Chemical characteristics of dissolved organic matter in an oligotrophic subtropical wetland/estuarine ecosystem

Fluorescence properties of whole water samples and molecular characteristics of ultrafiltrated dissolved organic matter (UDOM > 1,000 D) such as lignin phenol and neutral sugar compositions and 13C nuclear magnetic resonance (NMR) spectra were determined along a freshwater to marine gradient in Everglades National Park. Furthermore, UDOM samples were categorized by hierarchical cluster analysis based on their pyrolysis gas chromatography/mass spectrometry products. Fluorescence properties suggest that autochthonous DOM leached/exuded from biomass is quantitatively important in this system. 13C NMR spectra showed that UDOM from the oligotrophic Taylor Slough (TS) and Florida Bay (FB) ecosystems has low aromatic C (13% ± 3% for TS; 2% ± 2% for FB) and very high O-alkyl C (54% ± 4% for TS; 75% ± 4% for FB) concentrations. High O-alkyl C concentrations in FB suggest seagrass/phytoplankton communities as dominant sources of UDOM. The amount of neutral sugars was not appreciably different between the TS and FB sites (115 ± 12 mg C g C-1 UDOM) but their concentrations suggest a low level of diagenesis and high production rates of this material in this oligotrophic environment. Total yield of lignin phenols (vanillyl + syringyl phenols) in TS was low (0.20–0.39 mg 100 mg C-1 UDOM) compared with other riverine environments and even lower in FB (0.04–0.07 mg 100 mg C-1 UDOM) and could be a result of photodegradation and/or dilution by other utochthonous DOM. The high O-alkyl and low aromatic nature of this UDOM suggests significant biogenic inputs (as compared with soils) and limited bioavailability in this ecosystem.

Effects of Land Use on Sources and Ages of Inorganic and Organic Carbon in Temperate Headwater Streams

The amounts, sources and relative ages of inorganic and organic carbon pools were assessed in eight headwater streams draining watersheds dominated by either forest, pasture, cropland or urban development in the lower Chesapeake Bay region (Virginia, USA). Streams were sampled at baseflow conditions six different times over 1 year. The sources and ages of the carbon pools were characterized by isotopic (δ13C and ∆14C) analyses and excitation emission matrix fluorescence with parallel factor analysis (EEM–PARAFAC). The findings from this study showed that human land use may alter aquatic carbon cycling in three primary ways. First, human land use affects the sources and ages of DIC by controlling different rates of weathering and erosion. Relative to dissolved inorganic carbon (DIC) in forested streams which originated primarily from respiration of young, 14C-enriched organic matter (OM; δ13C = −22.2 ± 3 ‰; ∆14C = 69 ± 14 ‰), DIC in urbanized streams was influenced more by sedimentary carbonate weathering (δ13C = −12.4 ± 1 ‰; ∆14C = −270 ± 37 ‰) and one of pasture streams showed a greater influence from young soil carbonates (δ13C = −5.7 ± 2.5 ‰; ∆14C = 69 ‰). Second, human land use alters the proportions of terrestrial versus autochthonous/microbial sources of stream water OM. Fluorescence properties of dissolved OM (DOM) and the C:N of particulate OM (POM) suggested that streams draining human-altered watersheds contained greater relative contributions of DOM and POM from autochthonous/microbial sources than forested streams. Third, human land uses can mobilize geologically aged inorganic carbon and enable its participation in contemporary carbon cycling. Aged DOM (∆14C = −248 to −202 ‰, equivalent14C ages of 1,811–2,284 years BP) and POM (∆14C = −90 to −88 ‰, 14C ages of 669–887 years BP) were observed exclusively in urbanized streams, presumably a result of autotrophic fixation of aged DIC (−297 to −244 ‰, 14C age = 2,251–2,833 years BP) from sedimentary shell dissolution and perhaps also watershed export of fossil fuel carbon. This study demonstrates that human land use may have significant impacts on the amounts, sources, ages and cycling of carbon in headwater streams and their associated watersheds.

Photochemical and Microbial Alteration of Dissolved Organic Matter in Temperate Headwater Streams Associated with Different Land Use

[1] Photochemical and microbial transformations of DOM were evaluated in headwater streams draining forested and human-modified lands (pasture, cropland, and urban development) by laboratory incubations. Changes in DOC concentrations, DOC isotopic signatures, and DOM fluorescence properties were measured to assess the amounts, sources, ages, and properties of reactive and refractory DOM under the influence of photochemistry and/or bacteria. DOC in streams draining forest-dominated watersheds was more photoreactive than in streams draining mostly human-modified watersheds, possibly due to greater contributions of terrestrial plant-derived DOC and lower amounts of prior light exposure in forested streams. Overall, the percentage of photoreactive DOC in stream waters was best predicted by the relative content of terrestrial fluorophores. The bioreactivity of DOC was similar in forested and human-modified streams, but variations were correlated with temperature and may be further controlled by the diagenetic status of organic matter. Alterations to DOC isotopes and DOM fluorescence properties during photochemical and microbial incubations were similar between forested and human-modified streams and included (1) negligible effects of microbial alteration on DOC isotopes and DOM fluorescence properties, (2) selective removal of 13C-depleted and 14C-enriched DOC under the combined influence of photochemical and microbial processes, and (3) photochemical alteration of DOM resulting in a preferential loss of terrestrial humic fluorescence components relative to microbial fluorescence components. This study provides a unique comparison of DOC reactivity in a regional group of streams draining forested and human-modified watersheds and indicates the importance of land use on the photoreactivity of DOC exported from upstream watersheds.

Application of excitation emission matrix fluorescence monitoring in the assessment of spatial and seasonal drivers of dissolved organic matter composition: Sources and physical disturbance controls

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.

Using Optical Properties to Quantify Fringe Mangrove Inputs to the Dissolved Organic Matter (DOM) Pool in a Subtropical Estuary

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.

Fluorescence Characteristics of Size-Fractionated Dissolved Organic Matter: Implications for a Molecular Assembly Based Structure?

Surface freshwater samples from Everglades National Park, Florida, were used to investigate the size distributions of natural dissolved organic matter (DOM) and associated fluorescence characteristics along the molecular weight continuum. Samples were fractionated using size exclusion chromatography (SEC) and characterized by spectroscopic means, in particular Excitation-Emission Matrix fluorescence modeled with parallel factor analysis (EEM-PARAFAC). Most of the eight components obtained from PARAFAC modeling were broadly distributed across the DOM molecular weight range, and the optical properties of the eight size fractions for all samples studied were quite consistent among each other. Humic-like components presented a similar distribution in all the samples, with enrichment in the middle molecular weight range. Some variability in the relative distribution of the different humic-like components was observed among the different size fractions and among samples. The protein like fluorescence, although also generally present in all fractions, was more variable but generally enriched in the highest and lowest molecular weight fractions. These observations are in agreement with the hypothesis of a supramolecular structure for DOM, and suggest that DOM fluorescence characteristics may be controlled by molecular assemblies with similar optical properties, distributed along the molecular weight continuum. This study highlights the importance of studying the molecular structure of DOM on a molecular size distribution perspective, which may have important implications in understanding the environmental dynamics such materials.

Evaluating the Distribution of Terrestrial Dissolved Organic Matter in a Complex Coastal Ecosystem Using Fluorescence Spectroscopy

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.