Chlorination of dibenzofuran and dibenzo-p-dioxin vapor by copper (II) chloride

Dibenzofuran (DF) is formed from phenol and benzene in combustion gas exhaust streams prior to particle collection equipment. Subsequent chlorination at lower temperatures on particle surfaces is a potential source of chlorinated dibenzofuran (CDF). Gas streams containing 8% O₂ and approximately 0.1% DF vapor were passed through particle beds containing copper (II) chloride (0.5% Cu, mass) at temperatures ranging from 200 to 400 °C to investigate the potential for CDF formation during particle collection. Experiment duration was sufficient to provide an excess amount of DF (DF/Cu=3). The efficiency of DF chlorination by CuCl₂ and the distribution of CDF products were measured, with effects of temperature, gas velocity, and experiment duration assessed. Results of a more limited investigation of dibenzo-p-dioxin (DD) chlorination by CuCl₂ to form chlorinated DD (CDD) products are also presented.

The efficiency of DF/DD chlorination by CuCl₂ was high, both in terms of CuCl₂ utilization and DF/DD conversion. Total yields of Cl on CDF/CDD products of up to 0.5 mole Cl per mole CuCl₂ were observed between 200 and 300 °C; this suggests that nearly 100% CuCl₂ was utilized, assuming a conversion of two moles of CuCl₂ to CuCl per mole Cl added to DD/DF. In a short duration experiment (DF/Cu=0.3), nearly 100% DF adsorption and conversion to CDF was achieved. The degree of CDF chlorination was strongly dependent on gas velocity. At high gas velocity, corresponding to a gas–particle contact time of 0.3 s, mono-CDF (MCDF) yield was largest, with yields decreasing with increasing CDF chlorination. At low gas velocity, corresponding to a gas–particle contact time of 5 s, octa-CDF yield was largest. DF/DD chlorination was strongly favored at lateral sites, with the predominant CDF/CDD isomers within each homologue group those containing Cl substituents at only the 2,3,7,8 positions. At the higher temperatures and lower gas velocities studied, however, broader isomer distributions, particularly of the less CDD/CDF products, were observed, likely due to preferential destruction of the 2,3,7,8 congeners.     

Modeling Hydrological and Environmental Consequences of Climate Change and Urbanization in the Boise River Watershed,Idaho

The potential impacts driven by climate variability and urbanization in the Boise River Watershed (BRW), located in southwestern Idaho, are evaluated. The outcomes from Global Circulation Models (GCMs) and land use and land cover (LULC) analysis have been incorporated into a hydrological and environmental modeling framework to characterize how climate variability and urbanization can affect the local hydrology and environment at the BRW. The combined impacts of future climate and LULC change are also evaluated relative to the historical baseline conditions. For modeling exercises, Hydrological Simulation Program‐Fortran (HSPF) is used in parallel computing and statistical techniques, including spatial downscaling and bias correlation, are employed to evaluate climate consequences derived from GCMs as well. The implications of climate variability and land use change driven by urbanization are then observed to evaluate how these overall global challenges can affect water quantity and quality conditions at the BRW. The results show the combined impacts of both climate change and urbanization can lead to more seasonal variability of streamflow (from ?27.5% to 12.5%) and water quality, including sediment (from ?36.5% to 49.3%), nitrogen (from ?24% to 124.2%), and phosphorus (from ?13.3% to 21.2%) during summer and early fall over the next several decades.     

Effects of Stock Use and Backpackers on Water Quality in Wilderness in Sequoia and Kings Canyon National Parks, USA

During 2010–2011, a study was conducted in Sequoia and Kings Canyon National Parks (SEKI) to evaluate the influence of pack animals (stock) and backpackers on water quality in wilderness lakes and streams. The study had three main components: (1) a synoptic survey of water quality in wilderness areas of the parks, (2) paired water quality sampling above and below several areas with differing types and amounts of visitor use, and (3) intensive monitoring at six sites to document temporal variations in water quality. Data from the synoptic water quality survey indicated that wilderness lakes and streams are dilute and have low nutrient and Escherichia coli concentrations. The synoptic survey sites were categorized as minimal use, backpacker-use, or mixed use (stock and backpackers), depending on the most prevalent type of use upstream from the sampling locations. Sites with mixed use tended to have higher concentrations of most constituents (including E. coli) than those categorized as minimal-use (P ≤ 0.05); concentrations at backpacker-use sites were intermediate. Data from paired-site sampling indicated that E. coli, total coliform, and particulate phosphorus concentrations were greater in streams downstream from mixed-use areas than upstream from those areas (P ≤ 0.05). Paired-site data also indicated few statistically significant differences in nutrient, E. coli, or total coliform concentrations in streams upstream and downstream from backpacker-use areas. The intensive-monitoring data indicated that nutrient and E. coli concentrations normally were low, except during storms, when notable increases in concentrations of E. coli, nutrients, dissolved organic carbon, and turbidity occurred. In summary, results from this study indicate that water quality in SEKI wilderness generally is good, except during storms; and visitor use appears to have a small, but statistically significant influence on stream water quality.     

A resilience-based approach for comparing expert preferences across two large-scale coastal management programs

This report proposes a method for assessing resilience-building components in coastal social–ecological systems. Using the proposed model, the preferences of experts in Masan Bay (South Korea) and Puget Sound (USA) are compared. A total of 30 management objectives were determined and used to build a hierarchic tree designed using the principles of the Analytic Hierarchy Process (AHP). Surveys were performed with 35 Puget Sound experts using face-to-face interviews and with 28 Masan Bay experts by mail. The results demonstrate that the legal objective, which enables legislation, was the highest preferred component in both regions. The knowledge translation variable was also given a high preference score in both regions. An analysis of variance (ANOVA) showed that the Puget Sound experts significantly favored attention to education, habitat restoration and species protection objectives in comparison to the Masan Bay experts. The Masan Bay experts placed greater emphasis on legislation and the type of institutional design than did the Puget Sound experts. Using cluster analysis, four distinct groups of respondents were independently identified in Puget Sound and three groups were identified in Masan Bay. One unique subgroup in the Puget Sound experts group, which was characterized by its high preferences for habitat restoration and species protection, was not observed in Masan Bay. Demographic variables (length of career and role in coastal issue) failed to account for the differences in groupings and preferences in either region, except for the variable ‘favoring information source’ in the Puget Sound group. This finding implies that the demographic information was not related to differences in group opinions in both regions. The analysis framework presented here was effective in identifying expert preferences regarding the overall structure and emphasis in coastal management programs. Thus, this framework can be applied towards coastal policy development.     

Chlorinated naphthalene formation from the oxidation of dichlorophenols

Polychlorinated naphthalenes (PCNs) formed along with dibenzo-p-dioxin and dibenzofuran products in the slow combustion of dichlorophenols (DCPs) at 600 degrees C were identified. Each DCP reactant produced a unique set of PCN products. Major PCN congeners observed in the experiments were consistent with products predicted from a mechanism involving an intermediate formed by ortho-ortho carbon coupling of phenoxy radicals; polychlorinated dibenzofurans (PCDFs) are formed from the same intermediate. Tautomerization of the intermediate and H2O elimination produces PCDFs; alternatively, CO elimination to form dihydrofulvalene and fusion produces naphthalenes. Only trace amounts of tetrachloronaphthalene congeners were formed, suggesting that the preferred PCN formation pathways from chlorinated phenols involve loss of chlorine. 3,4-DCP produced the largest yields of PCDF and PCN products with two or more chlorine substituents. 2,6-DCP did not produce tri- or tetra-chlorinated PCDF or PCN congeners. It did produce 1,8-DCN, however, which could not be explained.     

Hydrogen sulfide effects on ammonia removal by a biofilter seeded with earthworm casts

Ammonia (NH3) removal efficencies were evaluated when hydrogen sulfide (H2S) and NH3 in binary mixture gases were supplied to a ceramic biofilter seeded with earthworm (Lumbricus terrestris) casts. The effect of inlet H2S concentration and space velocity (SV) on the removal of NH3 was investigated after the acclimation of the biofilter with NH3 gas. When NH3 was singly supplied to the biofilter, NH3 removal was maintained at almost 100% until inlet NH3 concentration was increased up to 600 microL L(-1) and SV up to 330 h(-1), at which the elimination capacity of NH3 was 148 g N m(-3) h(-1). When H2S was supplied simultaneously, however, the accumulation of toxic sulfide ions showed dual effects on NH3 removal efficiencies. First, no effects were observed at inlet H2S loading below 60 g S m(-3) h(-1); however, inhibition by H2S at higher loading was observed above 60 g S m(-3) h(-1). The point at which loading achieved a maximum of more than 99% NH3 removal efficiency was 139 g N m(-3) h(-1), when inlet H2S concentration was held under 100 microL L(-1), but it dropped to 76 and 30 g N m(-3) h(-1) when the inlet H2S concentration increased to 220 and 460 microL L(-1), respectively. The critical points of inlet H2S loading that guaranteed over 99% NH3 removal were determined as 100, 100, 60, and 40 g S m(-3) h(-1) at inlet NH3 concentrations of 100, 200, 400, and 600 microL L(-1), respectively. Inlet NH3 loading had synergic effects of increasing the inhibition of inlet H2S loading on the NH3 removability of the biofilter.     

Estimation of methane emission potential using the Clean Development Mechanism (CDM) tool for municipal solid waste landfill in Mandalay,Myanmar

Journal of Material Cycles and Waste Management - Municipal solid waste (MSW) landfills are the third largest source of global methane emissions as biogas (11%). In developing countries, MSW...     

First-trimester screening for Down syndrome; the role of nasal bone assessment in the Korean population

Objectives The aim of this study was to evaluate the role of nasal bone assessment in first-trimester screening for Down syndrome (DS) in the Korean population. Methods From July 2004 to March 2006, we prospectively evaluated the fetal nasal bones at 11–14 weeks' gestation in the Korean population. Results A successful evaluation was possible in 6490 of 6787 fetuses (95.6%). Absent, hypoechoic, and short nasal bones were seen in 4 (26.7%), 4 (26.7%), and 1 (6.7%) of 15 fetuses with DS, respectively, whereas in 5 (0.1%), 11 (0.2%), and 246 (3.8%) of 6456 normal fetuses. The incidence of absent and hypoechoic nasal bone showed significant differences between normal fetuses and fetuses with DS (P < 0.0005, both). Screening for DS using an absent or hypoechoic nasal bone resulted in a sensitivity of 53.3%, a specificity of 99.8%, a positive likelihood ratio of 215.2, and a negative likelihood ratio of 0.5. Conclusion Our study showed that nasal bone abnormality at 11–14 weeks of gestation had a high association with DS in the Korean population. This suggests that nasal bone assessment can be used to supplement the current first-trimester screening for DS in the Korean population. Copyright © 2007 John Wiley & Sons, Ltd.     

Combined simulation of combustion and gas flow in a grate-type incinerator

Computational fluid dynamic (CFD) analysis of the thermal flow in the combustion chamber of a solid waste incinerator provides crucial insight into the incinerator's performance. However, the interrelation of the gas flow with the burning waste has not been adequately treated in many CFD models. A strategy for a combined simulation of the waste combustion and the gas flow in the furnace is introduced here. When coupled with CFD, a model of the waste combustion in the bed provides the inlet conditions for the gas flow field and receives the radiative heat flux onto the bed from the furnace wall and gaseous species. An unsteady one-dimensional bed model was used for the test simulation, in which the moving bed was treated as a packed bed of homogeneous fuel particles. The simulation results show the physical processes of the waste combustion and its interaction with the gas flow for various operational parameters.     

Metal-mediated chlorinated dibenzo-p-dioxin (CDD) and dibenzofuran (CDF) formation from phenols

Heterogeneous formation of chlorinated dibenzo-p-dioxins (CDDs) and dibenzofurans (CDFs) on CuCl2 from three phenols without ortho chlorine and one phenol with two ortho chlorines was studied in a flow reactor over a temperature range of 325-450 degrees C. Heated nitrogen gas streams containing 8% oxygen, 1.5% benzene vapor, and equal amounts of phenol, 3-chlorophenol, 3,4-dichlorophenol and 2,4,6-trichlorophenol vapor (700 ppmv, each) were passed through a 1 g particle bed of silica and 0.5% (Cu mass) CuCl2. Maximum product yields of greater than 1.4% phenol conversion to CDD and 5.7% phenol conversion to CDF were observed between 400 and 450 degrees C. CDDs formed with loss of one chlorine atom were favored. While total CDD/F yield varied with temperature, CDD/F homologue and isomer distributions did not vary significantly with temperature. Based on the results of experiments with single phenol precursors, phenol precursors could be assigned to all PCDD/F products. Of the chlorinated phenols without ortho chlorine that were studied, 3,4-dichlorophenol was found to have the greatest propensity to form CDFs.