In compliance with the Clean Air Act regulations for fuel and fuel additive registration, the petroleum industry, additive manufacturers, and oxygenate manufacturers have conducted comparative toxicology testing on evaporative emissions of gasoline alone and gasoline containing fuel oxygenates. To mimic real world exposures, a generation method was developed that produced test material similar in composition to the re-fueling vapor from an automotive fuel tank at near maximum in-use temperatures. Gasoline vapor was generated by a single-step distillation from a 1000-gallon glass-lined kettle wherein approximately 15-23% of the starting material was slowly vaporized, separated, condensed and recovered as test article. This fraction was termed vapor condensate (VC) and was prepared for each of the seven test materials, namely: baseline gasoline alone (BGVC), or gasoline plus an ether (G/MTBE, G/ETBE, G/TAME, or G/DIPE), or gasoline plus an alcohol (G/EtOH or G/TBA). The VC test articles were used for the inhalation toxicology studies described in the accompanying series of papers in this journal. These studies included evaluations of subchronic toxicity, neurotoxicity, immunotoxicity, genotoxicity, reproductive and developmental toxicity. Results of these studies will be used for comparative risk assessments of gasoline and gasoline/oxygenate blends by the US Environmental Protection Agency.
The effect of soil moisture on chlorine (Cl(2)) deposition was examined in laboratory chamber experiments at high Cl(2) exposures by measuring the concentration of chloride (Cl(-)) in soil columns. Soil mixtures with varying amounts of clay, sand, and organic matter and with moisture contents up to 20% (w/w) were exposed to ?3×10(4)ppm Cl(2) vapor. For low water content soils, additional water increased the reaction rate as evidenced by higher Cl(-) concentration at higher soil moisture content. Results also showed that the presence of water restricted transport of Cl(2) into the soil columns and caused lower overall deposition of Cl(2) in the top 0.48-cm layer of soil when water filled ?60% or more of the void space in the column. Numerical solutions to partial differential equations of Fick's law of diffusion and a simple rate law for Cl(2) reaction corroborated conclusions derived from the data. For the soil mixtures and conditions of these experiments, moisture content that filled 30-50% of the available void space yielded the maximum amount of Cl(2) deposition in the top 0.48cm of soil.
Synthetic soil blends were exposed to dense chlorine (Cl2) plumes released at Dugway Proving Ground, UT, during Spring 2010 with the purpose of determining the magnitude of Cl2 deposition onto soil and assessing its potential for attenuating a high-concentration plume. Samples were exposed at varying distances from the release point to include exposure to the pooling liquid (2-3m) and dense vapor (10-17 m). Following exposure, soil samples were cored, fractionated vertically and analyzed for chloride (Cl(-)) to quantify the integrated amount of Cl2 deposited. Cl(-) was detected as deep as 4 cm in samples exposed to dense Cl2 vapor and in the deepest fractions (13 cm) of samples exposed to liquid Cl2. Chloride concentration, [Cl(-)], in the soil samples positively correlated with soil mass fractions of organic matter and water, and while their individual contributions to Cl2 deposition could not be quantitatively determined, the data suggest that organic matter was the primary contributor. [Cl(-)] results from the top vertical fractions (1.3 cm nearest the surface) were used in an analysis to determine the magnitude of deposition as a loss term under low-wind (? 1.6m/s) conditions. The analysis revealed up to 50% of a 1814-kg release could be deposited within 20 m from the release point for soil with high organic matter (43%) and/or water content (29%).
Active chlorine comprising hypochlorite (OCl?), hypochlorous acid (HOCl) and chlorine (Cl?) is the active constituent in bleach formulations for a variety of industrial and consumer applications. However, the strong oxidative reactivity of active chlorine can cause adverse effects on both human health and the environment. In this study, aerosolized Oxone® [2KHSO?, KHSO?, K?SO?] with saline solution has been utilized to produce active chlorine (HOCl and Cl?). To investigate the impact of active chlorine on volatile organic compound (VOC) oxidation, 2-methyl-2-butene (MB) was photoirradiated in the presence of active chlorine using a 2-m³ Teflon film indoor chamber. The resulting carbonyl products produced from photooxidation of MB were derivatized with O-(2,3,4,5,6-pentafluorobenzyl) hydroxyamine hydrochloride (PFBHA) and analyzed using gas chromatograph-ion trap mass spectrometer (GC/ITMS). The photooxidation of MB in the presence of active chlorine was simulated with an explicit kinetic model using a chemical solver (Morpho) which included both Master Chemical Mechanism (MCM) and Cl radical reactions. The reaction rate constants of a Cl radical with MB and its oxidized products were estimated using a Structure-Reactivity Relationship method. Under dark conditions no effect of active chlorine on MB oxidation was apparent, whereas under simulated daylight conditions (UV irradiation) rapid MB oxidation was observed due to photo-dissociation of active chlorine. The model simulation agrees with chamber data showing rapid production of oxygenated products that are characterized using GC/ITMS. Ozone formation was enhanced when MB was oxidized in the presence of irradiated active chlorine and NO(x).
Molecular targets in prostate cancer are continually being explored, especially in the poor-prognosis androgen-independent phase of the disease, for which there are currently few therapeutic options. One such target is the mammalian target of rapamycin (mTOR) protein. Activation of mTOR results in sequential activation of downstream molecules, which ultimately results in cell division. In this review, we consider the rationale for pursuing mTOR as a therapeutic target in prostate cancer and summarize preclinical and clinical studies of mTOR inhibition in prostate cancer.
Coral reefs are experiencing unprecedented degradation due to human activities, and protecting specific reef habitats may not stop this decline, because the most serious threats are global (i.e., climate change), not local. However, ex situ preservation practices can provide safeguards for coral reef conservation. Specifically, modern advances in cryobiology and genome banking could secure existing species and genetic diversity until genotypes can be introduced into rehabilitated habitats. We assessed the feasibility of recovering viable sperm and embryonic cells post-thaw from two coral species, Acropora palmata and Fungia scutaria that have diffferent evolutionary histories, ecological niches and reproductive strategies. In vitro fertilization (IVF) of conspecific eggs using fresh (control) spermatozoa revealed high levels of fertilization (>90% in A. palmata; >84% in F. scutaria; P>0.05) that were unaffected by tested sperm concentrations. A solution of 10% dimethyl sulfoxide (DMSO) at cooling rates of 20 to 30°C/min most successfully cryopreserved both A. palmata and F. scutaria spermatozoa and allowed producing developing larvae in vitro. IVF success under these conditions was 65% in A. palmata and 53% in F. scutaria on particular nights; however, on subsequent nights, the same process resulted in little or no IVF success. Thus, the window for optimal freezing of high quality spermatozoa was short (?5 h for one night each spawning cycle). Additionally, cryopreserved F. scutaria embryonic cells had?50% post-thaw viability as measured by intact membranes. Thus, despite some differences between species, coral spermatozoa and embryonic cells are viable after low temperature (-196°C) storage, preservation and thawing. Based on these results, we have begun systematically banking coral spermatozoa and embryonic cells on a large-scale as a support approach for preserving existing bio- and genetic diversity found in reef systems.
Deposition of chlorine gas, Cl(2), on synthetic soil sample matrices was examined in a small chamber to ascertain its potential significance as a chemical sink during large-scale releases. The effects of organic matter, clay and sand mass fractions of the soil matrix, soil packing, and exposure to ultraviolet (UV) light on the observed Cl(2) deposition were examined. Organic matter content was found to be the dominant soil variable investigated that affected Cl(2) deposition; all other variables exhibited no measurable effect. Analytical results from the top 8.5mm of soil columns exposed to Cl(2) were fit to a simple kinetic model with six adjustable parameters. The kinetic model included two reactive bins to account for fast- and slow-reacting material in the soil matrices. The resulting empirical equation agreed with the data to within a factor of two and accurately predicted results from soil mixes not used to optimize the adjustable parameters. Total Cl(2) deposition, assuming a penetration depth of 8.5mm, was calculated to be as high as 160 metric tons per square kilometer for soil with an organic content of 10%, and inferred deposition velocities were as high as 0.5 cm/s for organically rich soil.
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