Photocatalytic decomposition of organophosphonates and fluorophenols in irradiated titanium dioxide suspensions

Dimethyl methyl phosphonate (DMMP), diethyl methyl phosphonate (DEMP), and fluorophenols undergo rapid decomposition upon TiO$\sb2$ catalyzed photooxidation in air saturated aqueous solution. The degradation rates of DMMP were determined over a range of temperatures, under solar and artificial irradiation with and without simultaneous sonication. Solar illumination is effective for the degradation and the use of low energy of sonication increases the rate of mineralization. The surface area and the type of TiO$\sb2$ dramatically affect the photoactivity of the catalyst. A number of intermediate products are formed and ultimately oxidized to phosphate and carbon dioxide. Possible reaction mechanisms and pathways for DMMP and DEMP are proposed. The Langmuir-Hinshelwood kinetic parameters for the photocatalysis of fluorophenols suggest modestly different reactivity for each isomer. The adsorption constant is largest for the ortho isomer consistent with the adsorption onto TiO$\sb2$ through both hydroxyl and fluoride groups to form a chelated type structure. ^

Correlation of detector dog alerts to cocaine decomposition products found in illicit forensic specimens

The volatile chemicals which comprise the odor of the illicit drug cocaine have been analyzed by adsorption onto activated charcoal followed by solvent elution and GC/MS analysis. A series of field tests have been performed to determine the dominant odor compound to which dogs alert. All of our data to date indicate that the dominant odor is due to the presence of methyl benzoate which is associated with the cocaine, rather than the cocaine itself. When methyl benzoate and cocaine are spiked onto U.S. currency, the threshold level of methyl benzoate required for a canine to signal an alert is typically 1-10 $\mu$g. Humans have been shown to have a sensitivity similar to dogs for methyl benzoate but with poorer selectivity/reliability. The dominant decomposition pathway for cocaine has been evaluated at elevated temperatures (up to 280$\sp\circ$C). Benzoic acid, but no detectable methyl benzoate, is formed. Solvent extraction and SFE were used to study the recovery of cocaine from U.S. currency. The amount of cocaine which could be recovered was found to decrease with time. ^

Robert Twilley sewing decomposition bags for mangrove root decomposition experiment

This material is based upon work supported by the National Science Foundation through the Florida Coastal Everglades Long-Term Ecological Research program under Cooperative Agreements #DBI-0620409 and #DEB-9910514. This image is made available for non-commercial or educational use only.

Belowground decomposition of mangrove roots in Florida coastal everglades

Mangrove root decomposition rates were measured by distributing mesh bags containing fine root material across six sites with different soil fertility and hydroperiod to compare ambient differences to substrate quality. Roots from a site with lower soil phosphorus concentration were used as a reference and compared to ambient roots at five other sites with increased phosphorus concentration. Four mesh bags of each root type (ambient versus reference), separated into four 10-cm replicate intervals, were buried up to 42 cm depth at each site and incubated for 250 d (initiation in May 2004). Mass loss of ambient mangrove roots was significant at all study sites and ranged from 17% to 54%; there was no significant difference with depth at any one site. Reference decomposition constants (−k) ranged from 0.0012 to 0.0018 d−1 among Taylor Slough sites compared to 0.0023–0.0028 d−1 among Shark River sites, indicating slower decomposition rates associated with lower soil phosphorous and longer flood duration. Reference roots had similar decomposition rates as ambient roots in four of the six sites, and there were no significant correlations between indices of root substrate quality and decomposition rates. Among these distinct landscape gradients of south Florida mangroves, soil environmental conditions have a greater effect on belowground root decomposition than root substrate quality.

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.

Changes in mass and nutrient content of wood during decomposition in a south Florida mangrove forest

1. Large pools of dead wood in mangrove forests following disturbances such as hurricanes may influence nutrient fluxes. We hypothesized that decomposition of wood of mangroves from Florida, USA (Avicennia germinans, Laguncularia racemosa and Rhizophora mangle), and the consequent nutrient dynamics, would depend on species, location in the forest relative to freshwater and marine influences and whether the wood was standing, lying on the sediment surface or buried. 2. Wood disks (8–10 cm diameter, 1 cm thick) from each species were set to decompose at sites along the Shark River, either buried in the sediment, on the soil surface or in the air (above both the soil surface and high tide elevation). 3. A simple exponential model described the decay of wood in the air, and neither species nor site had any effect on the decay coefficient during the first 13 months of decomposition. 4. Over 28 months of decomposition, buried and surface disks decomposed following a two-component model, with labile and refractory components. Avicennia germinans had the largest labile component (18 ± 2% of dry weight), while Laguncularia racemosa had the lowest (10 ± 2%). Labile components decayed at rates of 0.37–23.71% month−1, while refractory components decayed at rates of 0.001–0.033% month−1. Disks decomposing on the soil surface had higher decay rates than buried disks, but both were higher than disks in the air. All species had similar decay rates of the labile and refractory components, but A. germinans exhibited faster overall decay because of a higher proportion of labile components. 5. Nitrogen content generally increased in buried and surface disks, but there was little change in N content of disks in the air over the 2-year study. Between 17% and 68% of total phosphorus in wood leached out during the first 2 months of decomposition, with buried disks having the greater losses, P remaining constant or increasing slightly thereafter. 6. Newly deposited wood from living trees was a short-term source of N for the ecosystem but, by the end of 2 years, had become a net sink. Wood, however, remained a source of P for the ecosystem. 7. As in other forested ecosystems, coarse woody debris can have a significant impact on carbon and nutrient dynamics in mangrove forests. The prevalence of disturbances, such as hurricanes, that can deposit large amounts of wood on the forest floor accentuates the importance of downed wood in these forests.

Hydroperiod and seasonal effects on fish decomposition in an oligotrophic Everglades marsh

In the Everglades, the majority of fish detrital inputs occur during the dry scason, when waterlevel drawdown reduces aquatic habitat. While these mortality events are highly seasonal, the remineralization and recycling of fish detrital nutrients may represent an important stimulus to the ecosystem in the following wet season. The goal of this study was to quantify the rate of detrital fish decomposition during three periods of the year to determine seasonal variations in decomposition patterns in this ecosystem. A multiple regression analysis showed that hydroperiod and water depth both played a role in determining fish decomposition rates within this ecosystem. Decomposition rates ranged from a low of 13% day−1 in December 2000 to a high of 50% day−1 in April 2001, the height of the dry season. Phosphorus analysis showed that Gambusia holbrooki, the dominant small fish species in the Everglades, contains 7.169±1.46 mg P g−1 wet fish weight. Based on the observed decomposition rates and the average biomass added, the estimafed daily flux of phosphorus from the experimental detrital loading ranged from a low of 27.04 mg P day−1 to a high of 108.14 mg P day−1 during the decomposition period. We estimated that these inputs could represent an input of 43 μg P m−2 day−1 to the total temporal Everglades phosphorus budget. Although much of this phosphorus is likely incorporated into the macroinvertebrate pool, detrital inputs peak during the dry season when nutrients are most likely to be incorporated into the soil and occur when decomposition of vegetative material is moisture-limited. These inputs may therefore play an important role in stimulating vegetative production during the early wet season.

Identification of characteristic volatile organic compounds released during the decomposition process of human remains and analogues

The manner in which remains decompose has been and is currently being researched around the world, yet little is still known about the generated scent of death. In fact, it was not until the Casey Anthony trial that research on the odor released from decomposing remains, and the compounds that it is comprised of, was brought to light. The Anthony trial marked the first admission of human decomposition odor as forensic evidence into the court of law; however, it was not "ready for prime time" as the scientific research on the scent of death is still in its infancy. This research employed the use of solid-phase microextraction (SPME) with gas chromatography-mass spectrometry (GC-MS) to identify the volatile organic compounds (VOCs) released from decomposing remains and to assess the impact that different environmental conditions had on the scent of death. Using human cadaver analogues, it was discovered that the environment in which the remains were exposed to dramatically affected the odors released by either modifying the compounds that it was comprised of or by enhancing/hindering the amount that was liberated. In addition, the VOCs released during the different stages of the decomposition process for both human remains and analogues were evaluated. Statistical analysis showed correlations between the stage of decay and the VOCs generated, such that each phase of decomposition was distinguishable based upon the type and abundance of compounds that comprised the odor. This study has provided new insight into the scent of death and the factors that can dramatically affect it, specifically, frozen, aquatic, and soil environments. Moreover, the results revealed that different stages of decomposition were distinguishable based upon the type and total mass of each compound present. Thus, based upon these findings, it is suggested that the training aids that are employed for human remains detection (HRD) canines should 1) be characteristic of remains that have undergone decomposition in different environmental settings, and 2) represent each stage of decay, to ensure that the HRD canines have been trained to the various odors that they are likely to encounter in an operational situation.

Photocatalytic decomposition of organophosphonates fluorophenols in irradiated titanium dioxide suspensions

Dimethyl methyl phosphonate (DMMP), diethyl methyl phosphonate (DEMP), and fluorophenols undergo rapid decomposition upon TiO2 catalyzed photooxidation in air saturated aqueous solution. The degradation rates of DMMP were determined over a range of temperatures, under solar and artificial irradiation with and without simultaneous sonication. Solar illumination is effective for the degradation and the use of low energy of sonication increases the rate of mineralization. The surface area and the type of TiO2 dramatically affect the photoactivity of the catalyst. A number of intermediate products are formed and ultimately oxidized to phosphate and carbon dioxide. Possible reaction mechanisms and pathways for DMMP and DEMP are proposed. The Langmuir- Hinshelwood kinetic parameters for the photocatalysis of fluorophenols suggest modestly different reactivity for each isomer. The adsorption constant is largest for the ortho isomer consistent with the adsorption onto TiO2 through both hydroxyl and fluoride groups to form a chelated type structure.

Nicole Poret retrieving decomposition bags to measure mangrove fine root decomposition rates, Shark River Slough

This material is based upon work supported by the National Science Foundation through the Florida Coastal Everglades Long-Term Ecological Research program under Cooperative Agreements #DBI-0620409 and #DEB-9910514. This image is made available for non-commercial or educational use only.

Left to right: Robert Twilley and Nicole Poret. Washing mangrove fine roots to set up a decomposition experiment, Taylor Slough

This material is based upon work supported by the National Science Foundation through the Florida Coastal Everglades Long-Term Ecological Research program under Cooperative Agreements #DBI-0620409 and #DEB-9910514. This image is made available for non-commercial or educational use only.

Nicole Poret weighing mangrove fine roots to set up a decomposition experiment, Shark River Slough

This material is based upon work supported by the National Science Foundation through the Florida Coastal Everglades Long-Term Ecological Research program under Cooperative Agreements #DBI-0620409 and #DEB-9910514. This image is made available for non-commercial or educational use only.

Left to right: Nicole Poret and Carlos Coronado-Molina deploying bags to determine decomposition rates of mangrove fine roots, Taylor Slough

This material is based upon work supported by the National Science Foundation through the Florida Coastal Everglades Long-Term Ecological Research program under Cooperative Agreements #DBI-0620409 and #DEB-9910514. This image is made available for non-commercial or educational use only.