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. ^

Spatial and temporal variation of microbial properties in the water column of Florida Bay

Physical and biological properties of the water column of Florida Bay were examined at seven study sites over an eighteen month period. The results indicated seasonality in some parameters, but was not evident in others. The data displayed statistically significant (P < 0.05) differences between study sites indicating spatial variation. The presence of seagrass affected the overlying water column, especially with respect to the biological parameters: those areas overlying seagrass beds displayed statistically significantly higher values than those over sparsely covered or barren areas. During the period of the study, Florida Bay experienced a seagrass die-off event: microbial activity and numbers were statistically significantly higher over areas of dying seagrass than over healthy or dead areas. The results of this study pointed to phosphorus being the controlling, or limiting factor, for microbial activity in the water column of Florida Bay.

A study of methods used to analyze total oil and polycyclic aromatic hydrocarbons in produced water: steps towards the validation of molecularly imprinted polymers for use in marine environmetns

Produced water is a by-product of offshore oil and gas production, and is released in large volumes when platforms are actively processing crude oil. Some pollutants are not typically removed by conventional oil/water separation methods and are discharged with produced water. Oil and grease can be found dispersed in produced water in the form of tiny droplets, and polycyclic aromatic hydrocarbons (PAHs) are commonly found dissolved in produced water. Both can have acute and chronic toxic effects in marine environments even at low exposure levels. The analysis of the dissolved and dispersed phases are a priority, but effort is required to meet the necessary detection limits. There are several methods for the analysis of produced water for dispersed oil and dissolved PAHs, all of which have advantages and disadvantages. In this work, EPA Method 1664 and APHA Method 5520 C for the determination of oil and grease will be examined and compared. For the detection of PAHs, EPA Method 525 and PAH MIPs will be compared, and results evaluated. APHA Method 5520 C Partition-Infrared Method is a liquid-liquid extraction procedure with IR determination of oil and grease. For analysis on spiked samples of artificial seawater, extraction efficiency ranged from 85 – 97%. Linearity was achieved in the range of 5 – 500 mg/L. This is a single-wavelength method and is unsuitable for quantification of aromatics and other compounds that lack sp³-hybridized carbon atoms. EPA Method 1664 is the liquid-liquid extraction of oil and grease from water samples followed by gravimetric determination. When distilled water spiked with reference oil was extracted by this procedure, extraction efficiency ranged from 28.4 – 86.2%, and %RSD ranged from 7.68 – 38.0%. EPA Method 525 uses solid phase extraction with analysis by GC-MS, and was performed on distilled water and water from St. John’s Harbour, all spiked with naphthalene, fluorene, phenanthrene, and pyrene. The limits of detection in harbour water were 0.144, 3.82, 0.119, and 0.153 g/L respectively. Linearity was obtained in the range of 0.5-10 g/L, and %RSD ranged from 0.36% (fluorene) to 46% (pyrene). Molecularly imprinted polymers (MIPs) are sorbent materials made selective by polymerizing functional monomers and crosslinkers in the presence of a template molecule, usually the analytes of interest or related compounds. They can adsorb and concentrate PAHs from aqueous environments and are combined with methods of analysis including GC-MS, LC-UV-Vis, and desorption electrospray ionization (DESI)- MS. This work examines MIP-based methods as well as those methods previously mentioned which are currently used by the oil and gas industry and government environmental agencies. MIPs are shown to give results consistent with other methods, and are a low-cost alternative improving ease, throughput, and sensitivity. PAH MIPs were used to determine naphthalene spiked into ASTM artificial seawater, as well as produced water from an offshore oil and gas operation. Linearity was achieved in the range studied (0.5 – 5 mg/L) for both matrices, with R² = 0.936 for seawater and R² = 0.819 for produced water. The %RSD for seawater ranged from 6.58 – 50.5% and for produced water, from 8.19 – 79.6%.

Iron concentration and fluxes in the water column during POLARSTERN cruises in the Southern Ocean

In large parts of the Southern Ocean, primary production is limited due to shortage of iron (Fe). We measured vertical Fe profiles in the western Weddell Sea, Weddell-Scotia Confluence, and Antarctic Circumpolar Current (ACC), showing that Fe is derived from benthic Fe diffusion and sediment resuspension in areas characterized by high turbulence due to rugged bottom topography. Our data together with literature data reveal an exponential decrease of dissolved Fe (DFe) concentrations with increasing distance from the continental shelves of the Antarctic Peninsula and the western Weddell Sea. This decrease can be observed 3500 km eastward of the Antarctic Peninsula area, downstream the ACC. We estimated DFe summer fluxes into the upper mixed layer of the Atlantic sector of the Southern Ocean and found that horizontal advection dominates DFe supply, representing 54 ± 15% of the total flux, with significant vertical advection second most important at 29 ± 13%. Horizontal and vertical diffusion are weak with 1 ± 2% and 1 ± 1%, respectively. The atmospheric contribution is insignificant close to the Antarctic continent but increases to 15 ± 10% in the remotest waters (>1500 km offshore) of the ACC. Translating Southern Ocean carbon fixation by primary producers into biogenic Fe fixation shows a twofold excess of new DFe input close to the Antarctic continent and a one-third shortage in the open ocean. Fe recycling, with an estimated 'fe' ratio of 0.59, is the likely pathway to balance new DFe supply and Fe fixation.

Dissolved Iron, Aluminium, and Dissolved Inorganic Phosphorus in the (Sub-)Tropical Atlantic Surface Ocean

Inorganic nitrogen depletion restricts productivity in much of the low-latitude oceans, generating a selective advantage for diazotrophic organisms capable of fixing atmospheric dinitrogen (N2). However, the abundance and activity of diazotrophs can in turn be controlled by the availability of other potentially limiting nutrients, including phosphorus (P) and iron (Fe). Here we present high-resolution data (~0.3°) for dissolved iron, aluminum, and inorganic phosphorus that confirm the existence of a sharp north-south biogeochemical boundary in the surface nutrient concentrations of the (sub)tropical Atlantic Ocean. Combining satellite-based precipitation data with results from a previous study, we here demonstrate that wet deposition in the region of the intertropical convergence zone acts as the major dissolved iron source to surface waters. Moreover, corresponding observations of N2 fixation and the distribution of diazotrophic Trichodesmium spp. indicate that movement in the region of elevated dissolved iron as a result of the seasonal migration of the intertropical convergence zone drives a shift in the latitudinal distribution of diazotrophy and corresponding dissolved inorganic phosphorus depletion. These conclusions are consistent with the results of an idealized numerical model of the system. The boundary between the distinct biogeochemical systems of the (sub)tropical Atlantic thus appears to be defined by the diazotrophic response to spatial-temporal variability in external Fe inputs. Consequently, in addition to demonstrating a unique seasonal cycle forced by atmospheric nutrient inputs, we suggest that the underlying biogeochemical mechanisms would likely characterize the response of oligotrophic systems to altered environmental forcing over longer timescales.

Sintered Sewage Sludge As Support Material Used In Drinking Water Filtration

The processing of industry and domestic effluents in wastewater treatment plants reduces the amount of polluted material and forms reusable water and dehydrated sludge. the generation of hazardous municipal sludge can be decreased, as well as the impact on surface and underground water and the risk to human health. The aim this study is to verify the possibility to use sintered sewage sludge as support material after thermal treatment in the production of a filtering material to water supply systems. After thermal treatment the sewage sludge ash was characterized by X-ray fluorescence (XRF), leaching test and water solubilization. Dehydration of sludge was performed by controlled heating at temperatures of 180 degrees C, 350 degrees C, 600 degrees C, 850 degrees C and 1000 degrees C for 3 hours.

Impact of potassium and phosphorus in biomass on the properties of fast Pyrolysis bio-oil

This study investigates fast pyrolysis bio-oils produced from alkali-metal-impregnated biomass (beech wood). The impregnation aim is to study the catalytic cracking of the pyrolysis vapors as a result of potassium or phosphorus. It is recognized that potassium and phosphorus in biomass can have a major impact on the thermal conversion processes. When biomass is pyrolyzed in the presence of alkali metal cations, catalytic cracking of the pyrolysis liquids occurs in the vapor phase, reducing the organic liquids produced and increasing yields of water, char, and gas, resulting in a bio-oil that has a lower calorific value and an increased chance of phase separation. Beech wood was impregnated with potassium or phosphorus (K impregnation and P impregnation, respectively) in the range of 0.10-2.00 wt %. Analytical pyrolysis-gas chromatography-mass spectrometry (Py-GC-MS) was used to examine the pyrolysis products during thermal degradation, and thermogravimetric analysis (TGA) was used to examine the distribution of char and volatiles. Both potassium and phosphorus are seen to catalyze the pyrolytic decomposition of biomass and modify the yields of products. 3-Furaldehyde and levoglucosenone become more dominant products upon P impregnation, pointing to rearrangement and dehydration routes during the pyrolysis process. Potassium has a significant influence on cellulose and hemicellulose decomposition, not just on the formation of levoglucosan but also other species, such as 2(5H)-furanone or hydroxymethyl-cyclopentene derivatives. Fast pyrolysis processing has also been undertaken using a laboratory-scale continuously fed bubbling fluidized-bed reactor with a nominal capacity of 1 kg h-1 at the reaction temperature of 525 °C. An increase in the viscosity of the bio-oil during the stability assessment tests was observed with an increasing percentage of impregnation for both additives. This is because bio-oil undergoes polymerization while placed in storage as a result of the inorganic content. The majority of inorganics are concentrated in the char, but small amounts are entrained in the pyrolysis vapors and, therefore, end up in the bio-oil.