Metals in Okefenokee peat-forming environments: relation to constituents found in coal

Ba, Ca, Co, Cr, Cu, Fe, Hg, K, Mg, Mn, Na, Ni, Pb and Zn were studied in cores of peat from two major vegetational areas of the Okefenokee Swamp, Georgia; both total peat and organic fractions were investigated. Except for Hg and Pb, metal concentrations were either higher or equal to Clarke values. The sandy bedrock is not an important contributor to metal concentrations found in peat. Levels of metals in a given peat sample were related to plant materials which gave rise to the peat; it does not appear that vegetational environment plays a critical role in determining trace metal distribution, but does play a role in determining the amount of humic or pre-vitrinitic constituents that eventually are found in coal.     

Occurrence and distribution of sulfur in peat-forming environments of southern Florida

Cores and surface samples of peats from the Everglades—Mangrove region of Southern Florida were analyzed for total sulfur and pyritic sulfur. These values were compared with the petrographic-botanical components of the peats as determined from point-counts of oriented microtome sections. Pyrite occurs as individual euhedral crystals, loosely packed framboids, and lenses or crusts of minute crystals. Framboids and minute crystals are often associated with organic matter and sometimes with bacteria and fungi. Pyrite tends to selectively occur in void spaces in or between peat tissues. In samples containing very small amounts of pyrite, framboidal pyrite is the prevalent form.Marine to brackish peats contain the highest pyrite and total sulfur contents, with brackish peats generally containing more pyrite than marine peats. Pyrite tends to be lower in all peats within 30 cm of the surface, whether marine or brackish.Burial of freshwater peats beneath marine or brackish peats tends to increase the total sulfur and pyritic sulfur in the underlying peats. Burial beneath brackish-water, clay-rich deposits (such as splays) tends to increase total sulfur and pyritic sulfur in the underlying deposits more than burial beneath less clay-rich deposits.     

Distribution of forms of sulfur in peats from saline environments in the Florida Everglades

Although there is published information on the mechanism of sedimentary pyrite formation resulting from bacterial reduction of sulfate, little is known about the distribution of forms of sulfur, including organic, in peats. In order to increase understanding of the geochemistry of sulfur in coals, we have determined distributions of forms of sulfur in five cores of saline peat and one of brackish peat, all from areas near the Shark River and Whitewater Bay in the coastal swamps of south Florida. All concentrations vary widely with depth. Total sulfur concentrations range up to 6% of dry solids. Minor amounts of sulfur are present as H₂S, S⁰, SO₄²⁻, and acid-soluble sulfide, but the principal forms are usually pyritic and organic. The ratio, organic/pyritic, is highly variable, but at a majority of levels in a profile is considerably greater than unity. It is inferred that topochemical factors are important in determining the distribution of sulfur forms in any element of volume.     

The distribution of sulfur and organic matter in various fractions of peat: origins of sulfur in coal

The peat-forming systems of the Okefenokee Swamp are viewed as modern progenitors of coal. Taxodium and Nymphaea-derived peat-forming systems were characterized in terms of (1) organic fractions and (2) the distribution of organic/inorganic sulfur in each organic fraction (water soluble, benzene/methanol soluble, humin, humic acid, fulvic acid). The humin fraction is the largest organic fraction in both environments, approaching 70% of the total organic matter in the Nymphaea-derived environment. Humin origins are discussed in terms of a humic acid precursor, and undecomposed plant material. It is suggested that each depth of peat represents a diagenetic history of events which the authors believe occurred primarily when the currently buried peat was at the surface. The sulfur content of both peat-forming areas is low (0.23–0.27%); organic sulfur is the dominant sulfur form. Humin contains 50–80% of the total sulfur and of this, 80% is organic sulfur. Ester-sulfate appears to be especially prevalent in the fulvic acid fraction. The sulfur content of freshwater-derived peats is similar in quantity and distribution to that found in low sulfur coals.     

Iron and Pyritization in Wetland Soils of the Florida Coastal Everglades

We explored environmental factors influencing soil pyrite formation within different wetland regions of Everglades National Park. Within the Shark River Slough (SRS) region, soils had higher organic matter (62.65 ± 1.88 %) and lower bulk density (0.19 ± 0.01 g cm^?3) than soils within Taylor Slough (TS; 14.35 ± 0.82 % and 0.45 ± 0.01 g cm^?3, respectively), Panhandle (Ph; 15.82 ± 1.37 % and 0.34 ± 0.009 g cm^?3, respectively), and Florida Bay (FB; 5.63 ± 0.19 % and 0.73 ± 0.02 g cm^?3, respectively) regions. Total reactive sulfide and extractable iron (Fe) generally were greatest in soils from the SRS region, and the degree of pyritization (DOP) was higher in soils from both SRS (0.62 ± 0.02) and FB (0.52 ± 0.03) regions relative to TS and Ph regions (0.30 ± 0.02 and 0.31 ± 0.02, respectively). Each region, however, had different potential limits to pyrite formation, with SRS being Fe and sulfide limited and FB being Fe and organic matter limited. Due to the calcium-rich soils of TS and Ph regions, DOP was relatively suppressed. Annual water flow volume was positively correlated with soil DOP. Soil DOP also varied in relation to distance from water management features and soil percent organic matter. We demonstrate the potential use of soil DOP as a proxy for soil oxidation state, thereby facilitating comparisons of wetland soils under different flooding regimes, e.g., spatially or between wet years versus dry years. Despite its low total abundance, Fe plays an important role in sulfur dynamics and other biogeochemical cycles that characterize wetland soils of the Florida coastal Everglades.     

Deposition and early diagenesis of microbial mud in the Florida Everglades

Microbial carbonate mud in the modern (<4 kyr) palustrine environment of the Florida Everglades is surprisingly susceptible to early diagenetic alteration. The low‐Mg calcite crystals show an open, trellis‐like crystal structure that yields a high surface area to volume ratio. This textural complexity, likely to be a result of organic influence, leads to abundant reaction sites vulnerable to both dissolution and subsequent precipitation. Rapid degradation of organics is attributed to both aerobic and anaerobic metabolisms. Geochemical signatures suggest increased denitrification within the freshwater environment and increased sulphate reduction at the (slightly) brackish mangrove transition zone. A transition from a freshwater to brackish depositional environment is likely to follow the Holocene sea‐level transgression. The textural complexity in these microbial carbonates causes an unexpectedly low preservation potential of original textural and geochemical signatures, even in low‐Mg calcite. Given the potential for early diagenesis of palustrine and perhaps other microbial carbonates, they should be used cautiously as archives for palaeoenvironmental proxies.     

Sulfur Isotopic Characteristics of Coal in China and Sulfur Isotopic Fractionation during Coal—burning Process

The determined results of the sulfur contents and isotopic composition of coal samples from major coal mines in 15 provinces and regions of China show that the coal mined in the north of China is characterized by higher ^34S and lower sulfur content, but that in the south of China has lower ^34S and higher sulfur content.During the coal-burning process in both indrstrial and daily use of coal as fuel the released sulfur dioxide is always enriched in lighter sulfur isotope relative to the corresponding coal;the particles are always enriched in heavier sulfur isotope.The discussion on the environmental geochemical significance of the above-mentioned results also has been made.     

Controls on herbaceous litter decomposition in the estuarine ecotones of the Florida Everglades

The effects of nutrient availability and litter quality on litter decomposition were measured in two oligotrophic phosphorus (P)-limited Florida Everglades esturies, United States. The two estuaries differ, in that one (Shark River estuary) is directly connected to the Gulf of Mexico and receives marine P, while the other (Taylor Slough estuary) does not receive marine P because Florida Bay separates it from the Gulf of Mexico. Decomposition of three macrophytes.Cladium jamaicense, Eleochaaris spp., andJuncus roemerianus, was studied using a litter bag technique over 18 mo. Litter was exposed to three treatments: soil surface+macroinvertebrates (=macro), soil surface without macroinvertebrates (=wet), and above the soil and water (=aerial). The third treatment replicated the decomposition of standing dead leaves. Decomposition rates showed that litter exposed to the wet and macro treatments decomposed significantly faster than the aerial treatment, where atmospheric deposition was the only source of nutrients. Macroinvertebrates had no influence on litter decompostion rates.C. jamaicense decomposed faster at sites, with higher P, andEleocharis spp. decomposed significantly faster at sites with higher nitrogen (N). Initial tissue C:N and C:P molar ratios revealed that the nutrient quality of litter of bothEleocharis spp. andJ. roemerianus was higher thanC. jamaicense, but onlyEleocharis spp. decomposed faster thanC. jamaicense. C. jamaicense litter tended to immobilize P, whileEleocharis spp. litter showed net remineralization of N and P. A comparison with other estuarine and wetland systems revealed the dependence of litter decomposition on nutrient availability and litter quality. The results from this experiment suggest that Everglades restoration may have an important effect on key ecosystem processes in the estuarine ecotone of this landscape.     

Sediment and Nutrient Deposition Associated with Hurricane Wilma in Mangroves of the Florida Coastal Everglades

The distribution of mangrove biomass and forest structure along Shark River estuary in the Florida Coastal Everglades (FCE) has been correlated with elevated total phosphorus concentration in soils thought to be associated with storm events. The passage of Hurricane Wilma across Shark River estuary in 2005 allowed us to quantify sediment deposition and nutrient inputs in FCE mangrove forests associated with this storm event and to evaluate whether these pulsing events are sufficient to regulate nutrient biogeochemistry in mangrove forests of south Florida. We sampled the spatial pattern of sediment deposits and their chemical properties in mangrove forests along FCE sites in December 2005 and October 2006. The thickness (0.5 to 4.5 cm) of hurricane sediment deposits decreased with distance inland at each site. Bulk density, organic matter content, total nitrogen (N) and phosphorus (P) concentrations, and inorganic and organic P pools of hurricane sediment deposits differed from surface (0–10 cm) mangrove soils at each site. Vertical accretion resulting from this hurricane event was eight to 17 times greater than the annual accretion rate (0.30 ± 0.03 cm year⁻¹) averaged over the last 50 years. Total P inputs from storm-derived sediments were equivalent to twice the average surface soil nutrient P density (0.19 mg cm⁻³). In contrast, total N inputs contributed 0.8 times the average soil nutrient N density (2.8 mg cm⁻³). Allochthonous mineral inputs from Hurricane Wilma represent a significant source of sediment to soil vertical accretion rates and nutrient resources in mangroves of southwestern Everglades. The gradient in total P deposition to mangrove soils from west to east direction across the FCE associated with this storm event is particularly significant to forest development due to the P-limited condition of this carbonate ecosystem. This source of P may be an important adaptation of mangrove forests in the Caribbean region to projected impacts of sea-level rise.     

Interactions between dissolved organic carbon and mercury species in surface waters of the Florida Everglades

An ultrafiltration procedure has been developed to study the interaction between organic C and Hg species in natural waters, and a pilot study was conducted in the surface waters of the Florida Everglades. Compared to total Hg, CH₃Hg shows different distribution patterns in the suspended particulate, colloidal, and truly dissolved phases. Colloidal forms (0.22 μm, 3 kDa) contain the majority of the total dissolved Hg, while the amount found in the truly dissolved fraction (<3 kDa) is small (about 10%). However, CH₃Hg, which shows strong binding capability with low molecular-weight dissolved organic C, is present almost entirely in the lower molecular-weight fraction of the colloids and in the truly dissolved fraction. Quantitative CH₃Hg data correlate well with those for dissolved organic C, an indication that the organic matter present in the system plays an important role in the fate and transport of organomercury. Distribution coefficients between water and the different-sized fractions of the dissolved organic C were determined for both total Hg and CH₃Hg. Results for total Hg were in general agreement with other reports resulting from studies of molecular size distributions of total Hg in freshwater systems. This is, to the best of our knowledge, the first report of such distribution profiles for CH₃Hg between different-sized fractions of dissolved organic C in natural waters.     

Use of 234U and 238U isotopes to identify fertilizer-derived uranium in the Florida Everglades

Surface water and peat in the northern Everglades have very low natural concentrations of U and are therefore sensitive to the addition of small amounts of U from anthropogenic sources such as fertilizer. Peat samples collected along a nutrient gradient in the northern Everglades have unusually high concentrations of U (>1 μg/g, dry basis) and also have a distinctive ²³⁴U/²³⁸U activity ratio (AR). AR values for U-enriched peat fall in the narrow range of AR values for commercial phosphate fertilizer (1.00±0.05). In contrast, AR values for low-U peat from background sites exceed 1.05. The spatial distribution of anomalous U concentration, and of fertilizer-like AR values in peat, parallel a previously documented pattern of P enrichment. These results strongly suggest that some of the U in nutrient-impacted peatlands is fertilizer-derived. Agricultural drainage water sampled in the northern Everglades has high concentrations of dissolved U (0.3–2.4 μg/l) compared to surface water from background sites (<0.1 μg/l). Measured AR values in drainage water (0.949–0.990) are also permissive of a fertilizer origin for the U and are different from AR values in surface water or peat at background sites (AR>1.05). Synoptic sampling of surface water along drainage canals indicate that Lake Okeechobee, and some drainage from agricultural fields, are sources of dissolved U, whereas wetlands farther downstream act as sinks for U. Historically cultivated agricultural soil has only a marginally elevated (+0.2 μg/g) average concentration of U compared to nearby uncultivated soil and incorporates only 20% of the U from an aqueous solution that was slurried with the soil. In contrast, a similar experiment with fresh Everglades peat indicated uptake of 90% of the added U. These experiments support the proposed removal of U from agricultural fields and concentration of U in downstream peatlands. The methodology of this study can be used to describe the behavior of fertilizer-derived U in other low-U environments.     

Retrospective analysis of the impacts of major hurricanes on sediments in the lower Everglades and Florida Bay

A record of the impacts of major hurricanes on sediment stratigraphy and composition in subtropical ecosystems has been preserved in the lower Everglades and Florida Bay. These impacts were observed in discontinuous layers of sediment that were identified from high-resolution, vertical profiles of excess ²¹⁰Pb and ¹³⁷Cs. Discontinuities were found at different geographic locations and at two to three different depths in the sediment column; however, the layers were each deposited within time periods that corresponded with the passing of category 3–5 hurricanes during 1960, 1948 and 1935. A simple mass balance model for excess ²¹⁰Pb was used to show net changes of ±20–100% in excess ²¹⁰Pb inventory that resulted from sediment disturbances of <1 to >22 cm. Abrupt shifts in sediment composition were often observed in hurricane-impacted layers. Ratios of organic (C/P) were four- to fivefold higher than normal in post-hurricane layers of sediment at open bay sites. These layers are phosphorus poor and seem to reflect preferential decomposition of organic P relative to organic C in association with hurricanes. The net effect is for major hurricanes to redistribute sediment, organic matter and nutrients.This revised version was published online in July 2003.     

Characteristics and origins of coal cleat: A review

Cleats are natural opening-mode fractures in coal beds. They account for most of the permeability and much of the porosity of coalbed gas reservoirs and can have a significant effect on the success of engineering procedures such as cavity stimulations. Because permeability and stimulation success are commonly limiting factors in gas well performance, knowledge of cleat characteristics and origins is essential for successful exploration and production. Although the coal–cleat literature spans at least 160 years, mining issues have been the principal focus, and quantitative data are almost exclusively limited to orientation and spacing information. Few data are available on apertures, heights, lengths, connectivity, and the relation of cleat formation to diagenesis, characteristics that are critical to permeability. Moreover, recent studies of cleat orientation patterns and fracture style suggest that new investigations of even these well-studied parameters can yield insight into coal permeability. More effective predictions of cleat patterns will come from advances in understanding cleat origins. Although cleat formation has been speculatively attributed to diagenetic and/or tectonic processes, a viable mechanical process for creating cleats has yet to be demonstrated. Progress in this area may come from recent developments in fracture mechanics and in coal geochemistry.     

Tracing the origins of polymethylene moieties in coal

Many coals have been shown to contain long polymethylene segments (up to C₃₀ and longer) which crack to ethylene, propylene, butadiene and other low molecular weight hydrocarbons when the coals are pyrolyzed. The polymethylene content varies in different coals and can be 10% or more in low rank coals. Cannel coals may contain up to 20% polymethylene. Polymethylene moieties are either very low or absent in low-volatile bituminous coals and anthracite.A method of analysis for polymethylene in coals, based on liquefaction in a donor solvent followed by ¹H NMR spectroscopy has been described. With this analysis, it has been shown that polymethylene moieties are present in higher concentrations in exinite macerals than in vitrinites or inertinites. Analysis of peats also show the presence of polymethylene components at levels similar to that found in coal. Analysis of various parts of present-day plants also shows the presence of polymethylene materials in concentrations varying significantly from one kind of plant to another. Within a given plant type, some parts of the plant appear to be richer in polymethylene than others. Spores and pollen are frequently especially rich in polymethylene, accounting for the corresponding high concentration in exinite macerals in coal.Samples of Texas Eocene lignites representing a depositional time interval of 15–20 million years and three distinctly different climatic and vegetational conditions were analyzed for polymethylene contents. The differences in polymethylene levels are consistent with differences in flora and support the idea that the original plants are the sources of polymethylene components in coal.     

Hydrologic processes on tree islands in the Everglades (Florida, USA): tracking the effects of tree establishment and growth

The hydrodynamics of tree islands during the growth of newly planted trees has been found to be influenced by both vegetation biomass and geologic conditions. From July 2007 through June 2009, groundwater and surface-water levels were monitored on eight recently planted tree islands at the Loxahatchee Impoundment Landscape Assessment (LILA) facility in Boynton Beach, Florida, USA. Over the 2-year study, stand development coincided with the development of a water-table depression in the center of each of the islands that was bounded by a hydraulic divide along the edges. The water-table depression was greater in islands composed of limestone as compared to those composed of peat. The findings of this study suggest that groundwater evapotranspiration by trees on tree islands creates complex hydrologic interactions between the shallow groundwater in tree islands and the surrounding surface water and groundwater bodies.     

Projected Reorganization of Florida Bay Seagrass Communities in Response to the Increased Freshwater Inflow of Everglades Restoration

Historic changes in water-use management in the Florida Everglades have caused the quantity of freshwater inflow to Florida Bay to decline by approximately 60% while altering its timing and spatial distribution. Two consequences have been (1) increased salinity throughout the bay, including occurrences of hypersalinity, coupled with a decrease in salinity variability, and (2) change in benthic habitat structure. Restoration goals have been proposed to return the salinity climates (salinity and its variability) of Florida Bay to more estuarine conditions through changes in upstream water management, thereby returning seagrass species cover to a more historic state. To assess the potential for meeting those goals, we used two modeling approaches and long-term monitoring data. First, we applied the hydrological mass balance model FATHOM to predict salinity climate changes in sub-basins throughout the bay in response to a broad range of freshwater inflow from the Everglades. Second, because seagrass species exhibit different sensitivities to salinity climates, we used the FATHOM-modeled salinity climates as input to a statistical discriminant function model that associates eight seagrass community types with water quality variables including salinity, salinity variability, total organic carbon, total phosphorus, nitrate, and ammonium, as well as sediment depth and light reaching the benthos. Salinity climates in the western sub-basins bordering the Gulf of Mexico were insensitive to even the largest (5-fold) modeled increases in freshwater inflow. However, the north, northeastern, and eastern sub-basins were highly sensitive to freshwater inflow and responded to comparatively small increases with decreased salinity and increased salinity variability. The discriminant function model predicted increased occurrences of Halodule wrightii communities and decreased occurrences of Thalassia testudinum communities in response to the more estuarine salinity climates. The shift in community composition represents a return to the historically observed state and suggests that restoration goals for Florida Bay can be achieved through restoration of freshwater inflow from the Everglades.     

Sulfur cycling at the Mid-Atlantic Ridge: A multiple sulfur isotope approach

The role of sulfur in two hydrothermal vent systems, the Logatchev hydrothermal field at 14°45′N/44°58′W and several different vent sites along the southern Mid-Atlantic Ridge (SMAR) between 4°48′S and 9°33′S and between 12°22′W and 13°12′W, is examined by utilizing multiple sulfur isotope and sulfur concentration data. Isotope compositions for sulfide minerals and vent H₂S from different SMAR sites range from + 1.5 to + 8.9‰ in δ³⁴S and from + 0.001 to + 0.051‰ in Δ³³S. These data indicate mixing of mantle sulfur with sulfur from seawater sulfate. Combined δ³⁴S and Δ³³S systematics reveal that vent sulfide from SMAR is characterized by a sulfur contribution from seawater sulfate between 25 and 33%. This higher contribution, compared with EPR sulfide, indicates increased seawater sulfate reduction at MAR, because of a deeper seated magma chamber and longer fluid upflow path length, and points to fundamental differences with respect to subsurface structures and fluid evolution at slow and fast spreading mid-ocean ridges.Additionally, isotope data uncover non-equilibrium isotopic exchange between dissolved sulfide and sulfate in an anhydrite bearing zone below the vent systems at fluid temperatures between 335 and 400 °C. δ³⁴S values between + 0.2 to + 8.8‰ for dissolved and precipitated sulfide from Logatchev point to the same mixing process between mantle sulfur and sulfur from seawater sulfate as at SMAR. δ³⁴S values between ? 24.5 and + 6.5‰ and Δ³³S values between + 0.001 and + 0.125‰ for sulfide-bearing sediments and mafic/ultramafic host rocks from drill cores taken in the region of Logatchev indicate a clear contribution of biogenic sulfides formed via bacterial sulfate reduction. Basalts and basaltic glass from SMAR sites with Δ³³S = ? 0.008‰ reveal lower Δ³³S lower values than suggested on the basis of previously published isotopic measurements of terrestrial materials.We conclude that the combined use of both δ³⁴S and Δ³³S provides a more detailed picture of the sulfur cycling in hydrothermal systems at the Mid-Atlantic Ridge and uncovers systematic differences to hydrothermal sites at different mid-ocean ridge sites. Multiple sulfur isotope measurements allow identification of incomplete isotope exchange in addition to isotope mixing as a second important factor influencing the isotopic composition of dissolved sulfide during fluid upflow. Furthermore, based on Δ³³S we are able to clearly distinguish biogenic from hydrothermal sulfides in sediments even when δ³⁴S were identical.     

Stable Sulfur Isotopic Evidence for Historical Changes of Sulfur Cycling in Estuarine Sediments from Northern Florida

Data on abundance and isotopic composition of porewater and sedimentary sulfur species are reported for relatively uncontaminated and highly contaminated fine-grained anoxic sediments of St. Andrew Bay, Florida. A strong contrast in amount and composition of sedimentary organic matter at the two sites allows a comparative study of the historical effects of increased organic loading on sulfur cycling and sulfur isotopic fractionation. In the contaminated sediments, an increase in organic loading caused increased sedimentary carbon/sulfur ratios and resulted in higher rates of bacterial sulfate reduction, but a lower efficiency of sulfide oxidation. These differences are well reflected in the isotopic composition of dissolved sulfate, sulfide, and sedimentary pyrite. Concentration and isotopic profiles of dissolved sulfate, organic carbon, and total sulfur suggest that the anaerobic decomposition of organic matter is most active in the upper 8cm but proceeds at very slow rates below this depth. The rapid formation of more than 90% of pyrite in the uppermost 2 cm which corresponds to about 3 years of sediment deposition allows the use of pyrite isotopic composition for tracing changing diagenetic conditions. Sediment profiles of the sulfur isotopic composition of pyrite reflect present-day higher rates of bacterial sulfate reduction and lower rates of sulfide oxidation, and record a profound change in the diagenetic cycling of sulfur in the contaminated sediments coincident with urban and industrial development of the St. Andrew Bay area.