Associations Between the Molecular and Optical Properties of Dissolved Organic Matter in the Florida Everglades, a Model Coastal Wetland System

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\u27s 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

Dissolved Organic Matter Dynamics in the Oligo/Meso-Haline Zone of Wetland-Influenced Coastal Rivers

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 \u3c 10) tidal zone of upper estuaries has been suggested to be more complex and locally influenced by geomorphological and hydrological features, the environmental dynamics of dissolved organic matter (DOM) and the environmental drivers controlling its source, transport, and fate have scarcely been evaluated. Here, we investigated the distribution patterns of DOC and CDOM optical properties determined by UV absorbance at 254 nm (A254) and excitation–emission matrix (EEM) fluorescence coupled with parallel factor analysis (PARAFAC) along the lower salinity range (salinity \u3c 10) of the oligo/meso-haline zone for three distinct wetland-influenced rivers; namely the Bekanbeushi River, a cool-temperate river with estuarine lake in Hokkaido, Japan, the Harney River, a subtropical river with tidally-submerged mangrove fringe in Florida, USA, and the Judan River, a small, acidic, tropical rainforest river in Borneo, Malaysia. For the first two rivers, a clear decoupling between DOC and A254 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

Comparison of Microbial Communities in the Sediments and Water Columns of Frozen Cryoconite Holes in the McMurdo Dry Valleys, Antarctica

Although cryoconite holes, sediment-filled melt holes on glacier surfaces, appear small and homogenous, their microbial inhabitants may be spatially partitioned. This partitioning could be particularly important for maintaining biodiversity in holes that remain isolated for many years, such as in Antarctica. We hypothesized that cryoconite holes with greater species richness and biomass should exhibit greater partitioning between the sediments and water, promoting greater biodiversity through spatial niche partitioning. We tested this hypothesis by sampling frozen cryoconite holes along a gradient of biomass and biodiversity in the Taylor Valley, Antarctica, where ice-lidded cryoconite holes are a ubiquitous feature of glaciers. We extracted DNA and chlorophyll a from the sediments and water of these samples to describe biodiversity and quantify proxies for biomass. Contrary to our expectation, we found that cryoconite holes with greater richness and biomass showed less partitioning of phylotypes by the sediments versus the water, perhaps indicating that the probability of sediment microbes being mixed into the water is higher from richer sediments. Another explanation may be that organisms from the water were compressed by freezing down to the sediment layer, leaving primarily relic DNA of dead cells to be detected higher in the frozen water. Further evidence of this explanation is that the dominant sequences unique to water closely matched organisms that do not live in cryoconite holes or the Dry Valleys (e.g., vertebrates); so this cryptic biodiversity could represent unknown microbial animals or DNA from atmospheric deposition of dead biomass in the otherwise low-biomass water. Although we cannot rule out spatial niche partitioning occurring at finer scales or in melted cryoconite holes, we found no evidence of partitioning between the sediments and water in frozen holes. Future work should include more sampling of cryoconite holes at a finer spatial scale, and characterizing the communities of the sediments and water when cryoconite holes are melted and active

Spatial and temporal variability in summertime dissolved carbon dioxide and methane in temperate ponds and shallow lakes

Small waterbodies have potentially high greenhouse gas emissions relative to their small footprint on the landscape, although there is high uncertainty in model estimates. Scaling their carbon dioxide (CO2) and methane (CH4) exchange with the atmosphere remains challenging due to an incomplete understanding and characterization of spatial and temporal variability in CO2 and CH4. Here, we measured partial pressures of CO2 (pCO2) and CH4 (pCH4) across 30 ponds and shallow lakes during summer in temperate regions of Europe and North America. We sampled each waterbody in three locations at three times during the growing season, and tested which physical, chemical, and biological characteristics related to the means and variability of pCO2 and pCH4 in space and time. Summer means of pCO2 and pCH4 were inversely related to waterbody size and positively related to floating vegetative cover; pCO2 was also positively related to dissolved phosphorus. Temporal variability in partial pressure in both gases weas greater than spatial variability. Although sampling on a single date was likely to misestimate mean seasonal pCO2 by up to 26%, mean seasonal pCH4 could be misestimated by up to 64.5%. Shallower systems displayed the most temporal variability in pCH4 and waterbodies with more vegetation cover had lower temporal variability. Inland waters remain one of the most uncertain components of the global carbon budget; understanding spatial and temporal variability will ultimately help us to constrain our estimates and inform research priorities

The National Ecological Observatory Network: Creating stage-discharge rating curves by combining physical channel inputs with probabilistic modeling techniques

International audienceA detailed characterization of channel geometry is a critical component in developing stage-discharge rating curves that can enhance the forecasting of hydrologic events. The National Ecological Observatory Network (NEON) collects physical streamflow gauging measurements and high-resolution channel geometry data at 27 stream and river monitoring sites across the United States over a 30-year period, beginning in 2018. NEON creates stage-discharge rating curves using a Bayesian modeling (BaM) technique developed by the Bayesian Rating Curve Advanced Graphical Environment (BaRatinAGE) development team (Le Coz et al., 2013; Le Coz et al., 2014). Each rating curve relies on a "prior" model that is developed based on hydraulic channel controls that govern the stage-discharge relationship in a given aquatic reach. Section and channel controls are characterized by analyzing long-profile and cross-sectional survey data derived from high-resolution total station surveys. The physical dimensions of the channel, the number of hydraulic controls selected, and the physical dimensions of the hydraulic controls are all derived from these survey data. NEON then calculates exponential equations for each channel control which include associated uncertainty values. A "posterior" rating curve is then fit using the "prior" model and the gauging records using Bayesian estimation of the rating curve and a Markov Chain Monte Carlo (MCMC) sampling (Le Coz, 2014). These methods provide 500 realizations from the posterior distribution, which are used to quantify uncertainty in continuous discharge values (Le Coz et al., 2014). By combining prior knowledge of channel controls (with associated uncertainties) with uncertainties contained in individual streamflow gauging measurements, rigorous stage-discharge rating curves can be developed and maintained that result in accurate streamflow forecasting. Over the next 30 years, NEON aims to serve these data to the research community in order to better understand the degree in which aquatic ecosystems are changing at the continental scale

Evaluation of Forest Disturbance Legacy Effects on Dissolved Organic Matter Characteristics in Streams at the Hubbard Brook Experimental Forest, New Hampshire

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

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

Environmental Dynamics of Dissolved Black Carbon in Wetlands

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