Chitsan Lin

Applications of open-path Fourier transform infrared for identification of volatile organic compound pollution sources and characterization of source emission behaviors.

Abstract An open-path Fourier transform infrared spectroscopy (OP-FTIR) system was set up for 3-day continuous line-averaged volatile organic compound (VOC) monitoring in a paint manufacturing plant. Seven VOCs (toluene, m-xylene, p-xylene, styrene, methanol, acetone, and 2-butanone) were identified in the ambient environment. Daytime-only batch operation mode was well explained by the time-series concentration plots. Major sources of methanol, m-xylene, acetone, and 2-butanone were identified in the southeast direction where paint solvent manufacturing processes are located. However, an attempt to uncover sources of styrene was not successful because the method detection limit (MDL) of the OP-FTIR system was not sensitive enough to produce conclusive data. In the second scenario, the OP-FTIR system was set up in an industrial complex to distinguish the origins of several VOCs. Eight major VOCs were identified in the ambient environment. The pollutant detected wind-rose percentage plots that clearly showed that ethylene, propylene, 2-butanone, and toluene mainly originated from the tank storage area, whereas the source of n-butane was mainly from the butadiene manufacturing processes of the refinery plant, and ammonia was identified as an accompanying reduction product in the gasoline desulfuration process. Advantages of OP-FTIR include its ability to simultaneously and continuously analyze many compounds, and its long path length monitoring has also shown advantages in obtaining more comprehensive data than the traditional multiple, single-point monitoring methods.

Influence of Sea-Land Breezes on the Tempospatial Distribution of Atmospheric Aerosols over Coastal Region

ABSTRACT The influence of sea-land breezes (SLBs) on the spatial distribution and temporal variation of particulate matter (PM) in the atmosphere was investigated over coastal Taiwan. PM was simultaneously sampled at inland and offshore locations during three intensive sampling periods. The intensive PM sampling protocol was continuously conducted over a 48-hr period. During this time, PM2.5 and PM2.5–10 (PM with aerodynamic diameters ≤2.5 μm and between 2.5 and 10 μm, respectively) were simultaneously measured with dichotomous samplers at four sites (two inland and two offshore sites) and PM10 (PM with aerodynamic diameters ≤10 μm) was measured with β-ray monitors at these same 4 sites and at 10 sites of the Taiwan Air Quality Monitoring Network. PM sampling on a mobile air quality monitoring boat was further conducted along the coastline to collect offshore PM using a β-ray monitor and a dichotomous sampler. Data obtained from the inland sites (n = 12) and offshore sites (n = 2) were applied to plot the PM10 concentration contour using Surfer software. This study also used a three-dimensional meteorological model (Pennsylvania State University/National Center for Atmospheric Research Meteorological Model 5) and the Comprehensive Air Quality Model with Extensions to simulate surface wind fields and spatial distribution of PM10 over the coastal region during the intensive sampling periods. Spatial distribution of PM10 concentration was further used in investigating the influence of SLBs on the transport of PM10 over the coastal region. Field measurement and model simulation results showed that PM10 was trans ported back and forth across the coastline. In particular, a high PM10 concentration was observed at the inland sites during the day because of sea breezes, whereas a high PM10 concentration was detected offshore at night because of land breezes. This study revealed that the accumulation of PM in the near-ocean region because of SLBs influenced the tempospatial distribution of PM10 over the coastal region. IMPLICATIONS Model simulation and field measurements show that PM was transported back and forth across the coastline because of SLBs and that this regularly influenced the tempospatial distribution of PM10 over the coastal region. A high PM10 concentration was observed at the inland sites because of daytime onshore breezes, whereas a high PM10concentration was detected over the ocean because of nighttime offshore breezes. The implications of these results suggest that relevant authorities should work to prevent pollution episodes by reducing regional PM emissions that lead to stagnant or recirculating air under specific weather conditions.

Assessing the altitude effect on distributions of volatile organic compounds from different sources by principal component analysis

Emissions of volatile organic compounds (VOCs), particularly those from industrial sources, have been of substantial concern because they have had adverse effects on the nearby environment and human health. In this study, the effect of altitude on the distributions of VOCs from petrochemical industrial sources was studied by analyzing the VOC concentrations at ground level and three different altitudes (100, 300, and 500 m above the ground) during three monitoring seasons from 2009 to 2010 and assessing the results by principal component analysis (PCA) and cluster analysis. Kaohsiung city in southern Taiwan, known for its high levels of air contaminants due to many pollution-intensive industries in the city, was selected as the area to be examined. Of various types of aliphatic and aromatic hydrocarbons being detected, acetone and toluene were the dominant VOC species with relatively high concentrations. By PCA application and cluster analysis, aromatic and aliphatic compounds were found to be the main VOCs accounting for the maximum variance of the data observed at ground level and high altitude, respectively. The presence of mono-aromatic hydrocarbons at ground level suggested an important contribution from traffic, while the presence of both saturated and unsaturated hydrocarbons at high altitudes was likely to be due to the local petrochemical industries given the heights of flare stacks in the examined areas and short lifetimes of unsaturated hydrocarbons such as alkenes. 3-D loading plots exhibited clear grouping of the VOCs in terms of their chemical structures and/or physicochemical characteristics for the data at ground level and 500 m and less clear differentiation for the data at 100 and 300 m, possibly resulted by atmospheric dispersion and mixing. The influence of altitude on the VOC distributions appeared not to be negligible and was greatly impacted by the location (e.g., height) of emission sources and the physicochemical properties of the VOCs including their molecular weights/sizes and lifetimes in the atmosphere. These findings prove the complications in the current knowledge of VOC pollution and are of help in managing the adverse impacts on the environment and public health by VOCs from industrial or other sources.

Vertical and diurnal characterization of volatile organic compounds in ambient air in urban areas.

ABSTRACT More than half of the worlds population lives in cities, and their populations are rapidly increasing. Information on vertical and diurnal characterizations of volatile organic compounds (VOCs) in urban areas with heavy ambient air pollution can help further understand the impact of ambient VOCs on the local urban environment. This study characterized vertical and diurnal variations in VOCs at 2, 13, 32, 58, and 111 m during four daily time periods (7:00 to 9:00 a.m., 12:00 to 2:00 p.m., 5:00 to 7:00 p.m., and 11:00 p.m. to 1:00 a.m.) at the upwind of a high-rise building in downtown, Kaohsiung City, Taiwan. The study used gas chromatography–mass spectrometry to analyze air samples collected by silica-coated canisters. The vertical distributions of ambient VOC profiles showed that VOCs tended to decrease at greater heights. However, VOC levels were found to be higher at 13 m than at ground level at midnight from 11:00 p.m. to 1:00 a.m. and higher at 32 than 13 m between 7:00 and 9:00 a.m. These observations suggest that vertical dispersion and dilution of airborne pollutants could be jointly affected by local meteorological conditions and the proximity of pollution sources. The maximum concentration of VOCs was recorded during the morning rush hours from 7:00 to 9:00 a.m., followed by rush hours from 5:00 to 7:00 p.m., hours from 12:00 to 2:00 p.m., and hours from 11:00 p.m. to 1:00 a.m., indicating that the most VOC compounds in urban air originate from traffic and transportation emissions. The benzene-toluene-ethyl benzene-xylene (BTEX) source analysis shows that BTEX at all heights were mostly associated with vehicle transportation activities on the ground. IMPLICATIONS The vertical distributions of ambient VOC profiles tend to decrease with height. However, levels of VOCs that originate from upwind industrial sources can accumulate at higher altitudes because of thermal inversions. These observations suggest that vertical dispersion and dilution of airborne pollutants could be jointly affected by local meteorological conditions and the proximity of pollution sources. Whether such vertical variation in VOC profiles can affect the prediction of air quality model is of interest and needs to be considered in future air quality management.

Fugitive Coke Oven Gas Emission Profile by Continuous Line Averaged Open-Path Fourier Transform Infrared Monitoring

Abstract Although most coke oven research is focused on the emission of polycyclic aromatic hydrocarbons, well-known carcinogens, little has been done on the emission of volatile organic compounds, some of which are also thought to be hazardous to workers and the environment. To profile coke oven gas (COG) emissions, we set up an open-path Fourier transform infrared (OP-FTIR) system on top of a battery of coke ovens at a steel mill located in Southern Taiwan and monitored average emissions in a coke processing area for 16.5 hr. Nine COGs were identified, including ammonia, CO, methane, ethane, ethylene, acetylene, propylene, cyclohexane, and o-xylene. Time series plots indicated that the type of pollutants differed over time, suggesting that different emission sources (e.g., coke pushing, quench tower, etc.) were involved at different times over the study period. This observation was confirmed by the low cross-correlation coefficients of the COGs. It was also found that, with the help of meteorological analysis, the data collected by the OP-FTIR system could be analyzed effectively to characterize differences in the location of sources. Although the traditional single-point samplings of emissions involves sampling various sources in a coke processing area at several different times and is a credible profiling of emissions, our findings strongly suggest that they are not nearly as efficient or as cost-effective as the continuous line average method used in this study. This method would make it easier and cheaper for engineers and health risk assessors to identify and to control fugitive volatile organic compound emissions and to improve environmental health.

Microwave-induced nanoscale zero-valent iron degradation of perchloroethylene and pentachlorophenol

Microwave (MW) is applied to enhance perchloroethylene (PCE) or pentachlorophenol (PCP) removal using zero-valent iron (ZVI; Fe0) as the dielectric medium. ZVI has a much higher dielectric loss factor (39.5) than other media; it is capable of absorbing MW radiation rapidly to speed up the release of electrons, leading to rises of the ZVI particle surface temperature. If the MW power is continued, excessive electricity will accumulated inside ZVI particles, resulting in sparks. The results show that during the initial 5 sec (700 W), the linear aliphatic PCE has a faster decomposing rate than the ringed PCP (82.0% vs. 4.8%) because less energy is required for decomposing the linear-chlorine bond (90 kcal mol−1) than ring-chlorine bonds (95 kcal mol−1). Later, the removal rate for either PCE or PCP remains the same when the exposure time is between 5 and 60 sec. Without MW irradiation, linear PCE molecules have larger surface area to contact ZVI, and hence they have better removal efficiencies than PCP molecules. Using Fe0 as a microwave dielectric medium to treat PCE or PCP is a new and worthwhile treatment technology; it is environmentally friendly, and its use will eliminate the secondary pollution. Implications Nanoscale iron particles are characterized by high surface-area-to-volume ratios, high specific surface area, and high surface reactivity. With a much higher dielectric loss factor, it is capable of absorbing MW radiation rapidly to speed up the release of electrons, leading to rise in temperature. The time needed to achieve a satisfactory treatment is also reduced, leading to significant saving of energy consumption to make this method cost-effective and also environmentally friendly for the industry to pursuit sustainable development.

Optimizing chemical oxygen demand removal from synthesized wastewater containing lignin by catalytic wet-air oxidation over CuO/Al2O3 catalysts

In this study, 10% CuO/Al2O3 catalyst was used in a catalytic wet-air oxidation process to remove chemical oxygen demand (COD) and color from experimentally designed wastewater containing lignin. The catalyst was prepared using an impregnation method and was characterized by X-ray diffraction (XRD), atomic absorption spectroscopy (AAS), and Brunauer-Emmett-Teller method (BET) for surface area before use. A series of Box-Behnken design (BBD) experiments were used to identify the conditions (temperature, pressure, reaction time, and catalysts) necessary for the COD removal process. The predicted model had R2 and R2adj correlation coefficients of 0.98 and 0.97, respectively. Pressure only and the interaction effect between temperature and pressure were found to have a significant effect on COD removal (both confidence interval [CI] 95%). Finally, response surface methodology (RSM)-optimized results suggested that 92% of COD could be removed in 1 L of experimental wastewater with a lignin concentration 350 g/L in 120 min under the following conditions: a reaction temperature of 185 °C, a pressure of 10 bars, and catalyst loading of 1 mg/L. The experiment, performed in triplicate, yielded a COD removal of 90 ± 2%. The results are believed to be of importance to pulp and paper industrial wastewater treatment and other similar applications. Implications: Catalytic wet-air oxidation (CWAO) has been used as an alternative to overcome problems related to the high temperatures and pressures required by the traditional wet-air oxidation. CWAO has been widely applied to treat various industrial wastewaters. To reduce the overall operational cost, it is necessary to identify the optimal condition required when designing wastewater treatment plant processes. In this work, the authors had successfully demonstrated the application of response surface methodology (RSM) with the Box-Behnken design (BBD) as a means of elucidating the complicated interaction effects between parameters.

Multivariate analysis of effects of diurnal temperature and seasonal humidity variations by tropical savanna climate on the emissions of anthropogenic volatile organic compounds.

Volatile organic compounds (VOCs), particularly those from anthropogenic sources, have been of substantial concern. In this study, the influences of diurnal temperature and seasonal humidity variations by tropical savanna climate on the distributions of VOCs from stationary industrial sources were investigated by analyzing the concentrations during the daytime and nighttime in the dry and wet seasons and assessing the results by principal component analysis (PCA) and cluster analysis. Kaohsiung City in Southern Taiwan, known for its severe VOC pollution, was chosen as the location to be examined. In the results, the VOC concentrations were lower during the daytime and in the wet season, possibly attributed to the stronger photochemical reactions and increasing inhibition of VOC emissions and transports by elevating humidity levels. Certain compounds became appreciably more important at higher humidity, as these compounds were saturated hydrocarbons with relatively low molecular weights. The influence of diurnal temperature variation on VOC distribution behaviors seemed to be less important than and interacted with that of seasonal humidity variation. Heavier aromatic hydrocarbons with more complex structures and some aliphatic compounds were found to be the main species accounting for the maximum variances of the data observed at high humidity, and the distinct grouping of compounds implied a pronounced inherent characteristic of each cluster in the observed VOC distributions. Under the influence of diurnal temperature variation, selected VOCs that may have stronger photochemical resistances and/or longer lifetimes in the atmosphere were clustered with each other in the cluster analysis, whereas the other groups might consist of compounds with different levels of vulnerability to sunlight or high temperatures. These findings prove the complications in the current knowledge regarding the VOC contaminations and providing insight for managing the adverse impacts of the anthropogenic VOCs on the environment and public health.

Characterization of spent nickel-metal hydride batteries and a preliminary economic evaluation of the recovery processes.

Abstract Valuable metal materials can be recovered from spent nickel–metal hydride (NiMH) batteries. However, little attention has been paid to the metal compositions of individual components of NiMH batteries, although this is important for the selection of the appropriate recycling process. In this study, NiMH batteries were manually disassembled to identify the components and to characterize the metals in each of these. A preliminary economic analysis was also conducted to evaluate the recovery of valuable metals from spent NiMH batteries using thermal melting versus simple mechanical separation. The results of this study show that metallic components account for more than 60% of battery weight. The contents of Ni, Fe, Co, and rare earth elements (REEs) (i.e., valuable metals of interest for recovery) in a single battery were 17.9%, 15.4%, 4.41%, and 17.3%, respectively. Most of the Fe was in the battery components of the steel cathode collector, cathode cap, and anode metal grid, while Ni (>90%) and Co (>90%) were mainly in the electrode active materials (anode and cathode metal powders). About 1.88 g of REEs (Ce, La, and Y) could be obtained from one spent NiMH battery. The estimated profits from recovering valuable metals from spent NiMH batteries by using thermal melting and mechanical processes are 2,329 and 2,531 USD/ton, respectively, when including a subsidy of 1,710 USD/ton. The findings of this study are very useful for further research related to technical and economic evaluations of the recovery of valuable metals from spent NiMH batteries. Implications: The spent nickel–metal hydride (NiMH) batteries were manually disassembled and their components were identified. The metals account for more than 60% of battery weight, when Ni, Fe, Co, and rare earth elements (REEs) were 17.9%, 15.4%, 4.41%, and 17.3%, respectively, in a single battery. The estimated profits of recovering valuable metals from NiMH batteries by using thermal melting and mechanical processing are 2,329 and 2,531 USD/ton, respectively, when including a subsidy of 1,710 USD/ton. These findings are very useful to develop or select the recovery methods of valuable metals from spent NiMH batteries.

Characteristics and determinants of ambient volatile organic compounds in primary schools

This study evaluates the effects of a sampling strategy that includes the sampling season, time period, ambient environment, and location on determining the concentrations and species of ambient volatile organic compounds (VOCs) that may affect children in primary schools. Air samples were collected from playgrounds in primary schools, with four sites near an oil refinery plant in Taoyuan and two sites in Zhongli (one site near a bus terminal and the other site in a suburban area) in Taiwan. The samples were obtained on eight occasions from August 2010 to June 2011. One sample was collected from 09:00 to 11:00 and the other was collected from 13:00 to 15:00 on each occasion using passive flow controller canisters (40 mL min-1 flow rate) assembled with silica-coated stainless steel. The United States Environmental Protection Agency Method TO-15 with Photochemical Assessment Monitoring System and Urban Air Toxics standards was used to analyze the samples. The ratios of benzene, toluene, ethylbenzene, and xylenes (BTEXs) were also estimated. This study found that the sampling location and wind direction are the main determinants to monitor the concentrations and species of ambient VOCs, and the effects from the sampling season and time period are minor. Alkane, ketone, and aromatics have been ranked as the top three categories with high concentrations, and toluene, 2-butanone, and acetone have been detected with the highest concentrations among the investigated VOCs. Several VOCs emitted from stationary sources, including propane, isoprene, n-decane, chloromethane, chloroethene, chloroethane and 1,2-dichloroethane, were detected only in Taoyuan. Higher concentrations of VOC species associated with automobiles and common community sources were detected in Zhongli but not in Taoyuan. Among BTEXs ratios, toluene/ethylbenzene ratios were as high as 31.52 (standard deviation [S.D.] = 13.53) in Taoyuan and 13.66 (S.D. = 3.87) in Zhongli. Toluene/benzene ratios were as high as 15.7 in Taoyuan and 4.30 in Zhongli. This study suggests that the susceptible population exposed to ambient VOCs should be considered in planning public service facilities and the presence of VOCs should be investigated regularly.