Catalytic hydrogenation of polyaromatic hydrocarbon (PAH) compounds in supercritical carbon dioxide over supported palladium

A series of supported palladium catalysts were evaluated for their ability to mediate the complete hydrogenation of polycyclic aromatic hydrocarbon (PAH) compounds. Benzo[a]pyrene (B[a]P) or phenanthrene (Phe) in hexane was merged with a hydrogen-carbon dioxide [5% (w/w) H(2)/CO(2)] stream and transferred to a flow through mini-reactor (capacity ca. 1 g) that was maintained at 90 degrees C under a back-pressure of 20.68 MPa. Effluent from the reactor trapped in hexane was monitored/quantified by gas chromatography-mass spectrometry. Catalyst formulations supported on iron powder, high density polyethylene (HDPE) or gamma-alumina were prepared and compared in terms of hydrogenation activity as measured by the quantity of substrate per unit time that could be perhydrogenated to toxicologically innocuous products. Both of the Pd preparations supported on gamma-alumina were more efficient than a commercial Pd(0) (5% w/w) on gamma-Al(2)O(3) formulation or preparations supported on HDPE or the iron powder. Bimetallic mixtures with Pd increased the hydrogenation activity when co-deposited with Cu or Ni but not with Ag or Co. However, increases in hydrogenation activity by increasing the loading of Pd (or bimetallic mixture) on this surface were limited. Despite using supercritical carbon dioxide (scCO(2)) to swell the surfaces of the polymer, the deposition of nanoparticles within the polyethylene formulation was appreciably less active than either the oxidic or the Fe(0) formulations.     

Mega-Development Trends in the Amazon: Implications for Global Change

This paper describes four global-change phenomena that are having major impacts on Amazonian forests. The first is accelerating deforestation and logging. Despite recent government initiatives to slow forest loss, deforestation rates in Brazilian Amazonia have increased from 1.1 million ha yr^–1 in the early 1990s, to nearly 1.5 million ha yr^–1 from 1992–1994, and to more than 1.9 million ha yr^–1 from 1995–1998. Deforestation is also occurring rapidly in some other parts of the Amazon Basin, such as in Bolivia and Ecuador, while industrialized logging is increasing dramatically in the Guianas and central Amazonia.The second phenomenon is that patterns of forest loss and fragmentation are rapidly changing. In recent decades, large-scale deforestation has mainly occurred in the southern and eastern portions of the Amazon — in the Brazilian states of Pará, Maranho, Rondônia, Acre, and Mato Grosso, and in northern Bolivia. While rates of forest loss remain very high in these areas, the development of major new highways is providing direct conduits into the heart of the Amazon. If future trends follow past patterns, land-hungry settlers and loggers may largely bisect the forests of the Amazon Basin.The third phenomenon is that climatic variability is interacting with human land uses, creating additional impacts on forest ecosystems. The 1997/98 El Niño drought, for example, led to a major increase in forest burning, with wildfires raging out of control in the northern Amazonian state of Roraima and other locations. Logging operations, which create labyrinths of roads and tracks in forsts, are increasing fuel loads, desiccation and ignition sources in forest interiors. Forest fragmentation also increases fire susceptibility by creating dry, fire-prone forest edges.Finally, recent evidence suggests that intact Amazonian forests are a globally significant carbon sink, quite possibly caused by higher forest growth rates in response to increasing atmospheric CO₂ fertilization. Evidence for a carbon sink comes from long-term forest mensuration plots, from whole-forest studies of carbon flux and from investigations of atmospheric CO₂ and oxygen isotopes. Unfortunately, intact Amazonian forests are rapidly diminishing. Hence, not only is the destruction of these forests a major source of greenhouse gases, but it is reducing their intrinsic capacity to help buffer the rapid anthropogenic rise in CO₂.     

Optimization of mining by application of the equality principle

This paper shows how the equality principle can be applied to traditional mining activities as a theoretical economic basis for “environmentally friendly” waste management of natural resources. A cost structure is proposed to generally improve the exploitation of the natural resources and save energy due to the promotion of corporate economic incentives to a more cost-effective waste management related to these resources. The methodology proposed is based on the cost-benefit analysis concept. It employs the previously introduced equality principle and the model for Efficient Use of Resources for Optimal Production Economy (EUROPE) featuring shadow prices so as to optimize the mining slope and the ore-concentration when utilizing the resources of the rock and provide management with a one digit indicator of the performance of a certain mining activity to get in just once glance an instant comprehension of their mine's overall performance. This approach simultaneously improves the profitability, the technology used and the environment. A case study presents the practical application of the proposed theory on a Swedish copper mine. It is concluded that the presented methodology improves the exploitation of natural resources in mainly technological, economical and environmental terms. The methods that are developed are regarded as being suitable information support tools for decision-making in waste management and optimization of the exploitation of natural resources in the corporate and public context.     

Nitrate controls methyl mercury production in a streambed bioreactor

Organic carbon bioreactors provide low-cost, passive treatment of a variety of environmental contaminants but can have undesirable side effects in some cases. This study examines the production of methyl mercury (MeHg) in a streambed bioreactor consisting of 40 m3 of wood chips and designed to treat nitrate (NO?) in an agricultural drainage ditch in southern Ontario (Avon site). The reactor provides 30 to 100% removal of NO?-N concentrations of 0.6 to 4.4 mg L(-1), but sulfate (SO?(2-)) reducing conditions develop when NO? removal is complete. Sulfate reducing conditions are known to stimulation the production of MeHg in natural wetlands. Over one seasonal cycle, effluent MeHg ranged from 0.01 to 0.76 ng L(-1) and total Hg ranged from 1.3 to 3.4 ng L(-1). During all sampling events when reducing conditions were only sufficient to promote NO?(-) reduction (or denitrification) ( = 5, late fall 2009, winter 2010), MeHg concentrations decreased in the reactor and it was a net sink for MeHg (mean flux of -5.1 μg m(-2) yr(-1)). During all sampling events when SO?(2-) reducing conditions were present ( = 6, early fall 2009, spring 2010), MeHg concentrations increased in the reactor and it was a strong source of MeHg to the stream (mean flux of 15.2 μg m(-2) yr(-1)). Total Hg was consistently removed in the reactor (10 of 11 sampling events) and was correlated to the total suspended sediment load ( r2 = 0.69), which was removed in the reactor by physical filtration. This study shows that organic carbon bioreactors can be a strong source of MeHg production when SO?(2-) reducing conditions develop; however, maintaining NO?-N concentrations > 0.5 mg L suppresses the production of MeHg.     

Ash and deposit formation from oxy-coal combustion in a 100 kW test furnace

Ash deposition is still an unresolved problem when retrofitting existing air-fired coal power plants to oxy-fuel combustion. Experimental data are quite necessary for mechanism validation and model development. This work was designed to obtain laboratory combustor data on ash and deposits from oxy-coal combustion, and to explore the effects of oxy-firing on their formation. Two bituminous coals (Utah coal and Illinois coal) and one sub-bituminous coal (PRB coal) were burned on a down-fired combustor under both oxy- and air-firing. Two oxy-fired cases, i.e., 27 vol% O₂/73 vol% CO₂ and 32 vol% O₂/68 vol% CO₂, were selected to match the radiation flux and the adiabatic flame temperature of air combustion, respectively. Once-through CO₂ was used to simulate fully cleaned recycled flue gas. The flue gas excess oxygen was fixed at 3 vol%. For each case, both size-segregated fly ash and bulk fly ash samples were obtained. Simultaneously, ash deposits were collected on an especially designed un-cooled deposition probe. Ash particle size distributions and chemical composition of all samples were characterized. Data showed that oxy-firing had insignificant impacts on the tri-modal ash particle size distributions and composition size distributions in the size range studied. Bulk ash compositions also showed no significant differences between oxy- and air-firing, except for slightly higher sulfur contents in some oxy-fired ashes. The oxy-fired deposits were thicker than those from air-firing, suggesting enhanced ash deposition rates in oxy-firing. Oxy-firing also had apparent impacts on the deposit composition, especially for those components (e.g., CaO, Fe₂O₃, SO₃, etc.) that could contribute significantly to ash deposition. Based on these results, aerodynamic changes in gas flow and changes in combustion temperature seemed more important than chemical changes of ash particles in determining deposit behavior during oxy-coal combustion.     

Methane emissions from natural wetlands

Methane is considered one of the most important greenhouse gases in the atmosphere. Because of the strict anaerobic conditions required by CH₄-generating microorganisms, natural wetland ecosystems are one of the main sources of biogenic CH₄. The total natural wetland area is estimated to be 5.3 to 5.7 × 10¹² m², making up less than 5% of the Earth's land surface. However, natural wetland plays a disproportionately large role in CH₄ emissions. Wetlands are likely the largest natural sources of CH₄ to the atmosphere, accounting for about 20% of the current global annual emission. Out of the total amount of CH₄ emitted, northern wetlands contribute 34%, temperate wetlands 5%, and tropical systems about 60%.Because of the unique characteristics and high productivity, wetland ecosystems are important in the global carbon cycle. Natural wetlands are permanently or temporarily saturated. Strict anaerobic conditions consequently develop, which allows methanogenesis to occur. But the thin oxic layer and the oxic plant rhizophere promote activity of CH₄-oxidizing bacteria or methanotrophs. Thus, both CH₄ formation and consumption in wetland systems are microbiological processes and are controlled by many factors. Eight of the controlling factors, including carbon supply, soil oxidation-reduction status, pH, temperature, vegetation, salinity and sulfate content, soil hydrological conditions and CH₄ oxidation are discussed in this paper.     

The efficacy of protoporphyrin as a predictive biomarker for lead exposure in canvasback ducks: Effect of sample storage time

We used 363 blood samples collected from wild canvasback dueks (Aythya valisineria) at Catahoula Lake, Louisiana, U.S.A. to evaluate the effect of sample storage time on the efficacy of erythrocytic protoporphyrin as an indicator of lead exposure. The protoporphyrin concentration of each sample was determined by hematofluorometry within 5 min of blood collection and after refrigeration at 4 °C for 24 and 48 h. All samples were analyzed for lead by atomic absorption spectrophotometry. Based on a blood lead concentration of 0.2 ppm wet weight as positive evidence for lead exposure, the protoporphyrin technique resulted in overall error rates of 29%, 20%, and 19% and false negative error rates of 47%, 29% and 25% when hematofluorometric determinations were made on blood at 5 min, 24 h, and 48 h, respectively. False positive error rates were less than 10% for all three measurement times. The accuracy of the 24-h erythrocytic protoporphyrin classification of blood samples as positive or negative for lead exposure was significantly greater than the 5-min classification, but no improvement in accuracy was gained when samples were tested at 48 h. The false negative errors were probably due, at least in part, to the lag time between lead exposure and the increase of blood protoporphyrin concentrations. False negatives resulted in an underestimation of the true number of canvasbacks exposed to lead, indicating that hematofluorometry provides a conservative estimate of lead exposure.The U.S. Government's right to retain a non-exclusive, royalty-free licence in and to any copyright is acknowledgedDeceased     

Case Study and Retrospective: Aerobic Fixed Film Biological Treatment Process for 1,4‐Dioxane at the Lowry Landfill Superfund Site

An aerobic fixed film biological treatment system has been successfully treating recovered groundwater/landfill leachate containing 1,4‐dioxane, tetrahydrofuran (THF), and other constituents since 2003. The most likely mode of 1,4‐dioxane biotransformation is via a cometabolic pathway in the presence of THF. Pilot studies conducted during the process development phase established a design basis process loading factor of 0.6 g 1,4‐dioxane and THF (as chemical oxygen demand [COD])/g total solids per day and proved the efficacy of the process. Full‐scale design includes the use of three parallel moving bed bioreactors with effluent recycle capability. Removal efficiencies in excess of 98 percent have been documented for 1,4‐dioxane. Evolving operational challenges are associated with recent trends in 1,4‐dioxane pretreatment discharge limitations in combination with ongoing process optimization and increased influent flow rate conditions associated with seasonal precipitation patterns. ©2016 Wiley Periodicals, Inc.     

The efficacy of a limestone doser to mitigate stream acidification in a Maryland coastal plain stream: Implications for migratory fish species

The objective of this two-year study was to determine the efficacy of an automated limestone slurry doser to neutralize acidic pulses and improve water quality conditions for enhancing survival of early life stages of migratory fish species in a Maryland coastal plain stream. Implications for survival of early life stages of migratory fish species such as yellow perch (Perca flavescens), white perch (Morone americana), blueback herring (Alosa aestivalis) and alewife (Alosa pseudoharengus) are discussed based on the improved chemical conditions in the dosed area of the stream. Despite problems with overdosing in 1991 and failure of the stage transducer to work properly in 1992, the doser was generally effective in neutralizing acidic pulses (pH depressions) in the stream during three major rain events in both years. Chemical conditions (pH and inorganic monomeric aluminum) reported in the non-dosed area during major rainfall events were potentially stressful to both alewife and blueback herring although neither species was reported spawning in the stream during either year. Mitigating the potential impact of acidic conditions on early life stages of important migratory fish species was not sufficient to ensure spawning. It is therefore recommended that habitat improvement measures and well designed fish stocking programs be implemented concurrently with doser operations if the goal is to create optimum spawning conditions for migratory species.