On the thermal stabilization of carbon-supported SiO2 catalysts by phosphorus:evaluation in the oxidative dehydrogenation of ethylbenzene to styrene and a comparison with relevant catalysts

A strategy to enhance the thermal stability of C/SiO2 hybrids for the O2-based oxidative dehydrogenation of ethylbenzene to styrene (ST) by P addition is proposed. The preparation consists of the polymerization of furfuryl alcohol (FA) on a mesoporous precipitated SiO2. The polymerization is catalyzed by oxalic acid (OA) at 160 °C (FA:OA = 250). Phosphorous was added as H3PO4 after the polymerization and before the pyrolysis that was carried out at 700 °C and will extend the overall activation procedure. Estimation of the apparent activation energies reveals that P enhances the thermal stability under air oxidation, which is a good indication for the ODH tests. Catalytic tests show that the P/C/SiO2 hybrids are readily active, selective and indeed stable in the applied reactions conditions for 60 h time on stream. Coke build-up during the reaction attributed to the P-based acidity is substantial, leading to a reduction of the surface area and pore volume. The comparison with a conventional MWCNT evidences that the P/C/SiO2 hybrids are more active and selective at high temperatures (450–475 °C) while the difference becomes negligible at lower temperature. However, the comparison with reference P/SiO2 counterparts shows a very similar yield than the hybrids but more selective to ST. The benefit of the P/C/SiO2 hybrid is the lack of stabilization period, which is observed for the P/SiO2 to create an active coke overlayer. For long term operation, P/SiO2 appears to be a better choice in terms of selectivity, which is crucial for commercialization.

Phosphorus bearing minerals in iron ores and their possible benefication

Modern electron optical techniques together with X-ray and mineralogical examination have been used to study the occurrence and form of phosphorus bearing minerals in iron ores. Three ores have been studied - Bahariya and Aswan from Egypt and Frodingham ironstone from U.K. The iron in the Bahariya iron ore is mainly as hematite and goethite. The gangue minerals are halite, gypsum, barytes, quartz and calcite. Iron content is between 49.8 to 63.2% and phosphorus 0.14 to 0.34%. The phosphorus occurs as very fine particles of apatite which are distributed throughout the ore. Removal of the phosphorus would require very fine grinding followed by acid leaching. Aswan iron ore is an oolitic iron ore; the iron content between 41-57% and phosphorus content 0.1 to 2.9%. It is mainly hematitic with variable quantities of quartz, apatite and small amount of clay minerals. In the oolitic iron ore beds, apatite occurs in the hematite matrix; filling in the pores of the oolithic surfaces, or as matrix cementing the ooliths with the hematite grains. In sandstone claybeds the distribution of the apatite is mainly in the matrix. It is suggested that the liberation size for the apatite would be -80 m and flotation concentration could be applied for the removal of apatite from Aswan ore. Frodingham ironstone occurs in the lower Jurassic bed of the South Humberside area. The average iron content is 25% and the phosphorus is 0.32%. Seven mineral phases were identified by X-ray; calcite, quartz, chamosite, hematite, siderite, apatite, and chlorite. Apatite occurs as very fine grains in the hematite and chamosite ooliths; as matrix of fine grains intergrown with chamosite and calcite grains; and as anhedral and sub rounded grains in the ooliths (8-28 m). It is suggested that two processes are possible for the dephosphorisation; the Flox process or a reduction roast followed by fine grinding, magnetic separation, and acid leaching.

Phosphorus catalysis in the pyrolysis behaviour of biomass

Phosphorus is a key plant nutrient and as such, is incorporated into growing biomass in small amounts. This paper examines the influence of phosphorus, present in either acid (HPO) or salt ((NH)PO) form, on the pyrolysis behaviour of both Miscanthus × giganteus, and its cell wall components, cellulose, hemicellulose (xylan) and lignin (Organosolv). Pyrolysis-gas chromatography-mass spectrometry (PY-GC-MS) is used to examine the pyrolysis products during thermal degradation, and thermogravimetric analysis (TGA) is used to examine the distribution of char and volatiles. Phosphorus salts are seen to catalyse the pyrolysis and modify the yields of products, resulting in a large increase in char yield for all samples, but particularly for cellulose and Miscanthus. The thermal degradation processes of cellulose, xylan and Miscanthus samples occur in one step and the main pyrolysis step is shifted to lower temperature in the presence of phosphorus. A small impact of phosphorus was observed in the case of lignin char yields and the types of pyrolysis decomposition products produced. Levoglucosan is a major component produced in fast pyrolysis of cellulose. Furfural and levoglucosenone become more dominant products upon P-impregnation pointing to new rearrangement and dehydration routes. The P-catalysed xylan decomposition route leads to a much simpler mixture of products, which are dominated by furfural, 3-methyl-2-cyclopenten-1-one and one other unconfirmed product, possibly 3,4-dihydro-2-methoxy-2H-pyran or 4-hydroxy-5,6-dihydro-(2H)-pyran-2-one. Phosphorus-catalysed lignin decomposition also leads to a modified mixture of tar components and desaspidinol as well as other higher molecular weight component become more dominant relative to the methoxyphenyl phenols, dimethoxy phenols and triethoxy benzene. Comparison of the results for Miscanthus lead to the conclusion that the understanding of the fast pyrolysis of biomass can, for the most part, be gained through the study of the individual cell wall components, provided consideration is given to the presence of catalytic components such as phosphorus.

Short-term changes in phosphorus storage in an oligotrophic Everglades wetland ecosystem receiving experimental nutrient enrichment

Natural, unenriched Everglades wetlands are known to be limited by phosphorus (P) and responsive to P enrichment. However, whole-ecosystem evaluations of experimental P additions are rare in Everglades or other wetlands. We tested the response of the Everglades wetland ecosystem to continuous, low-level additions of P (0, 5, 15, and 30 μg L−1 above ambient) in replicate, 100 m flow-through flumes located in unenriched Everglades National Park. After the first six months of dosing, the concentration and standing stock of phosphorus increased in the surface water, periphyton, and flocculent detrital layer, but not in the soil or macrophytes. Of the ecosystem components measured, total P concentration increased the most in the floating periphyton mat (30 μg L−1: mean = 1916 μg P g−1, control: mean = 149 μg P g−1), while the flocculent detrital layer stored most of the accumulated P (30 μg L−1: mean = 1.732 g P m−2, control: mean = 0.769 g P m−2). Significant short-term responses of P concentration and standing stock were observed primarily in the high dose (30 μg L−1 above ambient) treatment. In addition, the biomass and estimated P standing stock of aquatic consumers increased in the 30 and 5 μg L−1 treatments. Alterations in P concentration and standing stock occurred only at the upstream ends of the flumes nearest to the point source of added nutrient. The total amount of P stored by the ecosystem within the flume increased with P dosing, although the ecosystem in the flumes retained only a small proportion of the P added over the first six months. These results indicate that oligotrophic Everglades wetlands respond rapidly to short-term, low-level P enrichment, and the initial response is most noticeable in the periphyton and flocculent detrital layer.

The exchange of carbon, nitrogen, and phosphorus in dwarf and fringe mangroves of the oligotrophic southern Everglades

Water management has altered both the natural timing and volume of freshwater delivered to Everglades National Park. This is especially true for Taylor Slough and the C-111 basin, as hypersaline events in Florida Bay have been linked to reduced freshwater flow in this area. In light of recent efforts to restore historical flows to the eastern Everglades, an understanding of the impact of this hydrologic shift is needed in order to predict the trajectory of restoration. I conducted a study to assess the importance of season, water chemistry, and hydrologic conditions on the exchange of nutrients in dwarf and fringe mangrove wetlands along Taylor Slough. I also performed mangrove leaf decomposition studies to determine the contribution of biotic and abiotic processes to mass loss, the effect of salinity and season on degradation rates, and the importance of this litter component as a rapid source of nutrients. ^ Dwarf mangrove wetlands consistently imported total nutrients (C, N, and P) and released NO2− +NO3 −, with enhanced release during the dry season. Ammonium flux shifted from uptake to release over the study period. Dissolved phosphate activity was difficult to discern in either wetland, as concentrations were often below detection limits. Fluxes of dissolved inorganic nitrogen in the fringe wetland were positively related to DIN concentrations. The opposite was found for total nitrogen in the fringe wetland. A dynamic budget revealed a net annual export of TN to Florida Bay that was highest during the wet season. Simulated increases and decreases in freshwater flow yielded reduced exports of TN to Florida Bay as a result of changes in subsystem and water flux characteristics. Finally, abiotic processes yielded substantial nutrient and mass losses from senesced leaves with little influence of salinity. Dwarf mangrove leaf litter appeared to be a considerable source of nutrients to the water column of this highly oligotrophic wetland. To summarize, nutrient dynamics at the subsystem level were sensitive to short-term changes in hydrologic and seasonal conditions. These findings suggest that increased freshwater flow has the potential to lead to long-term, system-level changes that may reach as far as eastern Florida Bay. ^

Phosphorus enrichment effects on interactions among the ecosystem components in a long-hydroperiod oligotrophic marsh in Everglades National Park

Hydrology and a history of oligotrophy unite the massive landscape comprising freshwater marsh in Everglades National Park. With restoration of water flow to the Everglades, phosphorus (P) enrichment, both from agricultural and domestic sources, may increase nutrient load to the marsh ecosystem. Previous research of P enrichment of Everglades soil, periphyton, and macrophytes revealed each of these ecosystem components responds to increased P loads with increased production and nutrient content. Interactions among these ecosystem components and how P affects the magnitude and direction of interaction are poorly understood and are the focus of my research. Here I present results of a two-year, two-factor experiment of P enrichment and manipulation in Everglades National Park. I quantified biomass, nutrient content, and production for periphyton and macrophyes and found macrophyte removal drives change in nutrient content, biomass, and production of periphyton. Periphyton removal did not appear to control macrophyte dynamics. Soil chemical and physical characteristics were explained primarily by site differences but there was an enrichment effect of soil porewater nitrite + nitrate, nitrite, and soluble reactive phosphorus. Flocculent materials production and depth were significantly affected by macrophyte removal where depth and production were significantly greater with the no macrophyte treatment. The dominant macrophyte of the marsh, Eleocharis cellulosa, increased more in the unenriched marsh than in the enriched marsh. The combination of these findings suggests that dynamics in floc and periphyton are controlled primarily by the presence of periphyton and that this relationship is significantly affected by low-level P enrichment. These results may be valuable in their application to both managers and policy makers who are involved in the Everglades restoration process. ^

Relative significance of pelagic, benthic and allochthonous organic matter to microbial carbon cycling in a phosphorus-depleted subtropical estuary (Florida Bay)

Heterotrophic bacteria are important decomposers and transformers of primary production and provide an important link between detritus and the aquatic food web. In seagrass ecosystems, much of seagrass primary production is unavailable through direct grazing and must undergo microbial reworking before seagrass production can enter the aquatic food web. The goal of my dissertation research is to understand better the role heterotrophic bacteria play in carbon cycling in seagrass estuaries. My dissertation research focuses on Florida Bay, a seagrass estuary that has experienced recent changes in carbon source availability, which may have altered ecosystem function. My dissertation research investigates the importance of seagrass, algal and/or cyanobacterial, and allochthonous-derived organic matter to heterotrophic bacteria in Florida Bay and helps establish the carbon base of the estuarine food web. ^ A three tiered approach to the study of heterotrophic bacterial carbon cycling and trophic influences in Florida Bay was used: (1) Spatiotemporal observations of environmental parameters (hydrology, nutrients, extracellular enzymes, and microbial abundance, biomass, and production); (2) Microbial grazing experiments under different levels of top-down and bottom-up influence; and (3) Bulk and compound-specific (bacteria-biomarker fatty acid analysis) stable carbon isotope analysis. ^ In Florida Bay, spatiotemporal patterns in microbial extracellular enzyme (also called ectoenzyme) activities indicate that microorganisms hydrolyzed selectively fractions of the estuarine organic matter pool. The microbial community hydrolyzed organic acids, peptides, and phosphate esters and did not use storage and structural carbohydrates. Organic matter use by heterotrophic bacterioplankton in Florida Bay was co-regulated by bottom-up (resource availability) and top-down (grazer mediated) processes. A bacterial carbon budget based on bacterial, epiphytic, and seagrass production indicates that heterotrophic bacterial carbon cycles are supported primarily through epiphytic production with mixing from seagrass production. Stable carbon isotope analysis of bacteria biomarkers and carbon sources in Florida Bay corroborate the results of the bacterial carbon budget. These results support previous studies of aquatic consumers in Florida Bay, indicating that epiphytic/benthic algal and/or cyanobacterial production with mixing from seagrass-derived organic matter is the carbon base of the seagrass estuarine food web. ^

The Influence of Phosphorus on Periphyton Mats from the Everglades and Three Tropical Karstic Wetlands

The distinctive karstic, freshwater wetlands of the northern Caribbean and Central American region support the prolific growth of calcite-rich periphyton mats. Aside from the Everglades, very little research has been conducted in these karstic wetlands, which are increasingly threatened by eutrophication. This study sought to (i) test the hypothesis that water depth and periphyton total phosphorus (TP) content are both drivers of periphyton biomass in karstic wetland habitats in Belize, Mexico and Jamaica, (ii) provide a taxonomic inventory of the periphytic diatom species in these wetlands and (iii) examine the relationship between periphyton mat TP concentration and diatom assemblage at Everglades and Caribbean locations. ^ Periphyton biomass, nutrient and diatom assemblage data were generated from periphyton mat samples collected from shallow, marl-based wetlands in Belize, Mexico and Jamaica. These data were compared to a larger dataset collected from comparable sites within Everglades National Park. A diatom taxonomic inventory was conducted on the Caribbean samples and a combination of ordination and weighted-averaging modeling techniques were used to compare relationships between periphyton TP concentration, periphyton biomass and diatom assemblage composition among the locations. ^ Within the Everglades, periphyton biomass showed a negative correlation with water depth and mat TP, while periphyton mat percent organic content was positively correlated with these two variables. These patterns were also exhibited within the Belize, Mexico and Jamaica locations, suggesting that water depth and periphyton TP content are both drivers of periphyton biomass in karstic wetland systems within the northern Caribbean region. ^ A total of 146 diatom species representing 39 genera were recorded from the three Caribbean locations, including a distinct core group of species that may be endemic to this habitat type. Weighted averaging models were produced that effectively predicted mat TP concentration from diatom assemblages for both Everglades (R2=0.56) and Caribbean (R2=0.85) locations. There were, however, significant differences among Everglades and Caribbean locations with respect to species TP optima and indicator species. This suggests that although diatoms are effective indicators of water quality in these wetlands, differences in species response to water quality changes can reduce the predictive power of these indices when applied across systems. ^

Cascading ecological effects of low-level phosphorus enrichment in the Florida Everglades

Few studies have examined long-term ecological effects of sustained low-level nutrient enhancement on wetland biota. To determine sustained effects of phosphorus (P) addition on Everglades marshes we added P at low levels (5, 15, and 30 µg L-1 above ambient) for 5 yr to triplicate 100-m flow-through channels in pristine marsh. A cascade of ecological responses occurred in similar sequence among treatments. Although the rate of change increased with dosing level, treatments converged to similar enriched endpoints, characterized most notably by a doubling of plant biomass and elimination of native, calcareous periphyton mats. The full sequence of biological changes occurred without an increase in water total P concentration, which remained near ambient levels until Year 5. This study indicates that Everglades marshes have a near-zero assimilative capacity for P without a state change, that ecosystem responses to enrichment accumulate over time, and that downstream P transport mainly occurs through biota rather than the water column.