Uptake of Aromatic Hydrocarbon Vapors (Benzene and Phenanthrene) at the Air-Water Interface of Micron-Size Water Droplets

Abstract

Uptake of aromatic hydrocarbon vapors (benzene and phenanthrene) by typical micrometer-sized fog-water droplets was studied using a falling droplet reactor at temperatures between 296 and 316 K. Uptake of phenan-threne vapor greater than that predicted by bulk (air-water)-phase equilibrium was observed for diameters less than 200 μm, and this was attributed to surface adsorption. The experimental values of the droplet-vapor partition constant were used to obtain the overall mass transfer coefficient and the mass accommodation coefficient for both benzene and phenanthrene. Mass transfer of phenanthrene was dependent only on gas-phase diffusion and mass accommodation at the interface. However, for benzene, the mass transfer was limited by liquid-phase diffusion and mass accommodation. A large value of the mass accommodation coefficient, α = (1.4 ± 0.4) × 10^?2 was observed for the highly surface-active (hydrophobic) phenanthrene, whereas a small α = (9.7 ± 1.8) × 10^?5 was observed for the less hydrophobic benzene. Critical cluster numbers ranging from 2 for benzene to 5.7 for phenanthrene were deduced using the critical cluster nucleation theory for mass accommodation. The enthalpy of mass accommodation was more negative for phenanthrene than it was for benzene. Consequently, the temperature effect was more pronounced for phenanthrene. A linear correlation was observed for the enthalpy of accommodation with the excess enthalpy of solution. A natural organic carbon surrogate (Suwannee Fulvic acid) in the water droplet increased the uptake for phenanthrene and benzene, the effect being more marked for phenanthrene. A characteristic time constant analysis showed that uptake and droplet scavenging would compete for the fog deposition of phenanthrene, whereas deposition would be unimpeded by the uptake rate for benzene vapor. For both compounds, the characteristic atmospheric reaction times were much larger and would not impact fog deposition.     

A relationship between the natural radioactivity and mineralogical composition of the Ponnaiyar river sediments, India

The natural radiation level has been determined for the sediment samples of Ponnaiyar River, India with an aim of evaluating the radiation hazard. The average activity concentrations are within the world and Indian average values although some extreme values have been determined. The magnetic susceptibility measurement has been carried out to know the magnetization nature of the sediments. More downstream (mouth) of the river has quite higher magnetic susceptibility values. The mineralogical characterizations of the sediments have been carried out using Fourier Transform Infrared (FTIR) spectroscopic and XRD technique. The minerals such as quartz, microcline feldspar, orthoclase feldspar, kaolinite, calcite, gibbsite, montmorillonite, smectite, palygorskite and organic carbon are identified from FTIR analysis. Few minerals like zircon, monazite and hornblende are identified only in XRD analysis. The relative distribution of major minerals is determined by calculating extinction coefficient. The calculated values show that the amount of quartz is greater than microcline feldspar and very much greater than kaolinite in all the sites. The content of quartz and microcline feldspar is decreases, and kaolinite gradually increases towards the river mouth. Multivariate Statistical analyses were carried out between the parameters obtained from radioactivity analysis and other analyses to know the existing relations. Obtained results are discussed and suggested that the natural radioactivity level of the present sediments is mainly controlled by clay content and lesser extent to magnetic susceptibility.     

Air Pollution and Hospital Admissions for Diseases of the Circulatory System in Three U.S. Metropolitan Areas

ABSTRACT

Generalized additive models were used to analyze the time series of daily hospital admissions for cardiovascular and cerebrovascular diseases over the period of 19871995 in three major metropolitan areas—Cook County, IL; Los Angeles County, CA; and Maricopa County, AZ— in the United States. In Cook and Maricopa Counties, admissions information was only available for the elderly (ages 65 and over), while in Los Angeles County, admissions information was available for all ages. In Cook County, daily monitoring information was available on PM₁₀, CO, SO₂, NO₂, and O₃. In Los Angeles and Maricopa Counties, monitoring information was available daily on the gases, and information on PM₁₀ was available every sixth day. In Los Angeles County, information on PM₂₅ was also available every sixth day. In Cook and Los Angeles Counties, associations were found between each pollutant, with the exception of O₃, and admissions for cardiovascular disease, with the gases showing the strongest associations. In two-pollutant models with PM and one of the gases, the effect of the gases remained stable, while the effect of PM became unstable and insignificant. In Maricopa County, the gases, with the exception of O₃, were weakly associated with hospital admissions for cardiovascular disease, while PM was not. In two-pollutant models with two of CO, SO₂, and NO₂, the pattern of results is heterogeneous in the three counties. In all three counties, only weak evidence of any association between air pollution and cere-brovascular admissions was found.     

Controlled release formulations of metribuzin: Release kinetics in water and soil

Controlled release (CR) formulations of metribuzin in Polyvinyl chloride [(PVC) (emulsion)], carboxy methyl cellulose (CMC), and carboxy methyl cellulose-kaolinite composite (CMC-KAO), are reported. Kinetics of its release in water and soil was studied in comparison with the commercial formulation (75 DF). Metribuzin from the commercial formulation became non-detectable after 35 days whereas it attained maxima between 35–49 days and became non-detectable after 63 days in the developed products. Amongst the CR formulations, the release in both water and soil was the fastest in CMC and slowest in PVC. The CMC-KAO composite reduced the rate of release as compared to CMC alone. The diffusion exponent (n value) of metribuzin in water and soil ranged from 0.515 to 0.745 and 0.662 to 1.296, respectively in the various formulations. The release was diffusion controlled with half release time (t_1/2) from different controlled release matrices of 12.98 to 47.63 days in water and 16.90 to 51.79 days in soil. It was 3.25 and 4.66 days, respectively in the commercial formulation. The period of optimum availability of metribuzin in water and soil from controlled released formulations ranged from 15.09 to 31.68 and 17.99 to 34.72 days as against 5.03 and 8.80 days in the commercial formulation.     

Microwave assisted solvent-free synthesis and biological activities of novel imines (Schiff bases)

Twelve new ortho-Hydroxyketimines were synthesized by conventional as well as microwave method and evaluated for their antinemic activity against Meloidogyne incognita [(Kofoid and White) Chitwood]. Conventional methods for synthesis of Schiff bases require refluxing at 140°C of the reactants in different solvents for at least 24 h or more, where as the microwave-assisted synthesis has brought down the reaction time from 24 h to 1 minute. The procedure reported is simple as it does not require any organic solvents and the time has been reduced to only 1 minute. Comparative yields of all compounds by different methods revealed that the yield was low in conventional method (79–87%) as compared to microwave assisted synthesis (94–97%). The bioassay revealed that all the test compounds exhibited promising nematicidal activity; N-propyl-2-hydroxypropiophenonimine being the most effective with LC₅₀ value of 74.46 mgL^?1 followed by N-hexyl-2-hydroxyacetophenonimine with LC₅₀ value of 99.60 mgL^?1 after 72 h of exposure. The results obtained from bioassay indicated that this class of compounds has not only given a lead with regard to potential of Schiff bases in pest control, but has suggested that a carbon chain length of 6 atoms in the side chain is optimum on the basis of structure activity relationship (SAR).     

Monitoring of toxic elements present in sludge of industrial waste using CF-LIBS

Industrial waste is one of the main causes of environmental pollution. Laser-induced breakdown spectroscopy (LIBS) was applied to detect the toxic metals in the sludge of industrial waste water. Sludge on filter paper was obtained after filtering the collected waste water samples from different sections of a water treatment plant situated in an industrial area of Kanpur City. The LIBS spectra of the sludge samples were recorded in the spectral range of 200 to 500 nm by focusing the laser light on sludge. Calibration-free laser-induced breakdown spectroscopy (CF-LIBS) technique was used for the quantitative measurement of toxic elements such as Cr and Pb present in the sample. We also used the traditional calibration curve approach to quantify these elements. The results obtained from CF-LIBS are in good agreement with the results from the calibration curve approach. Thus, our results demonstrate that CF-LIBS is an appropriate technique for quantitative analysis where reference/standard samples are not available to make the calibration curve. The results of the present experiment are alarming to the people living nearby areas of industrial activities, as the concentrations of toxic elements are quite high compared to the admissible limits of these substances.     

Comparative investigation of coal- and oil-fired boilers based on emission factors, ozone and secondary organic aerosol formation potentials of VOCs

Volatile organic compounds(VOCs) are the important precursors of the tropospheric ozone(O_3) and secondary organic aerosols(SOA),both of which are known to harm human health and disrupt the earth's climate system.In this study,VOC emission factors,O_3 and SOA formation potentials were estimated for two types of industrial boilers:coal-fired boilers(n=3) and oil-fired boilers(n=3).Results showed that EVOCs concentrations were more than nine times higher for oil-fire d boilers compared to those for coal-fired boilers.Emission factors of ΣVOCs were found to be higher for oil-fired boilers(9.26-32.83 mg-VOC/kg) than for coal-fired boilers(1.57-4.13 mg-VOC/kg).Alkanes and aromatics were obtained as the most abundant groups in coal-fired boilers,while oxygenated organics and aromatics were the most contributing groups in oil-fired boilers.Benzene,n-hexane and o-ethyl toluene were the abundant VOC species in coal-fired boiler emissions,whereas toluene was the most abundant VOC species emitted from oil-fired boilers.O_3 and SOA formation potentials were found 12 and 18 times,respectively,higher for oil-fired than for coal-fired boilers.Total OFP ranged from 3.99 to 11.39 mg-O_3/kg for coal-fired boilers.For oil-fired boilers,total OFP ranged from 36.16 to 131.93 mg-O_3/kg.Moreover,total secondary organic aerosol potential(SOAP) ranged from 65.4 to 122.5 mg-SOA/kg and 779.9 to 2252.5 mg-SOA/kg for the coal-fired and oil-fired boilers,respectively.     

Environmental physiology of the mole crab Emerita asiatica, at a power plant discharge area on the east coast of India

Cage experiments at the discharge area of Madras Atomic Power Station (MAPS) facilitated studies of thermal tolerance in Emerita asiatica. At the laboratory, oxygen consumption at various temperatures and varying salinities was also investigated. In the field 100% mortality of crabs was recorded at the Condenser Cooling Water Pumps (CCWP) discharge site compared to no mortality at the Processed Sea Water Pumps (PSWP) site. This observation implicated temperature as a stress factor at the CCWP outfall, because other factors, including residual chlorine and water velocity, were the same at the PSWP and CCWP sites. Laboratory experiments on tolerance revealed that 38.5 degrees C was lethal to mole crabs. The time taken for 100% mortality decreased as the temperature increased from 35 to 40 degrees C. Oxygen metabolism showed a progressive increase with temperature from 29 to 36 degrees C, and declined at 37 degrees C. The influence of salinity on oxygen consumption was marginal at salinities of 20 to 35 per thousand but, when reduced to 15 per thousand, the oxygen consumption declined. The present study thus indicates that temperature could be the lethal factor, determining the distribution of mole crabs near the power station, where water temperature can exceed 40 degrees C.     

Detection of Lead in Vegetables with New Chromogenic Reagent by Spectrophotometry

A new simple, rapid selective and highly sensitive chromogenic reagent dibromo-p-methyl-carboxyazo (DBMCA) was synthesized and studied in detail for the spectrophotometric detection of lead. In 0.25 M phosphoric acid medium, which greatly increases the selectivity, Lead reacts with DBMCA to form a 1:2 blue complex having a sensitivity absorption peak at 646 nm. Under optimal conditions, Beer's Law is obeyed over the range from 0.09 to 0.8 microg mL(-1) Pb (II) and the apparent molar absorptivity is 1.03 x 10(5) mL(-1) cm(-1). The detection limit and the variation coefficient were found to be 2.12 microg mL(-1) and 1.0% respectively. It is found that, except for Ca (II) and Ba (II) all foreign ions studied do not interfere with detection. The interference caused by Ca (II) and Ba (II) can be easily eliminated by prior extraction with potassiumiodide-methylisobutylketone. The proposed method has been applied successfully for to the detection of Lead in vegetable leaves with good results.     

Oxygenated fuel induced cosolvent effects on the dissolution of polynuclear aromatic hydrocarbons from contaminated soil

The cosolvent-induced dissolution of polynuclear aromatic hydrocarbons (PAHs) from contaminated soil caused by oxygenated fuel spills was studied. Oxygenated fuel induces a solvent flushing effect on the contaminated soil due to the high content of oxygenated compounds (i.e., methanol, ethanol, and methyl tert butyl ether (MTBE)). The miscible displacement techniques were applied to evaluate the increased potential for secondary contamination in an impacted site. Significant solubility enhancement of the 18 PAHs monitored during fuel spill simulation and cosolvent flushing is clearly evident when compared to normal water dissolution. The breakthrough concentration profile for each PAH constituent was integrated over the cumulative effluent volume (i.e., the zeroth moment) to determine the total PAH mass removed during the experiment. The removal efficiency of PAHs ranges from 46.6% to 99.9% in three oxygenated fuels (i.e., M85, E85, and oxygenated gasoline) during the fuel spill. Several factors including hydrophobicity of compounds, nonequilibrium dissolution due to nonuniform coal tar distribution, and heterogeneous media properties affect the oxygenated compound-induced dissolution process. This study provides a basis to predict the facilitated transport of hydrophobic organic compounds from subsurface environment due to the cosolvent effects of oxygenated fuels.