Modern developments in hypersonic wind tunnels

The development of new methods of producing hypersonic wind-tunnel flows at increasing velocities during the last few decades is reviewed with attention to airbreathing propulsion, hypervelocity aerodynamics and superorbital aerodynamics. The role of chemical reactions in these flows leads to use of a binary scaling simulation parameter, which can be related to the Reynolds number, and which demands that smaller wind tunnels require higher reservoir pressure levels for simulation of flight phenomena. The use of combustion heated vitiated wind tunnels for propulsive research is discussed, as well as the use of reflected shock tunnels for the same purpose. A flight experiment validating shock-tunnel results is described, and relevant developments in shock tunnel instrumentation are outlined. The use of shock tunnels for hypervelocity testing is reviewed, noting the role of driver gas contamination in determining test time, and presenting examples of air dissociation effects on model flows. Extending the hypervelocity testing range into the superorbital regime with useful test times is seen to be possible by use of expansion tube/tunnels with a free piston driver.

Limitations on bioassays in macronutrient deficiency determination

Short-term nutrient bioassays can be used to assess labile nutrient availability in soils. These bioassays rely on a high number of plants and small soil volumes to exploit labile soil resources rapidly and assess potential nutrient deficiency. A comparison of the Neubauer bioassay with conventional pot trial assessment of P and S availability in a Yellow Kurosol was undertaken. Changes in labile soil nutrients and enzyme activity after bioassay assessment were also measured. The Neubauer bioassay was able to detect increased labile P availability following P fertiliser application to the soil. This corresponded with response to added P in a longer-term pot trial using maize. As expected, phosphatase activity increased following the bioassay and labile P was depleted by the plants. However, although a longer-term pot trial demonstrated the Yellow Kurosol was responsive to S fertilisation, labile S pools were sufficiently large that the short-term Neubauer bioassay detected no difference in S availability to plants. Both soil sulphatase activity and labile soil S were elevated following the bioassay. The short period of contact between the roots of the bioassay and the soil may have limited S uptake and therefore the ability of the bioassay to identify a S responsive soil. When using bioassay techniques to assess labile nutrient availability, it is critical that the size of the labile nutrient pool present be considered for each element, and that the period of contact between the bioassay and soil being tested is long enough for plant uptake to lower the nutrient supply to a level that limits further uptake.

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. ^

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.^

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.

Forest Resource Islands in a Sub-tropical Marsh: Soil–Site Relationships in Everglades Hardwood Hammocks

Spatial heterogeneity in soils is often characterized by the presence of resource-enriched patches ranging in size from a single shrub to wooded thickets. If the patches persist long enough, the primary constraint on production may transition from one limiting environmental factor to another. Tree islands that are scattered throughout the Florida Everglades basin comprise nutrient-enriched patches, or resource islands, in P-limited oligotrophic marshes. We used principal component analysis and multiple regressions to characterize the belowground environment (soil, hydrology) of one type of tree island, hardwood hammocks, and examined its relationship with the three structural variables (basal area, biomass, and canopy height) indicative of site productivity. Hardwood hammocks in the southern Everglades grow on two distinct soil types. The first, consisting of shallow, organic, relatively low-P soils, is common in the seasonally flooded Marl Prairie landscape. In contrast, hammocks on islands embedded in long hydroperiod marsh have deeper, alkaline, mineral soils with extremely high P concentrations. However, this edaphic variation does not translate simply into differences in forest structure and production. Relative water depth was unrelated to all measures of forest structure and so was soil P, but the non-carbonate component of the mineral soil fraction exhibited a strong positive relationship with canopy height. The development of P-enriched forest resource islands in the Everglades marsh is accompanied by the buildup of a mineral soil; however, limitations on growth in mature islands appear to differ substantively from those that dominate incipient stages in the transformation from marsh to forest. Key words: resource island; tree

Occurrence and distribution of novel botryococcene hydrocarbons in freshwater wetlands of the Florida Everglades

A high abundance of isoprenoid hydrocarbons, the botryococcenes, with carbon numbers from 32 to 34 were detected in the Florida Everglades freshwater wetlands. These compounds were present in varying amounts up to 106 μg/gdw in periphyton, 278 μg/gdw in floc, and 46 μg/gdw in soils. Their structures were determined based on comparison to standards, interpretation of their mass spectra and those of their hydrogenation products, and comparison of Kovats indexes to those reported in the literature. A total of 26 cyclic and acyclic botryococcenes with 8 skeletons were identified, including those with fewer degrees of unsaturation, which are proposed as early diagenetic derivatives from the natural products. This is the first report that botryococcenes occur in the Everglades freshwater wetlands. Their potential biogenetic sources from green algae and cyanobacteria were examined, but neither contained botryococcenes. Thus, the source implication of botryococcenes in this ecosystem needs further study.

Ecosystem structure, nutrient dynamics, and hydrologic relationships in tree islands of the southern Everglades, Florida, USA

Tree islands are an important structural component of many graminoid-dominated wetlands because they increase ecological complexity in the landscape. Tree island area has been drastically reduced with hydrologic modifications within the Everglades ecosystem, yet still little is known about the ecosystem ecology of Everglades tree islands. As part of an ongoing study to investigate the effects of hydrologic restoration on short hydroperiod marshes of the southern Everglades, we report an ecosystem characterization of seasonally flooded tree islands relative to locations described by variation in freshwater flow (i.e. locally enhanced freshwater flow by levee removal). We quantified: (1) forest structure, litterfall production, nutrient utilization, soil dynamics, and hydrologic properties of six tree islands and (2) soil and surface water physico-chemical properties of adjacent marshes. Tree islands efficiently utilized both phosphorus and nitrogen, but indices of nutrient-use efficiency indicated stronger P than N limitation. Tree islands were distinct in structure and biogeochemical properties from the surrounding marsh, maintaining higher organically bound P and N, but lower inorganic N. Annual variation resulting in increased hydroperiod and lower wet season water levels not only increased nitrogen use by tree species and decreased N:P values of the dominant plant species (Chrysobalanus icaco), but also increased soil pH and decreased soil temperature. When compared with other forested wetlands, these Everglades tree islands were among the most nutrient efficient, likely a function of nutrient immobilization in soils and the calcium carbonate bedrock. Tree islands of our study area are defined by: (1) unique biogeochemical properties when compared with adjacent short hydroperiod marshes and other forested wetlands and (2) an intricate relationship with marsh hydrology. As such, they may play an important and disproportionate role in nutrient and carbon cycling in Everglades wetlands. With the loss of tree islands that has occurred with the degradation of the Everglades system, these landscape processes may have been altered. With this baseline dataset, we have established a long-term ecosystem-scale experiment to follow the ecosystem trajectory of seasonally flooded tree islands in response to hydrologic restoration of the southern Everglades.

Elemental analysis and forensic comparison of soils by laser-induced breakdown spectroscopy (LIBS) and laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS)

The elemental analysis of soil is useful in forensic and environmental sciences. Methods were developed and optimized for two laser-based multi-element analysis techniques: laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) and laser-induced breakdown spectroscopy (LIBS). This work represents the first use of a 266 nm laser for forensic soil analysis by LIBS. Sample preparation methods were developed and optimized for a variety of sample types, including pellets for large bulk soil specimens (470 mg) and sediment-laden filters (47 mg), and tape-mounting for small transfer evidence specimens (10 mg). Analytical performance for sediment filter pellets and tape-mounted soils was similar to that achieved with bulk pellets. An inter-laboratory comparison exercise was designed to evaluate the performance of the LA-ICP-MS and LIBS methods, as well as for micro X-ray fluorescence (μXRF), across multiple laboratories. Limits of detection (LODs) were 0.01-23 ppm for LA-ICP-MS, 0.25-574 ppm for LIBS, 16-4400 ppm for μXRF, and well below the levels normally seen in soils. Good intra-laboratory precision (≤ 6 % relative standard deviation (RSD) for LA-ICP-MS; ≤ 8 % for μXRF; ≤ 17 % for LIBS) and inter-laboratory precision (≤ 19 % for LA-ICP-MS; ≤ 25 % for μXRF) were achieved for most elements, which is encouraging for a first inter-laboratory exercise. While LIBS generally has higher LODs and RSDs than LA-ICP-MS, both were capable of generating good quality multi-element data sufficient for discrimination purposes. Multivariate methods using principal components analysis (PCA) and linear discriminant analysis (LDA) were developed for discriminations of soils from different sources. Specimens from different sites that were indistinguishable by color alone were discriminated by elemental analysis. Correct classification rates of 94.5 % or better were achieved in a simulated forensic discrimination of three similar sites for both LIBS and LA-ICP-MS. Results for tape-mounted specimens were nearly identical to those achieved with pellets. Methods were tested on soils from USA, Canada and Tanzania. Within-site heterogeneity was site-specific. Elemental differences were greatest for specimens separated by large distances, even within the same lithology. Elemental profiles can be used to discriminate soils from different locations and narrow down locations even when mineralogy is similar.

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.

Dissolved Black Nitrogen (DBN) in Freshwater Environments

Biomass burning results in the formation and accumulation of pyrogenic products such as black carbon (BC) and black nitrogen (BN) in soils. The ubiquitous presence of pyrogenic products in natural dissolved organic matter (DOM) and potential implications in global carbon cycling have recently been reported. However, little is known about the environmental dynamics or the importance in the global N cycle of dissolved BN (DBN; or heteroaromatic N). Here we report the coupling between DBN and dissolved BC (DBC) in ultrafiltered DOM from six headwater streams across a climatic region of North America, suggesting similar combustion sources, and that DOC may play an important role in the translocation of soil BN to the dissolved phase. The export of potentially recalcitrant riverine DBN to the ocean may affect the biogeochemical cycling of N and possibly the microbial community structure in aquatic environments.

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.

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. ^

Potential rates of methanogenesis in peat and marl sawgrass wetlands in the Florida Everglades

Methanogenesis was studied in soils from two sawgrass wetlands of the Florida Everglades. Marl soils exhibited a significantly higher potential rate of methanogenesis than peat soils. In these wetlands, methanogenesis: (1) decreased rapidly with increasing soil depth, (2) increased at higher temperatures and lower Eh, (3) was stimulated by organic compounds (cellulose, glucose and acetate), and (4) remained unaffected by added ammonium. Lowering the Eh in the peat and marl soils with sulfide or sulfate stimulated methanogenesis. In January 1990, phosphate caused a significant increase in methanogenesis. The potential rates of methanogenesis decreased to undetectable levels when water levels dropped below the surface, and peaked one month after the start of the wet season. Methanogenesis appeared to be a relatively important process in carbon cycling in marl soils and these soils do not accumulate peat. Therefore, one possible explanation for peat accumulation in sawgrass wetlands may be their low rates of methanogenesis.

Depth-related variations of trace metal abundances in south Florida sediments

Variations in trace element abundances with depth in soils and sediments may be due to natural processes or reflect anthropogenic influences. The depth related variations of five major elements (Fe, Si, Al, Ca and Mg), seventeen trace elements (Mn, Cr, Ti, P, Ni, Ba, Sc, Sr, Sb, Zn, Pb, Cd, Co, V, Be, Cu and Y) and volatile loss patterns were examined for sediment cores from five sites in South Florida (Lake Okeechobee, SFWMD Water Conservation area 3B, F.I.U., the Everglades and Chekika State Recreation Area). Principal component analysis of the chemical data combined with microscopic examination of the soils reveal that depth-related variations can be explained by varying proportions of three natural soil constituents and one anthropogenic component. The results can be used as a geochemical baseline for human influence on South Florida soils.