TiO2纳米粒子光催化降解室内挥发性有机污染物苯的研究

利用溶胶凝胶法制备了纳米TiO2粒子。通过X射线粉末衍射分析，晶相为锐钛矿和金红石混晶，晶粒尺寸约为13nm。以苯为目标污染物，研究了不同的苯初始浓度、氧气、催化剂的用量以及光源强度和波长对光催化效率的影响。结果发现，氧气可以提高光催化降解苯的效率；无论在有氧条件还是无氧条件下，随着苯初始浓度的降低，光催化效率升高；光源的强度和波长对光催化效率具有影响；对于光催化降解0．70μg／cm^3苯而言，最佳的TiO2投入量为0.1g。     

TiO2纳米粒子光催化降解室内挥发性有机污染物苯的研究

利用溶胶凝胶法制备了纳米TiO2粒子.通过X射线粉末衍射分析,晶相为锐钛矿和金红石混晶,晶粒尺寸约为13 nm.以苯为目标污染物,研究了不同的苯初始浓度、氧气、催化剂的用量以及光源强度和波长对光催化效率的影响.结果发现,氧气可以提高光催化降解苯的效率;无论在有氧条件还是无氧条件下,随着苯初始浓度的降低,光催化效率升高;光源的强度和波长对光催化效率具有影响;对于光催化降解0.70μg/cm3苯而言,最佳的TiO2投入量为0.1g.     

The use of environmental risk assessment methodologies for an indoor air quality investigation

The authors of this paper chose several target compounds that have been found in average US homes, applied the current United States Environmental Protection Agency (USEPA) Superfund risk assessment methodologies to indoor air quality, and produced risk numbers for hazard quotients and predicted increases in incidence of cancer which would be unacceptable at US hazardous waste sites. The calculations were made for the average child and adult with USEPA default exposure values. Calculations were also made for a worst case scenario using maximum concentrations and exposure estimates defined by the USEPA as describing the reasonable exposure (RME). Significant cancer risks and non-cancer hazard quotients were predicted.     

The transfer of trichloroethylene (TCE) from a shower to indoor air: experimental measurements and their implications

Experiments were performed to measure the transfer of trichloroethylene (TCE), a volatile organic compound (VOC), from tap water in showers to indoor air. In these experiments, the loss of TCE from tap water in the shower is based on the difference between influent and effluent concentrations. We have developed and previously published a three-compartment model, which we use to simulate the 24-h concentration history of VOCs in the shower, bathroom, and remaining household volumes resulting from the use of contaminated tap water. An important input to this model is the transfer efficiency of the VOC from water to air. The experiments reveal that the transfer efficiency of TCE from shower water to air has an arithmetic mean value of 61 percent and an arithmetic standard deviation of 9 percent. Analysis of the results shows that there is no statistically significant difference between the transfer efficiency measured with hot (37 degrees C) or cold (22 degrees C) shower water and that there is no statistically significant change in transfer efficiency with time during a 20-min shower. The implications for exposure assessment are considered.     

The transfer of trichloroethylene (TCE) from a shower to indoor air: experimental measurements and their implications

Experiments were performed to measure the transfer of trichloroethylene (TCE), a volatile organic compound (VOC), from tap water in showers to indoor air. In these experiments, the loss of TCE from tap water in the shower is based on the difference between influent and effluent concentrations. We have developed and previously published a three-compartment model, which we use to simulate the 24-h concentration history of VOCs in the shower, bathroom, and remaining household volumes resulting from the use of contaminated tap water. An important input to this model is the transfer efficiency of the VOC from water to air. The experiments reveal that the transfer efficiency of TCE from shower water to air has an arithmetic mean value of 61 percent and an arithmetic standard deviation of 9 percent. Analysis of the results shows that there is no statistically significant difference between the transfer efficiency measured with hot (37 degrees C) or cold (22 degrees C) shower water and that there is no statistically significant change in transfer efficiency with time during a 20-min shower. The implications for exposure assessment are considered.     

NORMACAT project: normalized closed chamber tests for evaluation of photocatalytic VOC treatment in indoor air and formaldehyde determination

Background, aim

The aims of the NORMACAT project are: to develop tools and unbiased standardized methods to measure the performance and to validate the safety of new materials and systems integrating photocatalysis, to develop new photocatalytic media with higher efficiency and to give recommendations aimed at improving the tested materials and systems.

Method

To achieve this objective, it was necessary to design standardized test benches and protocols to assess photocatalytic efficiency of materials or systems used in the treatment of volatile organic compounds (VOCs) and odour under conditions close to applications. The tests are based on the validation of robust analytical methods at the parts per billion by volume level that not only follow the disappearance of the initial VOCs but also identify the secondary species and calculate the mineralization rates.

Results

The first results of inter-laboratory closed chamber tests, according to XP B44-013 AFNOR standard, are described. The photocatalytic degradation of mixtures of several defined pollutants under controlled conditions (temperature, relative humidity, initial concentration) was carried out in two independent laboratories with the same photocatalytic device and with various analytical procedures. Comparison of the degradation rate and of the mineralization efficiency allowed the determination of the clean air delivery rate in both cases. Formaldehyde was the only by-product detected during photocatalytic test under standardized experimental conditions. The concentration of transient formaldehyde varied according to the initial VOC concentration. Moreover the photocatalytic reaction rate of formaldehyde in mixture with other pollutants was analysed. It was concluded that formaldehyde concentration did not increase with time.

Conclusion??perspective

This type of experiment should allow the comparison of the performances of different photoreactors and of photocatalytic media under controlled and reproducible conditions against mixtures of pollutants including formaldehyde.     

The treatment of waste air containing phenol vapors in biotrickling filter

This research aimed at investigating the biodegradation of phenol contaminated-air streams in biotrickling filter. The effect of inlet concentration (200-1000 ppmv) and empty bed contact time (EBCT) (15-60 s) were investigated under steady state, transient and shock loading, and shutdown periods. Upon rapid start up operation, inlet phenol concentrations of up to 1000 ppmv did not significantly affect the performance of the biotrickling filter at EBCT of 60 s, so that removal efficiency was well greater than 99%. In addition, the EBCT as low as 30 s did not have detrimental effects on the efficiency of the bioreactor and phenol removal was greater than 99%. Decreasing the EBCT to 15s reduced the removal efficiency to around 92%. The maximum elimination capacity obtained in the biotrickling filter was 642 g(phenol) m(-3) h(-1), where the removal efficiency was only 57%. Results from the transient loading experiments revealed that the biotrickling filter could effectively handle the variations of the inlet loads without the phenol removal capacity being significantly affected.     

Determination of organic compounds in indoor air with potential reference to air quality

Concentrations of 15 volatile organic compounds have been investigated in the air of two schoolrooms. The chemical analysis included enrichment on porous polymer beads, heat desorption and gas Chromatographic separation on a capillary column connected to either a flame ionization detector or a mass spectrometer. Samples were collected from the indoor air both in the presence and in the absence of the pupils (boys and girls, age 16–19) as well as from the ambient outdoor air. The qualitative composition of indoor and outdoor air was found to be about the same : aliphatic and aromatic hydrocarbons predominate, though indoors the number of compounds detected is larger and the concentrations are higher. Both the number and the concentration increase in the presence of humans. The mean concentrations of acetone and the sum of the concentrations of C₂-alkylbenzenes were 7.7 and 8.2 μg m⁻³ respectively in an unoccupied room and increased to 19.8 and 12.1 μg m⁻³ respectively in an occupied room.     

Use of an indoor air quality model (IAQM) to estimate indoor ozone levels

Currently, outdoor ozone levels in many U.S. cities exceed the primary health-based national ambient air quality standard. While outdoor ozone levels are an important measure of the severity of those exceedances, people typically spend more than 80 percent of their time indoors, where ozone levels are lower. Indoor ozone levels range from 10 to 80 percent of outdoor levels, with many people receiving a substantial portion of their ozone exposure while indoors. This paper uses an indoor air quality model (IAQM) to estimate indoor ozone levels by microenvironment type (home, office, and vehicle) and configuration (windows open, windows closed, older construction, weatherized, and air conditioned). The formulation of IAQM is discussed, along with specification of model parameters for ozone. The multicompartment version of IAQM is described, with a single-compartment version used for the analyses. IAQM-calculated ozone indoor-outdoor ratios compare well with research-reported values. Results indicate that ozone peak-concentration indoor-outdoor ratios range as follows: home--0.65 (windows open), 0.36 (air conditioned), 0.23 (typical construction, windows closed), and 0.05 (energy-efficient construction, windows closed); office--0.82 (heating, ventilation and air conditioning systems supplying 100 percent outdoor air), 0.60 (typical HVAC), and 0.32 (energy-efficient HVAC); and vehicle--0.41 (85 mph), 0.33 (55 mph), and 0.21 (10 mph). Analysis results are presented to characterize IAQM's sensitivity to assumed model parameters.     

The effects of evaporating essential oils on indoor air quality

Essential oils, predominantly comprised of a group of aromatic chemicals, have attracted increasing attention as they are introduced into indoor environments through various forms of consumer products via different venues. Our study aimed to characterize the profiles and concentrations of emitted volatile organic compounds (VOCs) when evaporating essential oils indoors. Three popular essential oils in the market, lavender, eucalyptus, and tea tree, based on a nation-wide questionnaire survey, were tested. Specific aromatic compounds of interest were sampled during evaporating the essential oils, and analyzed by GC-MS. Indoor carbon monoxide (CO), carbon dioxide (CO₂), total volatile organic compounds (TVOCs), and particulate matters (PM₁₀) were measured by real-time, continuous monitors, and duplicate samples for airborne fungi and bacteria were collected in different periods of the evaporation. Indoor CO (average concentration 1.48 vs. 0.47 ppm at test vs. background), CO₂ (543.21 vs. 435.47 ppm), and TVOCs (0.74 vs. 0.48 ppm) levels have increased significantly after evaporating essential oils, but not the PM₁₀ (2.45 vs. 2.42 ppm). The anti-microbial activity on airborne microbes, an effect claimed by the use of many essential oils, could only be found at the first 30–60 min after the evaporation began as the highest levels of volatile components in these essential oils appeared to emit into the air, especially in the case of tea tree oil. High emissions of linalool (0.092–0.787 mg m⁻³), eucalyptol (0.007–0.856 mg m⁻³), d-limonene (0.004–0.153 mg m⁻³), ρ-cymene (0.019–0.141 mg m⁻³), and terpinene-4-ol-1 (0.029–0.978 mg m⁻³), all from the family of terpenes, were observed, and warranted for further examination for their health implications, especially for their potential contribution to the increasing indoor levels of secondary pollutants such as formaldehyde and secondary organic aerosols (SOAs) in the presence of ozone.     

Concentration of tetrachloroethylene in indoor air at a former dry cleaner facility as a function of subsurface contamination: a case study

A field study was performed to evaluate indoor air concentrations and vapor intrusion (VI) of tetrachloroethylene (PCE) and other chlorinated solvents at a commercial retail site in Dallas, TX. The building is approximately 40 yr old and once housed a dry cleaning operation. Results from an initial site characterization were used to select sampling locations for the VI study. The general approach for evaluating VI was to collect time-integrated canister samples for off-site U.S. Environmental Protection Agency Method TO-15 analyses. PCE and other chlorinated solvents were measured in shallow soil gas, subslab soil-gas, indoor air, and ambient air. The subslab soil gas exhibited relatively high values: PCE < or =2,600,000 parts per billion by volume (ppbv) and trichloroethylene < or =170 ppbv. The attenuation factor, the ratio of indoor air and subslab soil-gas concentrations, was unusually low: approximately 5 x 10(-6) based on the maximum subslab soil-gas concentration of PCE and 1.4 x 10(-5) based on average values.     

室外交通污染物对临街建筑室内环境的影响分析

采用计算流体动力学(CFD)模拟和CONTAM模型结合的方法,分析室外典型交通污染物CO对临街建筑室内环境的影响。结果表明,来流风向、建筑间距和建筑排布形式均对临街建筑室内CO浓度分布产生影响。来流风向角(θ)为15°时,室内CO浓度最低,而θ为45°时,CO浓度最高;随着建筑间距增加,室内CO浓度不断降低;交错排布的建筑形式下,室内CO浓度明显低于对称排布的建筑形式。临街建筑室内CO浓度逐时变化与室外街道峡谷内车流量变化保持一致。     

Vertical variability of volatile organic compound (VOC) levels in ambient air of high-rise apartment buildings with and without occurrence of surface inversion

If there are potential vertical variations in ambient air pollution concentrations, these should be considered when evaluating the exposure of residents living in high-rise apartment buildings. Accordingly, the current study examined this assertion for VOC, while also assessing the potential influence of the atmospheric stability and sampling period on the exposure level of apartment residents. Thirty apartment buildings with 10 or more stories were surveyed in both winter and summer. The atmospheric stability and sampling period were both found to have a potential influence on the variation in the ambient concentrations according to the floor level in the high-rise apartment buildings. Consequently, the current findings emphasize the need to consider these factors in the vertical variation of urban air pollutants when evaluating the exposure of high-rise apartment residents. Moreover, the ambient concentrations of all the target compounds were significantly higher in the winter than in the summer for both the low and high floors. The proportions for the low floors were similar to those for the high floors, plus significant correlations between the target compounds were exhibited for both the low and high floors.     

Identification of redundant air quality measurements through the use of principal component analysis

This study aims to show how principal component analysis (PCA) can be used to identify redundant measurements in air quality monitoring networks. The minimum number of air quality monitoring sites in Oporto Metropolitan Area (Oporto-MA) was evaluated using PCA and then compared to the one settled by the legislation. Nine sites, monitoring NO₂, O₃ and PM₁₀, were selected and the air pollutant concentrations were analysed from January 2003 to December 2005. PCA was applied to the data corresponding to the first two years that were divided into annual quarters to verify the persistence of the PCA results. The number of principal components (PCs) was selected by applying two criteria: Kaiser (PCs with eigenvalues greater than 1) and ODV₉₀ (PCs representing at least 90% of the original data variance). Each pollutant was analysed separately. The two criteria led to different results. Using Kaiser criterion for the eight analysed periods, two PCs were selected in: (i) five periods for O₃ and PM₁₀; and (ii) six periods for NO₂. These PCs had important contributions of the same groups of monitoring sites. The percentage of the original data variance contained in the selected PCs using this criterion was always below 90%. Thus, the results obtained using ODV₉₀ were considered with more confidence. Using this criterion, only five monitoring sites for NO₂, three for O₃ and seven for PM₁₀ were needed to characterize the region. The number of monitoring sites for NO₂ and O₃ was in agreement with what was established by the legislation. However, for PM₁₀, Oporto-MA needed two more monitoring sites. To validate PCA results, statistical models were determined to estimate air pollutant concentrations at removed monitoring sites using the concentrations measured at the remaining monitoring sites. These models were applied to a year's data. The good performance obtained by the models showed that the monitoring sites selected by the procedure presented in this study were enough to infer the air pollutant concentrations in the region defined by the initial monitoring sites. Additionally, the air pollutant analysers corresponding to the redundant measurements can be installed in non-monitored regions, allowing the enlargement of the air quality monitoring network.     

Simulating the fate and transport of TCE from groundwater to indoor air

This work provides an exploratory analysis on the relative importance of various factors controlling the fate and transport of volatile organic contaminants (in this case, TCE) from a DNAPL source zone located below the water table and into the indoor air. The analysis is conducted using the multi-phase compositional model CompFlow Bio, with the base scenario problem geometry reminiscent of a field experiment conducted by Rivett [Rivett, M.O., (1995), Soil–gas signatures from volatile chlorinated solvents: Borden field experiments. Groundwater, 33(1), 84–98.] at the Borden aquifer where groundwater was observed to transport a contaminant plume a substantial distance without vertical mass transport of the contaminant across the capillary fringe and into the vadose zone. Results for the base scenario model indicate that the structure of the permeability field was largely responsible for deflecting the groundwater plume upward towards the capillary fringe, permitting aqueous phase diffusion to transport the TCE into the vadose zone. Alternative permeability realizations, generated as part of a Monte Carlo simulation process, at times deflected the groundwater plume downwards causing the extended thickness of the saturated zone to insulate the vadose zone from exposure to the TCE by upward diffusive transport. Comparison of attenuation coefficients calculated using the CompFlow Bio and Johnson and Ettinger [Johnson, P.C. and Ettinger, R.A., (1991), Heuristic model for predicting the intrusion rate of contaminant vapors into buildings. Environmental Science and Technology, 25, 1445–1452.] heuristic model exhibited fortuitous agreement for the base scenario problem geometry, with this agreement diverging for the alternative permeability realizations as well as when parameters such as the foundation slab fracture aperture, the indoor air pressure drop, the capillary fringe thickness, and the infiltration rate were varied over typical ranges.     

Emission rates of chlorinated volatile organics from new and used consumer products found during vapor intrusion investigations: Impact on indoor air concentrations

Consumer products can emit chlorinated volatile organic compounds (CVOCs) that complicate vapor intrusion (VI) assessments. Assessment protocols acknowledge the need to remove these products during VI investigations, but they can be problematic to identify and locate. Predicting if the products cause detectable air concentrations is also difficult since emission rate information is limited and can vary with product use and age. In this study, the emission rates of 1,2-dichloroethane, trichloroethene, tetrachloroethene, and carbon tetrachloride from four consumer products identified as indoor sources during VI field investigations were measured under laboratory conditions using a flow through system. Emissions of PCE from an adhesive container tube ranged from 1.33 ± 1.13 μg/min (unopened) to 23.9 ± 2.93 μg/min (previously opened). The laboratory-measured emission rates were used to estimate indoor air concentrations, which were then compared to concentrations measured after the products placed were into an actual residence. The estimated and measured indoor air concentrations were generally comparable, showing that emission rate information can be used to determine the relative impact of internal CVOC sources.     

The use of real-time monitoring data to evaluate major sources of airborne particulate matter

Real-time chemical measurements have been made as part of a field study of air quality in the city and harbour of Cork, Ireland. The data relate to the year 2008, with particular attention paid to the period between May and August. Eight air quality parameters were measured: NO, O₃, NO₂, SO₂, EC, OC, particulate SO₄^2? and PM_2.5. The data have been used in a novel way involving wind and temporal averaging, along with Principal Component Analysis (PCA) and Positive Matrix Factorisation (PMF) methodologies to extrapolate major source contributions for PM_2.5. It is demonstrated that continuous monitoring of standard air quality parameters, such as NO, NO₂, SO₂, along with EC, OC and particulate SO₄^2?, can be used to provide relevant, cost-effective initial estimates of source contributions to ambient PM_2.5 levels. It is also shown that the benefit of including OC and particulate SO₄^2? in the monitoring protocol is considerable. Three major source groups of ambient PM_2.5 mass in Cork were identified and quantified using this combined monitoring and modelling approach; road transport (19%), domestic solid fuel burning (14%) and oil-fired domestic and industrial boilers, including power generation plants (31%).     

The impact of wood stove technology upgrades on indoor residential air quality

Fine particulate matter (PM_2.5) air pollution has been linked to adverse health impacts, and combustion sources including residential wood-burning may play an important role in some regions. Recent evidence suggests that indoor air quality may improve in homes where older, non-certified wood stoves are exchanged for lower emissions EPA-certified alternatives. As part of a wood stove exchange program in northern British Columbia, Canada, we sampled outdoor and indoor air at 15 homes during 6-day sampling sessions both before and after non-certified wood stoves were exchanged. During each sampling session two consecutive 3-day PM_2.5 samples were collected onto Teflon filters, which were weighed and analyzed for the wood smoke tracer levoglucosan. Residential PM_2.5 infiltration efficiencies (F_inf) were estimated from continuous light scattering measurements made with nephelometers, and estimates of F_inf were used to calculate the outdoor- and indoor-generated contributions to indoor air. There was not a consistent relationship between stove technology and outdoor or indoor concentrations of PM_2.5 or levoglucosan. Mean F_inf estimates were low and similar during pre- and post-exchange periods (0.32 ± 0.17 and 0.33 ± 0.17, respectively). Indoor sources contributed the majority (～65%) of the indoor PM_2.5 concentrations, independent of stove technology, although low indoor-outdoor levoglucosan ratios (median ≤ 0.19) and low indoor PM_2.5-levoglucosan correlations (r ≤ 0.19) suggested that wood smoke was not a major indoor PM_2.5 source in most of these homes. In summary, despite the potential for extensive wood stove exchange programs to reduce outdoor PM_2.5 concentrations in wood smoke-impacted communities, we did not find a consistent relationship between stove technology upgrades and indoor air quality improvements in homes where stoves were exchanged.     

PCB and dioxin-like PCB in indoor air of public buildings contaminated with different PCB sources--deriving toxicity equivalent concentrations from standard PCB congeners

Data on dioxin-like PCB in indoor air of buildings with PCB-containing materials and on possible correlation between toxicity equivalent concentrations (TEQ) and levels of non-dioxin-like standard PCB is sparse. As part of a larger survey on indoor-air contamination with PCB, the connection between the concentration of standard PCB congeners and the dioxin-like toxicity expressed as TEQ was investigated. Indoor air samples (n=8) were collected in four public buildings with known PCB sources and total PCB levels in the range from 715 to 2250 ng/m3 and analyzed for the six non-dioxin-like standard PCB (congeners 28, 52, 101, 138, 153, 180), the twelve dioxin-like PCB congeners according to WHO and the 17 2,3,7,8-substituted PCDD/PCDF congeners. In three buildings where PCB were used as flame retardant coatings of acoustic ceiling tiles, PCB 101 had the maximum level among the six standard PCB, while in the building with permanent elastic sealants as PCB source, congeners 28 and 52 dominated the pattern by far. In the case of permanent elastic sealants as PCB source (n=3) a total PCB concentration of 1000 ng/m3 corresponded to a total TEQ level of 0.3-0.6 pg/m3. In contrast, in rooms with acoustic ceiling tiles as PCB source, 1.8-4.7 pg TEQ/m3 per 1000 ng total PCB/m3 were found. Linear regression analysis between PCB and TEQ indicated that PCB 118 might be used to calculate the total TEQ of dioxin-like PCB and PCDD/PCDF. By means of such a correlation it is possible to estimate TEQ by extrapolation from the results of less sophisticated analytical methods. It is tentatively recommended to use PCB 118 for screening purposes or re-evaluation of standard PCB indoor-air measurements. If only the six non-dioxin-like PCB standard congeners are available, a regression algorithm using the sum of PCB 101, 138, 153 and 180 might be used instead.     

The impact of NOx,CO and VOC emissions on the air quality of Zurich airport

To study the impact of emissions at an airport on local air quality, a measurement campaign at the Zurich airport was performed from 30 June 2004 to 15 July 2004. Measurements of NO, NO₂, CO and CO₂ were conducted with open path devices to determine real in-use emission indices of aircraft during idling. Additionally, air samples were taken to analyse the mixing ratios of volatile organic compounds (VOC). Temporal variations of VOC mixing ratios on the airport were investigated, while other air samples were taken in the plume of an aircraft during engine ignition. CO concentrations in the vicinity of the terminals were found to be highly dependent on aircraft movement, whereas NO concentrations were dominated by emissions from ground support vehicles. The measured emission indices for aircraft showed a strong dependence upon engine type. Our work also revealed differences from emission indices published in the emission data base of the International Civil Aviation Organisation. Among the VOC, reactive C₂–C₃ alkenes were found in significant amounts in the exhaust of an engine compared to ambient levels. Also, isoprene, a VOC commonly associated with biogenic emissions, was found in the exhaust, however it was not detected in refuelling emissions. The benzene to toluene ratio was used to discriminate exhaust from refuelling emission. In refuelling emissions, a ratio well below 1 was found, while for exhaust this ratio was usually about 1.7.