Titanium dioxide photocatalytic degradation of aliphatic ethers and their primary oxidation products

Two studies were performed to obtain fundamental mechanistic information on the TiO2 catalyzed degradation of organic substrates irradiated at 350 nm in dilute aqueous solutions under oxygenated conditions: (a) The photodecomposition of methyl tert-butyl ether (MTBE) and its intermediate products from β-oxidation, 2-methoxy-2-methylpropanol and 2-methoxy-2-methylpropanol. (b) The photodecomposition of two haloethers, bis-(2-chloroethyl) ether, and bis-(2-chloroisopropyl) ether. Controls were carried out throughout the two studies in the absence of light, and without the semiconductor in order to evaluate the role of photolysis. ^ The syntheses of proposed intermediate products, 2-methoxy-2-methylpropanol, 2-methoxy-2-methylpropanal, 2-methoxy-2-methylpropanoic acid, 2-chloroethyl formate, and 1-chloro-2-propyl acetate, were performed. The formation of these products in the titanium dioxide photocatalytic oxidation of the substrates of interest was also confirmed. TiO2 photocatalysis is a very effective method for the mineralization of aliphatic ethers and their primary oxidation products. ^

Mangrove production and carbon sinks: A revision of global budget estimates

Mangrove forests are highly productive but globally threatened coastal ecosystems, whose role in the carbon budget of the coastal zone has long been debated. Here we provide a comprehensive synthesis of the available data on carbon fluxes in mangrove ecosystems. A reassessment of global mangrove primary production from the literature results in a conservative estimate of ∼218 ± 72 Tg C a−1. When using the best available estimates of various carbon sinks (organic carbon export, sediment burial, and mineralization), it appears that >50% of the carbon fixed by mangrove vegetation is unaccounted for. This unaccounted carbon sink is conservatively estimated at ∼112 ± 85 Tg C a−1, equivalent in magnitude to ∼30–40% of the global riverine organic carbon input to the coastal zone. Our analysis suggests that mineralization is severely underestimated, and that the majority of carbon export from mangroves to adjacent waters occurs as dissolved inorganic carbon (DIC). CO2 efflux from sediments and creek waters and tidal export of DIC appear to be the major sinks. These processes are quantitatively comparable in magnitude to the unaccounted carbon sink in current budgets, but are not yet adequately constrained with the limited published data available so far.

Allocation of Biomass and Net Primary Productivity of Mangrove Forests along Environmental Gradients in the Florida Coastal Everglades, USA

Vegetation patterns of mangroves in the Florida Coastal Everglades (FCE) result from the interaction of environmental gradients and natural disturbances (i.e., hurricanes), creating an array of distinct riverine and scrub mangroves across the landscape. We investigated how landscape patterns of biomass and total net primary productivity (NPPT), including allocation in above- and below-ground mangrove components, vary inter-annually (2001–2004) across gradients in soil properties and hydroperiod in two distinct FCE basins: Shark River Estuary and Taylor River Slough. We propose that the allocation of belowground biomass and productivity (NPPB) relative to aboveground allocation is greater in regions with P limitation and permanent flooding. Porewater sulfide was significantly higher in Taylor River (1.2 ± 0.3 mM) compared to Shark River (0.1 ± 0.03 mM) indicating the lack of a tidal signature and more permanent flooding in this basin. There was a decrease in soil P density and corresponding increase in soil N:P from the mouth (28) to upstream locations (46–105) in Shark River that was consistent with previous results in this region. Taylor River sites showed the highest P limitation (soil N:P > 60). Average NPPT was double in higher P environments (17.0 ± 1.1 Mg ha−1 yr−1) compared to lower P regions (8.3 ± 0.3 Mg ha−1 yr−1). Root biomass to aboveground wood biomass (BGB:AWB) ratio was 17 times higher in P-limited environments demonstrating the allocation strategies of mangroves under resource limitation. Riverine mangroves allocated most of the NPPT to aboveground (69%) while scrub mangroves showed the highest allocation to belowground (58%). The total production to biomass (P:B) ratios were lower in Shark River sites (0.11 yr−1); whereas in Taylor River sites P:B ratios were higher and more variable (0.13–0.24 yr−1). Our results suggest that the interaction of lower P availability in Taylor River relative to Shark River basin, along with higher sulfide and permanent flooding account for higher allocation of belowground biomass and production, at expenses of aboveground growth and wood biomass. These distinct patterns of carbon partitioning between riverine and scrub mangroves in response to environmental stress support our hypothesis that belowground allocation is a significant contribution to soil carbon storage in forested wetlands across FCE, particularly in P-limited scrub mangroves. Elucidating these biomass strategies will improve analysis of carbon budgets (storage and production) in neotropical mangroves and understanding what conditions lead to net carbon sinks in the tropical coastal zone.

Simulating Mechanisms for Dispersal, Production and Stranding of Small Forage Fish in Temporary Wetland Habitats

Movement strategies of small forage fish (<8 cm total length) between temporary and permanent wetland habitats affect their overall population growth and biomass concentrations, i.e., availability to predators. These fish are often the key energy link between primary producers and top predators, such as wading birds, which require high concentrations of stranded fish in accessible depths. Expansion and contraction of seasonal wetlands induce a sequential alternation between rapid biomass growth and concentration, creating the conditions for local stranding of small fish as they move in response to varying water levels. To better understand how landscape topography, hydrology, and fish behavior interact to create high densities of stranded fish, we first simulated population dynamics of small fish, within a dynamic food web, with different traits for movement strategy and growth rate, across an artificial, spatially explicit, heterogeneous, two-dimensional marsh slough landscape, using hydrologic variability as the driver for movement. Model output showed that fish with the highest tendency to invade newly flooded marsh areas built up the largest populations over long time periods with stable hydrologic patterns. A higher probability to become stranded had negative effects on long-term population size, and offset the contribution of that species to stranded biomass. The model was next applied to the topography of a 10 km × 10 km area of Everglades landscape. The details of the topography were highly important in channeling fish movements and creating spatiotemporal patterns of fish movement and stranding. This output provides data that can be compared in the future with observed locations of fish biomass concentrations, or such surrogates as phosphorus ‘hotspots’ in the marsh.