Global comparison of VOC and CO observations in urban areas

Speciated volatile organic compound (VOC) and carbon monoxide (CO) measurements from the Marylebone Road site in central London from 1998 through 2008 are presented. Long-term trends show statistically significant decreases for all the VOCs considered, ranging from ?3% to ?26% per year. Carbon monoxide decreased by ?12% per year over the measurement period. The VOC trends observed at the kerbside site in London showed greater rates of decline relative to trends from monitoring sites in rural England (Harwell) and a remote high-altitude site (Hohenpeissenberg), which showed decreases for individual VOCs from ?2% to ?13% per year. Over the same 1998 through 2008 period VOC to CO ratios for London remained steady, an indication that emissions reduction measures affected the measured compounds equally. Relative trends comparing VOC to CO ratios between Marylebone Road and Hohenpeissenberg showed greater similarities than absolute trends, indicating that emissions reductions measures in urban areas are reflected by regional background locations. A comparison of VOC mixing ratios and VOC to CO ratios was undertaken for London and other global cities. Carbon monoxide and VOCs (alkanes greater than C₅, alkenes, and aromatics) were found to be strongly correlated (>0.8) in the Annex I countries, whereas only ethene and ethyne were strongly correlated with CO in the non-Annex I countries. The correlation results indicate significant emissions from traffic-related sources in Annex I countries, and a much larger influence of other sources, such as industry and LPG-related sources in non-Annex I countries. Yearly benzene to ethyne ratios for London from 2000 to 2008 ranged from 0.17 to 0.29 and compared well with previous results from US cities and three global megacities.     

Isocyanatocyclohexane and isothiocyanatocyclohexane levels in urban and industrial areas and possible emission-related activities

Isocyanatocyclohexane and isothiocyanatocyclohexane are becoming relevant compounds in urban and industrial air, as they are used in important amounts in automobile industry and building insulation, as well as in the manufacture of foams, rubber, paints and varnishes. Glass multi-sorbent tubes (Carbotrap, Carbopack, Carboxen) were connected to LCMA-UPC pump samplers for the retention of iso- and isothiocyanatocyclohexanes. The analysis was performed by automatic thermal desorption (ATD) coupled with capillary gas chromatography (GC)/mass spectrometry detector (MSD). TD-GC/MS was chosen as analytical method due to its versatility and the possibility of analysis of a wide range of volatility and polarity VOC in air samples. The method was satisfactory sensitive, selective and reproducible for the studied compounds. The concentrations of iso- and isothioisocyanatocyclohexanes were evaluated in different urban, residential and industrial locations from extensive VOC air quality and odour episode studies in several cities in the Northeastern edge of Spain. Around 200–300 VOC were determined qualitatively in each sample. Higher values of iso- and isothiocyanatocyclohexane were found in industrial areas than in urban or residential locations. The concentrations ranged between n.d.−246 and n.d.−29 μg m⁻³ for isocyanatocyclohexane and isothiocyanatocyclohexane, respectively, for industrial areas. On the other hand, urban and residential locations showed concentrations ranging between n.d.−164 and n.d.−29 μg m⁻³ for isocyanatocyclohexane and isothiocyanatocyclohexane, respectively. The site location (urban or industrial), the kind and nearness of possible iso- and isothiocyanatocyclohexane emission activities (industrial or building construction) and the changes of wind regimes throughout the year have been found the most important factors influencing the concentrations of these compounds in the different places.     

VOC in an urban and industrial harbor on the French North Sea coast during two contrasted meteorological situations

Two measurement campaigns of volatile organic compounds (VOC) were carried out in the industrial city of Dunkerque, using Radiello passive samplers during winter (16–23 January) and summer (6–13 June) 2007. 174 compounds were identified belonging to six chemical families. Classifying sampling sites with similar chemical profiles by hierarchical ascending classification resulted in 4 groups that reflected the influence of the main industrial and urban sources of pollution. Also, the BTEX (Benzene, Toluene, Ethylbenzene and Xylenes) quantification allowed us to map their levels of concentration. Benzene and toluene (BT) showed high concentrations in Northern Dunkerque reflecting the influence of two industrial plants. Differences among spatial distributions of the BT concentrations over contrasted meteorological conditions were also observed. An atypical ratio of T/B in the summer samples led us to investigate the BTEX origins shedding light on the contribution of pollutants transported across various zones of VOC emissions situated in Europe.     

CFD model simulation of dispersion from chlorine railcar releases in industrial and urban areas

To assist in emergency response decisions and planning in case of releases of pressurized liquefied chlorine from railroad tank cars in industrial sites and cities, the FLACS Computational Fluid Dynamics (CFD) model has been used to simulate the transport and dispersion of the dense chlorine cloud. Two accident locations are studied: an actual railcar accident at an industrial site in Festus, MO, and a hypothetical railcar accident at a rail junction in the Chicago urban area. The results show that transport of a large dense gas release at ground level in an industrial site or large city could initially extend a hundred meters or more in the upwind and crosswind directions. The dense cloud may follow terrain drainage, such as river channels. Near the source, the obstacles tend to slow down the dense gas cloud and may constrain it and cause increased concentrations. Farther downwind, the obstacles may cause enhanced mixing and dilution once the cloud has grown larger. In some cases, significant amounts of cloud mass may become “trapped” in obstacle wakes for many minutes after the main cloud has passed. Although the CFD model can account for the details of the flow and dispersion much better than standard widely-used simple dense gas models, many similarities are found among the various models in their simulated variations with downwind distance of the maximum cloud centerline concentration.     

Longitudinal variations in indoor VOC concentrations after moving into new apartments and indoor source characterization

This study examined the indoor concentrations of a wide range of volatile organic compounds (VOCs) in currently built new apartments every month over a 24-month period and the source characteristics of indoor VOCs. The indoor total VOC (TVOC) concentrations exhibited a decreasing tendency over the 24-month follow-up period. Similar to TVOCs, the median indoor concentrations of 33 of 40 individual VOCs (all except for naphthalene and six halogenated VOCs) revealed decreasing tendencies. In contrast, the indoor concentrations of the six halogenated VOCs did not reveal any definite trend with time. Moreover, the indoor concentrations of those halogenated VOCs were similar to the outdoor concentrations, suggesting the absence of any notable indoor sources of halogenated VOCs. For naphthalene (NT), the indoor concentrations were significantly higher than the outdoor concentrations, suggesting the presence of indoor NT source(s). The floor/wall coverings (39 %) were the most influential indoor source of indoor VOCs, followed by household cleaning products (32 %), wood paneling/furniture (17 %), paints (7 %), and moth repellents (5 %).     

Mutagenicity of particulate matter fractions in areas under the impact of urban and industrial activities

Organisms in the environment are exposed to a mixture of pollutants. Therefore the purpose of this study was to analyze the mutagenicity of organic and inorganic responses in two fractions of particulates (TSP and PM2.5) and extracts (organic and aqueous). The mutagenicity of organic and aqueous particulate matter extracts from urban-industrial and urban-residential areas was evaluated by Salmonella/microsome assay, through the microsuspension method, using strain TA98 with and without liver metabolization. Additionally, strains YG1021 and YG1024 (nitro-sensitive) were used for organic extracts. Aqueous extracts presented negative responses for mutagenesis and cytotoxicity was detected in 50% of the samples. In these extracts the presence of potential bioavailable metals was identified. All organic extracts presented mutagens with a higher potential associated with PM2.5. This study presents a first characterization of PM2.5 in Brazil, through the Salmonella/microsome assay. The evaluation strategy detected the anthropic influence of groups of compounds characteristically found in urban and industrial areas, even in samples with PM values in accordance with quality standards. Thus, the use of a genotoxic approach in areas under different anthropic influences will favor the adoption of preventive measures in the health/environment relation.     

VOC concentration profiles in an ozone non-attainment area: A case study in an urban and industrial complex metroplex in southern Taiwan

VOCs are important precursors of the atmospheric ozone formation species. This study investigated the airborne concentrations of 52 VOCs at two air quality monitoring stations, Daliao and Tzouying, during wintertime in southern Taiwan. Airborne VOCs samples were taken in stainless steel canisters four times per day and analyzed via gas chromatography/mass spectrometry. Maximum increment reactivity (MIR) was used to evaluate the ozone formation potential in this ozone non-attainment region. Toluene, propane, isopentane, propene, n-butane, n-pentane and isoprene contributed 78–79% of the 52 VOCs in Daliao. Toluene, 1-butene, isopentane, propene, propane, n-undecane, and n-butane contributed 71–77% of the 52 VOCs in Tzouying. The VOCs concentrations were higher in Daliao due to the high toluene emissions from a paint plant and a solvent plant in the nearby industrial district. The 24-h VOC concentrations averaged 25 ppb higher in Tzouying than in Daliao. The ozone formation potential of airborne VOCs was 1687–2730 and 1717–2261 μg-O₃/g-VOCs in Daliao and Tzouying, respectively. Ozone concentrations in Tzouying were 44 ppb higher than in Daliao during the 1200–1600 sampling period.     

A method of assessing air toxics concentrations in urban areas using mobile platform measurements

The objective of this paper is to demonstrate an approach to characterize the spatial variability in ambient air concentrations using mobile platform measurements. This approach may be useful for air toxics assessments in Environmental Justice applications, epidemiological studies, and environmental health risk assessments. In this study, we developed and applied a method to characterize air toxics concentrations in urban areas using results of the recently conducted field study in Wilmington, DE. Mobile measurements were collected over a 4- x 4-km area of downtown Wilmington for three components: formaldehyde (representative of volatile organic compounds and also photochemically reactive pollutants), aerosol size distribution (representing fine particulate matter), and water-soluble hexavalent chromium (representative of toxic metals). These measurements were,used to construct spatial and temporal distributions of air toxics in the area that show a very strong temporal variability, both diurnally and seasonally. An analysis of spatial variability indicates that all pollutants varied significantly by location, which suggests potential impact of local sources. From the comparison with measurements at the central monitoring site, we conclude that formaldehyde and fine particulates show a positive correlation with temperature, which could also be the reason that photochemically generated formaldehyde and fine particulates over the study area correlate well with the fine particulate matter measured at the central site.     

Variability of atmospheric pesticide concentrations between urban and rural areas during intensive pesticide application

Intensive pesticide use leads to the contamination of water, soil and atmosphere. Atmospheric transport is responsible for pesticide dispersal over long distances. In this study, we evaluate the local dispersal of pesticides from agricultural to urban areas. For this purpose, three high-volume samplers, each equipped with a glass fiber filter and XAD-2 resin for the sampling of particulate and gas phase have been placed in a south-west transect (predominant wind direction) characteristic of rural and urban areas. The urban site (Strasbourg centre) is situated in the middle of two rural sites. Samples were taken simultaneously at three sites during pesticide treatments in autumn and spring 2002–2003. Sampling took place for 24 h at a flow rate of 10–15 m³ h⁻¹. The pesticides studied were those commonly used in the Alsace region for all crops (maize, cereal, vines …). Many of the pesticides analysed in atmospheric samples were not detected or observed very episodically at very low concentrations. For metolachlor, alachlor, trifluralin, atrazine and diflufenican, higher concentrations were observed, essentially during the application of these compounds. Moreover, some “spraying peaks” were observed for alachlor in the south rural site (near crops) at a level of 31 ng m⁻³ on 16–17 May 2003. These results show site and time dependence of atmospheric contamination by pesticides. A limited dispersal was also observed especially in the urban area during the application periods of pesticides.     

Relationships between size segregated mass concentration data and ultrafine particle number concentrations in urban areas

Mass concentration data derived from samples collected with a micro-orifice uniform deposit impactor (MOUDI) in six Australian urban centers during periods of significant particle loading have been used to investigate the relationships between TSP, PM10, PM2.5, PM1 and ultrafine particles. While PM10 and PM2.5 display a clear relationship, the lack of correlation between PM10 and the coarse fraction of PM10 (PM10–PM2.5) suggests that variation in PM10 is dominated by variance in PM2.5. Given that particles of less than 2.5 μm are suspected to have adverse health effects, increasing the extent of PM2.5 monitoring may improve detection of relationships between air pollution and human health. A lack of correlation between both PM10 and PM2.5 with ultrafine mass concentrations indicates that PM10 and PM2.5 cannot be used as a surrogate for ultrafine mass concentration. Similarly, ultrafine number concentrations cannot be inferred from mass concentration information determined by the MOUDI.     

A diagnostic comparison of measured and model-predicted speciated VOC concentrations

This study compares speciated model-predicted concentrations (i.e., mixing ratios) of volatile organic compounds (VOCs) with measurements from the Photochemical Assessment Monitoring Stations (PAMS) network at sites within the northeastern US during June–August of 2006. Measurements of total non-methane organic compounds (NMOC), ozone (O₃), oxides of nitrogen (NO_x) and reactive nitrogen species (NO_y) are used for supporting analysis. The measured VOC species were grouped into the surrogate classes used by the Carbon Bond IV (CB4) chemical mechanism. It was found that the model typically over-predicted all the CB4 VOC species, except isoprene, which might be linked to overestimated emissions. Even with over-predictions in the CB4 VOC species, model performance for daily maximum O₃ was typically within ±15%. Analysis at an urban site in NY, where both NMOC and NO_x data were available, suggested that the reasonable ozone performance may be possibly due to compensating overestimated NO_x concentrations, thus modulating the NMOC/NO_x ratio to be in similar ranges as that of observations.     

Dependence of home outdoor particulate mass and number concentrations on residential and traffic features in urban areas

The associations between residential outdoor and ambient particle mass, fine particle absorbance, particle number (PN) concentrations, and residential and traffic determinants were investigated in four European urban areas (Helsinki, Athens, Amsterdam, and Birmingham). A total of 152 nonsmoking participants with respiratory diseases, not exposed to occupational pollution, were included in the study, which comprised a 7-day intensive exposure monitoring period of both indoor and home outdoor particle mass and number concentrations. The same pollutants were also continuously measured at ambient fixed sites centrally located to the studied areas (fixed ambient sites). Relationships between concentrations measured directly outside the homes (residential outdoor) and at the fixed ambient sites were pollutant-specific, with substantial variations among the urban areas. Differences were more pronounced for coarse particles due to resuspension of road dust and PN, which is strongly related to traffic emissions. Less significant outdoor-to-fixed variation for particle mass was observed for Amsterdam and Birmingham, predominantly due to regional secondary aerosol. On the contrary, a strong spatial variation was observed for Athens and to a lesser extent for Helsinki. This was attributed to the overwhelming and time-varied inputs from traffic and other local sources. The location of the residence and traffic volume and distance to street and traffic light were important determinants of residential outdoor particle concentrations. On average, particle mass levels in suburban areas were less than 30% of those measured for residences located in the city center. Residences located less than 10 m from a street experienced 133% higher PN concentrations than residences located further away. Overall, the findings of this multi-city study, indicated that (1) spatial variation was larger for PN than for fine particulate matter (PM) mass and varied between the cities, (2) vehicular emissions in the residential street and location in the center of the city were significant predictors of spatial variation, and (3) the impact of traffic and location in the city was much larger for PN than for fine particle mass.     

Trends in large-scale VOC concentrations in the Southern Netherlands between 1991 and 1997

Results of C₆–C₁₂ hydrocarbon measurements at three sites in the southern part of The Netherlands, a polluted region in Western Europe, are presented. The measurements were carried out over the period March 1991–February 1997. The concentrations at the sites, with 100–150 km distance between them, are quite similar and they are predominantly determined by large-scale transport. The concentrations in this part of the country are substantially higher than those observed at a coastal site in the north of The Netherlands, but much lower compared to the concentrations in cities and near streets. A distinct difference between the trends of aromatics and aliphatics was observed. The concentrations of the aromatic components display trends that are systematically 4–5% yr^-1 lower than the trends of the aliphatics, which is possibly related to the increased use of catalysts in cars and, partly, to an enhanced atmospheric chemical activity. For the chlorinated species the trends are highly significant. The trend of 1,1,1-trichloroethane is in the order of 8–12% yr^-1 downward while for tetrachloromethane an annual downward trend of 4–6% is found. These downward trends suggest that measures have been taken to fulfil the requirements of the Montreal Protocol to ban the production of these species in a few years time from now.     

Application of GIS and modelling in health risk assessment for urban road mobility

Transport is an essential sector in modern societies. It connects economic sectors and industries. Next to its contribution to economic development and social interconnection, it also causes adverse impacts on the environment and results in health hazards. Transport is a major source of ground air pollution, especially in urban areas, and therefore contributes to the health problems, such as cardiovascular and respiratory diseases, cancer and physical injuries. This paper presents the results of a health risk assessment that quantifies the mortality and the diseases associated with particulate matter pollution resulting from urban road transport in Haiphong City, Vietnam. The focus is on the integration of modelling and geographic information system approaches in the exposure analysis to increase the accuracy of the assessment and to produce timely and consistent assessment results. The modelling was done to estimate traffic conditions and concentrations of particulate matters based on geo-referenced data. The study shows that health burdens due to particulate matter in Haiphong include 1,200 extra deaths for the situation in 2007. This figure can double by 2020 as the result of the fast economic development the city pursues. In addition, 51,000 extra hospital admissions and more than 850,000 restricted activity days are expected by 2020.     

A statistical assessment of saturation and mobile sampling strategies to estimate long-term average concentrations across urban areas

The objectives of this study were: (1) to quantify the errors associated with saturation air quality monitoring in estimating the long-term (i.e., annual and 5 yr) mean at a given site from four 2-week measurements, once per season; and (2) to develop a sampling strategy to guide the deployment of mobile air quality facilities for characterizing intraurban gradients of air pollutants, that is, to determine how often a given location should be visited to obtain relatively accurate estimates of the mean air pollutant concentrations. Computer simulations were conducted by randomly sampling ambient monitoring data collected in six Canadian cities at a variety of settings (e.g., population-based sites, near-roadway sites). The 5-yr (1998-2002) dataset consisted of hourly measurements of nitric oxide (NO), nitrogen dioxide (NO2), oxides of nitrogen (NOx), sulfur dioxide (SO2), coarse particulate matter (PM10), fine particulate matter (PM2.5), and CO. The strategy of randomly selecting one 2-week measurement per season to determine the annual or long-term average concentration yields estimates within 30% of the true value 95% of the time for NO2, PM10 and NOx. Larger errors, up to 50%, are expected for NO, SO2, PM2.5, and CO. Combining concentrations from 85 random 1-hr visits per season provides annual and 5-yr average estimates within 30% of the true value with good confidence. Overall, the magnitude of error in the estimates was strongly correlated with the variability of the pollutant. A better estimation can be expected for pollutants known to be less temporally variable and/or over geographic areas where concentrations are less variable. By using multiple sites located in different settings, the relationships determined for estimation error versus number of measurement periods used to determine long-term average are expected to realistically portray the true distribution. Thus, the results should be a good indication of the potential errors one could expect in a variety of different cities, particularly in more northern latitudes.     

Measurements of nitrogen dioxide and sulphur dioxide concentrations in urban and rural areas of Poland using a passive sampling method

Measurements of 1-month concentrations of NO(2) and SO(2) were carried out in the period from May 1993 to April 1994 in 147 points in 30 major cities of Poland and in 31 points in rural areas. The measurement points were divided into five classes representing: centres of cities, residential areas, industrial areas, traffic locations and rural areas. Passive samplers were prepared in one laboratory, mailed to local laboratories for sampling and then returned for analysis. The same samplers were used for collecting both NO(2) and SO(2). Analyses for NO(2) absorbed as nitrite were made spectrophotometrically after reaction with Saltzman reagent. Sulphur dioxide was determined as sulphate with ion chromatography. The consistency of data allowed comparison of levels of air pollution in different cities and the production of maps of spatial distribution of NO(2) and SO(2) in rural areas of Poland.     

Spatio-temporal trends and influencing factors of PM2.5 concentrations in urban agglomerations in China between 2000 and 2016

An urban agglomeration (UA), similar to a megalopolis or a metropolitan area, is a region where cities and people are concentrated, and where air pollution has adversely impacted on sustainable and high quality development. Studies on the spatio-temporal trends and the factors which influence PM_2.5 concentrations may be used as a reference to support air pollution control policy for major UAs throughout the world. Nineteen UAs in China covering the years 2000–2016 were chosen as the research object, the PM_2.5 concentrations being used to reflect air pollution and being estimated from analysis of remote sensing images. The Exploratory Spatial Data Analysis method was used to study the spatio-temporal trends for PM_2.5 concentrations, and the Geodetector method was used to examine the factors influencing the PM_2.5 concentrations. The results revealed that (i) the temporal trend for the average values of the PM_2.5 concentrations in the UAs followed an inverted U-shaped curve and the inflection points of the curve occurred in 2007. (ii) The PM_2.5 concentrations in the UAs exhibited significant global spatial autocorrelation with the high–high type and the low–low type being the main categories. (iii) The rate of land urbanization and the structure of energy consumption were the main factors which influenced the PM_2.5 concentrations in the UAs.

     

Testing VOC emission measurement techniques in wood-coating industrial processes and developing a cost-effective measurement methodology

Availability of reliable emission measurements of concentrated volatile organic compounds (VOCs) bear great significance in facilitating the selection of a feasible emission abatement technique. There are numerous methods, which can be used to measure VOC emissions, however, there is no single method that would allow sampling of the whole range of volatile organics. In addition, research efforts are usually directed to the development of measuring VOCs in diluted concentrations. Therefore, there is a need for a novel measurement method, which can give reliable results while entailing simple operations and low costs. This paper represents a development effort of finding a reliable measurement procedure. A methodology is proposed and used to measure solvent emissions from coating processes.     

Transferring the heterogeneity of surface emissions to variability in pollutant concentrations over urban areas through a chemistry-transport model

Horizontal resolution of grid-based chemistry-transport models is limited to a few square kilometers which has been proved insufficient for assessing human exposure and health impact. We propose a general methodology, applicable on any kind of grid-based air-quality model, that combines subgrid scale information on emission and land-use data in order to disaggregate the grid-averaged emission flux into a set of source-specific components (subgrid-environments). Different subgrid concentrations are calculated inside each one of these environments providing a direct estimate of pollutant variability along with the ‘standard’ grid-averaged model output. The method was first validated over a controlled emissions case by comparing concentrations modeled in the subgrid-environments with concentrations modeled directly at higher model resolution and next over a real case-study, where subgrid concentrations were compared with monitor data from sites representing different types of urban environments (i.e. roads and residential blocks). It was shown that the method is capable to yield accurate estimates of small scale pollutant variability.