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

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

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 (<8 months), ridge type plants (Cladium). These δ13C and δD changes seem to be driven by vegetation shifts associated with hydrological change. The application of the compound-specific stable isotope determinations may strongly complement the biomarker approach for paleo-hydrological assessments in wetland ecosystems.

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.

Large world rivers are significant sources of dissolved organic matter (DOM) to the oceans. Watershed geomorphology and land use can drive the quality and reactivity of DOM. Determining the molecular composition of riverine DOM is essential for understanding its source, mobility and fate across landscapes. In this study, DOM from the main stem of 10 global rivers covering a wide climatic range and land use features was molecularly characterized via ultrahigh-resolution Fourier-transform ion cyclotron resonance mass spectrometry (FT-ICR-MS). FT-ICR mass spectral data revealed an overall similarity in molecular components among the rivers. However, when focusing specifically on the contribution of nonoxygen heteroatomic molecular formulas (CHON, CHOS, CHOP, etc.) to the bulk molecular signature, patterns relating DOM composition and watershed land use became apparent. Greater abundances of N- and S-containing molecular formulas were identified as unique to rivers influenced by anthropogenic inputs, whereas rivers with primarily forested watersheds had DOM signatures relatively depleted in heteroatomic content. A strong correlation between cropland cover and dissolved black nitrogen was established when focusing specifically on the pyrogenic class of compounds. This study demonstrated how changes in land use directly affect downstream DOM quality and could impact C and nutrient cycling on a global scale.

•DBC is unequally distributed among DOM size fractions.•DBC is preferentially associated with humic-rich HMW DOM size fractions.•Photodegradation selectively removes DBC from these fractions.•Size of aromatic ring structure drives DBC–DOM association along the MW continuum.•Suggests varying fates of DBC among different DOM molecular size fractions.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.

•Molecular characterization of dissolved black nitrogen (DBN) from FT-ICRMS.•DBN molecular formulae were validated via isotopic comparison.•Possible DBN chemical structures were proposed from fragmentation pathways.•N appears to be incorporated into condensed aromatic ring structures of pyrogenic compounds.•DBN compounds are polysubstituted primarily with carboxylic acid groups.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.

•n-Alkyl coumarates and ferulates were identified in cattails.•Differences in composition between leaf, root and detritus are reported.•Mass spectra for the identified compounds are provided.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.

•Three end member mixing model, including terrestrial, estuarine and marine end-member contributions was developed.•Model was validated to assess POC sources in an estuary.•Incoming tide is an important factor in re-suspension and tidal pumping of mangrove-derived POC.•Mangrove-derived POC flux from Shark River to the Gulf of Mexico estimated as ca. 5.3 × 105 to 1.0 × 106 kg/yr POC.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.

•Dissolved black nitrogen (DBN) is ubiquitous in the aquatic environment.•Dynamics of DBN and dissolved organic carbon are coupled.•Dissolved heteroaromatic N (DBN) is likely derived from char remains in soils.Biomass burning results in the formation and accumulation of pyrogenic products such as black carbon (BC) and black nitrogen (BN) in soils. The ubiquitous presence of pyrogenic products in natural dissolved organic matter (DOM) and potential implications in global carbon cycling have recently been reported. However, little is known about the environmental dynamics or the importance in the global N cycle of dissolved BN (DBN; or heteroaromatic N). Here we report the coupling between DBN and dissolved BC (DBC) in ultrafiltered DOM from six headwater streams across a climatic region of North America, suggesting similar combustion sources, and that DOC may play an important role in the translocation of soil BN to the dissolved phase. The export of potentially recalcitrant riverine DBN to the ocean may affect the biogeochemical cycling of N and possibly the microbial community structure in aquatic environments.

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.

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.

Dissolved organic matter (DOM) is recognized as a major component in the global carbon cycle and is an important driver in aquatic ecosystem function. Climate, land use, and forest cover changes all impact stream DOM and alter biogeochemical cycles in terrestrial environments. We determined the temporal variation in DOM quantity and quality in headwater streams at a reference watershed (REF), a watershed clear-cut 30 years ago (CC), and a watershed converted to a white pine plantation 50 years ago (WP) at the US Forest Service, Coweeta Hydrologic Laboratory, in the Nantahala Mountains of western North Carolina, USA. Average stream dissolved organic carbon (DOC) concentrations in CC or WP were 60 and 80% of those in REF, respectively. Stream DOM composition showed that the difference was mainly due to changes in humic-like components in chromophoric DOM. In addition, excitation–emission matrix fluorescence data with parallel factor analysis indicate that although the concentration of protein-like components did not differ significantly among watersheds, their relative abundance showed an enrichment in CC and WP compared to REF. The ratio of humic acid-type to fulvic acid-type components was highest and lowest at REF and WP, respectively. Our data suggest that forest ecosystem disturbance history affects the DOM quantity and quality in headwater streams over decades as a result of changes in watershed soil organic matter characteristics due to differences in organic matter inputs.

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.

Natural dissolved organic matter (DOM) is composed of a variety of organic compounds, which can interact with metals in aquatic environments. The interactions between DOM and two metals of environmental concern (Cu(II) and Hg(II)) were studied using fluorescence quenching titrations combined with excitation−emission matrix (EEM) spectra and parallel factor analysis (PARAFAC). This allowed characterizing the specific interactions between eight fluorescent components in DOM and two metals. Triplicate titration experiments showed good reproducibility when assessing the interactions between humic-like components with Cu(II). Our data show clear differences in metal−DOM interaction for samples of different DOM composition and between two different metals. The results demonstrate that the combination of fluorescence quenching titrations with EEM−PARAFAC was reproducible and sensitive to determine the binding properties of humic-like components with trace metals. The enhancement in fluorescence intensity after its initial decrease for the protein-like components with addition of Cu(II) was observed at mangrove-dominated sites, suggesting changes in the molecular environments of protein-like components due to increased Cu(II) interaction. The application of EEM−PARAFAC in fluorescence quenching studies is a useful tool to evaluate intermolecular DOM and DOM–trace metals interactions.

Long-chain mid-chain diols and keto-ols have been reported mainly in marine environments but only rarely in lacustrine sediments. In this work, exceptionally high abundances and diversity of keto-ols, diols and structurally related long-chain n-alkenols and secondary alkanols were detected in sediments from a hypereutrophic, freshwater lake (Lake Valencia, Venezuela). The maximum concentrations are 241 μg/g TOC for n-alkenols, 75 μg/g TOC for diols, 367 μg/g TOC for keto-ols, and 8.7 μg/g TOC for secondary alkanols. Eleven keto-ol isomers were identified, which is the highest diversity yet reported for sediments. The presence of five keto-ol isomers, namely 1,12-C30 keto-ol, 1,14-C31 keto-ol, 1,15-C33 keto-ol, 1,16-C33 keto-ol and 1,18-C35 keto-ol is reported for the first time. The mass spectra for osmium tetroxide derivatives from long chain n-alkenols confirmed the double bond location at carbons 13, 14 or 15. The carbon isotope compositions were substantially enriched in 13C for n-alkenols, diols and keto-ols (δ13C = −22.0 ± 2.2‰) relative to the corresponding long-chain n-alkanols (−29.6 ± 0.8‰), suggesting an autochthonous aquatic microbial origin rather than from a terrestrial (i.e., fern) source. Although a strong predominance of cyanobacteria was reported for in the lake’s plankton community (>90%) and relatively low abundance of sedimentary sterols suggests cyanobacteria as a potential source, eustigmatophytes, a major reported producer of diols and keto-ols, cannot be excluded because eustigmatophytes are easily confused with other microalgae and may have been overlooked in previous studies. n-Alkenols and keto-ols displayed similar historical patterns over the past 10,000+ years, but there were distinct differences from the diol patterns. This result suggested that n-alkenols and keto-ols may be derived from the same sources, while diols either undergo different environmental diagenesis or have different sources. A keto-ol index coincides well with the hydrological changes of Lake Valencia over the last 10,000+ years, and corroborates its validity as a paleo-indicator.

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 C23n-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.

Two sub-tropical estuaries of south Florida, USA, were studied to determine the origin and transport of organic matter between the freshwater and marine end-members of these systems. Sediments, as well as main biomass components (vegetation) were analyzed for lipid composition and content. The molecular distribution of several biomarker compounds, organism-specific biomarkers and bulk sediment characteristics such as %OM, C/N and δ13C were used to assess differences in OM source and transport between a strongly tidally-influenced estuary (Harney River) and one that is only seasonally influenced by estuarine waters (Taylor River). The data show mixing of combined terrestrial and autochthonous freshwater-derived OM, with marine planktonic and seagrass-derived OM in the middle to lower estuary of the Harney River. In contrast, such mixing did not occur to a measurable degree at the Taylor River, where low water discharge and exchange does not allow for any significant mixing of OM from end-member sources. Differences in hydrological conditions and benthic plant biomass and productivity between the two systems results in different OM inputs, which are reflected in the quality and degree of diagenesis of the sedimentary OM. Specific applications and potential limitations of traditional biomarker compounds for OM source assessment are discussed.

Dissolved organic matter (DOM) in groundwater and surface water samples from the Florida coastal Everglades were studied using excitation–emission matrix fluorescence modeled through parallel factor analysis (EEM-PARAFAC). DOM in both surface and groundwater from the eastern Everglades S332 basin reflected a terrestrial-derived fingerprint through dominantly higher abundances of humic-like PARAFAC components. In contrast, surface water DOM from northeastern Florida Bay featured a microbial-derived DOM signature based on the higher abundance of microbial humic-like and protein-like components consistent with its marine source. Surprisingly, groundwater DOM from northeastern Florida Bay reflected a terrestrial-derived source except for samples from central Florida Bay well, which mirrored a combination of terrestrial and marine end-member origin. Furthermore, surface water and groundwater displayed effects of different degradation pathways such as photodegradation and biodegradation as exemplified by two PARAFAC components seemingly indicative of such degradation processes. Finally, Principal Component Analysis of the EEM-PARAFAC data was able to distinguish and classify most of the samples according to DOM origins and degradation processes experienced, except for a small overlap of S332 surface water and groundwater, implying rather active surface-to-ground water interaction in some sites particularly during the rainy season. This study highlights that EEM-PARAFAC could be used successfully to trace and differentiate DOM from diverse sources across both horizontal and vertical flow profiles, and as such could be a convenient and useful tool for the better understanding of hydrological interactions and carbon biogeochemical cycling.

The reactivity of higher plant derived 3-oxy-triterpenoids to sunlight was investigated using a series of pure reference standards both under simulated and real solar exposure. The majority of the exposed compounds showed reactivity to light, particularly to simulated sunlight and among others generated seco-derivatives. While photochemical processes have been suggested for the formation of such compounds, their abundances in some sediments have often been assumed to be the result of diagenetic reworking of parent triterpenoids. Analyses of mangrove leaf waxes, an important known source of taraxerol in coastal ecosystems, showed the presence of the 3,4-seco-derivative dihydrolacunosic acid, which could represent an important biotic source for des-A-triterpenoid precursors to such sediments, and is unrelated to aquatic organic matter diagenesis.

Temporal and spatial variations in the composition of particulate organic matter (POM) from Florida Bay, USA were examined. The predominance of short-chain homologues for n-alkanes, n-alcohols and n-fatty acids as well as relatively high abundance of C27 and C28 sterols suggested that an autochthonous/marine source of OM was dominant bay-wide. Several biomarker proxies such as Paq [(C23 + C25)/(C23 + C25 + C29 + C31) n-alkanes], short/long chain n-alkanes, (C29 + C31) n-alkanes and taraxerol indicated a spatial shift in OM sources, where terrestrial OM rapidly decreased while seagrass and microbial OM markedly increased along a northeastern to southwestern transect. Regarding seasonal variations, POM collected during the dry season was enriched in terrestrial constituents relative to the wet season, likely as a result of reduced primary productivity of planktonic species and seagrasses during the dry season. Principal component analysis (PCA) classified the sample set into sub-groups based on PC1 which seemed to be spatially controlled by OM origin (terrestrial-mangrove vs. marine-planktonic/seagrass). The PC2 seemed to be more seasonally controlled suggesting that hydrological fluctuations and seasonal primary productivity are the drivers controlling the POM composition in Florida Bay.

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.Highlights► Estuarine DOM composition was found to vary on spatial and temporal scales. ► Hydrological transport and primary productivity control DOM composition. ► Hurricane disturbance did affect DOM composition locally but not on a bay-wide scale.

•Organic matter dynamics in fjords were studied using fluorescence and stable isotopes.•Distinct changes in DOM character with depth were observed.•Terrestrial DOM source in deep fjord waters suggested as POM desorption derived.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.