Quantification and modelling of 2,4-dinitrotoluene reduction with high-purity and cast iron

Cast iron has been used as a reactive material in permeable reactive barriers (PRBs) for site remediation. While reactions are generally believed to occur on the iron (oxide) surface, a recent study by [Oh, S.Y., Cha, D.K., Chiu, P.C., 2002a. Graphite-mediated reduction of 2,4-dinitrotoluene with elemental iron. Environ. Sci. Technol. 36 (10), 2178-2184] showed that graphite inclusions in cast iron can also serve as reaction sites for 2,4-dinitrotoluene (DNT). These authors also found that graphite-mediated reduction of DNT has a regioselectivity that is different from that for iron surface. In this study, we quantified the observations reported by Oh et al. and examined the role of graphite in cast iron through numerical modelling. Models containing one and two reaction sites were developed to evaluate the mass transfer, sorption and reaction rates for DNT reduction in batch systems containing high-purity and cast iron. Our simulations showed that the regioselectivity, defined as the ratio of the ortho- and para-nitro reduction rate constants, was 0.37+/-0.04 S.E. (S.E.=one estimated standard error) for iron surface and 3.59+/-0.76 S.E. for graphite surface. In the cast iron-water system, we estimated that at least 66+/-2% S.E. of the DNT was reduced on graphite surface, despite the low graphite content and the lower DNT reduction rate with graphite than with iron. Graphite played such an important role because of the rapid adsorption of DNT to graphite. In the batch experiments conducted by Oh et al., external mass transfer was not rate limiting. Surface reaction was the rate-limiting step for DNT reduction on the graphite surface in cast iron, whereas internal mass transfer and/or adsorption and surface reaction were important for high-purity iron.     

The evolution of particles in the plume from a large coal-fired boiler with flue gas desulfurization

Airborne measurements were made of gaseous and particulate species in the plume of a large coal-fired power plant after flue gas desulfurization (FGD) controls were installed. These measurements were compared with measurements made before the controls were installed. The light scattering and number and volume distributions of plume excess particles were determined by nephelometry and optical particle counting techniques. The plume impact based on optical techniques was much lower than that observed in earlier measurements. Indeed, plume excess volumes as a function of particle size were of the same magnitude as the variability of the background volume distribution. In situ excess plume scattering actually decreased with distance from the source, in contrast to pre-FGD conditions. The upper limit for the dry rate of SO2-to-SO4(2-) conversion was estimated from plume excess volume measurements to be about 4% hr-1. This is slightly greater than the upper limit, 3.5% hr-1, estimated by earlier researchers, but the same as that estimated using the present technique with the earlier data. The cross-plume profile of volume suggests SO2-to-SO4(2-) conversion is highest at the plume edges. The greatest benefit of SO2 reduction on plume excess volume and visibility appears to occur far down-wind of the source.     

Rates of conversion of sulfur dioxide to sulfate in a scrubbed power plant plume.

The rate of conversion of SO2 to SO4(2-) was re-estimated from measurements made in the plume of the Cumberland power plant, located on the Cumberland River in north-central Tennessee, after installation of flue gas desulfurization (FGD) scrubbers for SO2 removal in 1994. The ratio of SO2 to NOy emissions into the plume has been reduced to approximately 0.1, compared with a prescrubber value of approximately 2. To determine whether the SO2 emissions reduction has correspondingly reduced plume-generated particulate SO4(2-) production, we have compared the rates of conversion before and after scrubber installation. The prescrubber estimates were developed from measurements made during the Tennessee Plume Study conducted in the late 1970s. The postscrubber estimates are based upon two series of research flights in the summers of 1998 and 1999. During two of these flights, the Cumberland plume did not mix with adjacent power plant plumes, enabling rate constants for conversion to be estimated from samples taken in the plume at three downwind distances. Dry deposition losses and the fact the fact that SO2 is no longer in large excess compared with SO4(2-) have been taken into account, and an upper limit for the conversion rate constant was re-estimated based on plume excess aerosol volume. The estimated upper limit values are 0.069 hr(-1) and 0.034 hr(-1) for the 1998 and 1999 data, respectively. The 1999 rate is comparable with earlier values for nonscrubbed plumes, and although the 1998 upper limit value is higher than expected, these estimates do not provide strong evidence for deviation from a linear relationship between SO2 emissions and SO4(2-) formation.     

上海地区霾时气溶胶类型垂直分布的季节变化

采用上海地区2007年1月~2010年11月CALIPSO星载激光雷达Level 2反演资料,对清洁海洋型、沙尘型、大陆污染型、大陆清洁型、污染沙尘型和烟尘型等类型气溶胶垂直分布进行了分析,研究了其季节变化规律.结果表明:霾发生时0~2km高度烟尘型气溶胶出现频率明显高于非霾时,而在2~8km高度,沙尘型、污染沙尘型与大陆污染型明显高于非霾时.0~2km高度春季霾大陆污染型气溶胶出现频率高于其他季节;0~2km夏季污染沙尘型气溶胶与海洋型气溶胶出现频率均高于其他季节,特别是污染沙尘型;秋季霾期间,0~2km高度范围内烟尘型出现频率明显高于2~6km高度;冬季污染沙尘型、烟尘、大陆污染型气溶胶出现频率高于其他季节.     

Scaling DNAPL migration from the laboratory to the field

A particular problem with the release of dense nonaqueous phase liquids (DNAPLs) into the environment is identifying where the DNAPL is and if it is still moving. This question is particularly important at sites where thousands of cubic meters of DNAPLs were disposed of. To date, results from laboratory models have not been scaled to predict analogous migration at the larger length and time scales appropriate for sites where large volumes of DNAPLs were released. Modified inspectional analysis is a technique for developing scaling relationships through nondimensionalizing the governing equations. It was applied in this study to scale observations of DNAPL migration in a laboratory model to four hypothetical scenarios in the field where large volumes of DNAPL were released. One scenario was compared to a large DNAPL spill site. The length and time scales of DNAPL movement predicted from our analysis are consistent with those predicted from a numerical model of this site. To our knowledge, this is the first application of modified inspectional analysis for release of DNAPLs in a laboratory model. This methodology may prove useful for scaling results from other laboratory investigations of DNAPL migration to field-scale systems.