H NMR spectra of DOM from different wetlands in comparison with the intrinsic variance among DOM within each wetland readily suggests the presence of an individual molecular signature, characteristic of each particular wetland. 2-D NMR spectroscopy for a particular sample revealed a large richness of aliphatic and unsaturated substructures, likely derived from microbial sources such as periphyton in the Everglades. In contrast, the chemical diversity of aromatic wetland DOM likely originates from a combination of higher plant sources, progressive microbial and photochemical oxidation, and contributions from combustion-derived products (e.g. black carbon). In addition, FT-ICRMS spectra allowed far-reaching classifications of wetland DOM. While DOM of both Okavango and Pantanal showed near 57 ± 2 % CHO, 8 ± 2 % CHOS, 33 ± 2 CHNO, and < 1 % CHNOS molecules, the mass spectra of Everglades samples were fundamentally different compared to those as well as among long and short hydroperiod samples, as they were markedly enriched in CHOS and CHNOS at the expense of CHO and CHNO compounds. Here, four groups of CHOS molecules were differentiated as (a) saturated sulfolipids, (b) unsaturated sulfolipids, (c) molecularly diverse DOM-type CHOS molecules, (d) and particularly enriched in the Everglades short hydroperiod site, a large set of aromatic and oxygen-deficient "black sulphur" compounds. The significantly higher proportion of CHOS compounds in general for the Everglades samples is likely the result of higher inputs of agriculture-derived and sea spray derived sulphate to this wetland compared to the others. Although wetland DOM samples were found to share many molecular features, each sample was unique in its composition, which reflected specific environmental drivers and/or specific biogeochemical processes.

The environmental dynamics of dissolved organic matter (DOM) were characterized for a shallow, subtropical, seagrass-dominated estuarine bay, namely Florida Bay, USA. Large spatial and seasonal variations in DOM quantity and quality were assessed using dissolved organic C (DOC) measurements and spectrophotometric properties including excitation emission matrix (EEM) fluorescence with parallel factor analysis (PARAFAC). Surface water samples were collected monthly for 2 years across the bay. DOM characteristics were statistically different across the bay, and the bay was spatially characterized into four basins based on chemical characteristics of DOM as determined by EEM-PARAFAC. Differences between zones were explained based on hydrology, geomorphology, and primary productivity of the local seagrass community. In addition, potential disturbance effects from a very active hurricane season were identified. Although the overall seasonal patterns of DOM variations were not significantly affected on a bay-wide scale by this disturbance, enhanced freshwater delivery and associated P and DOM inputs (both quantity and quality) were suggested as potential drivers for the appearance of algal blooms in high impact areas. The application of EEM-PARAFAC proved to be ideally suited for studies requiring high sample throughput methods to assess spatial and temporal ecological drivers and to determine disturbance-induced impacts in aquatic ecosystems.

Biogeochemical processing of dissolved organic matter (DOM) in aquatic environments can alter its chemical quality and its bioavailability to the microbial loop. In this study, we evaluated the relative importance to DOM character of allochthonous and autochthonous DOM inputs and photo-degradation in a large, pristine wetland, the Okavango Delta of Botswana. We performed an intensive spatial sampling of surface water and analyzed for chemical and physical parameters (pH, conductivity, dissolved oxygen saturation, temperature, and channel depth), dissolved organic matter (DOM), and particulate organic matter (POM). We used UV–vis absorbance, fluorescence spectroscopy, and parallel factor analysis of excitation emission matrix data (EEM-PARAFAC) to characterize DOM. Our findings from principal component analysis (PCA) show downstream changes in DOM chemistry to be dominated by photo-degradation, suggesting that DOM in the Okavango Delta is transformed photo-chemically in shallower downstream reaches after being mobilized from the permanent swamp and seasonal floodplains. Additionally, we found that the PARAFAC model developed for the Everglades, a large, anthropogenically-altered wetland in North America, was well suited to tracking DOM dynamics in the Okavango Delta and may be useful for characterizing DOM in other sub-tropical, seasonally flooded wetlands.

The authors summarize the main findings of the Florida Coastal Everglades Long-Term Ecological Research (FCE-LTER) program in the EMER, within the context of the Comprehensive Everglades Restoration Plan (CERP), to understand how regional processes, mediated by water flow, control population and ecosystem dynamics across the EMER landscape. Tree canopies with maximum height

Wetlands are known to be important sources of dissolved organic matter (DOM) to rivers and coastal environments. However, the environmental dynamics of DOM within wetlands have not been well documented on large spatial scales. To better assess DOM dynamics within large wetlands, we determined high resolution spatial distributions of dissolved organic carbon (DOC) concentrations and DOM quality by excitation–emission matrix spectroscopy combined with parallel factor analysis (EEM–PARAFAC) in a subtropical freshwater wetland, the Everglades, Florida, USA. DOC concentrations decreased from north to south along the general water flow path and were linearly correlated with chloride concentration, a tracer of water derived from the Everglades Agricultural Area (EAA), suggesting that agricultural activities are directly or indirectly a major source of DOM in the Everglades. The optical properties of DOM, however, also changed successively along the water flow path from high molecular weight, peat-soil and highly oxidized agricultural soil-derived DOM to the north, to lower molecular weight, biologically produced DOM to the south. These results suggest that even though DOC concentration seems to be distributed conservatively, DOM sources and diagenetic processing can be dynamic throughout wetland landscapes. As such, EEM–PARAFAC clearly revealed that humic-enriched DOM from the EAA is gradually replaced by microbial- and plant-derived DOM along the general water flow path, while additional humic-like contributions are added from marsh soils. Results presented here indicate that both hydrology and primary productivity are important drivers controlling DOM dynamics in large wetlands. The biogeochemical processes controlling the DOM composition are complex and merit further investigation.

A stable carbon isotope approach was taken to identify potential organic matter sources incorporated into biomass by the heterotrophic bacterial community of Florida Bay, a subtropical estuary with a recent history of seagrass loss and phytoplankton blooms. To gain a more complete understanding of bacterial carbon cycling in seagrass estuaries, this study focused on the importance of seagrass-derived organic matter to pelagic, seagrass epiphytic, and sediment surface bacteria. Particulate organic matter (POM), seagrass epiphytic, seagrass (Thalassia testudinum) leaf, and sediment surface samples were collected from four Florida Bay locations with historically different organic matter inputs, macrophyte densities, and primary productivities. Bulk (observed and those reported previously) and compound-specific bacterial fatty acid d 13 C values were used to determine important carbon sources to the estuary and benthic and pelagic heterotrophic bacteria. The d 13 C values of T. testudinum green leaves with epiphytes removed ranged from � 9.9 to � 6.9&. Thalassia testudinum d 13 C values were significant more enriched in 13 C than POM, epiphytic, and sediment samples, which ranged from � 16.4 to � 13.5, � 16.2 to � 9.6, and � 16.7 to � 11.0 &, respectively. Bacterial fatty acid d 13 C values (measured for br14:0, 15:0, i15:0, a15:0, br17:0, and 17:0) ranged from � 25.5 to � 8.2&. Assuming a � 3& carbon source fractionation from fatty acid to whole bacteria, pelagic, epiphytic, and sediment bacterial d 13 C values were generally more depleted in 13 C than T. testudinum d 13 C values, more enriched in 13 C than reported d 13 C values for mangroves, and similar to reported d 13 C values for algae. IsoSource mixing model results indicated that

We examined the impact of permafrost on dissolved organic matter (DOM) composition in Caribou-Poker Creeks Research Watershed (CPCRW), a watershed underlain with discontinuous permafrost, in interior Alaska. We analyzed long term data from watersheds underlain with varying degrees of permafrost, sampled springs and thermokarsts, used fluorescence spectroscopy, and measured the bioavailabity of dissolved organic carbon (DOC). Permafrost driven patterns in hydrology and vegetation influenced DOM patterns in streams, with the stream draining the high permafrost watershed having higher DOC and dissolved organic nitrogen (DON) concentrations, higher DOC:DON and greater specific ultraviolet absorbance (SUVA) than the streams draining the low and medium permafrost watersheds. Streams, springs and thermokarsts exhibited a wide range of DOC and DON concentrations (1.5–37.5 mgC/L and 0.14–1.26 mgN/L, respectively), DOC:DON (7.1–42.8) and SUVA (1.5–4.7 L mgC−1 m−1). All sites had a high proportion of humic components, a low proportion of protein components, and a low fluorescence index value (1.3–1.4), generally consistent with terrestrially derived DOM. Principal component analysis revealed distinct groups in our fluorescence data determined by diagenetic processing and DOM source. The proportion of bioavailable DOC ranged from 2 to 35%, with the proportion of tyrosine- and tryptophan-like fluorophores in the DOM being a major predictor of DOC loss (p

The distributions of fluorescent components in dissolved organic matter (DOM) from Ise Bay, Japan, were determined by excitation emission matrix (EEM) fluorescence spectroscopy combined with parallel factor analysis (PARAFAC). Three terrestrial humic-like, one marine humic-like, and three non-humic-like fluorescent components were identified by PARAFAC, and the environmental dynamics of individual fluorescent components in the bay area were evaluated. The observed linear relationships between salinity and abundance of two of the three humic-like components in the bay area indicate a terrestrial origin and conservative mixing behavior of these components. On the other hand, nonconservative mixing for the other terrestrial and the marine humic-like components was observed, indicating that the sources of these were other than solely riverine inputs. Thus, in addition to riverine sources, this terrestrial humic-like component may receive inputs from biogeochemical reworking of terrestrial DOM and/or particulate organic matter, while the most likely sources for the marine humic-like component are estuarine biological activity and/or microbial reworking of plankton-derived DOM. From the spatial distributions in the bay area as well as their relationships with salinity, two of the non-humic-like components were suggested to be of autochthonous estuarine origin and likely represent biologically labile components. Microbial degradation processes were suggested to be important factors driving the dynamics of another non-humic-like component. This study exemplifies the potential applicability of EEM-PARAFAC in studies of fluorescent DOM dynamics in estuaries.

Doubtful Sound, Fiordland National Park, New Zealand has a stable low salinity layer (LSL) at the surface due to the high annual rainfall and an additional freshwater input from the discharge of a hydroelectric power plant. Chromophoric dissolved organic matter (CDOM) distribution dynamics in this LSL were analyzed using Excitation Emission Matrix (EEM) fluorescence and UV/Vis absorption measurements. The levels of CDOM in surface water in Doubtful Sound were much higher than previously reported for coastal zones. CDOM analyzed by UV/Vis absorbance and EEM fluorescence decreased by about 90% within the first 5 m depth. In the first 5 m, the salinity gradient was extreme (5 – 34 salinity), creating a vertical mixing gradient, which appeared to be stable over time. The spectral slope S and the fluorescence index increased during vertical mixing within the first 5 m depth indicating changes in the CDOM chromophores. Observations during a strong rain event revealed that CDOM in a freshwater stream initially increased, but decreased with additional rain (same flow rate), which is an indication that most CDOM was quickly exported within these catchments. Furthermore, the lower CDOM input after substantial rain diluted the surface CDOM level and created a subsurface CDOM maximum. However, shortly after the rain event (

The extractable lipid compositions in four Florida Bay cores were determined in order to understand environmental changes over the last 160 years. The most significant environmental change was recorded by oscillations in the amplitude and frequency of biomarkers during the 20th century. Two seagrass molecular proxies ( Paq and the C 25 /C 27 n -alkan-2-one ratio) reached a maximum post 1900, suggesting that abundant seagrass communities existed during the 20th century. A sharp drop in the Paq value from 0.65 to 0.48 in the central Bay at about 1987 seems to reflect seagrass die-off. The concentrations of microbial biomarkers (C 20 HBIs, C 25 HBIs and dinosterol) substantially increased after 1950 in the TC, BA and NB cores, reflecting an increase in algal (planktonic organism) primary productivity. However, the RB core presented the highest abundance of C 25 HBIs and dinosterol during the period of 1880–1940, suggesting historically large inputs from diatoms and dinoflagellates. A substantial rise in abundance of taraxerol (a specific biomarker of mangroves) from 20 μg/g TOC in the 1830s to 279 μg/g TOC in the l980s is likely a result of increased mangrove primary productivity along the shore of the NE Bay. These changes are most likely the result of hydrological alterations in South Florida.

Optical properties are easy-to-measure proxies for dissolved organic matter (DOM) composition, source and reactivity. However, the molecular signature of DOM associated with such optical parameters remains poorly defined. The Florida coastal Everglades is a subtropical wetland with diverse vegetation (e.g., sawgrass prairies, mangrove forests, seagrass meadows) and DOM sources (e.g., terrestrial, microbial and marine). As such, the Everglades is an excellent model system from which to draw samples of diverse origin and composition to allow classically-defined optical properties to be linked to molecular properties of the DOM pool. We characterized a suite of seasonally- and spatially-collected DOM samples using optical measurements (EEM-PARAFAC, SUVA254, S275-295, S350-400, SR, FI, freshness index and HIX) and ultrahigh resolution mass spectrometry (FTICR-MS). Spearman’s rank correlations between FTICR-MS signal intensities of individual molecular formulae and optical properties determined which molecular formulae were associated with each PARAFAC component and optical index. The molecular families that tracked with the optical indices were generally in agreement with conventional biogeochemical interpretations. Therefore, although they represent only a small portion of the bulk DOM pool, absorbance and fluorescence measurements appear to be appropriate proxies for the aquatic cycling of both optically-active and associated optically-inactive DOM in coastal wetlands.

Seven surface sediment samples covering the general geographical area of Florida Bay were examined through the measurement of 13C isotopic abundance and lipid classes to assess the distributions and sources of organic matter (OM) in this estuarine environment. The bulk δ13Corg value shifted from a more isotopically depleted (−19.9‰) to a more isotopically enriched (−13.5‰) signal along the NE to SW transect. Two geochemical proxies (Paq and C25/C27n-alkan–2-ones) indicative of seagrass-derived OM significantly increased from near-shore to offshore areas, while taraxerol, a biomarker for mangroves, substantially decreased from 7200 to 284 ng/g along that transect. A clear spatial variation of OM sources was observed in Florida Bay. Generally, the sites in the NE contained mixed OM sources of terrestrial (mangrove) and seagrass-derived OM, where the terrestrial component accounted for over 60% of the OM. In contrast, the sites in central and SW Florida Bay were strongly dominated by seagrass-derived OM. Other lipid fractions such as fatty acids, n-alcohols and sterols revealed an important contribution of algae and bacteria especially in the central and SW section of the Bay. Relatively abundant C25 HBIs suggest important marine diatom inputs, while the presence of C20 HBIs particularly in central Florida Bay possibly reflects the contribution of cyanobacterial mats. The molecular proxies developed in this study to assess OM sources in Florida Bay are promising tools for the characterization and seasonal variability assessment of OM in this and other similar subtropical and tropical estuaries and for paleoenvironmental studies.

We measured the abundance of Cladium jamaicense (Crantz) seeds and three biomarkers in freshwater marsh soils in Shark River Slough (SRS), Everglades National Park (ENP) to determine the degree to which these paleoecological proxies reflect spatial and temporal variation in vegetation. We found that C. jamaicense seeds and the biomarkers Paq, total lignin phenols (TLP) and kaurenes analyzed from surface soils were all significantly correlated with extant aboveground C. jamaicense biomass quantified along a vegetation gradient from a C. jamaicense to a wet prairie/slough (WPS) community. Our results also suggest that these individual proxies may reflect vegetation over different spatial scales: Paq and kaurenes correlated most strongly (R2 = 0.88 and 0.99, respectively) with vegetation within 1 m of a soil sample, while seeds and TLP reflected vegetation 0–20 m upstream of soil samples. These differences in the spatial scale depicted by the different proxies may be complementary in understanding aspects of historic landscape patterning. Soil profiles of short (25 cm) cores showed that downcore variation in C. jamaicense seeds was highly correlated with two of the three biomarkers (Paq, R2 = 0.84, p

This paper demonstrates the usefulness of fluorescence techniques for long-term monitoring and assessment of the dynamics (sources, transport and fate) of chromophoric dissolved organic matter (CDOM) in highly compartmentalized estuarine regions with non-point water sources. Water samples were collected monthly from a total of 73 sampling stations in the Florida Coastal Everglades (FCE) estuaries during 2001 and 2002. Spatial and seasonal variability of CDOM characteristics were investigated for geomorphologically distinct sub-regions within Florida Bay (FB), the Ten Thousand Islands (TTI), and Whitewater Bay (WWB). These variations were observed in both quantity and quality of CDOM. TOC concentrations in the FCE estuaries were generally higher during the wet season (June–October), reflecting high freshwater loadings from the Everglades in TTI, and a high primary productivity of marine biomass in FB. Fluorescence parameters suggested that the CDOM in FB is mainly of marine/microbial origin, while for TTI and WWB a terrestrial origin from Everglades marsh plants and mangroves was evident. Variations in CDOM quality seemed mainly controlled by tidal exchange/mixing of Everglades freshwater with Florida Shelf waters, tidally controlled releases of CDOM from fringe mangroves, primary productivity of marine vegetation in FB and diagenetic processes such as photodegradation (particularly for WWB). The source and dynamics of CDOM in these subtropical estuaries is complex and found to be influenced by many factors including hydrology, geomorphology, vegetation cover, landuse and biogeochemical processes. Simple, easy to measure, high sample throughput fluorescence parameters for surface waters can add valuable information on CDOM dynamics to long-term water quality studies which can not be obtained from quantitative determinations alone.

16 pages, 4 figures, 6 tables., Water samples were collected from rivers and estuarine environments within the Florida Coastal Everglades (FCE) ecosystem, USA, and ultrafiltered dissolved organic matter (UDOM; 1 kDa) was isolated for characterization of its source, bioavailability and diagenetic state. A combination of techniques, including 15N cross-polarization magic angle spinning nuclear magnetic resonance (15N CPMAS NMR) and X-ray photoelectron spectroscopy (XPS), were used to analyze the N components of UDOM. The concentrations and compositions of total hydrolysable amino acids (HAAs) were analyzed to estimate UDOM bioavailability and diagenetic state. Optical properties (UV–visible and fluorescence) and the stable isotope ratios of C and N were measured to assess the source and dynamics of UDOM. Spectroscopic analyses consistently showed that the major N species of UDOM are in amide form, but significant contributions of aromatic-N were also observed. XPS showed a very high pyridinic-N concentration in the FCE–UDOM (21.7 ± 2.7%) compared with those in other environments. The sources of this aromatic-N are unclear, but could include soot and charred materials from wild fires. Relatively high total HAA concentrations (4 ± 2% UDOC or 27 ± 4% UDON) are indicative of bioavailable components, and HAA compositions suggest FCE–UDOM has not undergone extensive diagenetic processing. These observations can be attributed to the low microbial activity and a continuous supply of fresh UDOM in this oligotrophic ecosystem. Marsh plants appear to be the dominant source of UDOM in freshwater regions of the FCE, whereas seagrasses and algae are the dominant sources of UDOM in Florida Bay. This study demonstrates the utility of a multi-technique and multi-proxy approach to advance our understanding of DON biogeochemistry., This study was funded by the National Oceanographic and Atmospheric Administration (COP R.J.) and the National Science Foundation as part of the FCE-LTER program (DEB-9910514).

The sources and transformations of sedimentary organic matter along the Harney River, a representative subtropical river of the Florida Everglades, were assessed using a natural product biomarker approach. Sediment samples were collected from the headwaters to the Continental Shelf, with characteristic vegetation dominated by freshwater marsh species, mangrove (middle to lower estuary), and seagrass as the marine end-member. A peat sample was collected inland. All sample extracts were analyzed by GC-MS as underivatized and as silylated compounds. With these total extract analyses, major compound classes can be defined: n-alkanols, n-alkanoic acids, methyl alkanoates, methyl alpha- and omega-hydroxyalkanoates, triterpenoids, phytosterols and saccharides, with traces of hydrocarbons. In general, the peat sample extract has a different overall composition compared to the sediment extracts. The major differences include distinct carbon number maxima for the lipid series (e.g., C(max)=28 for n-alkanols) probably from sawgrass and periphyton biomass, and predominance of phytosterols (sitosterol and stigmasterol) from higher plant detritus. In contrast, river sediment extracts contain biomarkers predominantly from mangrove-derived organic matter, such as the triterpenoids taraxerol and myricadiol. Significant amounts of saccharides and omega-hydroxyalkanoates are also found. Generally, compound concentrations decrease downstream due to dilution, and alteration of organic compounds from plant waxes and coastal vegetation is obvious in both peat and sediment samples. This is confirmed by the significant low abundance of n-alkanes and n-alkenoic acids due to biodegradation, oxidation of alpha-tocopherol to homophytanic acid gamma-lactone, and presence of traces of dihydrolacunosic acid, a photochemical alteration product of taraxerol.

Flocculent materials (floc), in aquatic systems usually consist of a non-consolidated layer of biogenic, detrital material relatively rich in organic matter which represents an important food-web component for invertebrates and fish. Thus, variations in its composition could impact food webs and change faunal structure. Transport, remineralization rates and deposition of floc may also be important factors in soil/sediment formation. In spite of its relevance and sensitivity to external factors, few chemical studies have been carried out on the biogeochemistry of floc material. In this study, we focused on the molecular characterization of the flocculent organic matter (OM), the assessment of its origin and its environmental fate at five stations along a freshwater to marine ecotone, namely the Taylor Slough, Everglades National Park (ENP), Florida. To tackle this issue, suspended, unconsolidated, detrital floc samples, soils/sediments and plants were analyzed for bulk properties, biomarkers and pigments. Both geochemical proxies and biomass-specific biomarkers were used to assess OM sources and transformations. Our results show that the detrital organic matter of the flocculent material is largely regulated by local vegetation inputs, ranging from periphyton, emergent and submerged plants and terrestrial plants such as mangroves, with molecular evidence of different degrees of diagenetic reworking, including fungal activity. Evidence is presented for both hydrodynamic transport of floc materials, and incorporation of floc OM into soils/sediments. However, some molecular parameters showed a decoupling between floc and underlying soil/sediment OM, suggesting that physical transport, incorporation and degradation/remineralization of OM in floc may be controlled by a combination of a variety of complex biogeochemical variables including hydrodynamic transport, hydroperiod characteristics, primary productivity, nutrient availability, and OM quality among others. Further investigations are needed to better understand the ecological role of floc in freshwater and coastal wetlands.

The assessment of organic matter (OM) sources in sediments and soils is a key to better understand the biogeochemical cycling of carbon in aquatic environments. While traditional molecular marker-based methods have provided such information for typical two end member (allochthonous/terrestrial vs. autochthonous/microbial)-dominated systems, more detailed, biomass-specific assessments are needed for ecosystems with complex OM inputs such as tropical and sub-tropical wetlands and estuaries where aquatic macrophytes and macroalgae may play an important role as OM sources. The aim of this study was to assess the utility of a combined approach using compound specific stable carbon isotope analysis and an n-alkane based proxy (Paq) to differentiate submerged and emergent/terrestrial vegetation OM inputs to soils/sediments from a sub-tropical wetland and estuarine system, the Florida Coastal Everglades. Results show that Paq values (0.13–0.51) for the emergent/terrestrial plants were generally lower than those for freshwater/marine submerged vegetation (0.45–1.00) and that compound specific δ13C values for the n-alkanes (C23 to C31) were distinctively different for terrestrial/emergent and freshwater/marine submerged plants. While crossplots of the Paq and n-alkane stable isotope values for the C23 n-alkane suggest that OM inputs are controlled by vegetation changes along the freshwater to marine transect, further resolution regarding OM input changes along this landscape was obtained through principal component analysis (PCA), successfully grouping the study sites according to the OM source strengths. The data show the potential for this n-alkane based multi-proxy approach as a means of assessing OM inputs to complex ecosystems.

Measurements of dissolved organic carbon (DOC), UV–visible, fixed wavelength fluorescence, and synchronous fluorescence were performed in an effort to characterize spatial and temporal variability in concentration and source of dissolved organic matter (DOM) in surface waters of the southwest coast of Florida. Concentrations of DOC in the surface water ranged from 318 to 2043 μM and decreased from the upper estuary to the coastal areas, and were not only influenced by source strength but also by the hydrology and geomorphology of the mangrove-dominated southwest Florida estuarine area of Everglades National Park. Mangroves provided a significant input of DOM to the estuarine region. This terrestrially derived DOM underwent conservative mixing in these estuaries, but at salinities ≥30 a clear switch from terrestrial to marine DOM was observed indicating a change in the nature and origin of the dominant DOM. The results show that the dynamics of DOM in these subtropical estuaries are complex and that geomorphologically compartmentalized estuarine subregions can be distinguished based on the optical characteristics of their DOM.

In this study, the molecular composition of dissolved organic matter (DOM), collected from wetlands of the Southern Everglades, was examined using a variety of analytical techniques in order to characterize its sources and transformation in the environment. The methods applied for the characterization of DOM included fluorescence spectroscopy, solid state 13C CPMAS NMR spectroscopy, and pyrolysis-GC/MS. The relative abundance of protein-like components and carbohydrates increased from the canal site to more remote freshwater marsh sites suggesting that significant amounts of non-humic DOM are autochthonously produced within the freshwater marshes, and are not exclusively introduced through canal inputs. Such in situ DOM production is important when considering how DOM from canals is processed and transported to downstream estuaries of Florida Bay.

Wetlands are ecosystems commonly characterized by elevated levels of dissolved organic carbon (DOC), and although they cover a surface area less than 2 % worldwide, they are an important carbon source representing an estimated 15 % of global annual DOC flux to the oceans. Because of their unique hydrological characteristics, fire can be an important ecological driver in pulsed wetland systems. Consequently, wetlands may be important sources not only of DOC but also of products derived from biomass burning, such as dissolved black carbon (DBC). However, the biogeochemistry of DBC in wetlands has not been studied in detail. The objective of this study is to determine the environmental dynamics of DBC in different fire-impacted wetlands. An intensive, 2-year spatial and temporal dynamics study of DBC in a coastal wetland, the Everglades (Florida) system, as well as one-time sampling surveys for the other two inland wetlands, Okavango Delta (Botswana) and the Pantanal (Brazil), were reported. Our data reveal that DBC dynamics are strongly coupled with the DOC dynamics regardless of location, season or recent fire history. The statistically significant linear regression between DOC and DBC was applied to estimate DBC fluxes to the coastal zone through two main riverine DOC export routes in the Everglades ecosystem. The presence of significant amounts of DBC in these three fire-impacted ecosystems suggests that sub-tropical wetlands could represent an important continental-ocean carrier of combustion products from biomass burning. The discrimination of DBC molecular structure (i.e. aromaticity) between coastal and terrestrial samples, and between samples collected in wet and dry season, suggests that spatially-significant variation in DBC source strength and/or degree of degradation may also influence DBC dynamics.