Stabilities of 58 volatile organic compounds in fused-silica-lined and SUMMA polished canisters under various humidified conditions

Fused-silica-lined (FSL) canisters and SUMMA polished (SUMMA) canisters were compared for the recoveries and the stabilities of 58 volatile organic compounds (VOCs) at low ppbv (volume/volume) levels under various humidified conditions using a three-stage preconcentration method followed by GC-MS analysis. The target VOCs included non-polar VOCs (e.g. halogenated hydrocarbons and aromatic hydrocarbons) and polar VOCs (e.g. alcohols, ketones, esters, ethers, nitriles and thiols). The three-stage preconcentration method was initially optimized for simultaneous analysis of non-polar and polar VOCs because determination of canister stability is dependent on the accuracy of analytical measurements. The method showed good linearity over the concentration range from 1 to 25 ppbv for all target analytes, and the correlation coefficients were higher than 0.9974. The method detection limits ranged from 0.023 to 0.39 ppbv. The test mixtures loaded in both type of canisters (n = 3) had concentrations of 1.7-2.5 ppbv per compound at ambient pressure under various humidified conditions (%RH = 1.6, 8.0, 27, 39, 53 and >99% with excess water present). All canister samples were initially analyzed on day 0 (after 6-12 h). The effect of competitive adsorption of water vapor and polar VOCs on active sites of interior surface was remarkably observed for SUMMA canisters. Polar VOCs had a greater requirement for water vapor to be present. The RH percentages that ensured good recovery on day 0 were RH > 8% for non-polar VOCs and RH > 27% for polar VOCs (except alcohols under the condition of RH > 99%). All thiols were not recovered from SUMMA canisters under all conditions. FSL canisters showed good recoveries of more than 86% for all VOCs under all conditions on day 0 (except alcohols under the condition of RH > 99%). The recoveries of alcohols in both canisters under the condition of RH > 99% displayed relatively low recoveries in the range 25-76% because of the partitioning effect into condensed water. The canister samples under the conditions of RH 8.0, 27, 53 and > 99% were analyzed for the stability test on days 3, 7, 14 and 28 after loading. All non-polar VOCs were reasonably stable in the FSL canisters under all examined conditions over 28 days. However, several polar VOCs that have relatively lower vapor pressure, e.g. MIBK, butyl acetate and alcohols except ethanol, showed unstable characteristics under relatively dry conditions (RH 8 and 27%) during 28 days. RH > 53% was needed to ensure good stabilities of all analytes except thiols with the recoveries of > 80% over 28 days for both canisters. Although the FSL canister showed good recoveries of more than 86% for thiols on day 0, drastic degradations were observed after day 3 and they were not detected after day 14.     

Long-term measurement of volatile organic compounds in ambient air by canister-based one-week sampling method

A canister-based 1 week sampling method using a mechanical flow controller and a 6 L fused-silica-lined canister was evaluated for the long-term measurement of 47 VOCs in ambient air at pptv (volume/volume) to ppbv levels by use of a three-stage preconcentation method followed by GC-MS analysis. The GC conditions were initially optimized for complete separations of several pptv-level VOCs (e.g. vinyl chloride, 1,3-butadiene, acrylonitrile, 1,2-dichloroethane and chloroform) in ambient air because the selected ions are easily interfered with by coexisting C4-, C5-hydrocarbons and analytes presented at ppbv levels. Thirty-four VOCs determined by the 1 week and 24 h sampling method in December 16-22 (2002) had concentrations of 6.0-15000 pptv per compound. Concentrations of 28 VOCs (including polar VOCs (e.g. methyl isobutyl ketone and butyl acetate)) obtained by the method were approximately equal to the mean values calculated from 24 h sampling (< +/- 10% deviation). Six VOCs that had low concentrations of 6.0-43 pptv showed more than +/- 10% deviation. Thirteen VOCs were not detected during the entire sampling period. The effect of relative humidity or ozone for the specific VOCs (e.g. MIBK, butyl acetate, vinyl chloride, 1,3-butadiene and styrene) was negligible.     

24 h diffusive sampling of toxic VOCs in air onto Carbopack X solid adsorbent followed by thermal desorption/GC/MS analysis-laboratory studies

Diffusive sampling of a mixture of 42 volatile organic compounds (VOCs) in humidified, purified air onto the solid adsorbent Carbopack X was evaluated under controlled laboratory conditions. The evaluation included variations in sample air temperature, relative humidity and ozone concentration. Linearity of samples with loading was examined both for a constant concentration with time varied up to 24 h and for different concentrations over 24 h. Reverse diffusion and its increase with accumulation of sample were determined for all compounds. Tubes were examined for blank levels, change of blanks with storage time, and variability of blanks. Method detection limits were determined based on seven replicate samples. Based on this evaluation, 27 VOCs were selected for quantitative monitoring in the concentration range from approximately 0.1 to 4 ppbv. Comparison results of active and diffusive samples taken over 24 h and under the same simulated ambient conditions at a constant 2 ppbv were interpreted to estimate the effective diffusive sampling rates (ml min(-1)) and their uncertainties and to calculate the corresponding diffusive uptake rates (ng ppmv(-1) min(-1)).     

A comparison of sampling and analysis methods for low-ppbC levels of volatile organic compounds in ambient air

A carefully designed study was conducted during the summer of 1998 to collect samples of ambient air by canisters and compare the analysis results to direct sorbent preconcentration results taken at the time of sample collection. Thirty-two 1 h sample sets were taken, each composed of a "near-real-time" sample analyzed by an autoGC-MS XonTech 930/Varian Saturn 2000 system, and Summa and Silco canisters. Hourly total non-methane organic carbon (TNMOC), ozone, and meteorological measurements were also made. Each canister was analyzed on the autoGC-MS system for a target list of 108 volatile organic compounds (VOCs) and on a manual cryosampling GC-FID system. Comparisons were made between the collection and analysis methods. Because of the low sample loading (150-250 ppbC TNMOC), these comparisons were a stringent test of sample collection and analysis capabilities. The following specific conclusions may be drawn from this study. Reasonable precision (within 15% mean difference of duplicate analyses from the same canister) can be obtained for analyses of target VOCs at low-ppbC concentrations. Relative accuracy between the GC-MS and GC-FID analysis methods is excellent, as demonstrated by comparisons of analyses of the same canisters, if measurements are sufficiently above the detection limits. This is especially significant as the GC-MS and GC-FID were independently calibrated. While statistically significant differences may be observed between the results from canister and near-real-time samples, the differences were generally small and there were clear correlations between the canister results and the near-real-time results. Canister cleanliness limits detection below the EPA Method TO-14 acceptance standard of 0.2 ppbv (0.2-2 ppbC for target analytes).     

Influence of Relative Humidity and Ozone on the Sampling of Volatile Organic Compounds on Carbotrap/Carbosieve Adsorbents

By using a dynamic dilution system, the atmospheric measurement of 11 selected toxics VOCs (ethylene, acetylene, propene, 1-butene, 1,3-butadiene, 1-pentene, 1-hexene, benzene, toluene, ethylbenzene, m+p-xylene) from the list WHO of 1996 and TO-14 method of US EPA by preconcentration by thermal desorption (TD), analysis by gas chromatography (GC), identification and quantification with a flame ionisation detector (FID) was developed and validated in term of metrology, especially the techniques of sampling of these VOCs with adsorbents cartridges "Air Toxics" when used with an "UMEG sampler" equipped in the inlet with a nafion membrane. In particular the influence of climatic conditions (temperature and relative humidity) and the influence of chemical factors like ozone, on the representativity of sampling were studied. Experiments made with various humidities showed that the addition of a nafion membrane in the inlet of the sampling system was required. Without this membrane, losses of compounds were observed for RH >50%. With this membrane, storage for 2 weeks in a refrigerator, as for canisters, did not induce a loss of compounds. No significative decrease of concentrations of the studied VOCs after 14 days storage, which are known to react with ozone, were observed with an ozone concentrations of 55 ppb. One explanation is that nafion membrane, placed in the inlet of the sampler, will neutralize ozone before entering the sampling tubes. This observation is in accordance with literature which states that the sampling of VOCs on Carbotrap cartridges without ozone scrubber induce a loss of compounds.     

Characteristics of surface ozone at an urban site of Xi'an in Northwest China

Surface ozone concentrations in Xi'an, China were monitored from March 23, 2008 to January 12, 2009 using the Model ML/EC9810 ozone analyzer. The daily average O(3) ranged from <1 ppb to 64.2 ppbv with an annual average of 16.0 ppbv. The seasonal average of O(3) in summer (32.5 ppbv) was more than 10 times higher than that in winter (3.0 ppbv). A significant positive correlation was found between ozone concentration and ambient temperature, indicating that the intensity of solar radiation was one of the several major factors controlling surface ozone production. Using the NOAA HYSPLIT 4 trajectory model, the three longest O(3) pollution episodes were found to be associated with the high biogenic volatile organic carbon (BVOC) emissions from the vegetation of Qinling Mountains. No significant weekday and weekend difference in O(3) levels was detected due to the non-significant change in NO(x) emissions. O(3) depletion by NO emission directly emitted from vehicles, low oxygenated VOC concentrations, and low-level solar radiation caused by high aerosol loading all contributed to the low levels of O(3) found in Xi'an compared to other cities and rural areas.     

Measurement and Interpretation of Concentrations of Urban Atmospheric Organic Compounds

The presence of volatile organic compounds (VOCs) from traffic and other sources in urban areas is a cause for concern about public health. Canister, chemical derivatisation, particulate sampling and adsorption sampling techniques were used to measure VOC concentrations of a wide range of compounds (C6-C40) during a four day campaign in south London with subsequent laboratory analysis of the samples. Compounds quantified included alkanes, mono- and poly-nuclear aromatic hydrocarbons. Also the first sequential measurements of carbonyl compounds (C1-C8) in a UK urban area are presented. Results from canister and adsorption sampling methods are compared. A comparison of the results with other urban data is presented and the temporal variations in VOC concentrations were interpreted with reference to the prevalent wind speeds and directions. The CALINE4 line source dispersion model was generally successful in reproducing the daytime 12 hour average concentrations of selected VOCs.     

Measurements of nitrogen dioxide in Greenland using Palmes diffusion tubes

Measurements of nitrogen dioxide using the Palmes diffusion tubes in Uummannaq, Aasiaat, and Nuuk. all located along the west-coast of Greenland, have demonstrated that the levels of pollution at the most heavily impacted sites are comparable to levels in much larger towns in Denmark. The highest concentrations were, in general, observed near sites influenced by car traffic (peak concentrations of up to 16 ppbv), medium concentrations were observed in the residential areas (2 6 ppbv), and very low levels were found at the background locations in the town outskirts (1-2 ppbv). Observations of nitrogen dioxide concentrations less than 0.1 ppbv at a remote site, Akia, 25 km from Nuuk, indicate that, compared to local sources, long-range transport of nitrogen dioxide is not important in western Greenland.     

Validation of evacuated canisters for sampling volatile organic compounds in healthcare settings

Healthcare settings present a challenging environment for assessing low-level concentrations of specific volatile organic compounds (VOCs) in the presence of high background concentrations of alcohol from the use of hand sanitizers and surface disinfectants. The purposes of this laboratory-based project were to develop and validate a sampling and analysis methodology for quantifying low-level VOC concentrations as well as high-level alcohol concentrations found together in healthcare settings. Sampling was conducted using evacuated canisters lined with fused silica. Gas chromatography/mass spectrometry analysis was performed using preconcentration (for ppb levels) and loop injection (for ppm levels). For a select list of 14 VOCs, bias, precision, and accuracy of both the preconcentration and loop injection methods were evaluated, as was analyte stability in evacuated canisters over 30 days. Using the preconcentration (ppb-level) method, all validation criteria were met for 13 of the 14 target analytes-ethanol, acetone, methylene chloride, hexane, chloroform, benzene, methyl methacrylate, toluene, ethylbenzene, m,p-xylene, o-xylene, alpha-pinene, and limonene. Using the loop injection (ppm-level) method, all validation criteria were met for each analyte. At ppm levels, alpha-pinene and limonene remained stable over 21 days, while the rest of the analytes were stable for 30 days. All analytes remained stable over 30 days at ppb levels. This sampling and analysis approach is a viable (i.e., accurate and stable) methodology that will enable development of VOC profiles for mixed exposures experienced by healthcare workers.     

Investigation of Mtbe and Aromatic Compound Concentrations at a Gas Service Station

Methyl tert-butyl ether (MTBE) has been used as a fuel additive at levels of 2–11% in Taiwan for the past decade. The purpose of this additive is to enhance the octane, replace the use of lead-based anti-knock gasoline additives and reduce aromatic hydrocarbons. However, it is possible that oxygenated fuel has a potential health impact. To determine the air quality impact of MTBE, measurements were made of ambient MTBE and other gasoline constituents at a service station. Additionally, environmental conditions (wind speed, wind direction, and temperature, etc.) that could affect concentrations of emission constituents were measured. Gas samples were analyzed for target MTBE and volatile organic compounds, e.g., benzene and toluene. Ambient samples were collected using Tenax adsorbent tubes for mass spectrometric analysis at a service station located in Changhua County, Taiwan. The resulting measured ambient air concentrations were compared with Taiwans regulatory standards for hazardous air pollutants. Subsequently, the factors controlling the formation of high-VOC levels at the service station and in the residential neighborhoods were identified. Additionally, the results can provide the Environmental Protection Agency (EPA) of Taiwan with useful information and prompt them to mandate this gas service station to install a refueling vapor recovery system.     

Ambient level volatile organic compound (VOC) monitoring using solid adsorbents--recent US EPA studies

Ambient air spiked with 1-10 ppbv concentrations of 41 toxic volatile organic compounds (VOCs) listed in US Environmental Protection Agency (EPA) Compendium Method TO-14A was monitored using solid sorbents for sample collection and a Varian Saturn 2000 ion trap mass spectrometer for analysis. The adsorbent was a combination of graphitic carbon and a Carboxen-type carbon molecular sieve. The method detection limits (MDLs) for 11 samples were typically 0.5 parts per billion by volume (ppbv) and lower except for bromomethane and chloromethane, both of which exhibited breakthrough. Thirty-day sample storage on the sorbents resulted in less than a 20% change for most compounds, and water management was required for humid samples to avoid major anomalous decreases in response during analyses. The adsorbent-based system, a system using canister-based monitoring, and a semi-continuous automated GC/MS (autoGC) monitoring system with a Tenax GR/Carbotrap B/Carbosieve S-III adsorbent preconcentrator were compared using spiked ozone concentrations as a variable. In this comparison, the target compounds included a number of n-aldehydes as well as those listed in TO-14A. The effects of ozone on the TO-14A compounds were relatively minor with the exception of negative artifacts noted for styrene and 1,1,2,2-tetrachloroethane. However, a small, systematic decrease in response was evident for a number of aromatic VOCs and 1,1,2,2-tetrachloroethane when ozone was increased from 50 to 300 ppbv. Method averages for multiple runs under the same conditions were typically within +0.25 ppbv of their mean for most compounds. For n-aldehydes, strong positive artifacts using the autoGC preconcentrator and strong negative artifacts for the canister-based and carbon sorbent approaches caused major disagreement among methods. These artifacts were mostly eliminated by using MnO2 ozone scrubbers, although loss of the n-aldehydes for all methods occurred after a single sample collection of 1 h duration, apparently due to the interaction of the n-aldehydes and products of the O3, MnO2 reaction on the scrubber.     

Assessment of pumped mercury vapour adsorption tubes as passive samplers using a micro-exposure chamber

Mercury vapour adsorption tubes manufactured for pumped sampling and analysis have been evaluated for their performance as passive samplers. This has been done by exposing these tubes in a novel micro-exposure chamber. The uptake rates of these tubes have been found to be low (approximately 0.215 ml min(-1)) as compared to bespoke passive samplers for mercury vapour (typically in excess of 50 ml min(-1)). The measured uptake rates were shown to vary significantly between tubes and this was attributed to the variability in the air-sorbent interface and the proportion of the cross sectional area removed by the crimp in the quartz tubes used to secure the sorbent material. As a result of this variability the uptake rate of each tube must be determined using the micro-exposure chamber prior to deployment. Results have shown that the uptake rate determined in the micro-exposure chamber is invariant of concentration, and therefore these uptakes rates may be determined at a high mercury vapour concentration for many tubes at once in less than one hour. The uptake rate of the adsorption tubes under these conditions may be determined with a precision of 5%. Measurements made on a limited field trial in indoor and outdoor ambient air have shown that these tubes give results in acceptable agreement with more traditional pumped sampling methods, although longer sampling periods are required in order to reduce the uncertainty of the measurement, which is currently approximately 30%.     

Evaluation of the effect of different sampling time periods and ambient air pollutant concentrations on the performance of the Radiello diffusive sampler for the analysis of VOCs by TD-GC/MS

The effect of different sampling exposure times and ambient air pollutant concentrations on the performance of Radiello? samplers for analysis of volatile organic compounds (VOCs) is evaluated. Quadruplicate samples of Radiello? passive tubes were taken for 3, 4, 7 and 14 days. Samples were taken indoors during February and March 2010 and outdoors during July 2010 in La Canonja (Tarragona, Spain). The analysis was performed by automatic thermal desorption (ATD) coupled with capillary gas chromatography (GC)/mass spectrometry detection (MS). The results show significant differences (t-test, p < 0.05) between the amounts of VOCs obtained from the sum of two short sampling periods and a single equivalent longer sampling period for 65% of all the data. 17% of the results show significantly larger amounts of pollutant in the sum of two short sampling periods. Back diffusion due to changes in concentrations together with saturation and competitive effects between the compounds during longer sampling periods could be responsible for these differences. The other 48% of the results that are different show significantly larger amounts in the single equivalent longer sampling period. The remaining 35% of the results do not show significant differences. Although significant differences are observed in the amount of several VOCs collected over two shorter sampling intervals compared to the amount collected during a single equivalent longer sampling period, the ratios obtained are very close to unity (between 0.7 and 1.2 in 75% of cases). We conclude that Radiello? passive samplers are useful tools if their limitations are taken into account and the manufacturer's recommendations are followed.     

Characteristics and sources of non-methane hydrocarbons and halocarbons in wintertime urban atmosphere of Shanghai, China

The characteristics and sources of major hydrocarbons and halocarbons in the wintertime ambient air of urban center of Shanghai, a mega city of China, were investigated. Propane, toluene, ethyl acetate, and benzene were the most abundant hydrocarbons. The majority of species showed significant variability in mixing ratios with occasional episodic increases. The more common use of liquefied petroleum gas fuel for taxis and light motorcycles was believed to lead to high levels of ambient propane over the urban center of Shanghai. Correlating with toluene, dichloromethane, and 1,2-dichloroethane (1,2-DCE), abundant chloromethane (up to a daily mean of 1.61?±?0.99 ppbv and a maximum of 5.34 ppbv) was mainly associated with industrial emissions, although biomass burnings exist widely in east China. The Chinese New Year (CNY) holiday period with no industrial activity over China provides a platform for the study of industrial emissions over the urban atmosphere of Shanghai. The normal weekly cycles were characterized by higher and more variable mixing ratios during weekdays which dropped during weekends. Enhanced mixing ratios were observed in the fortnight before the CNY holidays due to increased industrial emissions as a result of overtime production to make up for the holiday losses. During the CNY holidays, lower level and less variable mixing ratios were observed. A benzene/toluene (B/T) ratio of 0.6?±?0.4 (mean?±?std.) for the morning rush hour samples was identified to be the characteristic ratio of vehicular emissions. However, a B/T ratio of 0.4?±?0.2 from vehicles and other sources was derived for the ambient air.     

Indoor/ambient residential air toxics results in rural western Montana

Indoor and ambient concentrations of 21 volatile organic compounds (including 14 hazardous air pollutants) were measured in the homes of nearly 80 western Montana (Missoula) high school students as part of the 'Air Toxics Under the Big Sky' program during the 2004/2005 and 2005/2006 school years. Target analytes were measured using low flow air sampling pumps and sorbent tubes, with analysis of the exposed samples by thermal desorption/gas chromatography/mass spectrometry (TD/GC/MS). The results reported here present the findings of the first indoor/ambient air toxics monitoring program conducted in a semi-rural valley location located in the Northern Rocky Mountain/Western Montana region. Of all of the air toxics quantified in this study, toluene was found to be the most abundant compound in both the indoor and ambient environments during each of the two school years. Indoor log-transformed mean concentrations were found to be higher when compared with ambient log-transformed mean concentrations at P < 0.001 for the majority of the compounds, supporting the results of previous studies conducted in urban areas. For the air toxics consistently measured throughout this program, concentrations were approximately six times higher inside the student's homes compared to those simultaneously measured directly outside their homes. For the majority of the compounds, there were no significant correlations between indoor and ambient concentrations.     

A catalogue of urban hydrocarbons for the city of Leeds: atmospheric monitoring of volatile organic compounds by thermal desorption-gas chromatography

A method has been developed for the speciation and quantitative determination of hydrocarbons in urban air in the city of Leeds. Hydrocarbons were pre-concentrated by adsorbent tube air sampling and analyzed using thermal desorption and gas chromatography with flame ionization detection and structural confirmation by mass spectrometric detection. While automated volatile organic compound (VOC) analyzers produced data for a maximum of about 30 compounds simultaneously, with the method described here, a total of 68 C6-C12 hydrocarbons were measured simultaneously in one analysis at parts per billion (ppb) levels. Several monitoring surveys were performed, one during the winter of 1993 and the other in the summer of 1994, at a number of sites to investigate the levels of VOCs identified in the urban air of Leeds.     

机动车排放尾气中挥发性有机污染物对环境空气质量影响初探

采用气相色谱/质谱检测技术,对汽油和柴油、汽油车和柴油车排放气体以及天津市环境空气中主要挥发性有机污染物(VOCs)的组成种类及比例进行探析.结果表明,机动车排放的尾气中主要有机污染物为芳香烃类、烷烃类和烯烃类化合物,其中芳香烃类含量最高;汽油车排放的芳香烃类化合物浓度高于柴油车排放的浓度;机动车尾气对交通区域空气质量的影响高于工厂区(非化工区)、生活小区和公园.     

南京市环境空气挥发性有机物监测方法比对研究

2018年9月20—29日,开展了南京市环境空气非甲烷烃(PAMS)原清单中57种挥发性有机物的手工和在线比对监测,监测项目主要包括碳氢化合物、卤代烃和含氧挥发性有机物。通过对VOCs 3 h均值、日均值和主要污染物指标等进行比对,分析在线监测数据与手工监测数据的相关性。测试结果表明,两种方法得到的3 h均值的差异度(1.43)和相关系数(0.897),日均值的差异度(2.16)和相关系数(0.946),呈现出差异度不显著、高度线性相关的特征。同时,进一步分析了监测数据产生偏离的原因,建议加强环境空气手工监测的质控管理,强化在线监测设备的运维管理,推进环境空气挥发性有机物监测的合理、有序发展。     

Volatile hydrocarbon emissions from vehicles and vertical ventilations in the Hsuehshan traffic tunnel, Taiwan

The concentrations of 56 volatile organic hydrocarbons (VOCs) were measured simultaneously in the southbound bore, the northbound bore and the exhaust air shafts of the Hsuehshan tunnel near Yilan, Taiwan during 2007 and 2008. A total of 60 integrated air samples were collected using stainless steel canisters and analyzed using GC/FID and GC/MS. The highest temperature and lowest relative humidity were observed at the exit of the tunnel owing to the accumulation in the tunnel of waste heat that was exhausted from vehicles. The five most abundant species in all samples were ethylene, acetylene, isopentane, propylene, and toluene. The exit/entrance ratios of total non-methane hydrocarbon (NMHC) concentration were 7.8 and 4.8 for the southbound and northbound bores, respectively. Furthermore, the most abundant species of emission rate (ER) is toluene (21.93-42.89 mg s(-1)), followed by isopentane, ethylene, propylene and 1-butene, with ER ranging from 2.50 to 9.31 mg s(-1) for the three shafts. The ozone formation potential (OFP)/total NMHC ratios in three exhaust air shafts show that the reactivities of these emissions are similar to those of vehicle emissions.     

Monitoring variation in greenhouse gases concentration in Urban Environment of Delhi

Cities across the globe are considered as major anthropogenic sources of greenhouse gases (GHG), yet very few efforts has been made to monitor ambient concentration of GHG in cities, especially in a developing country like India. Here, variations in the ambient concentrations of carbon dioxide (CO₂) and methane (CH₄) in residential, commercial, and industrial areas of Delhi are determined from fortnightly daytime observations from July, 2008 to March, 2009. Results indicate that the average daytime ambient concentration of CO₂ varied from 495 to 554 ppm in authorized residential areas, 503 to 621 ppm in the slums or jhuggies in the unauthorized residential areas, 489 to 582 ppm in commercial areas, and 512 to 568 ppm in industrial areas with an average of 541?±?27 ppm. CH₄ concentration varied from 652 to 5,356 ppbv in authorized residential areas, 500 to15,220 ppbv in the unauthorized residential areas, 921 to 11,000 ppbv in the commercial areas, and 250 to 2,550 ppbv in the industrial areas with an average of 3,226?±?1,090 ppbv. A low mid-afternoon CO₂ concentration was observed at most of the sites, primarily due to strong biospheric photosynthesis coupled with strong vertical mixing.