Chilling damage in a changing climate in coastal landscapes of the subtropical zone: a case study from south Florida

Extensive portions of the southern Everglades are characterized by series of elongated, raised peat ridges and tree islands oriented parallel to the predominant flow direction, separated by intervening sloughs. Tall herbs or woody species are associated with higher elevations and shorter emergent or floating species are associated with lower elevations. The organic soils in this “Ridge-and-Slough” landscape have been stable over millennia in many locations, but degrade over decades under altered hydrologic conditions. We examined soil, pore water, and leaf phosphorus (P) and nitrogen (N) distributions in six Ridge and Slough communities in Shark Slough, Everglades National Park. We found P enrichment to increase and N to decrease monotonically along a gradient from the most persistently flooded sloughs to rarely flooded ridge environments, with the most dramatic change associated with the transition from marsh to forest. Leaf N:P ratios indicated that the marsh communities were strongly P-limited, while data from several forest types suggested either N-limitation or co-limitation by N and P. Ground water stage in forests exhibited a daytime decrease and partial nighttime recovery during periods of surface exposure. The recovery phase suggested re-supply from adjacent flooded marshes or the underlying aquifer, and a strong hydrologic connection between ridge and slough. We therefore developed a simple steady-state model to explore a mechanism by which a phosphorus conveyor belt driven by both evapotranspiration and the regional flow gradient can contribute to the characteristic Ridge and Slough pattern. The model demonstrated that evapotranspiration sinks at higher elevations can draw in low concentration marsh waters, raising local soil and water P concentrations. Focusing of flow and nutrients at the evapotranspiration zone is not strong enough to overcome the regional gradient entirely, allowing the nutrient to spread downstream and creating an elongated concentration plume in the direction of flow. Our analyses suggest that autogenic processes involving the effects of initially small differences in topography, via their interactions with hydrology and nutrient availability, can produce persistent physiographic patterns in the organic sediments of the Everglades.

A Geospatial Database of Tree Islands within the Mustang Corner Fire Incident of 2008

Fire, which affects community structure and composition at all trophic levels, is an integral component of the Everglades ecosystem (Wade et al. 1980; Lockwood et al. 2003). Without fire, the Everglades as we know it today would be a much different place. This is particularly true for the short-hydroperiod marl prairies that predominate on the eastern and western flanks of Shark River Slough, Everglades National Park (Figure 1). In general, fire in a tropical or sub-tropical grassland community favors the dominance of C4 grasses over C3 species (Roscoe et al. 2000; Briggs et al. 2005). Within this pyrogenic graminoid community also, periodic natural fires, together with suitable hydrologic regime, maintain and advance the dominance of C4 vs C3 graminoids (Sah et al. 2008), and suppress the encroachment of woody stems (Hanan et al. 2009; Hanan et al. unpublished manuscript) originating from the tree islands that, in places, dominate the landscape within this community. However, fires, under drought conditions and elevated fuel loads, can spread quickly throughout the landscape, oxidizing organic soils, both in the prairie and in the tree islands, and, in the process, lead to shifts in vegetation composition. This is particularly true when a fire immediately precedes a flood event (Herndon et al. 1991; Lodge 2005; Sah et al. 2010), or if so much soil is consumed during the fire that the hydrologic regime is permanently altered as a result of a decrease in elevation (Zaffke 1983).

Sorption characteristics of a nonionic surfactant during remediation of contaminated soil with different organic content

Surfactant enhanced subsurface remediation has gained importance in soil remediation. Since surfactants can be sorbed on soils, the concentration of free surfactant could drop below the critical micelle concentration, CMC, which may reduce the ability of the surfactant to solubilize the contaminants in soils. ^ The main goal of this research was to study the factors affecting the surfactant sorption on soil such as surfactant concentration, soil organic content, and organic contaminants in soil and to determine the organic contaminants removed from soils by surfactant. The results would be served as the basis for the implementation of a future study in the pilot scale and field scale for surfactant enhanced subsurface remediation. ^ This research study investigated the relationship between the organic content of soils and the sorption characteristics of a nonionic surfactant, Triton X-100. The experiments were performed using uncontaminated soils and soil contaminated with naphthalene and decane. The first part of the experiments were conducted in batch mode utilizing surface tension technique to determine the CMC of surfactant Triton X-100 and the effective CMC in the soil/aqueous system. The sorption of Triton X-100 was calculated from the surface tension measurements. The second part of the experiments utilized the SPME/GC/FID technique to determine the concentration of the contaminants solubilized from the soils by the surfactant Triton X-100 at different concentrations. ^ The results indicated that when the concentration of surfactant was lower than the CMC, the amount of surfactant sorbed on soil increased with the increasing surfactant concentration and the surfactant sorption characteristics of the uncontaminated soils could be modeled by the Freundlich isotherm. For the contaminated soils, the amount of surfactant sorbed was higher than those for the uncontaminated soils. The amount of surfactant sorbed on soils also depends on the organic content in the soils. The higher the organic content in the soil, higher is the amount of surfactant sorbed onto the soil. When the concentration of surfactant was higher than the CMC, the amount of surfactant added into the soil/aqueous system will increase the number of micelle and it increase the solubilization of organic contaminant from the soils. The ratio of the moles of organic contaminant solubilized to the moles of surfactant present as micelles is called the molar solubilization ratio (MSR). MSR value for naphthalene was about 0.16 for the soil-water systems. The organic content of soil did not appear to affect MSR for naphthalene. On the other hand, the MSR values for decane were 0.52, 0.39 and 0.38 for soils with 25%, 50% and 75% organic content, respectively. ^

Organic matter dynamics in the Florida coastal Everglades: A molecular marker and isotopic approach

Everglades National Park (ENP) is about to undergo the world's largest wetland restoration with the aim of improving the quality, timing and distribution of water flow. The changes in water flow are hypothesized to alter the nutrient fluxes and organic matter (OM) dynamics within ENP, especially in the estuarine areas. This study used a multi-proxy approach of molecular markers and stable δ 13C isotope measurements, to determine the present day OM dynamics in ENP. ^ OM dynamics in wetland soils/sediments have proved to be difficult to understand using traditional geochemical approaches. These are often inadequate to describe the multitude of OM sources (e.g. higher land plant, emergent vegetation, submerged vegetation) to the soils/sediments and the complex diagenetic processes that can alter the OM characteristics. A multi-proxy approach, however, that incorporates both molecular level and bulk parameter information is ideal to comprehend complex OM dynamics in aquatic environments. Therefore, biomass-specific molecular markers or proxies can be useful in tracing the sources and processing of OM. This approach was used to examine the OM dynamics in the two major drainage basins, Shark River Slough and Taylor River Slough, of ENP. Freshwater to marine transects were sampled in both systems for soils/sediments and suspended particulate organic matter (SPOM) to be characterized through bulk OM analyses, lipid biomarker determinations (e.g. sterols, fatty acids, hydrocarbons and triterpenoids) and compound-specific stable carbon isotope (δ 13C) determinations. ^ One key accomplishment of the research was the assessment of a molecular marker proxy (Paq) to distinguish between emergent/higher plant vegetation from submerged vegetation within ENP. This proxy proved to be quite useful at tracing OM inputs to the soils/sediments of ENP. A second key accomplishment was the development of a 3-way model using vegetation specific molecular markers. This novel, descriptive model was successfully applied to the estuarine areas of Taylor and Shark River sloughs, providing clear evidence of mixing of freshwater, estuarine and marine derived OM in these areas. In addition, diagenetic transformations of OM in these estuaries were found to be quite different between Taylor and Shark Rivers, and are likely a result of OM quality and hydrological differences. ^

Natural organic matter and colloid-facilitated arsenic transport and transformation in porous soil media

Prediction of arsenic transport and transformation in soil environment requires understanding the transport mechanisms and proper estimation of arsenic partitioning tong all three phases in soil/aquifer systems: mobile colloids, mobile soil solution, and immobile soil solids. The primary purpose of this research is to study natural dissolved organic matter (DOM)/colloid-facilitated transport of arsenic and understand the role of soil derived carriers in the transport and transformation of both inorganic and organoarsenicals in soils. ^ DOM/colloid facilitated arsenic transport and transformation in porous soil media were investigated using a set of experimental approaches including batch experiment, equilibrium membrane dialysis experiment and column experiment. Soil batch experiment was applied to investigate arsenic adsorption on a variety of soils with different characteristics; Equilibrium membrane dialysis was employed to determine the 'free' and 'colloid-bound/complexed' arsenic in water extracts of chosen soils; Column experiments were also set up in the laboratory to simulate arsenic transport and transformation through golf course soils in the presence and absence of soil-derived dissolved substances. ^ The experimental results revealed that organic matter amendments effectively reduced soil arsenic adsorption. The majority of arsenic present in the soil extracts was associated with small substances of molecular weight (MW) between 500 and 3,500 Da, Only a small fraction of arsenic was associated with higher MW substances (MW > 3,500 Da), which was operationally defined as colloidal part in this study. The association of arsenic and DOM in the soil extracts strongly affected arsenic bioavailability, arsenic transport and transformation in soils. The results of column experiments revealed arsenic complicated behavior with various processes occurring in soils studied, including: soil arsenic' adsorption, facilitated arsenic transportation by dissolved substances presented in soil extracts and microorganisms involved arsenic species transformation. ^ Soil organic matter amendments effectively reduce soil arsenic adsorption capability either by scavenging 'soil arsenic adsorption sites or by interactions between arsenic species and dissolved organic chemicals in soil solution. Close attention must be paid for facilitated arsenic transport by dissolved substances presented in soil solution and microorganisms involved arsenic species transformation in arsenic-contaminated soils.^

Chemical characterization of soil organic matter in an oligotrophic, subtropical, freshwater wetland system: Sources, diagenesis and preservation

Freshwater wetland soils of the Everglades were studied in order to assess present environmental conditions and paleo-environmental changes using organic geochemistry techniques. Organic matter in dominant vegetation, peat and marl soils was characterized by geochemical means. Samples were selected along nutrient and hydrology gradients with the objective to determine the historical sources of organic matter as well as the extent of its preservation. Effective molecular proxies were developed to differentiate the relative input of organic matter from different biological sources to wetland soils. Thus historical vegetation shifts and hydroperiods were reconstructed using those proxies. The data show good correlations with historical water management practices starting at the turn of the century and during the mid 1900's. Overall, significant shortening of hydroperiods during this period was observed. The soil organic matter (SOM) preservation was assessed through elemental analysis and molecular characterizations of bulk 13C stable isotopes, solid state 13C NMR spectroscopy, UV-Vis spectroscopy, and tetramethyl ammonium hydroxide (TMAH) thermochemolysis-GC/MS. The relationship of the environmental conditions and degradation status of the soil organic matter (SOM) among the sites suggested that both high nutrient levels and long hydroperiod favor organic matter degradation in the soils. This is probably the result of an increase in the microbial activity in the soils which have higher nutrient levels, while longer hydroperiods may enhance physical/chemical degradation processes. The most significant transformations of biomass litter in this environment are controlled by very early physical/chemical processes and once the OM is incorporated into surface soils, the diagenetic change, even over extended periods of time is comparatively minimal, and SOM is relatively well preserved regardless of hydroperiod or nutrient levels. SOM accumulated in peat soils is more prone to continued degradation than the SOM in the marl soils. The latter is presumably stabilized early on through direct air exposure (oxidation) and thus, it is more refractory to further diagenetic transformations such as humification and aromatization reactions.

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.

Sediment and soil organic matter source assessment as revealed by the molecular distribution and carbon isotopic composition of n-alkanes

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.

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.

Contributions of humic substances to the dissolved organic carbon pool in wetlands from different climates

Wetlands are an important source of DOM. However, the quantity and quality of wetlands’ DOM from various climatic regions have not been studied comprehensively. The relationship between the concentrations of DOM (DOC), humic substances (HS) and non-humic substances (NHS) in wetland associated sloughs, streams and rivers, in cool temperate (Hokkaido, Japan), sub-tropical (Florida, USA), and tropical (Sarawak, Malaysia) regions was investigated. The DOC ranged from 1.0 to 15.6 mg C L−1 in Hokkaido, 6.0–24.4 mg C L−1 in Florida, and 18.9–75.3 mg C L−1 in Sarawak, respectively. The relationship between DOC and HS concentrations for the whole sample set was regressed to a primary function with y-intercept of zero (P < 0.005) and a slope value of 0.841. A similar correlation was observed between DOC and NHS concentrations, with a smaller slope value of 0.159. However, the correlation coefficient of the latter was much larger when the data was regressed to a logarithmic curve. These observations suggest the presence of a general tendency that the increased DOC in the river waters was mainly due to the increased supply of HS from wetland soils, whereas the rate of the increase in the NHS supply has an upper limit which may be controlled by primary productivity.

Application of biomarkers and compound specific stable isotopes for the assessment of hydrology as a driver of organic matter dynamics in the Everglades ecosystem

The Everglades is a sub-tropical coastal wetland characterized among others by its hydrological features and deposits of peat. Formation and preservation of organic matter in soils and sediments in this wetland ecosystem is critical for its sustainability and hydrological processes are important divers in the origin, transport and fate of organic matter. With this in mind, organic matter dynamics in the greater Florida Everglades was studied though various organic geochemistry techniques, especially biomarkers, bulk and compound specific δ13C and δD isotope analysis. The main objectives were focused on how different hydrological regimes in this ecosystem control organic matter dynamics, such as the mobilization of particulate organic matter (POM) in freshwater marshes and estuaries, and how organic geochemistry techniques can be applied to reconstruct Everglades paleo-hydrology. For this purpose organic matter in typical vegetation, floc, surface soils, soil cores, and estuarine suspended particulates were characterized in samples selected along hydrological gradients in the Water Conservation Area 3, Shark River Slough and Taylor Slough. ^ This research focused on three general themes: (1) Assessment of the environmental dynamics and source-specific particulate organic carbon export in a mangrove-dominated estuary. (2) Assessment of the origin, transport and fate of organic matter in freshwater marsh. (3) Assessment of historical changes in hydrological conditions in the Everglades (paleo-hydrology) though biomarkes and compound specific isotope analyses. This study reports the first estimate of particulate organic carbon loss from mangrove ecosystems in the Everglades, provides evidence for particulate organic matter transport with regards to the formation of ridge and slough landscapes in the Everglades, and demonstrates the applicability of the combined biomarker and compound-specific stable isotope approach as a means to generate paleohydrological data in wetlands. The data suggests that: (1) Carbon loss from mangrove estuaries is roughly split 50/50 between dissolved and particulate carbon; (2) hydrological remobilization of particulate organic matter from slough to ridge environments may play an important role in the maintenance of the Everglades freshwater landscape; and (3) Historical changes in hydrology have resulted in significant vegetation shifts from historical slough type vegetation to present ridge type vegetation. ^