Estimates of pollutant temporal and spatial variability in commercial buildings from the joint urban 2003 field experiments

In this paper, we report on the indoor concentrations from a suite of full-scale outdoor tracer-gas point releases conducted in the downtown area of Oklahoma City in 2003. A point release experiment consisted of releases of sulfur hexafluoride (SF₆) in multiple buildings and from different outdoor locations. From the measurements, we are able to estimate the concentration variations indoors for a building operating under “typical” operating conditions. The mean indoor spatial coefficients of variation are 30% to 45% from a daytime outdoor release are around 80% during an outdoor evening release. Having estimates of the spatial coefficient of variation provides stakeholders, including first responders, with the likely range of concentrations in the building when little is known about the building characteristics and operating behavior, such as developing urban-scale hazard and consequence analyses. We show differences in indoor measurements at different distances to the release points, floors of the building, and heating, ventilation, and air conditioning system (HVAC) operation. We also show estimates at different time resolutions. The statistics show that in the studied medium to large commercial buildings, spatial differences would result in peak indoor concentrations in certain parts of the buildings that may be substantially higher than the building average. To our knowledge, very few tracer gas measurements have been conducted in buildings of this scope, particularly with measurements on multiple floors and within a floor. The resulting estimates of spatial variability provide a unique opportunity for hazard assessment, and comparison to multi-zone models.     

Inhibition of 2-nitropropane-induced rat liver DNA and RNA damage by benzyl selenocyanate

We observed that pretreatment of male F344 rats with benzyl selenocyanate, a versatile organoselenium chemopreventive agent in several animal model systems, decreases the levels of DNA and RNA modifications produced in the liver by the hepatocarcinogen 2-nitropropane. To clarify the mechanisms involved, we pretreated male F344 rats with either benzyl selenocyanate, its sulfur analog benzyl thiocyanate, phenobarbital or cobalt protoporphyrin IX; the latter is a depletor of P450. We then determined (1) the ability of liver microsomes to denitrify 2-nitropropane, (2) effects on 2-nitropropane-induced liver DNA and RNA modifications and (3) amount of nitrate excreted in rat urine following administration of the carcinogen. Pretreatment with benzyl selenocyanate or phenobarbital increased the denitrification activity of liver microsomes by 217 and 765%, respectively, increased liver P4502B1 by 31- and 435-fold, respectively, decreased the levels of 2-nitropropane-induced modifications in liver DNA (29-70% and 17-30%, respectively) and RNA (67-85% and 30-50%, respectively), and increased the 24-h urinary excretion of nitrate by 157 and 209%, respectively. Pretreatment with benzyl thiocyanate had no significant effect on any of these parameters. Pretreatment with cobalt protoporphyrin IX decreased liver P4502B 1 by 87%, decreased the denitrification activity of liver microsomes by 76%, decreased the 24 h urinary excretion of nitrate by 88.5%, but increased the extent of 2-nitropropane-induced liver nucleic acid modifications by 17-67%. These results indicate that the metabolic sequence from 2-nitropropane to the reactive species causing DNA and RNA modifications does not involve the removal of the nitro group. Moreover, they suggest that benzyl selenocyanate inhibits 2-NP-induced liver nucleic acid modifications in part by increasing its detoxication through induction of denitrification, although it is evident that other mechanisms must also be involved.     

Structural evaluation of thermal stratification for PWR surge line

Recent observations at operating plants and subsequent US NRC requirements have identified flow stratification in surge lines as a phenomenon that must be considered in the design basis of surge lines. To address these concerns, the stratified loading conditions were included in the design of YGN 3 and 4 surge line as a design basis transient and pipe temperature and displacement measurement were taken during YGN 3 pre-core hot functional testing to determine the degree of surge line flow stratification. The measured displacements and temperatures were extensively reviewed and evaluated in detail: (1) to verify the validity of the thermal hydraulic model used to predict the pipe top-to-bottom temperature differentials; (2) to analytically correlate measured surge line temperatures and displacements; and (3) to confirm the validity of the stratified flow analysis procedure. This paper shows that the stratified flow phenomenon is generic and therefore generic loadings can be developed and evaluated for the surge line analyses.     

Identification of glycoprotein 330 as an endocytic receptor for apolipoprotein J/clusterin

Glycoprotein 330 (gp330) is a member of a family of endocytic receptors related to the low density lipoprotein receptor. gp330 has previously been shown to bind a number of ligands in common with its family member, the low density lipoprotein receptor-related protein (LRP). To identify ligands specific for gp330 and relevant to its localization on epithelia such as in the mammary gland, gp330-Sepharose affinity chromatography was performed. As a result, a 70-kDa protein was selected from human milk and identified by protein sequencing to be apolipoprotein J/clusterin (apoJ). Solid-phase binding assays confirmed that gp330 bound to apoJ with high affinity (Kd = 14.2 nM). Similarly, gp330 bound to apoJ transferred to nitrocellulose after SDS-polyacrylamide gel electrophoresis. LRP, however, showed no binding to apoJ in either type of assay. The binding of gp330 to apoJ could be competitively inhibited with excess apoJ as well as with the gp330 ligands apolipoprotein E, lipoprotein lipase, and the receptor-associated protein, a 39-kDa protein that acts to antagonize binding of all known ligands for gp330 and LRP. Several cultured cell lines that express gp330 and ones that do not express the receptor were examined for their ability to bind and internalize 125I-apoJ. Only cells that expressed gp330 endocytosed and degraded radiolabeled apoJ. Furthermore, F9 cells treated with retinoic acid and dibutyryl cyclic AMP to increase expression levels of gp330 displayed an increased capacity to internalize and degrade apoJ. Cellular internalization and degradation of radiolabeled apoJ could be inhibited with unlabeled apoJ, receptor-associated protein, and gp330 antibodies. The results indicate that gp330 but not LRP can bind to apoJ in vitro and that gp330 expressed by cells can mediate apoJ endocytosis leading to lysosomal degradation.     

A novel cyclic process using CaSO<Subscript>4</Subscript>/CaS pellets for converting sulfur dioxide to elemental sulfur without generating secondary pollutants: Part I. Feasibility and kinetics of the reduction of sulfur dioxide with calcium-sulfide pellets

Certain new sulfide-smelting processes and coal-gasification processes generate high-strength sulfur dioxide streams, for which a new process for converting sulfur dioxide to elemental sulfur needs to be developed because no process exists that is generally and economically applicable to the treatment of such streams. A thermodynamic and experimental investigation to develop a new process for converting sulfur dioxide to elemental sulfur by a cyclic process involving calcium sulfide and calcium sulfate without generating secondary pollutants was carried out. In this process, the starting raw material, calcium sulfate, is reduced by a suitable reducing agent, such as hydrogen, to produce calcium sulfide, which is used to reduce sulfur dioxide to elemental sulfur vapor and calcium sulfate. The latter is, in turn, reduced to regenerate calcium sulfide. In this Part I, detailed experimental results are presented on the kinetics of the reaction between sulfur dioxide and calcium-sulfide pellets, which produces elemental sulfur and calcium sulfate. The experiments were carried out at temperatures between 1023 and 1088 K and sulfur-dioxide partial pressures between 9 and 60 kPa by the use of a thermogravimetric analysis (TGA) technique. The rate of this reaction was demonstrated by the conversion of 40 pct calcium-sulfide pellets obtained from the hydrogen reduction of fresh calcium sulfate in 10 minutes at 1073 K under a sulfur-dioxide partial pressure of 43 kPa. The reactivity decreased somewhat during the first three cycles but remained largely unchanged thereafter up to the tenth cycle. This characteristic of the pellets is important because the solids must be reusable for repeated cycles to avoid generating secondary pollutants. A pore-blocking model was found to fit the reaction rate. The reaction is first order with respect to sulfur-dioxide partial pressure and has an activation energy of 101 to 134 kJ/mol (24 to 32 kcal/mol) for calcium-sulfide pellets reacted and regenerated several different times. Sulfur dioxide-containing streams from certain sources, such as the regenerator off-gas from an integrated-gasification, combined-cycle, desulfurization unit and new sulfide-smelting plants, contain much higher partial pressures of SO₂. In these cases, the rate of the first reaction is expected to be proportionally higher than in the test conditions reported in this article. The reduction kinetics of calcium-sulfate pellets with hydrogen gas is reported in the accompanying Part II.     

A novel cyclic process using CaSO4/CaS pellets for converting sulfur dioxide to elemental sulfur without generating secondary pollutants: Part II. Hydrogen reduction of calcium-sulfate pellets to calcium sulfide

The reduction of calcium sulfate to produce calcium sulfide is a part of the cyclic process for converting sulfur dioxide to elemental sulfur that is described in Part I. The kinetics of the hydrogen reduction of nickel-catalyzed calcium-sulfate pellets were investigated using a thermogravimetric analysis (TGA) technique at reaction temperatures between 1023 and 1088 K and hydrogen partial pressures between 12.9 and 86.1 kPa. The reactivity of nickel-catalyzed calcium-sulfate pellets was demonstrated by the conversion of 70 pct fresh nickel-catalyzed calcium sulfate to calcium sulfide in 20 minutes at 1073 K under a hydrogen partial pressure of 86.1 kPa. Furthermore, the reactivity remained relatively intact after ten cycles of reactions and regenerations. This observed characteristic of the pellets is important because the solids must be reusable for repeated cycles to avoid generating secondary pollutants. The nucleation and growth rate expression was found to be useful in describing the kinetics of the reaction, which had an activation energy of about 167 kJ/mol (∼40 kcal/mol) in all reaction cycles except for the first regenerated samples that were lower at 146 kJ/mol (35 kcal/mol). The reaction order with respect to hydrogen partial pressure was 0.22 in all cycles with the exception of the first regenerated sample for which it was 0.37.     

Improved Matrix-Filler Adhesion

Enhanced matrix-filler adhesion is realized after filler treatment with a surface treatment process. The hydrosol/coupling agent treatment was applied to a wide range of inorganic and organic fillers, and adhesion to a variety of matrix resins was improved. Scanning Electron Microscopy (SEM) was used to determine the locus of failure in the filled systems. The locus of failure shows the relative degree of adhesion between the filler and the polymer matrix. Significant improvement in adhesion in humid environments is also observed.     

Mutational analysis of the three cysteines and active-site aspartic acid 103 of ketosteroid isomerase from Pseudomonas putida biotype B

In order to clarify the roles of three cysteines in ketosteroid isomerase (KSI) from Pseudomonas putida biotype B, each of the cysteine residues has been changed to a serine residue (C69S, C81S, and C97S) by site-directed mutagenesis. All cysteine mutations caused only a slight decrease in the k(cat) value, with no significant change of Km for the substrate. Even modification of the sulfhydryl group with 5,5'-dithiobis(2-nitrobenzoic acid) has almost no effect on enzyme activity. These results demonstrate that none of the cysteines in the KSI from P. putida is critical for catalytic activity, contrary to the previous identification of a cysteine in an active-site-directed photoinactivation study of KSI. Based on the three-dimensional structures of KSIs with and without dienolate intermediate analog equilenin, as determined by X-ray crystallography at high resolution, Asp-103 was found to be located within the range of the hydrogen bond to the equilenin. To assess the role of Asp-103 in catalysis, Asp-103 has been replaced with either asparagine (D103N) or alanine (D103A) by site-directed mutagenesis. For D103A mutant KSI there was a significant decrease in the k(cat) value: the k(cat) of the mutant was 85-fold lower than that of the wild-type enzyme; however, for the D103N mutant, which retained some hydrogen bonding capability, there was a minor decrease in the k(cat) value. These findings support the idea that aspartic acid 103 in the active site is an essential catalytic residue involved in catalysis by hydrogen bonding to the dienolate intermediate.