For the presentation at the Air and Waste Management Association’s 98th Annual Meeting & Exhibition, June 21-24, Minneapolis, MN, USA Measurement and Prediction of Indoor Formaldehyde Concentration in Northeast China Control # 1179 Yu-hua Li , Kun Wang , Qing-liang Zhao School of Municipal & Environmental Engineering, Harbin Institute of Technology 202 Haihe Road, Nangang District, Harbin 150090, China Chung-shin Yuan Institute of Environmental Engineering, National Sun Yat-sen University, No.70, Lian-hai Road, Kaohsiung City, Taiwan 80424, China ABSTRACT With the development of economy and the improvement of living condition, decorating houses has been the hotspot of personal consumption in China for the past two decades. Indoor formaldehyde pollution is ubiquitous in China, while it has been mostly controlled in the developed countries. In this study, an investigation on the measurement of indoor formaldehyde concentration in residential houses was conducted in Harbin, located at the most chilly area in Northeast China. The results showed that the concentration of indoor formaldehyde ranged from 0.017 to 1.302mg/m3, and only 22.8% of the residential houses met the formaldehyde standard of 0.10 mg/m3 for National Air Quality Standard of China. The monthly average formaldehyde concentration in summer (June-August) was about twice higher than those in winter (November-March). A strong correlation between the monthly average indoor formaldehyde concentration and the monthly average temperature (R2=0.8652) was obtained. Furthermore, a mathematical model was successfully developed to predict the concentration of indoor formaldehyde in Chinese residential houses. Field measurements of indoor formaldehyde concentration in residential houses were also conducted for various decoration time in order to investigate the influence of decoration time on the indoor formaldehyde concentration. INTRODUCTION Indoor air pollution has become a serious problem in China for the past two decades, since people could expose to indoor air pollutants, due to poor ventilation and the existence of indoor air pollution sources. Chemical substances could be continuously and slowly released from the building materials, decorating materials, and commodities, which have been widely applied in the residential houses. There are many health symptoms appeared on people lived in contaminative rooms, such as headache, respiratory tract infection, nausea, hypersusceptibility and dermatitis.1 People recognize that indoor air quality may be more important than outdoor air quality because they spend over 80% of their time indoors.2-4 Recent studies in 1 different indoor environments such as office building, residential house, classroom, shopping mall and restaurant that in group demonstrate that, in most cases, the concentration of target air pollutants in indoor environments are higher than those in outdoor environments.5-10 In particular, indoor formaldehyde which is potential to cause cancer is ubiquitous in China, owing to the widely use of laminate board.11-13 The laminate board is one of the major sources that contribute to indoor formaldehyde pollution. Better manufactural technique of laminate board is required in China, which is especially important to improve indoor formaldehyde pollution. Indoor air pollution resulted from the fitment has been paid more attention in recent years in China. At present, the regulation is not completely established since indoor air pollution has not been thoroughly investigated. As a result, the indoor air pollution was serious increasingly. Actually, the investigation of indoor formaldehyde pollution has been conducted abroad and home. Their results show that the formaldehyde pollution widely exists in indoor environments all over the world, which has been paid much attention in many countries since 1980s. 14 Many investigations on indoor formaldehyde pollution have been conducted in America, Europe and Japan, which has been mostly controlled in the developed countries. 15-19 The results obtained from several cities in China showed that the maximal value of indoor formaldehyde concentration in newly decorating rooms was higher than 2.300 mg/m3 with an average of 0.219 mg/m3.20 Approximately 70%~80% of them had to remove the formaldehyde according to the National Air Quality Standard of China (0.1 mg/m3). Simulate to these cities, indoor air pollution resulted from the fitment may be more serious in Harbin, which located at the most chilly area in Northeast China. Harbin is the capital of Heilongjiang Province, the northernmost province in China. The space heating period in Harbin is about half a year long. The residents seldom open windows in winter for the reasons of cold weather and energy conservation. People lived in Harbin stay longer in indoors than those who lived in other cities in China. Therefore, the indoor air pollution becomes more serious and has higher influence on human health. The climate and life style have significant influences on indoor air pollution. The residents lived in Harbin have right to know the current status of indoor air quality. In addition, the city government needs those data to establish regulations to maintain good indoor air quality. Thus, it is highly required to provide the quantitative information of indoor formaldehyde pollution in Harbin. In this study, an investigation on the measurement of indoor formaldehyde concentration in residential houses that have been decorated was conducted in Harbin in 2003. A mathematical model was then developed based on the experimental data to predict the concentration of indoor formaldehyde. Factors including temperature, relative humidity, air exchange rate, the surface area of the board, the quality of the board and furniture, and the space of the room were taken into consideration in the model. Moreover, this study intended to know the duration of formaldehyde in residential houses, which could last for a long time and was harmful to the residents. 2 Therefore, the indoor formaldehyde concentration in the residential houses that have finished fitment for different duration was measured simultaneously. EXPERIMENTAL METHODS Site Selection The investigation of indoor formaldehyde pollution was conducted in Harbin from January to December in 2003. There are seven districts in Harbin, including Nangang, Daoli, Daowai, Taiping, Xiangfang, Dongli, and Pingfang. A total of 246 samples were sampled in these districts during the investigation period as shown in Figure 1. The sampling sites were selected randomly and their distribution fairly reflected the residents’ living condition as well as the decoration status of the residential houses in Harbin. After investigating the level of indoor formaldehyde in metro Harbin, another fifty decorated residential houses were further selected specially in Nangang district where most of the residential houses were decorated. The decoration time of the fifty residential houses ranged from one month to two years. Indoor formaldehyde concentration was measured in the fifty residential houses in order to know the duration of formaldehyde in the houses, which is very important for the exposure and health risk assessment of indoor formaldehyde. Sampling and Analysis In this study, the sampling of indoor formaldehyde followed a standard procedure reported in the control regulation of indoor air pollution and criterion of indoor air quality in China.20 The windows and doors of the residential houses were closed for approximately 12 hours till the sampling was completed. The distance between the sampling point and the wall were longer than 0.5 m and the height of the sampling point was 0.5~1.5 m above floor. Indoor temperature, relative humidity, and air Figure 1. Indoor air samples collected at 7 districts of Harbin in 2003. Taiping 5.28% Dongli 8.94% Pingfang 0.81% Xiangfang 9.35% Nangang 47.97% Daowai 2.44% Daoli 25.20% 3 pressure were simultaneously monitored during the sampling period. Factors including the weather condition, the area of the room, the finishing time of the building, and the decorating materials were also recorded. These factors are required for further analysis of measured data. In this study, the analysis of formaldehyde followed the Standard Hygienic Test Methods for the Analysis of Atmospheric Formaldehyde in Residential Area, Method (GB/T16129-1995)-AHMT. Indoor air was bubbled into distilled water in a flow rate of 1.0 L/min for twenty minutes to collect formaldehyde. An indoor air quality sampler manufactured by Electromechanical Equipment Company (Model KB-6A) was used to sample indoor air. The gas flow rate was proofread with a soap bubble flow meter to insure the accuracy of the sampler. An UV-visible spectrophotometer manufactured by Rainbow Analysis Instrument (Model UV-752) was applied to determine the concentration of formaldehyde. RESULTS AND DISCUSSION Analysis of Indoor Air Pollution Status Formaldehyde was detected in the indoor environments of the 246 residential houses in Harbin. The distribution of indoor formaldehyde concentration is shown in Table 1. The results of on-site measurements showed that the concentration of indoor formaldehyde ranged from 0.017 to 1.302 mg/m3 with an average of 0.219 mg/m3. The highest concentration of indoor formaldehyde was measured in June while the lowest was in November. Results from the statistical analysis of detected data showed that, at present, the formaldehyde pollution in indoor environments was quite serious in Harbin. According to the National Air Quality Standard of China (0.1mg/m3), 190 of the 246 residential houses violated the acceptable formaldehyde concentration and needed to remove formaldehyde from indoor air, while only 22.8% of the 246 residential houses met the acceptable formaldehyde concentration. According to the responses from the residents, approximately 77% of them have complained the irritation of eyes and fauces to some degree. The measurement of indoor formaldehyde showed that poor air quality of residential houses in Harbin resulted mainly from the furniture made of laminate board. In case of good furniture quality, the formaldehyde concentrations in most of the decoration house were less than 0.2 mg/m3 even if the floor was made of artificial board. The indoor formaldehyde concentration of residential houses that had new furniture was obviously higher than that had only old furniture. This study revealed that a close correlation between indoor formaldehyde pollution, and quality of decorating materials and furniture materials, and the status of ventilation was observed. Owing to very few control efforts on indoor air quality, the formaldehyde concentration has been maintained at high level in the residential houses throughout 4 Table 1. Statistical analysis of formaldehyde concentrations measured in the 246 residential houses in Harbin. Range of concentration (mg/m3) Overproof times Sample number (n) Percentage (%) 0.017~0.100 0.100~0.200 0.200~0.300 0.300~0.400 0.400~0.500 0.500~0.600 0 0~1 1~2 2~3 3~4 4~5 56 86 47 26 18 7 0 34. 96 19. 11 10. 57 7. 32 2. 85 0.600~0.700 0.700~0.800 0.800~1.00 5~6 6~7 7~9 5 0 0 2. 03 0 0 1.000~1.400 9~13 1 0.41 246 77.2 Total Harbin. Thus, the development of effective purification means for formaldehyde in indoor environments is highly required. Correlation of Indoor Formaldehyde Concentration and Room Temperature The urea-formaldehyde resin has been widely used as an adhesive in the laminate board and furniture. The resin could be decomposed and released formaldehyde from the artificial board used in fitment room and furniture under the effect of room temperature, humidity, light intensity, and etc. Previous studies reported that the moisture and acidity substances significantly influence the destruction of the artificial board in indoor enviroments.21-22 The formaldehyde emission rate of artificial board was significantly affected by room temperature. The release of formaldehyde will be quick when room temperature is high. On the contrary, the formaldehyde will be released slowly as room temperature is low and will further release as room temperature rises. In general, the amount of formaldehyde release became twice higher as the room temperature rose 5~6 ℃.21 However, the indoor formaldehyde concentration would fall quickly once if there is frequent natural ventilation. The amount of formaldehyde release became less as the room temperature was below 18 ℃. The formaldehyde tends to stay in artificial board at low temperature. Thus, the duration of formaldehyde could be extended and could exist in indoor air for a longer time.23 In Harbin, the winter lasts about half a year long (from November to March) and the 5 summer is relatively short (from June to August), which is the typical climate of the chilly area in Northeast China. The correlation of indoor formaldehyde concentration and the room temperature monitored in the 246 residential houses was further analyzed statistically in this study (see Table 2). The results showed that the indoor formaldehyde concentration during the space heating period (from the end of October to the end of April) was relatively low with the range of 0.134-0.198 mg/m3. The monthly average formaldehyde concentration in May and September was 0.262 and 0.260 mg/m3, respectively. The monthly average value of formaldehyde concentration in June, July and August were 0.380, 0.327 and 0.300 mg/m3, respectively, which were the highest in the year. In general, the monthly average formaldehyde concentration in summer (June~August) was about twice higher than those in winter (November~December, January~March). There might be some correlation between indoor formaldehyde concentration and room temperature, though the monthly average indoor formaldehyde concentration varied throughout the year. The comparison of the monthly average indoor formaldehyde concentration and room temperature was undertaken to know the variation of the indoor formaldehyde concentration with room temperature. The room temperature of the 246 residential houses ranged from 8.0 to 29.0 ℃ and the monthly average indoor temperature ranged from 17.0 to 26.5 ℃. The yearly average room temperature in Harbin was 21.5 ℃. A relatively strong correlation was observed as shown in Figure 2. It shows that the trend of monthly average indoor formaldehyde concentration and room temperature are quite similar. A linear regression model of monthly average indoor formaldehyde concentration as a function of room temperature is shown in Figure 3 and can be expressed in equation (1). C 0.0246T 0.304 (R2=0.8652) (1) where C is the monthly average indoor formaldehyde concentration, mg/m3; monthly average room temperature, ℃ T is the Table 2. Statistical analysis of indoor formaldehyde concentration in Harbin. Sampling time Spring (Apr.~May) Summer (June~Aug.) Fall (Sept.~Oct.) Winter (Jan.~March, Nov.~Dec.) Non-heating period Heating period All the year 35 62 42 107 Concentration range (mg/m3) 0.054~0.631 0.078~1.302 0.031~0.679 0.017~0.448 121 125 246 0.062~1.302 0.017~0.448 0.017~1.302 Sample number 0.222 0.336 0.207 0.154 Standard Deviation (mg/m3) 0.026 0.025 0.022 0.009 0.301 0.156 0.219 0.018 0.008 0.010 Average (mg/m3) Median (mg/m3) 0.183 0.286 0.164 0.132 0.269 0.134 0.176 6 Figure 2. Monthly variation of indoor formaldehyde concentrations and room temperature. 0.4 o Room Temperature ( C) 3 Formaldehyde Concentration (mg/m ) 30 0.3 20 0.2 10 0.1 Room Temperature Concentration 0 0.0 Jan. Feb. Mar.Apr.MayJuneJulyAug.Sep. Oct. Nov.Dec. Month Figure 3. Correlation of monthly average formaldehyde concentration with room temperature 3 Formaldehyde Concentration (mg/m ) 0.4 0.3 0.2 0.1 2 R =0.8652 0.0 15 18 21 24 27 30 o Room Temperature ( C) 7 .Environmental Factors that Affect Indoor Formaldehyde Concentration The concentration of indoor formaldehyde might be affected by some environmental factors. Indoor air quality varied with weather condition, outdoor air pollutant concentration, and etc. The air exchange rate influences the emission rate of formaldehyde from the sources and the duration for reducing air pollutant concentration due to dilution effect.24-25 Moreover, the indoor air pollutant concentration would increase with the decrease of the room volume. The distribution of air pollutants in indoor environments is not uniform, which is influenced by the location of emission sources and the circulation condition of indoor air. The emission of formaldehyde increases with the increase of room temperature and relative humidity. Therefore, room temperature and humidity are two major factors that affect the indoor formaldehyde concentration.26 Air pressure is another factor that indirectly affects the emission amount and concentration of indoor formaldehyde resulting from the influence of moisture content. Approximately 50% of total formaldehyde, which existing in the furniture and the artificial board used for decoration, would be released within five years.27 Prediction of Indoor Formaldehyde Concentration The measurement of indoor formaldehyde concentration and the investigation of its influence factors were further conducted in fifty residential houses. Six major factors including room temperature, relative humidity, air exchange rate, the surface area of the board, the quality of the board and furniture, and the space of the room was taken into consideration for their potential roles on the influences of the indoor formaldehyde concentration. A mathematical model was developed based on the dimension analysis of these factors and the detected indoor formaldehyde concentration (equation (2)), which can then be used to predict the indoor formaldehyde concentration. C fQ(rT a)(bH e) N (i j ) G (2) where C is the indoor formaldehyde concentration, mg/m3; T is the room temperature, ℃; H is the indoor relative humidity, g (H2O)/kg (dry air); Q is the board quality level, ranging from 1 to 5; N is the air exchange times per hour, 0.1~1.0 times/h; G is the surface area of the board per volume (the surface area of the board divided by the space volume of the room), m-1; r, a, b, e, f, i, j are the coefficients. The non-linear regression of measured data was undertaken for the mathematical model by using a statistical software. The results showed that the undetermined coefficients of r, a, b, e, f, I, and j were 0.108, 0.907, 0.001, 0.193, 0.582, 1.401 and 1.093, respectively. Thus, the indoor formaldehyde concentration can be predicted 8 by equation (3). C 0.582Q(0.108T 0.907)(0.001D 0.193) N 1.401 1.093 G (3) In order to know the confidence level, 36 groups of detected data were substituted into equation (3) and the predicted formaldehyde concentrations were obtained. The comparison of the detected and predicted formaldehyde concentration is shown in Figure 4. Comparison of the predicted and detected formaldehyde concentration showed that the determination coefficient R2of regression is 0.8670 with a standard deviation of 0.053 mg/m3. The detected formaldehyde concentration ranged from 0.036 to 0.610 mg/m3. The average and the standard deviation of the detected formaldehyde concentration were 0.210 and 0.024 mg/m3, respectively. The predicted formaldehyde concentration ranged from 0.059 to 0.612 mg/m3. The average and the standard deviation were 0.198 and 0.023 mg/m3, respectively. It concluded that the indoor formaldehyde concentration predicted by equation (3) derived in this study was relatively accurate while compared to the detected data. The indoor formaldehyde concentration can be predicted by equation (3) once if the factors such as room temperature, relative humidity and air exchange frequency were known. It implies that formaldehyde pollution in indoor environments can be controlled during the design process. As indoor formaldehyde concentration is predicted to be high, the sources of formaldehyde should be removed or replaced, which were expected to emit much less or even no formaldehyde. In addition, reducing the surface area of the artificial board and increasing ventilation frequency might be also effective to reduce indoor formaldehyde concentration. Duration of Indoor Formaldehyde Pollution Health effects resulting from the exposure of indoor formaldehyde have been associated primarily with irritant responses to the eyes, nasal and upper respiratory tracts.28 Though the formaldehyde concentration in residential houses is very low, some health effects would appear for long time exposure. Therefore, it is crucial to know the duration of the formaldehyde in indoor environments. Experimental results showed that the formaldehyde released from old artificial board was no less than that from new artificial board.21 Therefore, in indoor environments, the release of formaldehyde is persistent. According to the above investigation, fifty residential houses in the Nangang district of Harbin were selected for the measurement of indoor formaldehyde concentration. All of these residential houses have been decorated to some degree. The variation of indoor formaldehyde concentration with decoration time was investigated. The decoration time was divided into five levels in order to investigate the variation of indoor formaldehyde concentration with decoration time. The statistical analysis of 9 Figure 4. Verification of model predictions with the detected indoor formaldehyde concentration. 3 Detected Data (mg/m ) 0.8 0.6 0.4 0.2 2 R =0.8670 0.0 0.0 0.2 0.4 0.6 0.8 3 Predicted Data (mg/m ) these five levels was undertaken separately and summarized in Table 3. Results from statistical analysis showed that there is no significant difference between the indoor formaldehyde concentrations in the residential houses that have finished decoration for 1, 3 and 8 months. Furthermore, no significant difference between the formaldehyde concentration of residential houses that have finished decoration for 12 and 24 months was also observed. However, there is significant difference between the indoor formaldehyde concentration in the residential houses that have finished decoration for 8 and 12 months. The average concentration of indoor formaldehyde in the houses that have finished decoration for one year was approximately 40.2% of that in the houses that have finished decoration for one month. The average formaldehyde concentration in the houses that have finished decoration for two years was approximately 33.5% of that in houses that have finished decoration for one month. The average indoor formaldehyde concentration in the houses that have finished decoration for two years was approximately 1.6 times higher than the National Air Quality Standard of China (0.10 mg/m3). It concluded that the duration of indoor formaldehyde pollution was quite long in chilly area in Northeast China. Exposure to formaldehyde could cause adverse effects on human health. Therefore, the regulation that restricts the emission source of formaldehyde should be established. Besides, residents should choose high quality decorating materials and furniture to prevent the emission of formaldehyde. Moreover, the decorated residential houses should be ventilated for an enough time before moving in the houses since the formaldehyde can be removed by natural or forced ventilation. 10 Table 3. Formaldehyde concentration in fitment room with different decoration time. Standard Finished Sample Concentration Average Deviation Months Number (mg/m3) (mg/m3) (mg/m3) 1 10 0.187~0.798 0.478 0.064 3 10 0.181~1.302 0.449 0.103 8 10 0.092~0.694 0.355 0.061 12 10 0.056~0.413 0.192 0.036 24 10 0.020~0.317 0.160 0.030 CONCLUSIONS Results from indoor formaldehyde measurement in the residential houses in Harbin showed that the formaldehyde was commonly observed in the houses with the range of 0.017~1.302 mg/m3. The average indoor formaldehyde concentration in the year was 0.219 mg/m3 and only 22.8% of the residential houses met the acceptable formaldehyde concentration of 0.1 mg/m3 for National Air Quality Standard of China. The highest formaldehyde concentration in indoor environments was observed in June while the lowest was in November. The monthly average formaldehyde concentration ranged from 0.134 to 0.386 mg/m3, with the maximum in June and the minimum in December. The indoor formaldehyde concentration in summer was approximately twice higher than that in winter. It concluded that the indoor formaldehyde pollution was very much serious in Harbin. The duration of indoor formaldehyde pollution was quite long in Harbin. The indoor formaldehyde concentration in the residential houses that finished decoration for 2 years was approximately 1.6 times higher than National Air Quality Standard of China (0.10mg/m3). It concluded that the formaldehyde could exist in indoor environments for a long time and its concentration tended to decrease very slowly. A strong correlation between the monthly average indoor formaldehyde concentration and monthly average room temperature was obtained. 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