Review of indoor emission source models. Part 2. Parameter estimation

This review consists of two parts. Part 1 provides an overview of 52 indoor emission source models. Part 2--this paper-focuses on parameter estimation, a topic that is critical to modelers but has never been systematically discussed. A perfectly valid model may not be a useful one if some of its parameters are difficult to estimate in the absence of experimental data. This is true for both statistical and mass transfer models. Forty-eight methods are compiled and reviewed in this paper. Overall, developing methods for parameter estimation has fallen behind the development of models. Such imbalance is the main reason that many models have been left on the shelf since they were published.     

室内环境中挥发性有机物释放过程的数学模型

根据组成结构,将室内环境中释放挥发性有机物(VOCs)的建筑装饰材料划分为单层干材料、单层湿材料、多层组合材料等类型,总结了这三种材料的VOCs释放特征、传输过程和数学模型研究现状,分析了模型的特点和适用范围,指出了模型研究发展的趋势,对应用中模型的选择提出了指导性建议.     

Formation and emission of chloroanisoles as indoor pollutants

GOAL, SCOPE AND BACKGROUND: Complaints by residents of frame-houses about musty odour in the houses has become an increasing problem within the last years. An additional problem is that the odour is transferred to clothes and skin. The persons themselves do not recognize the smell after a while because of adaptation. Serious social problems are the result. For a long time, the smell was explained to be from mould due to construction-based humidity problems. However, in an increasing number of houses, no indications were found for elevated levels of mould growth. METHODS: Air and material samples were taken from 5 houses, which show typical musty odours, and analysed with respect to chlorophenols and chloroanisoles. Additionally, some samples were analysed for lindane and its metabolites, because lindane was commonly used together with pentachlorophenol (PCP) for wood protection. RESULTS AND DISCUSSION: Meticulous analysis resulted in the identification of chloroanisoles, mainly 2,3,4,6-tetrachloroanisole. These substances are known from corky wines and from contamination of food from pentachlorophenol (PCP) treated pallets and result from microbiological metabolic processes. Pentachlorophenol was commonly used to protect wood from fungi in Germany mainly in the later 60s and 70s. Details of these processes, as well as effective methods to identify chloroanisoles in the problem houses, are described. CONCLUSIONS: Chloroanisoles formed by metabolism of PCP have been well known to contaminate food or wine. Here, they were identified and are probably responsible for the musty odours in the frame houses. Since it is quite clear that these substances were not components of building materials used in the houses, an explanation for chloroanisole formation is proposed. Localized dampness probably favours microbial growth associated with metabolic conversion of chlorophenols to the corresponding chloroanisoles, primarily 2,3,4,6-tetrachloroanisol, which spread throughout the buildings, resulting in the observed odours. RECOMMENDATIONS AND OUTLOOK: The group of chloroanisoles has been recognized as important indoor pollutants as they possess musty odours at extremely low concentrations, e.g. for 2,4,6-trichloroanisole in a range of 5-10 ppt in air (Staples 2000). On the basis of currently available toxicological data, exposure of the occupants to the concentrations of chloroanisoles measured is not associated with a health risk. No correlation could be observed between concentrations of chloroanisoles and PCP in house dust and indoor air. However, chloroanisoles are good indicators for possible PCP-treatment of wood in frame houses and their detection should initiate investigations on PCP contamination. Research is continuing to identify the microorganisms involved and to devise a remediation procedure for affected houses.     

Unraveling the source of nitric oxide emission during nitrification.

Nitric oxide production was measured during nitrification in a laboratory-scale bioreactor, operated at conditions relevant to municipal nitrifying wastewater treatment plants. This study aims to determine which type of microorganism and which metabolic pathway is responsible for nitric oxide emission during nitrification. Simulation studies were used to identify which pathway is the main source of nitric oxide emission, based on the following three hypothetical pathways for nitric oxide emission: (a) nitrification, (b) denitrification by ammonia-oxidizing bacteria with ammonium as electron donor, and (c) heterotrophic denitrification. The results of the study suggest that, in a nitrifying reactor treating wastewater containing solely ammonium and nutrients, denitrification by ammonia-oxidizing bacteria is the main nitric-oxide-producing pathway. During the experiments, 0.025% of the treated ammonium is emitted as nitric oxide, independent of the aeration rate imposed. Nitrite presence and oxygen limitation were found to increase the nitric oxide emission.     

Fugacity models of indoor exposure to volatile chemicals

A method of calculating the atmospheric concentration of a volatile chemical in confined volumes is presented and illustrated which uses the fugacity concept to simplify the manipulation of the various transport and reaction terms. The method is particularly suitable for estimating exposure to chemicals which may be released by evaporation into a house, work place, or partially confined outdoor environment in which there are several volumes (eg. rooms) with known ventilation characteristics. Illustrative calculations are presented.     

机动车污染排放模型研究综述

过去几十年,为了掌握机动车污染排放的规律和特征,向决策者提供科学有效的机动车污染控制措施,研究者们致力于研究机动车污染物排放的物化原理和影响机动车污染的主要因素,并据此建立多种尺度的机动车排放模型,以模拟城市区域或者街道的污染物排放.为了分析机动车的瞬态排放特征,目前的机动车排放模型研究正逐渐从宏观向微观发展,排放测试方法注重获取逐秒的排放数据,排放模型模拟的时间尺度和空间尺度逐步趋向微观.此外,机动车模型研究正趋向与交通模型进行耦合,从而揭示机动车在实际道路交通流中的排放特征.从机动车排放的主要影响因素、机动车排放测试、机动车排放因子模型及机动车排放清单等4个方面综述了国内外机动车排放研究现状和发展动向,对比并评价各种机动车排放模型方法的优缺点和适用范围,对我国的机动车排放模型发展方向进行了展望.     

Combining neural network models to predict spatial patterns of airborne pollutant accumulation in soils around an industrial point emission source

Neural networks (NNs) have the ability to model a wide range of complex nonlinearities. A major disadvantage of NNs, however, is their instability, especially under conditions of sparse, noisy, and limited data sets. In this paper, different combining network methods are used to benefit from the existence of local minima and from the instabilities of NNs. A nonlinear k-fold cross-validation method is used to test the performance of the various networks and also to develop and select a set of networks that exhibits a low correlation of errors. The various NN models are applied to estimate the spatial patterns of atmospherically transported and deposited lead (Pb) in soils around an historical industrial air emission point source. It is shown that the resulting ensemble networks consistently give superior predictions compared with the individual networks because, for the ensemble networks, R2 values were found to be higher than 0.9 while, for the contributing individual networks, values for R2 ranged between 0.35 and 0.85. It is concluded that combining networks can be adopted as an important component in the application of artificial NN techniques in applied air quality studies.     

Review of Statistics of Extreme Values with Applications to Air Quality Data Part I. Review

In the field of air pollution control, the rare event is often of more significance than the common event. This is evidenced by the content of air quality standards which define acceptable upper limits of air pollution concentrations and acceptable frequencies with which such concentrations can be exceeded. The principles of extreme value statistics provide important tools for analyzing air quality data in an appropriately significant context.

The purpose of this paper is twofold. First the principles of extreme value statistics are reviewed. The presentation is decidedly utilitarian; no attempt is made to derive more than the simplest propositions. The underlying assumptions of the theory are carefully pointed out and discussed. Particular emphasis is placed on the second largest value and its relation to the largest value. Exact probability distributions, and approximations to them, are derived in terms of the total population probability function. The more familiar and useful asymptotic distributions and their uses are presented and discussed. Part II of the paper will present applications of the theory to air quality data.     

Dissociation of sulfur hexafluoride tracer gas in the presence of an indoor combustion source

As an odorless, nontoxic, and inert compound, sulfur hexafluoride (SF6) is one of the most widely used tracer gases in indoor air quality studies in both controlled and uncontrolled environments. This compound may be subject to reactions with water vapor under elevated temperature to form acidic inorganic compounds such as HF and H2SO4. Thus, in the presence of unvented combustion sources such as kerosene heaters, natural gas heaters, gas log fireplaces, candles, and lamps, the SF6 dissociation may interfere with measurements of the emissions from these sources. Tests were conducted in a research house with a vent-free natural gas heater to investigate these potential interferences. It was observed that the heater operation caused about a 5% reduction of SF6 concentration, which can be an error source for the ventilation rate measurement and consequently the estimated pollutant emission rates. Further analysis indicates that this error can be much greater than the observed 5% under certain test conditions because it is a function of the ventilation flow rate. Reducing the tracer gas concentration has no effect on this error. A simple theoretical model is proposed to estimate the magnitude of this error. The second type of interference comes from the primary and secondary products of the SF6 dissociation, mainly H2SO4, SO2, HF, and fine particulate matter (PM). In the presence of approximately 5 ppm SF6, the total airborne concentrations of these species increased by a factor of 4-10. The tests were performed at relatively high SF6 concentrations, which is necessary to determine the interferences quantitatively. The second type of interference can be significantly reduced if the SF6 concentration is kept at a low ppb level.     

Odor emission rate estimation of indoor industrial sources using a modified inverse modeling method

Odor emission rates are commonly measured in the laboratory or occasionally estimated with inverse modeling techniques. A modified inverse modeling approach is used to estimate source emission rates inside of a postdigestion centrifuge building of a water reclamation plant. Conventionally, inverse modeling methods divide an indoor environment in zones on the basis of structural design and estimate source emission rates using models that assume homogeneous distribution of agent concentrations within a zone and experimentally determined link functions to simulate airflows among zones. The modified approach segregates zones as a function of agent distribution rather than building design and identifies near and far fields. Near-field agent concentrations do not satisfy the assumption of homogeneous odor concentrations; far-field concentrations satisfy this assumption and are the only ones used to estimate emission rates. The predictive ability of the modified inverse modeling approach was validated with measured emission rate values; the difference between corresponding estimated and measured odor emission rates is not statistically significant. Similarly, the difference between measured and estimated hydrogen sulfide emission rates is also not statistically significant. The modified inverse modeling approach is easy to perform because it uses odor and odorant field measurements instead of complex chamber emission rate measurements.     

Overview of proposed air emission standards and guidelines for municipal waste combustors

The EPA proposed regulations for municipal waste combustors (MWCs) on December 20, 1989. The regulations include (1) performance standards under Section 111(b) of the Clean Air Act (CAA) for new, modified, or reconstructed MWCs and (2) draft emission guidelines and compliance schedules for the states to use to develop control requirements from existing MWCs under Section 111(d). This paper will outline the proposed air emission standards and guidelines, as well as the basis for the prescribed emission limits. The schedule for the remainder of the regulations development will also be discussed.     

Estimating the emission source reduction of PM10 in central Taiwan

Three theoretical parent frequency distributions; lognormal, Weibull and gamma were used to fit the complete set of PM10 data in central Taiwan. The gamma distribution is the best one to represent the performance of high PM10 concentrations. However, the parent distribution sometimes diverges in predicting the high PM10 concentrations. Therefore, two predicting methods, Method I: two-parameter exponential distribution and Method II: asymptotic distribution of extreme value, were used to fit the high PM10 concentration distributions more correctly. The results fitted by the two-parameter exponential distribution are better matched with the actual high PM10 data than that by the parent distributions. Both of the predicting methods can successfully predict the return period and exceedances over a critical concentration in the future year. Moreover, the estimated emission source reductions of PM10 required to meet the air quality standard by Method I and Method II are very close. The estimated emission source reductions of PM10 range from 34% to 48% in central Taiwan.     

Combustion sources of particles. 1. Health relevance and source signatures

Combustion processes result in generation of a large number of particle and gaseous products that create health and environmental risks. Of particular importance are the very small particles that are emitted in large quantities from all the combustion sources, and that have been shown to be potentially more significant in terms of their impact on health than larger particles. To control and mitigate the particles with a view of health and environmental risk reduction, a good understanding is necessary of the relative and absolute contribution from the emission sources to the airborne concentrations. This understanding could only be achieved by developing source signature libraries through direct emission measurements from the sources on one hand, and by measuring particle concentrations in the air, and apportioning them to the specific local and distant sources using the signatures, on the other hand. This paper is a review of particle characteristics that are used as source signatures as well as their general advantages and limitations. The second part of the paper reviews source signatures of the most common combustion pollution sources.     

Simplified contaminant source depletion models as analogs of multiphase simulators

Four simplified dense non-aqueous phase liquid (DNAPL) source depletion models recently introduced in the literature are evaluated for the prediction of long-term effects of source depletion under natural gradient flow. These models are simple in form (a power function equation is an example) but are shown here to serve as mathematical analogs to complex multiphase flow and transport simulators. The spill and subsequent dissolution of DNAPLs was simulated in domains having different hydrologic characteristics (variance of the log conductivity field=0.2, 1 and 3) using the multiphase flow and transport simulator UTCHEM. The dissolution profiles were fitted using four analytical models: the equilibrium streamtube model (ESM), the advection dispersion model (ADM), the power law model (PLM) and the Damkohler number model (DaM). All four models, though very different in their conceptualization, include two basic parameters that describe the mean DNAPL mass and the joint variability in the velocity and DNAPL distributions. The variability parameter was observed to be strongly correlated with the variance of the log conductivity field in the ESM and ADM but weakly correlated in the PLM and DaM. The DaM also includes a third parameter that describes the effect of rate-limited dissolution, but here this parameter was held constant as the numerical simulations were found to be insensitive to local-scale mass transfer. All four models were able to emulate the characteristics of the dissolution profiles generated from the complex numerical simulator, but the one-parameter PLM fits were the poorest, especially for the low heterogeneity case.     

世界化石能源部门CO2排放源状况及案例分析

能源部门是CO2排放的主要来源,1990-2005年,电力和热力是能源部门CO2排放的主要排放源,其次是交通运输业.从2005年经济合作与发展组织(OECD)和非OECD国家主要地区的能源部门各排放源对人均CO2排放的贡献率的情况看,北美OECD地区是电力和热力人均CO2排放量最高的地区,其他各排放源不同程度地高出世界平均水平;整体上,非OECD国家主要地区的能源部门各排放源对人均CO2排放的贡献率差异较大,各地区的经济结构、能源结构和生活水平影响能源部门各排放源对人均CO2排放的贡献率.从2005年主要国家的能源部门各排放源对人均CO2排放的贡献率的情况看,除印度外,电力和热力是大多数国家能源部门的CO2主要排放源.中国的电力和热力对能源部门人均CO2排放的贡献率最大.各国对能源部门人均CO2排放的贡献率的次排放源情况相差较大,美国和欧盟(27)主要是交通运输业等服务型产业,中国主要是制造业和建筑业等第二产业,其他国家的次排放源分布相对均衡.     

Characteristics of carbonyls: Concentrations and source strengths for indoor and outdoor residential microenvironments in China

Indoor and outdoor carbonyl concentrations were measured simultaneously in 12 urban dwellings in Beijing, Shanghai, Guangzhou, and Xi’an, China in summer (from July to September in 2004) and winter (from December 2004 to February 2005). Formaldehyde was the most abundant indoor carbonyls species, while formaldehyde, acetaldehyde and acetone were found to be the most abundant outdoor carbonyls species. The average formaldehyde concentrations in summer indoor air varied widely between cities, ranging from a low of 19.3 μg m⁻³ in Xi’an to a high of 92.8 μg m⁻³ in Beijing. The results showed that the dwellings with tobacco smoke, incense burning or poor ventilation had significantly higher indoor concentrations of certain carbonyls. It was noticed that although one half of the dwellings in this study installed with low emission building materials or furniture, the carbonyls levels were still significantly high. It was also noted that in winter both the indoor and outdoor acetone concentrations in two dwellings in Guangzhou were significantly high, which were mainly caused by the usage of acetone as industrial solvent in many paint manufacturing and other industries located around Guangzhou and relatively longer lifetime of acetone for removal by photolysis and OH reaction than other carbonyls species. The indoor carbonyls levels in Chinese dwellings were higher than that in dwellings in the other countries. The levels of indoor and ambient carbonyls showed great seasonal differences. Six carbonyls species were carried out the estimation of indoor source strengths. Formaldehyde had the largest indoor source strength, with an average of 5.25 mg h⁻¹ in summer and 1.98 mg h⁻¹ in winter, respectively. However, propionaldehyde, crotonaldehyde and benzaldehyde had the weakest indoor sources.     

C1–C8 volatile organic compounds in the atmosphere of Hong Kong: Overview of atmospheric processing and source apportionment

We present measurements of C₁–C₈ volatile organic compounds (VOCs) at four sites ranging from urban to rural areas in Hong Kong from September 2002 to August 2003. A total of 248 ambient VOC samples were collected. As expected, the urban and sub-urban sites generally gave relatively high VOC levels. In contrast, the average VOC levels were the lowest in the rural area. In general, higher mixing ratios were observed during winter/spring and lower levels during summer/fall because of seasonal variations of meteorological conditions. A variation of the air mass composition from urban to rural sites was observed. High ratios of ethyne/CO (5.6 pptv/ppbv) and propane/ethane (0.50 pptv/pptv) at the rural site suggested that the air masses over the territory were relatively fresh as compared to other remote regions. The principal component analysis (PCA) with absolute principal component scores (APCS) technique was applied to the VOC data in order to identify and quantify pollution sources at different sites. These results indicated that vehicular emissions made a significant contribution to ambient non-methane VOCs (NMVOCs) levels in urban areas (65±36%) and in sub-urban areas (50±28% and 53±41%). Other sources such as petrol evaporation, industrial emissions and solvent usage also played important roles in the VOC emissions. At the rural site, almost half of the measured total NMVOCs were due to combustion sources (vehicular and/or biomass/biofuel burning). Petrol evaporation, solvent usage, industrial and biogenic emissions also contributed to the atmospheric NMVOCs. The source apportionment results revealed a strong impact of anthropogenic VOCs to the atmosphere of Hong Kong in both urban/sub-urban and rural areas.     

Sensitivity of molecular marker-based CMB models to biomass burning source profiles

To assess the contribution of sources to fine particulate organic carbon (OC) at four sites in North Carolina, USA, a molecular marker chemical mass balance model (MM-CMB) was used to quantify seasonal contributions for 2 years. The biomass burning contribution at these sites was found to be 30–50% of the annual OC concentration. In order to provide a better understanding of the uncertainty in MM-CMB model results, a biomass burning profile sensitivity test was performed on the 18 seasonal composites. The results using reconstructed emission profiles based on published profiles compared well, while model results using a single source test profile resulted in biomass burning contributions that were more variable. The biomass burning contribution calculated using an average regional profile of fireplace emissions from five southeastern tree species also compared well with an average profile of open burning of pine-dominated forest from Georgia. The standard deviation of the results using different source profiles was a little over 30% of the annual average biomass contributions. Because the biomass burning contribution accounted for 30–50% of the OC at these sites, the choice of profile also impacted the motor vehicle source attribution due to the common emission of elemental carbon and polycyclic aromatic hydrocarbons. The total mobile organic carbon contribution was less effected by the biomass burning profile than the relative contributions from gasoline and diesel engines.     

PM2.5 source apportionment: reconciling receptor models for U.S. nonurban and urban long-term networks

Chemical mass balance (CMB) and trajectory receptor models were applied to speciated particulate matter with aerodynamic diameter < or =2.5 microm (PM2.5) measurements from Speciation Trends Network (STN; part of the Chemical Speciation Network [CSN]) and Interagency Monitoring of Protected Visual Environments (IMPROVE) monitoring network across the state of Minnesota as part of the Minnesota PM2.5 Source Apportionment Study (MPSAS). CMB equations were solved by the Unmix, positive matrix factorization (PMF), and effective variance (EV) methods, giving collective source contribution and uncertainty estimates. Geological source profiles developed from local dust materials were either incorporated into the EV-CMB model or used to verify factors derived from Unmix and PMF. Common sources include soil dust, calcium (Ca)-rich dust, diesel and gasoline vehicle exhausts, biomass burning, secondary sulfate, and secondary nitrate. Secondary sulfate and nitrate aerosols dominate PM2.5 mass (50-69%). Mobile sources outweigh area sources at urban sites, and vice versa at rural sites due to traffic emissions. Gasoline and diesel contributions can be separated using data from the STN, despite significant uncertainties. Major differences between MPSAS and earlier studies on similar environments appear to be the type and magnitude of stationary sources, but these sources are generally minor (<7%) in this and other studies. Ensemble back-trajectory analysis shows that the lower Midwestern states are the predominant source region for secondary ammoniated sulfate in Minnesota. It also suggests substantial contributions of biomass burning and soil dust from out-of-state on occasions, although a quantitative separation of local and regional contributions was not achieved in the current study. Supplemental materials are available for this article. Go to the publisher's online edition of the Journal of the Air & Waste Management Association for a summary of input data, Unmix and PMF factor profiles, and additional maps.