Atmospheric chemistry of perfluorobutenes (CF3CFCFCF3 and CF3CF2CFCF2): Kinetics and mechanisms of reactions with OH radicals and chlorine atoms,IR spectra,global warming potentials,and oxidation to perfluorocarboxylic acids

Relative rate techniques were used to determine k(Cl + CF₃CFCFCF₃) = (7.27 ± 0.88) × 10^?12, k(Cl + CF₃CF₂CFCF₂) = (1.79 ± 0.41) × 10^?11, k(OH + CF₃CFCFCF₃) = (4.82 ± 1.15) × 10^?13, and k(OH + CF₃CF₂CFCF₂) = (1.94 ± 0.27) × 10^?12 cm³ molecule^?1 s^?1 in 700 Torr of air or N₂ diluent at 296 K. The chlorine atom- and OH radical-initiated oxidation of CF₃CFCFCF₃ in 700 Torr of air gives CF₃C(O)F in molar yields of 196 ± 11 and 218 ± 20%, respectively. Chlorine atom-initiated oxidation of CF₃CF₂CFCF₂ gives molar yields of 97 ± 9% CF₃CF₂C(O)F and 97 ± 9% COF₂. OH radical-initiated oxidation of CF₃CF₂CFCF₂ gives molar yields of 110 ± 15% CF₃CF₂C(O)F and 99 ± 8% COF₂. The atmospheric fate of CF₃CF₂C(O)F and CF₃C(O)F is hydrolysis to give CF₃CF₂C(O)OH and CF₃C(O)OH. The atmospheric lifetimes of CF₃CFCFCF₃ and CF₃CF₂CFCF₂ are determined by reaction with OH radicals and are approximately 24 and 6 days, respectively. The contribution of CF₃CFCFCF₃ and CF₃CF₂CFCF₂ to radiative forcing of climate change will be negligible.     

Heterogeneous uptake of octamethylcyclotetrasiloxane (D4) and decamethylcyclopentasiloxane (D5) onto mineral dust aerosol under variable RH conditions

We have carried out kinetic studies to characterize the heterogeneous decay of octamethylcyclotetrasiloxane (D₄) and decamethylcyclopentasiloxane (D₅) in the presence of representative mineral dust aerosol in order to obtain a better understanding of the atmospheric fate of these siloxanes. The heterogeneous chemistry of D₄ and D₅ with various mineral dusts was studied in an environmental aerosol reaction chamber using FTIR absorption spectroscopy to monitor the reaction. The apparent heterogeneous uptake coefficient, γ_app, for D₄ and D₅ with various mineral dusts was measured under dry conditions and as a function of relative humidity (RH). In addition, the effect of initial D₄ and D₅ concentration on the rate and yield of the reaction was examined. The uptake coefficient, γ_app, for D₄ and D₅ was similar for the most reactive aerosols tested, with kaolinite ≈hematite > silica. Limited uptake onto carbon black and calcite surfaces was observed for either siloxane. Reaction with hematite and kaolinite resulted in multilayer coverages, suggesting extensive polymerization of D₄ and D₅ on the aerosol surface.     

Inactivation of Ascaris eggs in soil by microwave treatment compared to UV and ozone treatment

This study reports on the effect of microwave radiation for inactivation of Ascaris lumbricoides eggs in 25 g of soil compared to ultraviolet irradiation and ozone expose. Microwave radiation at 700 W with 14% water content (w/w) achieved approximately 2.5 log inactivation of eggs in soil within 60 s. On the other hand, UV irradiation at 3 mW cm⁻² with and without shaking soil for 3600 s achieved approximately 0.32 and 0.01 log inactivation of eggs, respectively. In ozone treatment, 0.13 log inactivation of eggs was achieved with 5.8 ± 0.7 mg L⁻¹ of dissolved ozone dose for 30 min in a continuous diffusion reactor. In addition, the inactivation of eggs by three disinfection techniques was conducted in water in order to compare the inactivation efficiency of eggs in soil. The inactivation efficiency of microwave radiation was found to be no significant difference between in soil and water. However, the inactivation efficiency of UV irradiation was significantly increased in water while in ozone expose there was no significant difference between in soil and water. Microwave treatment thus proved to be the most efficient method in controlling A. lumbricoides eggs in soil.     

Arsenic concentration in porewater of an alkaline coal ash disposal site: Roles of siderite precipitation/dissolution and soil cover

The geochemical behavior of As in porewaters of an alkaline coal ash disposal site was investigated using multilevel samplers. The disposal site was in operation from 1983 until 1994 and was covered with 0.3–0.5 m thick soils in 2001 when this study was initiated. Sequential extraction analyses and batch leaching experiments were also performed using the coal ash samples collected from the disposal site. The results suggest the important roles of siderite (FeCO₃) precipitation/dissolution and soil cover, which have been ignored previously. Arsenic levels in the porewater were very low (average of 10 μg L⁻¹) when the site was covered with soil due to coprecipitation with siderite. The soil cover enabled the creation of anoxic conditions, which raised the Fe concentration by the reductive dissolution of Fe-(hydr)oxides. Because of the high alkalinity generated from the alkaline coal ash, even a small increase in the Fe concentration (0.66 mg L⁻¹ on average) could cause siderite precipitation. When the soil cover was removed, however, an oxidizing condition was created and triggered the precipitation of dissolved Fe as (hydr)oxides. As a result, the dissolution of previously precipitated As-rich siderite caused higher As concentration in the porewater (average of 345 μg L⁻¹).     

Alkali borosilicate glass by fly ash from a coal-fired power plant

The possibility of using coal fly ash as a silica source for alkali borosilicate glass was investigated. Alkali borosilicate glasses were prepared from the coal fly ash mixed with 30 wt.% reagents composed of Na(2)O and B(2)O(3) by susceptor-induction heating. Their densities ranged from 2.24 to 2.55 g cm(-3) and decreased as the amount of B(2)O(3) addition increased. However, the Vickers microhardness showed a different tendency with the density since the glass network connectivity improved by boron anomaly, which was identified by a nuclear magnetic resonance analysis. The Vickers microhardness of the glass product, with the addition of 15 wt.% B(2)O(3) and 15 wt.% Na(2)O, was about 4030 MPa. Furthermore, the changes in microstructure were consistent with those in the chemical stability by the toxicity characteristic leaching procedure (TCLP).     

Arsenic species in ecosystems affected by arsenic-rich spring water near an abandoned mine in Korea

The objectives of this study were to quantitatively estimate the distribution of arsenic with its speciation and to identify potential pathways for transformation of arsenic species from samples of water, sediments, and plants in the ecosystem affected by the Cheongog Spring, where As(V) concentration reached levels up to 0.270 mg L⁻¹. After flowing about 100 m downstream, the arsenic level showed a marked reduction to 0.044 mg L⁻¹ (about 84% removal) without noticeable changes in major water chemistry. The field study and laboratory hydroponic experiments with the dominant emergent plants along the creek (water dropwort and thunbergian smartweed) indicated that arsenic distribution, reduction, and speciation appear to be controlled by, (i) sorption onto stream sediments in exchangeable fractions, (ii) bioaccumulation by and possible release from emergent plants, and (iii) transformation of As(V) to As(III) and organic species through biological activities.     

Sensitivity and Uncertainty of Ground‐Water Discharge Estimates for Semiarid Shrublands1

Abstract: We proposed a step‐by‐step approach to quantify the sensitivity of ground‐water discharge by evapotranspiration (ET) to three categories of independent input variables. To illustrate the approach, we adopt a basic ground‐water discharge estimation model, in which the volume of ground water lost to ET was computed as the product of the ground‐water discharge rate and the associated area. The ground‐water discharge rate was assumed to equal the ET rate minus local precipitation. The objective of this study is to outline a step‐by‐step procedure to quantify the contributions from individual independent variable uncertainties to the uncertainty of total ground‐water discharge estimates; the independent variables include ET rates of individual ET units, areas associated with the ET units, and precipitation in each subbasin. The specific goal is to guide future characterization efforts by better targeting data collection for those variables most responsible for uncertainty in ground‐water discharge estimates. The influential independent variables to be included in the sensitivity analysis are first selected based on the physical characteristics and model structure. Both regression coefficients and standardized regression coefficients for the selected independent variables are calculated using the results from sampling‐based Monte Carlo simulations. Results illustrate that, while as many as 630 independent variables potentially contribute to the calculation of the total annual ground‐water discharge for the case study area, a selection of seven independent variables could be used to develop an accurate regression model, accounting for more than 96% of the total variance in ground‐water discharge. Results indicate that the variability of ET rate for moderately dense desert shrubland contributes to about 75% of the variance in the total ground‐water discharge estimates. These results point to a need to better quantify ET rates for moderately dense shrubland to reduce overall uncertainty in estimates of ground‐water discharge. While the approach proposed here uses a basic ground‐water discharge model taken from an earlier study, the procedure of quantifying uncertainty and sensitivity can be generalized to handle other types of environmental models involving large numbers of independent variables.     

Modeling the Hydrology of Climate Change in California’s Sierra Nevada for Subwatershed Scale Adaptation1

Young, Charles A., Marisa I. Escobar‐Arias, Martha Fernandes, Brian Joyce, Michael Kiparsky, Jeffrey F. Mount, Vishal K. Mehta, David Purkey, Joshua H. Viers, and David Yates, 2009. Modeling the Hydrology of Climate Change in California’s Sierra Nevada for Subwatershed Scale Adaptation. Journal of the American Water Resources Association (JAWRA) 45(6):1409‐1423. Abstract: The rainfall‐runoff model presented in this study represents the hydrology of 15 major watersheds of the Sierra Nevada in California as the backbone of a planning tool for water resources analysis including climate change studies. Our model implementation documents potential changes in hydrologic metrics such as snowpack and the initiation of snowmelt at a finer resolution than previous studies, in accordance with the needs of watershed‐level planning decisions. Calibration was performed with a sequence of steps focusing sequentially on parameters of land cover, snow accumulation and melt, and water capacity and hydraulic conductivity of soil horizons. An assessment of the calibrated streamflows using goodness of fit statistics indicate that the model robustly represents major features of weekly average flows of the historical 1980‐2001 time series. Runs of the model for climate warming scenarios with fixed increases of 2°C, 4°C, and 6°C for the spatial domain were used to analyze changes in snow accumulation and runoff timing. The results indicated a reduction in snowmelt volume that was largest in the 1,750‐2,750 m elevation range. In addition, the runoff center of mass shifted to earlier dates and this shift was non‐uniformly distributed throughout the Sierra Nevada. Because the hydrologic model presented here is nested within a water resources planning system, future research can focus on the management and adaptation of the water resources system in the context of climate change.     

Enrichment of the metallic components from waste printed circuit boards by a mechanical separation process using a stamp mill

Printed circuit boards incorporated in most electrical and electronic equipment contain valuable metals such as Cu, Ni, Au, Ag, Pd, Fe, Sn, and Pb. In order to employ a hydrometallurgical route for the recycling of valuable metals from printed circuit boards, a mechanical pre-treatment step is needed. In this study, the metallic components from waste printed circuit boards have been enriched using a mechanical separation process. Waste printed circuit boards shredded to <10mm were milled using a stamp mill to liberate the various metallic components, and then the milled printed circuit boards were classified into fractions of <0.6, 0.6-1.2, 1.2-2.5, 2.5-5.0, and >5.0mm. The fractions of milled printed circuit boards of size <5.0mm were separated into a light fraction of mostly non-metallic components and a heavy fraction of the metallic components by gravity separation using a zig-zag classifier. The >5.0mm fraction and the heavy fraction were subjected to two-step magnetic separation. Through the first magnetic separation at 700 Gauss, 83% of the nickel and iron, based on the whole printed circuit boards, was recovered in the magnetic fraction, and 92% of the copper was recovered in the non-magnetic fraction. The cumulative recovery of nickel-iron concentrate was increased by a second magnetic separation at 3000 Gauss, but the grade of the concentrate decreased remarkably from 76% to 56%. The cumulative recovery of copper concentrate decreased, but the grade increased slightly from 71.6% to 75.4%. This study has demonstrated the feasibility of the mechanical separation process consisting of milling/size classification/gravity separation/two-step magnetic separation for enriching metallic components such as Cu, Ni, Al, and Fe from waste printed circuit boards.     

Estimation of mass transport parameters of gases for quantifying CH4 oxidation in landfill soil covers

Methane (CH(4)), which is one of the most abundant anthropogenic greenhouse gases, is produced from landfills. CH(4) is biologically oxidized to carbon dioxide, which has a lower global warming potential than methane, when it passes through a cover soil. In order to quantify the amount of CH(4) oxidized in a landfill cover soil, a soil column test, a diffusion cell test, and a mathematical model analysis were carried out. In the column test, maximum oxidation rates of CH(4) (V(max)) showed higher values in the upper part of the column than those in the lower part caused by the penetration of O(2) from the top. The organic matter content in the upper area was also higher due to the active microbial growth. The dispersion analysis results for O(2) and CH(4) in the column are counter-intuitive. As the upward flow rate of the landfill gas increased, the dispersion coefficient of CH(4) slightly increased, possibly due to the effect of mechanical dispersion. On the other hand, as the upward flow rate of the landfill gas increased, the dispersion coefficient of O(2) decreased. It is possible that the diffusion of gases in porous media is influenced by the counter-directional flow rate. Further analysis of other gases in the column, N(2) and CO(2), may be required to support this hypothesis, but in this paper we propose the possibility that the simulations using the diffusion coefficient of O(2) under the natural condition may overestimate the penetration of O(2) into the soil cover layer and consequently overestimate the oxidation of CH(4).