Local biomass control on the composition and reactivity of particulate organic matter in aquatic environments

Freshwater ecosystems have been recognized as important components of the global carbon cycle, and the flux of organic matter (OM) from freshwater to marine environments can significantly affect estuarine and coastal productivity. The focus of this study was the assessment of carbon dynamics in two aquatic environments, namely the Florida Everglades and small prairie streams in Kansas, with the aim of characterizing the biogeochemistry of OM. In the Everglades, particulate OM (POM) is mostly found as a layer of flocculent material (floc). While floc is believed to be the main energy source driving trophic dynamics in this oligotrophic wetland, not much is known about its biogeochemistry. The objective of this study was to determine the origin/sources of OM in floc using biomarkers and pigment-based chemotaxonomy to assess specific biomass contributions to this material, on a spatial (freshwater marshes vs. mangrove fringe) and seasonal (wet vs. dry) scales. It was found that floc OM is derived from the local vegetation (mainly algal components and macrophyte litter) and its composition is controlled by seasonal drivers of hydrology and local biomass productivity. Photo-reactivity experiments showed that light exposure on floc resulted in photo-dissolution of POC with the generation of significant amounts of both dissolved OM (DOM) and nutrients (N & P), potentially influencing nutrient dynamics in this ecosystem. The bio-reactivity experiments determined as the amount and rate of CO2 evolution during incubation were found to vary on seasonal and spatial scales and were highly influenced by phosphorus limitation. Not much is known on OM dynamics in small headwater streams. The objective of this study was to determine carbon dynamics in sediments from intermittent prairie streams, characterized by different vegetation cover for their watershed (C4 grasses) vs. riparian zone (C3 plants). In this study sedimentary OM was characterized using a biomarker and compound specific carbon stable isotope approach. It was found that the biomarker composition of these sediments is dominated by higher plant inputs from the riparian zone, although inputs from adjacent prairie grasses were also apparent. Conflicting to some extent with the River Continuum Concept, sediments of the upper reaches contained more degraded OM, while the lower reaches were enriched in fresh material deriving from higher plants and plankton sources as a result of hydrological regimes and particle sorting.

Surprises and Insights from Long-Term Aquatic Data Sets and Experiments

long-term research on freshwater ecosystems provides insights that can be difficult to obtain from other approaches. Widespread monitoring of ecologically relevant water-quality parameters spanning decades can facilitate important tests of ecological principles. Unique long-term data sets and analytical tools are increasingly available, allowing for powerful and synthetic analyses across sites. long-term measurements or experiments in aquatic systems can catch rare events, changes in highly variable systems, time-lagged responses, cumulative effects of stressors, and biotic responses that encompass multiple generations. Data are available from formal networks, local to international agencies, private organizations, various institutions, and paleontological and historic records; brief literature surveys suggest much existing data are not synthesized. Ecological sciences will benefit from careful maintenance and analyses of existing long-term programs, and subsequent insights can aid in the design of effective future long-term experimental and observational efforts. long-term research on freshwaters is particularly important because of their value to humanity.

Assessing the net effect of anthropogenic disturbance on aquatic communities in wetlands: community structure relative to distance from canals

Anthropogenic alterations of natural hydrology are common in wetlands and often increase water permanence, converting ephemeral habitats into permanent ones. Since aquatic organisms segregate strongly along hydroperiod gradients, added water permanence caused by canals can dramatically change the structure of aquatic communities. We examined the impact of canals on the abundance and structure of wetland communities in South Florida, USA. We sampled fishes and macroinvertebrates from marsh transects originating at canals in the central and southern Everglades. Density of all aquatic organisms sampled increased in the immediate proximity of canals, but was accompanied by few compositional changes based on analysis of relative abundance. Large fish (>8 cm), small fish (<8 >cm) and macroinvertebrates (>5 mm) increased in density within 5 m of canals. This pattern was most pronounced in the dry season, suggesting that canals may serve as dry-down refugia. Increases in aquatic animal density closely matched gradients of phosphorus enrichment that decreased with distance from canals. Thus, the most apparent impact of canals on adjacent marsh communities was as conduits for nutrients that stimulated local productivity; any impact of their role as sources of increased sources of predators was not apparent. The effect of predation close to canals was overcompensated by increased secondary productivity and/or immigration toward areas adjacent to canals in the dry season. Alternatively, the consumptive effect of predatory fishes using canals as dry-season refuges is very small or spread over the expanse of marshes with open access to canals.

Submerged aquatic vegetation and bulrush in Lake Okeechobee as indicators of greater Everglades ecosystem restoration

Lake Okeechobee, Florida, located in the middle of the larger Kissimmee River-Lake Okeechobee-Everglades ecosystem in South Florida, serves a variety of ecosystem and water management functions including fish and wildlife habitat, flood control, water supply, and source water for environmental restoration. As a result, the ecological status of Lake Okeechobee plays a significant role in defining the overall success of the greater Everglades ecosystem restoration initiative. One of the major ecological indicators of Lake Okeechobee condition focuses on the near-shore and littoral zone regions as characterized by the distribution and abundance of submerged aquatic vegetation (SAV) and giant bulrush (Scirpus californicus(C.A. Mey.) Steud.). The objective of this study is to present a stoplight restoration report card communication system, common to all 11 indicators noted in this special journal issue, as a means to convey the status of SAV and bulrush in Lake Okeechobee. The report card could be used by managers, policy makers, scientists and the public to effectively evaluate and distill information about the ecological status in South Florida. Our assessment of the areal distribution of SAV in Lake Okeechobee is based on a combination of empirical SAV monitoring and output from a SAV habitat suitability model. Bulrush status in the lake is related to a suitability index linked to adult survival and seedling establishment metrics. Overall, presentation of these performance metrics in a stoplight format enables an evaluation of how the status of two major components of Lake Okeechobee relates to the South Florida restoration program, and how the status of the lake influences restoration efforts in South Florida.

An assessment of the microbial contribution to aquatic dissolved organic nitrogen using amino acid enantiomeric ratios

There is increasing evidence that certain microbially-derived compounds may account for part of the aquatic dissolved organic nitrogen (DON) pool. Enantiomeric ratios of amino acids were used to assess the microbial input to the DON pool in the Florida Everglades, USA. Elevated levels of d-alanine, d-aspartic acid, d-glutamic acid and d-serine indicated the presence of peptidoglycan in the samples. The estimated peptidoglycan contribution to amino acid nitrogen ranged from 2.8 ± 0.1% to 6.4 ± 0.9%, increasing with salinity from freshwater to coastal waters. The distribution of individual d-amino acids in the samples suggests additional inputs to DON, possibly from archaea or from abiotic racemization of l-amino acids.

One-dimensional and two-dimensional polyacrylamide gel electrophoresis: a tool for protein characterisation in aquatic samples

Dissolved organic nitrogen (DON) represents the least understood part of the nitrogen cycle. Due to recent methodological developments, proteins now represent a potentially characterisable fraction of DON at the macromolecular level. We have applied polyacrylamide gel electrophoresis to characterise proteins in samples from a range of aquatic environments in the Everglades National Park, Florida, USA. Sodium dodecyl sulphate polyacrylamide gel electrophoresis (SDS-PAGE) showed that each sample has a complex and characteristic protein distribution. Some proteins appeared to be common to more than one site, and these might derive from dominant higher plant vegetation. Two-dimensional polyacrylamide gel electrophoresis (2D-PAGE) provided better resolution; however, strong background hindered interpretation. Our results suggest that the two techniques can be used in parallel as a tool for protein characterisation: SDS-PAGE to provide a sample-specific fingerprint and 2D-PAGE to focus on the characterisation of individual protein molecules.

Hydrological Conditions Control P Loading and Aquatic Metabolism in an Oligotrophic, Subtropical Estuary

Using high-resolution measures of aquatic ecosystem metabolism and water quality, we investigated the importance of hydrological inputs of phosphorus (P) on ecosystem dynamics in the oligotrophic, P-limited coastal Everglades. Due to low nutrient status and relatively large inputs of terrestrial organic matter, we hypothesized that the ponds in this region would be strongly net heterotrophic and that pond gross primary production (GPP) and respiration (R) would be the greatest during the “dry,” euhaline estuarine season that coincides with increased P availability. Results indicated that metabolism rates were consistently associated with elevated upstream total phosphorus and salinity concentrations. Pulses in aquatic metabolism rates were coupled to the timing of P supply from groundwater upwelling as well as a potential suite of hydrobiogeochemical interactions. We provide evidence that freshwater discharge has observable impacts on aquatic ecosystem function in the oligotrophic estuaries of the Florida Everglades by controlling the availability of P to the ecosystem. Future water management decisions in South Florida must include the impact of changes in water delivery on downstream estuaries.

Mangrove tannins in aquatic ecosystems: Their fate and possible influence on dissolved organic carbon and nitrogen cycling

We describe the fate of mangrove leaf tannins in aquatic ecosystems and their possible influence on dissolved organic nitrogen (DON) cycling. Tannins were extracted and purified from senescent yellow leaves of the red mangrove (Rhizophora mangle) and used for a series of model experiments to investigate their physical and chemical reactivity in natural environments. Physical processes investigated included aggregation, adsorption to organic matter-rich sediments, and co-aggregation with DON in natural waters. Chemical reactions included structural change, which was determined by excitation–emission matrix fluorescence spectra, and the release of proteins from tannin–protein complexes under solar-simulated light exposure. A large portion of tannins can be physically eliminated from aquatic environments by precipitation in saline water and also by binding to sediments. A portion of DON in natural water can coprecipitate with tannins, indicating that mangrove swamps can influence DON cycling in estuarine environments. The chemical reactivity of tannins in natural waters was also very high, with a half-life of less than 1 d. Proteins were released gradually from tannin–protein complexes incubated under light conditions but not under dark conditions, indicating a potentially buffering role of tannin– protein complexes on DON recycling in mangrove estuaries. Although tannins are not detected at a significant level in natural waters, they play an important ecological role by preserving nitrogen and buffering its cycling in estuarine ecosystems through the prevention of rapid DON export/loss from mangrove fringe areas and/or from rapid microbial mineralization.

Temporal Population Genetic Structure of Eastern Mosquitofish in a Dynamic Aquatic Landscape

We analyzed the effect of periodic drying in the Florida Everglades on spatiotemporal population genetic structure of eastern mosquitofish (Gambusia holbrooki). Severe periodic drying events force individuals from disparate sources to mix in dry season relatively deep-water refuges. In 1996 (a wet year) and 1999 (a dry year), we sampled mosquitofish at 20 dry-season refuges distributed in 3 water management regions and characterized genetic variation for 10 allozyme and 3 microsatellite loci. In 1996, most of the ecosystem did not dry, whereas in 1999, many of our sampling locations were isolated by expanses of dried marsh surface. In 1996, most spatial genetic variation was attributed to heterogeneity within regions. In 1999, spatial genetic variation within regions was not significant. In both years, a small but significant amount of variation (less than 1% of the total variation) was partitioned among regions. Variance was consistently greater than zero among long-hydroperiod sites within a region, but not among short-hydroperiod sites within a region, where hydroperiod was measured as time since last marsh surface dry-down forcing fishes into local refuges. In 1996, all sites were in Hardy–Weinberg equilibrium. In 1999, we observed fewer heterozygotes than expected for most loci and sites suggesting a Wahlund effect arising from fish leaving areas that dried and mixing in deep-water refuges.

Organic Biogeochemistry of Detrital Flocculent Material (Floc) in a Subtropical, Coastal Wetland

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.

Photo-dissolution of flocculent, detrital material in aquatic environments: Contributions to the dissolved organic matter pool

This study shows that light exposure of flocculent material (floc) from the Florida Coastal Everglades (FCE) results in significant dissolved organic matter (DOM) generation through photo-dissolution processes. Floc was collected at two sites along the Shark River Slough (SRS) and irradiated with artificial sunlight. The DOM generated was characterized using elemental analysis and excitation emission matrix fluorescence coupled with parallel factor analysis. To investigate the seasonal variations of DOM photo-generation from floc, this experiment was performed in typical dry (April) and wet (October) seasons for the FCE. Our results show that the dissolved organic carbon (DOC) for samples incubated under dark conditions displayed a relatively small increase, suggesting that microbial processes and/or leaching might be minor processes in comparison to photo-dissolution for the generation of DOM from floc. On the other hand, DOC increased substantially (as much as 259 mgC gC−1) for samples exposed to artificial sunlight, indicating the release of DOM through photo-induced alterations of floc. The fluorescence intensity of both humic-like and protein-like components also increased with light exposure. Terrestrial humic-like components were found to be the main contributors (up to 70%) to the chromophoric DOM (CDOM) pool, while protein-like components comprised a relatively small percentage (up to 16%) of the total CDOM. Simultaneously to the generation of DOC, both total dissolved nitrogen and soluble reactive phosphorus also increased substantially during the photo-incubation period. Thus, the photo-dissolution of floc can be an important source of DOM to the FCE environment, with the potential to influence nutrient dynamics in this system.

Aquatic fauna as indicators for Everglades restoration: Applying dynamic targets in assessments

A major goal of the Comprehensive Everglades Restoration Plan (CERP) is to recover historical (pre-drainage) wading bird rookeries and reverse marked decreases in wading bird nesting success in Everglades National Park. To assess efforts to restore wading birds, a trophic hypothesis was developed that proposes seasonal concentrations of small-fish and crustaceans (i.e., wading bird prey) were a key factor to historical wading bird success. Drainage of the Everglades has diminished these seasonal concentrations, leading to a decline in wading bird nesting and displacing them from their historical nesting locations. The trophic hypothesis predicts that restoring historical hydrological patterns to pre-drainage conditions will recover the timing and location of seasonally concentrated prey, ultimately restoring wading bird nesting and foraging to the southern Everglades. We identified a set of indicators using small-fish and crustaceans that can be predicted from hydrological targets and used to assess management success in regaining suitable wading bird foraging habitat. Small-fish and crustaceans are key components of the Everglades food web and are sensitive to hydrological management, track hydrological history with little time lag, and can be studied at the landscape scale. The seasonal hydrological variation of the Everglades that creates prey concentrations presents a challenge to interpreting monitoring data. To account for the variable hydrology of the Everglades in our assessment, we developed dynamic hydrological targets that respond to changes in prevailing regional rainfall. We also derived statistical relationships between density and hydrological drivers for species representing four different life-history responses to drought. Finally, we use these statistical relationships and hydrological targets to set restoration targets for prey density. We also describe a report-card methodology to communicate the results of model-based assessments for communication to a broad audience.

The effect of iron oxide nanoparticles on the fate and transformation of arsenic in aquatic environments

Iron oxides and arsenic are prevalent in the environment. With the increase interest in the use of iron oxide nanoparticles (IONPs) for contaminant remediation and the high toxicity of arsenic, it is crucial that we evaluate the interactions between IONPs and arsenic. The goal was to understand the environmental behavior of IONPs in regards to their particle size, aggregation and stability, and to determine how this behavior influences IONPs-arsenic interactions. ^ A variety of dispersion techniques were investigated to disperse bare commercial IONPs. Vortex was able to disperse commercial hematite nanoparticles into unstable dispersions with particles in the micrometer size range while probe ultrasonication dispersed the particles into stable dispersions of nanometer size ranges for a prolonged period of time. Using probe ultrasonication and vortex to prepare IONPs suspensions of different particle sizes, the adsorption of arsenite and arsenate to bare hematite nanoparticles and hematite aggregates were investigated. To understand the difference in the adsorptive behavior, adsorption kinetics and isotherm parameters were determined. Both arsenite and arsenate were capable of adsorbing to hematite nanoparticles and hematite aggregates but the rate and capacity of adsorption is dependent upon the hematite particle size, the stability of the dispersion and the type of sorbed arsenic species. Once arsenic was adsorbed onto the hematite surface, both iron and arsenic can undergo redox transformation both microbially and photochemically and these processes can be intertwined. Arsenic speciation studies in the presence of hematite particles were performed and the effect of light on the redox process was preliminary quantified. The redox behavior of arsenite and arsenate were different depending on the hematite particle size, the stability of the suspension and the presence of environmental factors such as microbes and light. The results from this study are important and have significant environmental implications as arsenic mobility and bioavailability can be affected by its adsorption to hematite particles and by its surface mediated redox transformation. Moreover, this study furthers our understanding on how the particle size influences the interactions between IONPs and arsenic thereby clarifying the role of IONPs in the biogeochemical cycling of arsenic.^

Development of an enhanced hydro-geochemical model to address mercury-speciation fate and transport in aquatic environments

An awareness of mercury (Hg) contamination in various aquatic environments around the world has increased over the past decade, mostly due to its ability to concentrate in the biota. Because the presence and distribution of Hg in aquatic systems depend on many factors (e.g., pe, pH, salinity, temperature, organic and inorganic ligands, sorbents, etc.), it is crucial to understand its fate and transport in the presence of complexing constituents and natural sorbents, under those different factors. An improved understanding of the subject will support the selection of monitoring, remediation, and restoration technologies. The coupling of equilibrium chemical reactions with transport processes in the model PHREEQC offers an advantage in simulating and predicting the fate and transport of aqueous chemical species of interest. Thus, a great variety of reactive transport problems could be addressed in aquatic systems with boundary conditions of specific interest. Nevertheless, PHREEQC lacks a comprehensive thermodynamic database for Hg. Therefore, in order to use PHREEQC to address the fate and transport of Hg in aquatic environments, it is necessary to expand its thermodynamic database, confirm it and then evaluate it in applications where potential exists for its calibration and continued validation. The objectives of this study were twofold: 1) to develop, expand, and confirm the Hg database of the hydrogeochemical PHREEQC to enhance its capability to simulate the fate of Hg species in the presence of complexing constituents and natural sorbents under different conditions of pH, redox, salinity and temperature; and 2) to apply and evaluate the new database in flow and transport scenarios, at two field test beds: Oak Ridge Reservation, Oak Ridge, TN and Everglades National Park, FL, where Hg is present and is of much concern. Overall, this research enhanced the capability of the PHREEQC model to simulate the coupling of the Hg reactions in transport conditions. It also demonstrated its usefulness when applied to field situations.

Data compilation on the biological response to ocean acidification: environmental and experimental context of data sets and related literature

The exponential growth of studies on the biological response to ocean acidification over the last few decades has generated a large amount of data. To facilitate data comparison, a data compilation hosted at the data publisher PANGAEA was initiated in 2008 and is updated on a regular basis (doi:10.1594/PANGAEA.149999). By January 2015, a total of 581 data sets (over 4 000 000 data points) from 539 papers had been archived. Here we present the developments of this data compilation five years since its first description by Nisumaa et al. (2010). Most of study sites from which data archived are still in the Northern Hemisphere and the number of archived data from studies from the Southern Hemisphere and polar oceans are still relatively low. Data from 60 studies that investigated the response of a mix of organisms or natural communities were all added after 2010, indicating a welcomed shift from the study of individual organisms to communities and ecosystems. The initial imbalance of considerably more data archived on calcification and primary production than on other processes has improved. There is also a clear tendency towards more data archived from multifactorial studies after 2010. For easier and more effective access to ocean acidification data, the ocean acidification community is strongly encouraged to contribute to the data archiving effort, and help develop standard vocabularies describing the variables and define best practices for archiving ocean acidification data.