Rapid measurements and mapping of tracer gas concentrations in a large indoor space

Rapid mapping of gas concentrations in air benefits studies of atmospheric phenomena ranging from pollutant dispersion to surface layer meteorology. Here we demonstrate a technique that combines multiple-open-path tunable-diode-laser spectroscopy and computed tomography to map tracer gas concentrations with approximately 0.5 m spatial and 7 s temporal resolution. Releasing CH₄ as a tracer gas in a large (7 m×9 m×11 m high) ventilated chamber, we measured path-integrated CH₄ concentrations over a planar array of 28 “long” (2–10 m) optical paths, recording a complete sequence of measurements every 7 s during the course of hour-long experiments. Maps of CH₄ concentration were reconstructed from the long path data using a computed tomography algorithm that employed simulated annealing to search for a best fit solution. The reconstructed maps were compared with simultaneous measurements from 28 “short” (0.5 m) optical paths located in the same measurement plane. On average, the reconstructed maps capture ∼74% of the variance in the short path measurements. The accuracy of the reconstructed maps is limited, in large part, by the number of optical paths and the time required for the measurement. Straightforward enhancements to the instrumentation will allow rapid mapping of three-dimensional gas concentrations in indoor and outdoor air, with sub-second temporal resolution.     

Abatement of sulfur hexafluoride emissions from the semiconductor manufacturing process by atmospheric-pressure plasmas

Sulfur hexafluoride (SF6) is an important gas for plasma etching processes in the semiconductor industry. SF6 intensely absorbs infrared radiation and, consequently, aggravates global warming. This study investigates SF6 abatement by nonthermal plasma technologies under atmospheric pressure. Two kinds of nonthermal plasma processes--dielectric barrier discharge (DBD) and combined plasma catalysis (CPC)--were employed and evaluated. Experimental results indicated that as much as 91% of SF6 was removed with DBDs at 20 kV of applied voltage and 150 Hz of discharge frequency for the gas stream containing 300 ppm SF6, 12% oxygen (O2), and 40% argon (Ar), with nitrogen (N2) as the carrier gas. Four additives, including Ar, O2, ethylene (C2H4), and H2O(g), are effective in enhancing SF6 abatement in the range of conditions studied. DBD achieves a higher SF6 removal efficiency than does CPC at the same operation condition. But CPC achieves a higher electrical energy utilization compared with DBD. However, poisoning of catalysts by sulfur (S)-containing species needs further investigation. SF6 is mainly converted to SOF2, SO2F4, sulfur dioxide (SO2), oxygen difluoride (OF2), and fluoride (F2). They do not cause global warming and can be captured by either wet scrubbing or adsorption. This study indicates that DBD and CPC are feasible control technologies for reducing SF6 emissions.     

复合钙基固硫添加剂对煤固硫与燃烧的影响

利用程序升温燃烧反应技术,考察了高岭土复合的CaO、Fe2O3-CaO、CoO-CaO添加剂对无烟煤的燃烧以及固硫的影响。实验发现,这些添加物质对煤的裂解产物的燃烧都具有促进作用,除了Fe2O3-CaO-高岭土复合添加剂对煤焦的燃烧有一定阻碍作用之外,其余都具有对煤焦燃烧的促进作用,尤以CoO-CaO-高岭土复合添加剂的效果最为显著。高岭土复合的硫酸钙本应具有较高的热稳定性,但受到高温下煤焦与CO的还原而分解,所以添加对煤焦具有明显催化燃烧作用的氧化钴,因减少了还原性气氛,稳定了硫酸钙产物而促进了固硫。     

Microwave-induced combustion of volatile organic compounds in an industrial flue gas over the magnetite fixed-bed

A modified domestic microwave oven was applied to heat a magnetite (Fe₃O₄) fixed-bed for continuous decomposition of volatile organic compounds (VOCs), such as acetone, n-hexane, and dichloromethane (DCM), in a simulated flue gas which contains VOCs equivalent to 2000 ppmv as DCM. Experimental results revealed that effect of the addition of water to the inlet stream on decomposition of DCM in the overall experiment was insignificant. Bulk temperature of the Fe₃O₄ fixed-bed was also found to reach 600 °C from an initial room temperature by 6.5 min under microwave radiation, even though the inlet gas was at a high gas hourly space velocity of 5240 h⁻¹ and a high relative humidity of 75%. Moreover, the VOCs in the inlet stream could be decomposed completely over the Fe₃O₄ fixed-bed by microwave heating at a power level of 645 W at heating time of 10 min. The conversion of VOCs is stable when the Fe₃O₄ fixed-bed has been heated longer than 10 min with microwave radiation. The microwave-induced heating upon Fe₃O₄ fixed-bed processing appears to be not only an energy efficient technique for air pollutions treatment but also a promising technology for variety of VOCs in a flue gas from industrial factory being decomposed simultaneously and completely.     

Kinetic limitations on tracer partitioning in ganglia dominated source zones

Quantification of the relationship between dense nonaqueous phase liquid (DNAPL) source strength, source longevity and spatial distribution is increasingly recognized as important for effective remedial design. Partitioning tracers are one tool that may permit interrogation of DNAPL architecture. Tracer data are commonly analyzed under the assumption of linear, equilibrium partitioning, although the appropriateness of these assumptions has not been fully explored. Here we focus on elucidating the nonlinear and nonequilibrium partitioning behavior of three selected alcohol tracers - 1-pentanol, 1-hexanol and 2-octanol in a series of batch and column experiments. Liquid-liquid equilibria for systems comprising water, TCE and the selected alcohol illustrate the nonlinear distribution of alcohol between the aqueous and organic phases. Complete quantification of these equilibria facilitates delineation of the limits of applicability of the linear partitioning assumption, and assessment of potential inaccuracies associated with measurement of partition coefficients at a single concentration. Column experiments were conducted under conditions of non-equilibrium to evaluate the kinetics of the reversible absorption of the selected tracers in a sandy medium containing a uniform entrapped saturation of TCE-DNAPL. Experimental tracer breakthrough data were used, in conjunction with mathematical models and batch measurements, to evaluate alternative hypotheses for observed deviations from linear equilibrium partitioning behavior. Analyses suggest that, although all tracers accumulate at the TCE-DNAPL/aqueous interface, surface accumulation does not influence transport at concentrations typically employed for tracer tests. Moreover, results reveal that the kinetics of the reversible absorption process are well described using existing mass transfer correlations originally developed to model aqueous boundary layer resistance for pure-component NAPL dissolution.     

Longitudinal variations in indoor VOC concentrations after moving into new apartments and indoor source characterization

This study examined the indoor concentrations of a wide range of volatile organic compounds (VOCs) in currently built new apartments every month over a 24-month period and the source characteristics of indoor VOCs. The indoor total VOC (TVOC) concentrations exhibited a decreasing tendency over the 24-month follow-up period. Similar to TVOCs, the median indoor concentrations of 33 of 40 individual VOCs (all except for naphthalene and six halogenated VOCs) revealed decreasing tendencies. In contrast, the indoor concentrations of the six halogenated VOCs did not reveal any definite trend with time. Moreover, the indoor concentrations of those halogenated VOCs were similar to the outdoor concentrations, suggesting the absence of any notable indoor sources of halogenated VOCs. For naphthalene (NT), the indoor concentrations were significantly higher than the outdoor concentrations, suggesting the presence of indoor NT source(s). The floor/wall coverings (39 %) were the most influential indoor source of indoor VOCs, followed by household cleaning products (32 %), wood paneling/furniture (17 %), paints (7 %), and moth repellents (5 %).     

Relating summer ambient particulate sulfur, sulfur dioxide, and light scattering to gaseous tracer emissions from the MOHAVE Power Project

Project MOHAVE was initiated in 1992 to examine the role of emissions from the 1580 MW coal-fired MOHAVE Power Project (MPP) on haze at the Grand Canyon National Park (GCNP), located about 130 km north-north-east of the power plant. Statistical relationships were analyzed between summertime ambient concentrations of a gaseous perfluorocarbon tracer released from MPP and ambient SO2, particulate sulfur, and light scattering to evaluate whether MPP's emissions could be transported to the GCNP and then impact haze levels there. Spatial analyses indicated that particulate sulfur levels were strongly correlated across the monitoring network, regardless of whether the monitoring stations were upwind or downwind of MPP. This indicates that particulate sulfur levels in this region were influenced by distant regional emission sources. A significant particulate sulfur contribution from a point source such as MPP would result in a non-uniform pattern downwind. There was no suggestion of this in the data. Furthermore, correlations between the MPP tracer and ambient particulate sulfur and light scattering at locations in the park were virtually zero for averaging times ranging from 24 hr to 1 hr. Hour-by-hour MPP tracer levels and light scattering were individually examined, and still no positive correlations were detected. Finally, agreement between tracer and particulate sulfur did not improve as a function of meteorological regime, implying that, even during cloudy monsoon days when more rapid conversion of SO2 to particulate sulfur would be expected, there was no evidence for downwind particulate sulfur impacts. Despite the fact that MPP was a large source of SO2 and tracer, neither time series nor correlation analyses were able to detect any meaningful relationship between MPP's SO2 and tracer emission "signals" to particulate sulfur or light scattering.     

Assessment of the fate of sulfur dioxide from a point source

A simplified plume transport model is adopted to assess reaction and scavenging processes. Experimental data on the conversion rate of SO₂ to SO₄²⁻ and the uptake rates by vegetation and soil are used to calculate the relative importance of the various fates of sulfur dioxide. Meteorological parameters include wind speed, day and night mixing heights, night diffusion above the mixing height and plume dispersion angle. Other parameters considered are length of day and night, region, season, type of canopy, and emission rate of SO₂ from a point source.     

Polychlorinated dibenzo-p-dioxins and dibenzofurans in plywood combustion gas

Polychlorinated dibenzo-p-dioxin and dibenzofuran (PCDD/DF) levels in plywood combustion gas were investigated for the effects of ammonium chloride (NH4Cl) and paint. For combustion systems in which neither NH4Cl nor paint were present in the plywood samples, total amounts of PCDD/DFs in the combustion gas were in the order of 35-529 ng/Nm3, and were higher in the systems with softwood trees than broadleaf ones, depending on the Cl concentrations. For the systems with added NH4Cl and no paint, and those without NH4Cl but were painted, higher PCDD/ DF rates were observed at combustion temperatures of 270 degrees C and 500 degrees C, respectively. However, for the systems with both NH4Cl and paint, their amounts in the range of 0.6-13 ng/Nm3 were the lowest in all systems. The PCDD/DF abundance profiles were similar to their patterns in pentachlorophenol (PCP). Furthermore, it was found that the 2,3,7,8-chlorine substituted penta- and hexa-CDDs contributed more than other 2,3,7,8-chlorine substitutes to toxicity equivalency (TEQ).     

Nonlinearities in source receptor relationships for sulfur and nitrogen compounds

The relationship between emissions and deposition of air pollutants, both spatially and in time forms an important focus for science and for policy makers. In practice, this relationship may become nonlinear if the underlying processes change with time, or in space. Nonlinearities may also appear due to errors in emission or deposition data, and careful scrutiny of both data sources and their relationship provides a means of picking up such deficiencies. Nonlinearities in source receptor relationships for sulfur and nitrogen compounds in Europe have been identified in measurement data for the UK. In the case of sulfur, the dry deposition process has been shown to be strongly influenced by ambient concentrations of NH3, leading to substantial increases in deposition rate as SO2 concentrations decline and the ratio SO2/NH3 decreases. The field evidence extends to measurements over three different surfaces in three countries across Europe. A mechanistic understanding of the cause of this nonlinearity has been provided. Apparent nonlinearities also exist in the sulfur deposition field through the influence of shipping emissions. The effect is clear at west coast locations, where during a period in which land-based sulfur emissions declined by 50%, no significant decline in concentrations of SO(2-) in precipitation were observed. The sites affected are primarily the coastal regions of southwestern UK, where shipping sources contribute a substantial fraction of the deposited sulfur, but the effect is not detectable elsewhere. Full quantification of the spatially disaggregated emission and their changes in time will eliminate this apparent nonlinearity in the source-receptor data. For oxidized nitrogen emission and deposition in the UK, there is strong evidence of nonlinearity in the source-receptor relationship. The concentrations and deposition of NO(3-) in precipitation have declined little following a reduction in emissions of 45% during the period 1987 to 2001. The data imply a significant decrease in the average transport distance for oxidized nitrogen and most probably an increase in the average oxidation rate. However, the net effect of changes in aerosol chemistry due to changes in sulfur emissions and less competition for the main oxidants as a consequence of reductions in sulfur emission have not been separated. A quantitative explanation of the cause of this nonlinearity is lacking and the effects are therefore identified as an important uncertainty for the development of further protocols to control acidification, eutrophication and photochemical oxidants in Europe.     

Partitioning gas tracer tests for measurement of water in municipal solid waste

A key component in the operation of almost all bioreactor landfills is the addition of water to maintain optimal moisture conditions. To determine how much water is needed and where to add it, in situ methods are required to measure water within solid waste. Existing technologies often result in measurements of unknown accuracy, because of the variability of solid waste materials and time-dependent changes in packing density, both of which influence most measurement methods. To overcome these problems, a new technology recently developed by hydrologists for measuring water in the vadose zone--the partitioning gas tracer test--was tested. In this technology, the transport behavior of two gas tracers within solid waste is used to measure the fraction of the void space filled with water. One tracer is conservative and does not react with solids or liquids, while a second tracer partitions into the water and is separated from the conservative tracer during transport. This technology was tested in four different solid waste packings and was capable of determining the volumetric water content to within 48% of actual values, with most measurement errors less than 15%. This technology and the factors that affect its applicability to landfills are discussed in this paper.     

Formation of chlorinated organic compounds during combustion of propane in the presence of HCl

Combustion of propane in the presence of hydrochloric acid yields a complicated mixture of chlorinated compounds some of which are known to be precursors to chlorinated dibenzo-p-dioxins and dibenzofurans.     

Application of dispersion modeling to indoor gas release scenarios

Many complex models are available to study the dispersion of contaminants or ventilation effectiveness in indoor spaces. Because of the computationally complex numerical schemes employed, most of these models require mainframe computers or workstations. However, simple design tools or guidelines are needed, in addition to complicated models. A dispersion model based on the basic governing equations was developed and uses an analytical solution. Because the concentration is expressed by an analytical solution, the grid size and time steps are user definable. A computer program was used to obtain numerical results and to obtain release history from a thermodynamic source model. The model can be used to estimate three-dimensional spatial and temporal variations in concentrations resulting from transient gas releases in an enclosure. The model was used to study a gas release scenario from a pressurized cylinder into a large ventilated building, in this case, a transit parking and fueling facility.     

Review of indoor emission source models. Part 1. Overview

Indoor emission source models are mainly used as a component in indoor air quality (IAQ) modeling, which, in turn, is part of exposure and risk modeling. They are also widely used to interpret the experimental data obtained from environmental chambers and buildings. This paper compiles 52 indoor emission source models found in the literature. Together, they represent the achievements that IAQ modelers have made in recent years. While most models have a certain degree of usefulness, genuine predictive models are still few, and there is undoubtedly much room for improvement. This review consists of two parts. Part 1--this paper-provides an overview of the 52 models, briefly discussing their validity, usefulness, limitations, and flaws (if any). Part 2 focuses on parameter estimation, a topic that is critically important to modelers but has not been systematically discussed.     

Indoor ozone/terpene reactions as a source of indoor particles

This paper reports effects of reactions between ozone and selected terpenes on the concentrations and size distributions of airborne particles in a typical indoor setting. The studies were conducted in adjacent, identical offices. In the first set of experiments, known concentrations of ozone and a selected terpene (either d-limonene, α-terpinene, or a terpene-based cleaner whose major constituent is α-pinene) were deliberately introduced into one of the offices while the other office served as a control. Subsequent particle formation and redistribution were monitored with an eight-channel optical particle counter. Particle formation was observed in each terpene system, but was greatest in the case of d-limonene. The number of particles in the 0.1–0.2 μm diameter size range was as much as 20 times larger in the office with deliberately supplemented ozone and d-limonene than in the office serving as the control. The concentration differences in the larger size ranges developed with time, indicating the importance of coagulation and condensation processes in this indoor environment. In the second set of experiments, d-limonene was deliberately introduced into one of the offices, but ozone was not supplemented in either office; instead, the indoor ozone concentrations were those that happened to be present (primarily as a consequence of outdoor-to-indoor transport). In the office that contained supplemental d-limonene, the concentrations of the 0.1–0.2 μm particles tracked those of indoor ozone (the limiting reagent) and were as much as 10 times greater than levels measured in the comparable office that did not contain supplemental d-limonene. The results demonstrate that ozone/terpene reactions can be a significant source of sub-micron particles in indoor settings, and further illustrate the potential for reactions among commonly occurring indoor pollutants to markedly influence indoor environments.     

Toxic oxide deposits from the combustion of landfill gas and biogas

Oxide deposits found in combustion systems of landfill gas fired power stations contain relatively high concentrations of elements which form volatile species such as P, As, Sb and Sn. These deposits should be handled with care because of their potential toxicity. By contrast, deposits in biogas system engines were found to contain much lower levels of such elements. The enrichment of these elements can be attributed to a hypothetical multistage process. The elements form volatile species in the landfill body. They are selectively transported as part of the landfill gas into the gas-burning devices. Inside the burners, they are immobilized as nonvolatile oxides.     

Assessment of coal spontaneous combustion index gas under different oxygen concentration environment: an experimental study

Environmental Science and Pollution Research - Oxygen plays a crucial role in coal spontaneous combustion (CSC), and the magnitude of oxygen concentration determines the oxidation reaction...