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.

Characterization, sources, and transformations of dissolved organic matter (DOM) in Florida coastal Everglades (FCE)

Dissolved organic matter (DOM) is one of the largest carbon reservoirs on this planet and is present in aquatic environments as a highly complex mixture of organic compounds. The Florida coastal Everglades (FCE) is one of the largest wetlands in the world. DOM in this system is an important biogeochemical component as most of the nitrogen (N) and phosphorous (P) are in organic forms. Achieving a better understanding of DOM dynamics in large coastal wetlands is critical, and a particularly important issue in the context of Everglades restoration. In this work, the environmental dynamics of surface water DOM on spatial and temporal scales was investigated. In addition, photo- and bio-reactivity of this DOM was determined, surface-to-groundwater exchange of DOM was investigated, and the size distribution of freshwater DOM in Everglades was assessed. The data show that DOM dynamics in this ecosystem are controlled by both hydrological and ecological drivers and are clearly different on spatial scales and variable seasonally. The DOM reactivity data, modeled with a multi-pool first order degradation kinetics model, found that fluorescent DOM in FCE is generally photo-reactive and bio-refractory. Yet the sequential degradation proved a “priming effect” of sunlight on the bacterial uptake and reworking of this subtropical wetland DOM. Interestingly, specific PARAFAC components were found to have different photo- and bio-degradation rates, suggesting a highly heterogeneous nature of fluorophores associated with the DOM. Surface-to-groundwater exchange of DOM was observed in different regions of the system, and compositional differences were associated with source and photo-reactivity. Lastly, the high degree of heterogeneity of DOM associated fluorophores suggested based on the degradation studies was confirmed through the EEM-PARAFAC analysis of DOM along a molecular size continuum, suggesting that the fluorescence characteristics of DOM are highly controlled by different size fractions and as such can exhibit significant differences in reactivity.

Effect of Water Management on Interannual Variation in Bulk Soil Properties from the Eastern Coastal Everglades

We examined interannual variation in soil properties from wetlands occurring in adjacent drainage basins from the southeastern Everglades. Triplicate 10-cm soil cores were collected, homogenized, and analyzed during the wet season 2006–2010 from five freshwater sawgrass wetland marshes and three estuarine mangrove forests. Soil bulk density from the Taylor Slough basin ranged from 0.15 gm-cm−3 to 0.5 gm-cm−3, was higher than from the Panhandle basin every year, and generally increased throughout the study period. Organic matter as a percent loss on ignition ranged from 7 % to 12 % from freshwater marshes and from 13 % to 56 % from estuarine mangroves. Extractable iron in soils was similar among drainage basins and wetland types, typically ranging from 0.6 to 2.0 g Fe kg−1. In contrast, inorganic sulfur was on average over four times higher from estuarine soils relative to freshwater, and was positively correlated with soil organic matter. Finally total soil phosphorus (P) was lower in freshwater soils relative to estuarine soils (84 ± 5 versus 326 ± 32 mg P kg−1). Total P from the freshwater marshes in the Panhandle basin rose throughout the study period from 54.7 ± 8.4 to 107 ± 17 mg P kg−1, a possible outcome of differences in water management between drainage basins.

The Effect of Nutrient-Rich Effluents from Shrimp Farming on Mangrove Soil Carbon Storage and Geochemistry Under Semi-Arid Climate Conditions in Northern Brazil

A semi-arid mangrove estuary system in the northeast Brazilian coast (Ceará state) was selected for this study to (i) evaluate the impact of shrimp farm nutrient-rich wastewater effluents on the soil geochemistry and organic carbon (OC) storage and (ii) estimate the total amount of OC stored in mangrove soils (0–40 cm). Wastewater-affected mangrove forests were referred to as WAM and undisturbed areas as Non-WAM. Redox conditions and OC content were statistically correlated (P < 0.05) with seasonality and type of land use (WAM vs. Non-WAM). Eh values were from anoxic to oxic conditions in the wet season (from − 5 to 68 mV in WAM and from < 40 to > 400 mV in Non-WAM soils) and significantly higher (from 66 to 411 mV) in the dry season (P < 0.01). OC contents (0–40 cm soil depth) were significantly higher (P < 0.01) in the wet season than the dry season, and higher in Non-WAM soils than in WAM soils (values of 8.1 and 6.7 kg m− 2 in the wet and dry seasons, respectively, for Non-WAM, and values of 3.8 and 2.9 kg m− 2 in the wet and dry seasons, respectively, for WAM soils; P < 0.01). Iron partitioning was significantly dependent (P < 0.05) on type of land use, with a smaller degree of pyritization and lower Fe-pyrite presence in WAM soils compared to Non-WAM soils. Basal respiration of soil sediments was significantly influenced (P < 0.01) by type of land use with highest CO2 flux rates measured in the WAM soils (mean values of 0.20 mg CO2 h− 1–g− 1 C vs. 0.04 mg CO2 h− 1–g− 1 C). The OC storage reduction in WAM soils was potentially caused (i) by an increase in microbial activity induced by loading of nutrient-rich effluents and (ii) by an increase of strong electron acceptors [e.g., NO3−] that promote a decrease in pyrite concentration and hence a reduction in soil OC burial. The current estimated OC stored in mangrove soils (0–40 cm) in the state of Ceará is approximately 1 million t.

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.

Benthic Exchange of C, N, and P Along the Estuarine Ecotone of Lower Taylor Slough, Florida (USA): Effect of Seasonal Flows and Phosphorus Availability

The southern Everglades and Florida Bay have experienced a nearly 50 % reduction in freshwater flow resulting in increased salinity and landward expansion of mangrove forest. Given the marine end-member is a natural source of P to this region, it is necessary to understand the interactions between inflows and P availability in controlling the exchange of materials across the mangrove ecotone. From 2007 to 2008, we used sediment core incubations to quantify fluxes of dissolved inorganic N and P and dissolved organic carbon (DOC) in three ecotone areas (dwarf mangrove, pond, and bay). Experiments were repeated seasonally over 2 years involving P-enriched surface water as a factor. We saw consistent uptake of soluble reactive P (SRP), DOC, and nitrate + nitrite (N+N) by the soils/sediments and release of ammonium (NH4 +) from soils/sediments to the water column across all sites and seasons. P enrichment had no discernible effect on DIN or DOC flux, suggesting that rapid P uptake may have been more geochemically mediated. However, uptake of added P occurred across all sites and seasons, reflecting high uptake capacity in this carbonate system and the potential of the mangrove ecotone to sequester P as it becomes more available.

The Effect of Sample and Sample Matrix on DNA Processing: Mechanisms for the Detection and Management of Inhibition in Forensic Samples

The presence of inhibitory substances in biological forensic samples has, and continues to affect the quality of the data generated following DNA typing processes. Although the chemistries used during the procedures have been enhanced to mitigate the effects of these deleterious compounds, some challenges remain. Inhibitors can be components of the samples, the substrate where samples were deposited or chemical(s) associated to the DNA purification step. Therefore, a thorough understanding of the extraction processes and their ability to handle the various types of inhibitory substances can help define the best analytical processing for any given sample. A series of experiments were conducted to establish the inhibition tolerance of quantification and amplification kits using common inhibitory substances in order to determine if current laboratory practices are optimal for identifying potential problems associated with inhibition. DART mass spectrometry was used to determine the amount of inhibitor carryover after sample purification, its correlation to the initial inhibitor input in the sample and the overall effect in the results. Finally, a novel alternative at gathering investigative leads from samples that would otherwise be ineffective for DNA typing due to the large amounts of inhibitory substances and/or environmental degradation was tested. This included generating data associated with microbial peak signatures to identify locations of clandestine human graves. Results demonstrate that the current methods for assessing inhibition are not necessarily accurate, as samples that appear inhibited in the quantification process can yield full DNA profiles, while those that do not indicate inhibition may suffer from lowered amplification efficiency or PCR artifacts. The extraction methods tested were able to remove >90% of the inhibitors from all samples with the exception of phenol, which was present in variable amounts whenever the organic extraction approach was utilized. Although the results attained suggested that most inhibitors produce minimal effect on downstream applications, analysts should practice caution when selecting the best extraction method for particular samples, as casework DNA samples are often present in small quantities and can contain an overwhelming amount of inhibitory substances.

Effect of pH and temperature on the carbonate promoted dissolution of sodium meta-autunite

Release of uranium from Na-autunite, an artificial mineral created as a result of polyphosphate injection in the subsurface at the DOE Hanford Site, takes place during slow dissolution of the mineral structure. Stability information of the uranyl-phosphate phases is limited to conditions involving pH, temperature, and a few aqueous organic materials. The carbonate ion, which creates very strong complexes with uranium, is the predominant ion in the groundwater composition. The polyphosphate technology with the formation of autunite was identified as the most feasible remediation strategy to sequester uranium in contaminated groundwater and soil in situ. The objectives of the experimental work were (i) to quantify the effect of bicarbonate on the stability of synthetic sodium meta-autunite created as a result of uranium stabilization through polyphosphate injection, (ii) calculate the kinetic rate law parameters of the uranium release from Na-autunite during dissolution, and (iii) to compare the process parameters with those obtained for natural calcium meta-autunite. Experiments were conducted using SPTF apparatus, which consists of syringe pumps for controlling flow rate, Teflon reactors and a heating/cooling system. 0.25 grams of synthetic Na-autunite was placed in the reactor and buffer solutions with varying bicarbonate concentrations (0.0005 to 0.003 M) at different pH (6 - 11) were pumped through the reactors. Experiments were conducted at four different temperatures in the range of 5 - 60oC. It was concluded that the rate of release of uranium from synthetic Na-autunite is directly correlated to the bicarbonate concentration. The rate of release of uranium increased from 1.90 x 10-12 at pH 6 to 2.64 x 10-10 (mol m-2 s-1) at pH 11 at 23oC over the bicarbonate concentration range tested. The activation energy values were invariant with the change in the bicarbonate concentration; however, pH is shown to influence the activation energy values. Uranyl hydroxides and uranyl carbonates complexes helped accelerate the dissolution of autunite mineral.

Effect of gamma-irradiation on total organic carbon and trihalomethane formation potential

This research was conducted to study the use of radiation in water treatment as an alternative to chlorination which has caused health concerns due to the formation of harmful disinfection by-products. Groundwater solutions from the Biscayne aquifer were radiated with Cobalt-60 gamma radiation and studied for changes in dissolved organic carbon (DOC), UV absorbance at 254 nm (UV254), fluorescence and trihalomethane formation potential (THMFP). Molecular fractionations were conducted by ultrafiltration. Effect of the combination of radiation/peroxide was studied for DOC and UV254. Radiation showed significant removal in DOC and THMFP. Similar results were seen in the fluorescence and UV absorbance experiments. Radiation/peroxide did not improve the DOC removal. Radiation of the groundwater samples broke the larger molecular weight fractions in to smaller fractions.

Soil carbon dynamics in primary and secondary tropical forests in Colombia

Soils play a central role in the dynamics of biospheric carbon and in climate change. They contain the largest carbon stock of terrestrial ecosystems and return to the atmosphere a significant proportion of carbon fixed by photosynthesis. Soils of tropical forests are tremendously important in the carbon cycle because they receive the largest organic matter inputs, they have the largest respiration rates, and they are among the largest carbon reservoirs among world soils. This research assesses the main components of the soil carbon dynamics in primary (PF) and secondary (SF) tropical forests in Colombia. I evaluated the production, stocks, and decomposition rates of aboveground detritus as well as the stocks, growth, mortality, and decomposition of fine roots in these two forest types. Soil carbon outputs were evaluated as total soil, heterotrophic, and root respiration. The stocks of soil organic carbon down to 4 m deep in these two cover types and in degraded pastures (PAS) were also evaluated. ^ Soil inputs of organic carbon from above and belowground sources were lower in SF than in PF. Litterfall in SF was 58% and production of fine root detritus was 60% of that in PF. When production of woody detritus and palm fronds was considered, the difference between these forest types was even larger. However, outputs of mineral carbon through heterotrophic soil respiration were similar; in SF they equaled 97% of those in PF. As a result, soil carbon balance was positive in PF and negative in SF. Despite that soil carbon balances suggest that soils of SF are losing carbon, soil carbon stocks of SF were higher than of degraded pastures, suggesting that they have already started to recover soil carbon stocks lost under degraded pastures. This discrepancy can be partially explained by the effect of drier conditions on heterotrophic soil respiration as a consequence of a moderate El Niño event during the period of soil respiration measurements. The positive carbon balance in soils of PF despite the El Niño event, suggests that soils of PF accumulated about 664 Kg C ha−1 yr−1. Therefore, soil carbon dynamics mainly depended on successional status of vegetation and on climatic conditions. ^

Exergoeconomic analysis of solar organic rankine cycle for geothermal air conditioned net zero energy buildings

This study is an attempt at achieving Net Zero Energy Building (NZEB) using a solar Organic Rankine Cycle (ORC) based on exergetic and economic measures. The working fluid, working conditions of the cycle, cycle configuration, and solar collector type are considered the optimization parameters for the solar ORC system. In the first section, a procedure is developed to compare ORC working fluids based on their molecular components, temperature-entropy diagram and fluid effects on the thermal efficiency, net power generated, vapor expansion ratio, and exergy efficiency of the Rankine cycle. Fluids with the best cycle performance are recognized in two different temperature levels within two different categories of fluids: refrigerants and non-refrigerants. Important factors that could lead to irreversibility reduction of the solar ORC are also investigated in this study. In the next section, the system requirements needed to maintain the electricity demand of a geothermal air-conditioned commercial building located in Pensacola of Florida is considered as the criteria to select the optimal components and optimal working condition of the system. The solar collector loop, building, and geothermal air conditioning system are modeled using TRNSYS. Available electricity bills of the building and the 3-week monitoring data on the performance of the geothermal system are employed to calibrate the simulation. The simulation is repeated for Miami and Houston in order to evaluate the effect of the different solar radiations on the system requirements. The final section discusses the exergoeconomic analysis of the ORC system with the optimum performance. Exergoeconomics rests on the philosophy that exergy is the only rational basis for assigning monetary costs to a system’s interactions with its surroundings and to the sources of thermodynamic inefficiencies within it. Exergoeconomic analysis of the optimal ORC system shows that the ratio Rex of the annual exergy loss to the capital cost can be considered a key parameter in optimizing a solar ORC system from the thermodynamic and economic point of view. It also shows that there is a systematic correlation between the exergy loss and capital cost for the investigated solar ORC system.

Patterns of Soil Bacteria and Canopy Community Structure Related to Tropical Peatland Development

Natural environmental gradients provide important information about the ecological constraints on plant and microbial community structure. In a tropical peatland of Panama, we investigated community structure (forest canopy and soil bacteria) and microbial community function (soil enzyme activities and respiration) along an ecosystem development gradient that coincided with a natural P gradient. Highly structured plant and bacterial communities that correlated with gradients in phosphorus status and soil organic matter content characterized the peatland. A secondary gradient in soil porewater NH4 described significant variance in soil microbial respiration and β-1-4-glucosidase activity. Covariation of canopy and soil bacteria taxa contributed to a better understanding of ecological classifications for biotic communities with applicability for tropical peatland ecosystems of Central America. Moreover, plants and soils, linked primarily through increasing P deficiency, influenced strong patterning of plant and bacterial community structure related to the development of this tropical peatland ecosystem.

Biogeochemical Effects of Simulated Sea Level Rise on Carbon Loss in an Everglades Mangrove Peat Soil

Saltwater intrusion and inundation can affect soil microbial activity, which regulates the carbon (C) balance in mangroves and helps to determine if these coastal forests can keep pace with sea level rise (SLR). This study evaluated the effects of increased salinity (+15 ppt), increased inundation (−8 cm), and their combination, on soil organic C loss from a mangrove peat soil (Everglades, Florida, USA) under simulated tides. Soil respiration (CO2 flux), methane (CH4) flux, dissolved organic carbon (DOC) production, and porewater nutrient concentrations were quantified. Soil respiration was the major pathway of soil organic C loss (94–98%) and was approximately 90% higher in the control water level than the inundated treatment under elevated salinity. Respiration rate increased with water temperature, but depended upon salinity and tidal range. CH4 flux was minimal, while porewater DOC increased with a concomitant, significant decline in soil bulk density under increased inundation. Porewater ammonium increased (73%) with inundation and soluble reactive phosphorus increased (32%) with salinity. Overall, the decline in soil organic C mineralization from combined saltwater intrusion and prolonged inundation was not significant, but results suggest SLR could increase this soil’s susceptibility to peat collapse and accelerate nutrient and DOC export to adjacent Florida Bay.

Spatial and Temporal Variability of Dissolved Organic Matter Quantity and Composition in an Oilgotrophic Subtropical Coastal Wetland

Dissolved organic matter (DOM) is an essential component of the carbon cycle and a critical driver in controlling variety of biogeochemical and ecological processes in wetlands. The quality of this DOM as it relates to composition and reactivity is directly related to its sources and may vary on temporal and spatial scales. However, large scale, long-term studies of DOM dynamics in wetlands are still scarce in the literature. Here we present a multi-year DOM characterization study for monthly surface water samples collected at 14 sampling stations along two transects within the greater Everglades, a subtropical, oligotrophic, coastal freshwater wetland-mangrove-estuarine ecosystem. In an attempt to assess quantitative and qualitative variations of DOM on both spatial and temporal scales, we determined dissolved organic carbon (DOC) values and DOM optical properties, respectively. DOM quality was assessed using, excitation emission matrix (EEM) fluorescence coupled with parallel factor analysis (PARAFAC). Variations of the PARAFAC components abundance and composition were clearly observed on spatial and seasonal scales. Dry versus wet season DOC concentrations were affected by dry-down and re-wetting processes in the freshwater marshes, while DOM compositional features were controlled by soil and higher plant versus periphyton sources respectively. Peat-soil based freshwater marsh sites could be clearly differentiated from marl-soil based sites based on EEM–PARAFAC data. Freshwater marsh DOM was enriched in higher plant and soil-derived humic-like compounds, compared to estuarine sites which were more controlled by algae- and microbial-derived inputs. DOM from fringe mangrove sites could be differentiated between tidally influenced sites and sites exposed to long inundation periods. As such coastal estuarine sites were significantly controlled by hydrology, while DOM dynamics in Florida Bay were seasonally driven by both primary productivity and hydrology. This study exemplifies the application of long term optical properties monitoring as an effective technique to investigate DOM dynamics in aquatic ecosystems. The work presented here also serves as a pre-restoration condition dataset for DOM in the context of the Comprehensive Everglades Restoration Plan (CERP).

Dissolved Black Carbon in Grassland Streams: Is There an Effect of Recent Fire History?

While the existence of black carbon as part of dissolved organic matter (DOM) has been confirmed, quantitative determinations of dissolved black carbon (DBC) in freshwater ecosystem and information on factors controlling its concentration are scarce. In this study, stream surface water samples from a series of watersheds subject to different burn frequencies in Konza Prairie (Kansas, USA) were collected in order to determine if recent fire history has a noticeable effect on DBC concentration. The DBC levels detected ranged from 0.04 to 0.11 mg L−1, accounting for ca. 3.32 ± 0.51% of dissolved organic carbon (DOC). No correlation was found between DBC concentration and neither fire frequency nor time since last burn. We suggest that limited DBC flux is related to high burning efficiency, possibly greater export during periods of high discharge and/or the continuous export of DBC over long time scales. A linear correlation between DOC and DBC concentrations was observed, suggesting the export mechanisms determining DOC and DBC concentrations are likely coupled. The potential influence of fire history was less than the influence of other factors controlling the DOC and DBC dynamics in this ecosystem. Assuming similar conditions and processes apply in grasslands elsewhere, extrapolation to a global scale would suggest a global grasslands flux of DBC on the order of 0.14 Mt carbon year−1.