Aromatic hydrocarbons in the atmospheric environment. Part III: personal monitoring

As part of a larger study, personal sampling of the aromatic hydrocarbons benzene, toluene, ethylbenzene and the isomeric xylenes (BTEX) was carried out by 55 nonsmoking volunteers for a period of 14 days. Thirty-nine persons lived in a rural area near Hannover (Germany) with hardly any traffic at all, while 16 persons lived in a high-traffic city street in Hannover. The personal exposure level of the persons in the rural area (some commuting to Hannover) was: 2.9, 24.8, 2.4 and 7.7 μg m⁻³ for benzene, toluene, ethylbenzene and the sum of xylenes, respectively, while the corresponding data for the high traffic city streets were 4.0, 22.2, 2.8 and 9.7 μg m⁻³ (geometric means). Four microenvironments have been monitored which contribute to the total exposure to BTEX, i.e. the home, the outdoor air, the workplace and the car cabin. The most important microenvironment for non-working persons is the private home. The concentration of most BTEX in the private home is almost equal to the personal exposure level, demonstrating that the indoor pollution in the home makes by far the highest contribution to the total exposure. For working people (mostly office workers), the workplace is the second most important microenvironment contributing to the total BTEX exposure. Taking all working persons into consideration (independent of the location of their private home) the personal exposure level is higher by a factor of 1.2–1.4 than that of the workplace (for toluene this factor is 2.2). As already found by others, very high BTEX concentrations may be found in car cabins, in particular, if the engine is gasoline-driven. In the cabin of 44 cars in the rural/urban area average benzene concentrations (geometric mean) of 12/14 μg m⁻³ and a maximum value of ∼550 μg m⁻³ were found. On average, the participating volunteers drove their car for 45 min day⁻¹ (i.e. 3% of the day). Nevertheless, the car cabin constitutes about 10% of the total benzene exposure. Refueling of the car during the 14-day sampling period has only a small effect on the personal exposure level.     

Benzene exposure in Helsinki,Finland

Personal exposures and microenvironmental concentrations of benzene were measured in the residential indoor, residential outdoor and workplace environments for 201 participants in Helsinki, Finland, as a component of the EXPOLIS-Helsinki study. Median benzene personal exposures were 2.47 (arithmetic standard deviation (ASD)=1.62) μg m⁻³ for non-smokers, 2.89 (ASD=3.26) μg m⁻³ for those exposed to environmental tobacco smoke in any microenvironment and 3.08 (ASD=10.04) μg m⁻³ for active smokers. Median residential indoor benzene concentrations were 3.14 (ASD=1.51) μg m⁻³ and 1.87 (ASD=1.93) μg m⁻³ for environments with and without tobacco smoke, respectively. Median residential outdoor benzene concentrations were 1.51 (ASD=1.11) μg m⁻³ and median workplace benzene concentrations were 3.58 (ASD=1.96) μg m⁻³ and 2.13 (ASD=1.49) μg m⁻³ for environments with and without tobacco smoke, respectively. Multiple step-wise regression identified indoor benzene concentrations as the strongest predictor for personal benzene exposures of those not exposed to tobacco smoke, followed sequentially by time spent in a car, time in the indoor environment, indoor workplace concentrations and time in the home workshop. Relationships between indoor and outdoor microenvironment concentrations and personal exposures showed considerable variation between seasons, due to differences in ventilation patterns of homes in these northern latitudes. Automobile use-related activities were significantly associated with elevated benzene levels in personal and indoor measurements when tobacco smoke was not present, which demonstrates the importance of personal measurements in the assessment of exposure to benzene.     

Reductions in human benzene exposure in the California South Coast Air Basin

Benzene typically contributes a significant fraction of the human cancer risk associated with exposure to urban air pollutants. In recent years, concentrations of benzene in ambient air have declined in many urban areas due to the use of reformulated gasolines, lower vehicle emissions, and other control measures. In the California South Coast Air Basin (SoCAB) ambient benzene concentrations have been reduced by more than 70% since 1989. To estimate the resulting effect on human exposures, the Regional Human Exposure (REHEX) model was used to calculate benzene exposures in the SoCAB for the years 1989 and 1997. Benzene concentration distributions in 14 microenvironments (e.g. outdoor, home, vehicle, work) were combined with California time-activity patterns and census data to calculate exposure distributions for 11 demographic groups in the SoCAB. For 1997, the calculated average benzene exposure for nonsmoking adults in the SoCAB was 2 ppb, compared to 6 ppb for 1989. For nonsmokers, about half of the 1997 exposure was due to ambient air concentrations (including their contributions to other microenvironments), but only 4% for smokers. Passive tobacco smoke contributed about one-fourth of all exposure for adult nonsmokers. In-transit microenvironments and attached garages contributed approximately 15 and 10%, respectively. From 1989 to 1997, decreases in passive smoke exposure accounted for about one-sixth of the decrease in exposure for nonsmoking adults, with the remainder due to decreases in ambient concentrations. The reductions in exposure during this time period indicate the effectiveness of reformulated fuels, more stringent emission standards, and smoking restrictions in significantly reducing exposure to benzene.     

Determinants of airborne benzene concentrations in rural areas of western Canada

This study estimated the level and determinants of airborne benzene concentrations in rural western Canada. A multi-site, multi-month unbalanced two-factorial design was used to collect air samples at 1206 fixed sites across a geographic area associated with primary oil and gas industry in Canadian provinces of Alberta, north-eastern British Columbia, and central and southern Saskatchewan from April 2001 to December 2002. Benzene concentrations integrated over 1 calendar month were determined using passive organic vapour monitors. Linear mixed effects models were applied to identify the determinants of airborne benzene concentrations, in particular the proximity to oil and gas facilities. The observed geometric mean of benzene concentrations was 158 ng m⁻³, with large geometric standard deviation: 4.9. Benzene concentrations showed a seasonal variation with maxima in winter and minima in summer. Emissions from oil well (within 2 km) and compressor influenced monthly airborne benzene concentrations. However, in our study, being located in the general area of a gas plant seems to be the most important in determining monthly airborne benzene concentrations. These findings support the need for investigation of the impact of oil and gas industry on quality of rural air.     

Bus,minibus, metro inter-comparison of commuters’ exposure to air pollution in Mexico City

Commuters’ exposure measurements were taken for PM_2.5, carbon monoxide (CO) and benzene in minibuses, buses and metro during morning and evening rush hours during January–March 2003 in Mexico City. For PM_2.5, the chemical composition was characterized. Total carbon was the most abundant species in fine particles (approximately 50%). Minibuses (49 μg m⁻³) and buses had similar concentrations of exposure for PM_2.5 (53 μg m⁻³). For CO and benzene the concentrations were higher in minibuses. Morning rush hour was the commuting period with the highest concentrations for minibuses and buses. Metro was the mode of transport with lower concentrations for all pollutants. Carbon monoxide concentrations were similar to those identified in a previous campaign in 2002 and approximately 3.5 times lower than those in a study conducted in 1991. Benzene was characterized systematically in the selected modes of transport. A strong association was observed between wind speed and pollutant concentrations in buses.     

Behavioral and environmental determinants of personal exposures to PM2.5 in EXPOLIS – Helsinki,Finland

Behavioral and environmental determinants of PM_2.5 personal exposures were analyzed for 201 randomly selected adult participants (25–55 years old) of the EXPOLIS study in Helsinki, Finland. Personal exposure concentrations were higher than respective residential outdoor, residential indoor and workplace indoor concentrations for both smokers and non-smokers. Mean personal exposure concentrations of active smokers (31.0±31.4 μg m⁻³) were almost double those of participants exposed to environmental tobacco smoke (ETS) (16.6±11.8 μg m⁻³) and three times those of participants not exposed to tobacco smoke (9.9±6.2 μg m⁻³). Mean indoor concentrations of PM_2.5 when a member of the household smoked indoors (20.8±23.9 μg m⁻³) were approximately 2.5 times the concentrations of PM_2.5 when no smoking was reported (8.2±5.2 μg m⁻³). Interestingly, however, both mean (8.2 μg m⁻³) and median (6.9 μg m⁻³) residential indoor concentrations for non-ETS exposed participants were lower than residential outdoor concentrations (9.5 and 7.3 μg m⁻³, respectively). In simple linear regression models residential indoor concentrations were the best predictors of personal exposure concentrations. Correlations (r²) between PM_2.5 personal exposure concentrations of all participants, both smoking and non-smoking, and residential indoor, workplace indoor, residential outdoor and ambient fixed site concentrations were 0.53, 0.38, 0.17 and 0.16, respectively. Predictors for personal exposure concentrations of non-ETS exposed participants identified in multiple regression were residential indoor concentrations, workplace concentrations and traffic density in the nearest street from home, which accounted for 77% of the variance. Subsequently, step-wise regression not including residential and workplace indoor concentrations as input (as these are frequently not available), identified ambient PM_2.5 concentration and home location, as predictors of personal exposure, accounting for 47% of the variance. Ambient fixed site PM_2.5 concentrations were closely related to residential outdoor concentrations (r²=0.9, p=0.000) and PM_2.5 personal exposure concentrations were higher in summer than during other seasons. Personal exposure concentrations were significantly (p=0.040) higher for individuals living downtown compared with individuals in suburban family homes. Further analysis will focus on comparisons of determinants between Helsinki and other EXPOLIS centers.     

Aromatic hydrocarbons at urban,sub-urban,rural (8°52′N; 67°19′W) and remote sites in Venezuela

Using the novel on-line proton transfer reaction mass spectrometry (PTR-MS) technique, atmospheric concentrations of benzene, toluene, xylenes, and C₉-benzenes were measured in Caracas (urban), Altos de Pipe (sub-urban), Calabozo (rural) and Parupa (remote), during various campaigns in 1999 and 2000.Average daytime mixing ratios measured in Caracas are 1.1, 3.2, 3.7, and 2.7 nmol/mol for benzene, toluene, xylenes, and C₉-benzenes. At the sub-urban site, located only few km from Caracas, relatively low levels (∼20% of the levels measured in Caracas) of these aromatic hydrocarbons were observed.At the rural site during the dry season, higher concentrations of benzene (0.15 nmol/mol) were recorded, whereas those of toluene (0.08 nmol/mol) were lower during that time. The aromatic hydrocarbon ratios in the wet season (benzene: 0.08 nmol/mol; toluene: 0.09 nmol/mol) are consistent with an aged urban plume, whereas biomass burning emissions dominate during the dry season. From rural and urban [benzene]/[toluene] ratios a mean HO concentration of 2.6×10⁶ molecules/cm³ was estimated during the wet season. This value must be considered an overestimate because it does not account for background concentrations which are likely for benzene and toluene.At the remote “La Gran Sabana” region (Parupa) very low mixing ratios (0.031 and 0.015 nmol/mol for benzene and toluene) are showing the pristine region to be unaffected by local sources. From the [benzene]/[toluene] ratio we deduced, that “urban” air arriving from the coastline (350 km) is likely mixed with air containing some background of benzene and toluene.Urban emissions (automobiles) should be the major source of aromatic compounds, however, during the dry season biomass burning seems to make an important contribution.     

Concentrations of benzene and toluene in the atmosphere of the southwestern area at the Mexico City Metropolitan Zone

The Mexico City Metropolitan Zone (MCMZ) presents important emissions of hazardous air pollutants. It is well documented that the MCMZ suffers a critical air pollution problem due to high ozone and particulate matter concentrations. However, toxic air pollutants such as benzene and toluene have not been considered. Benzene has accumulated sufficient evidence as a human carcinogen, and the ratio benzene/toluene is an excellent indicator to evaluate control strategies efficiency.In order to evaluate the levels of these two air toxic pollutants in the MCMZ, ambient air samples were collected in canisters and analyzed with a gas chromatograph with a flame ionization detector, according to procedures described in the United States Environmental Protection Agency (USEPA) method TO-15. Quality assurance was performed collecting duplicate samples which were analyzed in replicate to quantify the precision of air-quality measurements.Three different sites located in the Southwestern area in the MCMZ were selected for the sampling: the University campus, a gas station, and a vertical condominium area, in the same neighborhood, which presents different activities. At these sites, grab air samples were collected during the morning hours (7–8 a.m.), while for the University area, 24 h integrated air samples were collected simultaneously, with grab samples.Benzene concentrations (24 h sampling) in the atmosphere around the University campus have similar present levels as in other cities of North America. Mean values in this site were about 1.7 ppb.A significant variation exists between the benzene and toluene concentrations in the studied sites, being the more critical values than those registered at the gas station (an average of 25.8 ppb and a maximum of 141 ppb of benzene). There is a fuel regulation for gasoline in Mexico, which allows a maximum of 1 percent of benzene. However, since more than 60 percent of vehicles do not have catalytic converters (models before 1991) it is expected that most of this benzene be emitted through exhaust pipe. Another strategy being implemented is the use of vapor recovery systems at the gas stations. Vehicles emission control technology must be matched with adequate fuel characteristics in the problem area where it will be implemented, to achieve maximum emission reductions.     

Modelling of indoor exposure to nitrogen dioxide in the UK

A dynamic multi-compartment computer model has been developed to describe the physical processes determining indoor pollutant concentrations as a function of outdoor concentrations, indoor emission rates and building characteristics. The model has been parameterised for typical UK homes and workplaces and linked to a time-activity model to calculate exposures for a representative homemaker, schoolchild and office worker, with respect to NO₂. The estimates of population exposures, for selected urban and rural sites, are expressed in terms of annual means and frequency of hours in which air quality standards are exceeded. The annual mean exposures are estimated to fall within the range of 5–21 ppb for homes with no source, and 21–27 ppb for homes with gas cooking, varying across sites and population groups. The contribution of outdoor exposure to annual mean NO₂ exposure varied from 5 to 24%, that of indoor penetration of outdoor air from 17 to 86% and that of gas cooking from 0 to 78%. The frequency of exposure to 1 h mean concentrations above 150 ppb was very low, except for people cooking with gas.     

Assessment of road users’ elemental carbon personal exposure levels,London, UK

Little is known about particulate elemental carbon (EC) personal exposure levels, a key component of diesel exhaust, specifically in transport microenvironments. A method utilizing the optical properties of EC particles has been applied to personal exposure measurement filter samples. In a series of field studies carried out in London, UK, during 1999–2000 over 400 fine particle (PM_2.5) personal exposure level measurements were taken for journeys in bicycle, bus, car and underground rail transport microenvironments, along three main fixed routes. The particulate EC contribution to the PM_2.5 personal exposure was assessed indirectly by means of an optical technique and with the development and use of a size fraction specific and site-specific calibration curve. In this first EC personal exposure study of transport users geometric mean exposure levels in the summer field campaign were 11.2 μg m⁻³ (GSD=2.7) for cyclists, 13.6 μg m⁻³ (GSD=1.9) for bus passengers and 21.6 μg m⁻³ (GSD=2.1) for car drivers; corresponding exposure levels in the winter were 16.4 μg m⁻³ (GSD=1.8), 18.6 μg m⁻³ (GSD=2.3) and 27.3 μg m⁻³ (GSD=2.0), respectively. EC/PM_2.5 ratios were approximately 0.5–0.6 for bicycle and bus modes and 0.7–0.8 for the car mode. EC/PM_2.5 ratios for different routes ranged from approximately 0.7 for Route 1 to 0.4 for Route 3. Cyclists had the lowest exposure to EC, and car occupants the highest exposure. A large difference in exposure levels between a central high traffic density route and the other less central routes was observed. Particulate EC was a very significant proportion of the total PM_2.5 personal exposure and EC personal exposure levels were considerably higher than reported fixed site monitor EC concentrations.     

Personal exposure of children and adults to airborne benzene in four French cities

Atmospheric concentrations of and personal exposure to benzene have been measured in four French metropolitan areas for 210 subjects over two seasons. Half of the volunteers were 6–13-year-old children. The adult subjects were non-smokers, not occupationally exposed and they live and work in the monitored areas. Measurements were performed using diffusive samplers followed by GC-FID analysis. The average values for ambient air concentrations (μg m⁻³) were: Rouen: 1.5; Île de France (Paris area): 1.6; Grenoble: 2.3 and Strasbourg: 2.6, showing that benzene concentrations in the ambient air of the four cities satisfy the requirements of the European Directive 2000/69EC of the European Parliament which stipulates a limit value of 5 μg m⁻³. However, the 48 h exposures measured were found to be between 2.7 and 3.5 times higher than ambient air concentrations. As a consequence, 60% of the subjects investigated, including children, were exposed to concentrations higher than the ambient air limit value. This work confirms that air monitoring data collected by fixed stations should be used with caution when assessing population exposure to benzene, especially given the influence of indoor sources and other polluted microenvironments where people spend part of their time.     

Benzene,toluene, ozone,NO2 and SO2 measurements in an urban street canyon in Thessaloniki,Greece

Benzene, toluene, sulphur dioxide, ozone and nitrogen dioxide were measured at a mean level of 13.5 m above ground in a narrow, four-lane street canyon (height 30 m, width 20 m) in Thessaloniki, Greece during the period January–July 1997 by means of a commercial differential optical absorption spectrometer (OPSIS DOAS). Primary pollutant levels were found to be 2.5–4.4 times higher during the cold part of the year than during the warm part of the year, the winter/summer ratio increasing with the reaction rate constant with OH for each of the measured species. Ozone, on the other hand, exhibited a winter/summer ratio of 0.36. NO₂ originates from both primary and secondary sources; its winter/summer concentration ratio of 1.4 lies, therefore, between those of primary pollutants and ozone. Pollution levels were influenced considerably by wind speed, while for the street canyon under study wind direction did not influence pollutant levels considerably. While primary pollution was found to decrease with increasing wind speed, ozone increased. Benzene mean levels during the study period were around 6 ppb and hence much higher than the EU annual limit value of 5 μg m⁻³ (1.44 ppb at STP). Toluene mean levels were around 14 ppb and hence also several times above the WHO recommendation of 2 ppb for 24 h. The apportionment of traffic emissions in four time zones used in most inventories in urban airshed models was tested using benzene and toluene measurements at low (<1 m s⁻¹) wind speeds. The agreement between model emissions and calculated emissions apportionment into the four time zones was good, except for Zone D (23:00–1:59), where model inventory emissions were somewhat too low.     

Indoor exposure from building materials: A field study

The present study has been conducted in the frame of BUMA (Prioritization of Building Materials Emissions as indoor pollution sources), a European funded project, aiming at assessing the exposure to emitted compounds in indoor air. Field campaigns in five (5) European cities (Milan, Copenhagen, Dublin, Athens and Nicosia) were carried out. These campaigns covered weekly winter and summer concentration measurements in two (2) public buildings and two (2) private houses in each city. BTEX, terpenes, and carbonyls were measured using passive sampling in two sites inside the building and one outside. VOC emission measurements on selected building material have also been performed using Field and Laboratory Emission Cell (FLEC). The results on indoor concentrations for compounds such as formaldehyde (1.2–62.6 μg m^?3), acetaldehyde (0.7–41.6 μg m^?3), toluene (0.9–163.5 μg m^?3), xylenes (0.2–177.5 μg m^?3) and acetone (2.8–308.8 μg m^?3) have shown diversity and relatively significant indoor sources depending on the building type, age etc. Indoor concentrations of these substances are varied depending on the building age and type. The percentage of approximately 40% of the indoor air quality levels originated from building materials.     

Spatial variation of aerosol number concentration in Helsinki city

Aerosol number concentration was measured continuously in Helsinki from 1 of November, 1996 till 1 May, 1997. In addition to that number concentrations were measured simultaneously for 14 days in several places in a downtown area and in a remote site close to the city. The measured data allows us to investigate spatial variation of urban aerosol number concentration. In general, the number concentration time series measured in different places show high correlation. In areas, where traffic follows similar pattern and provides dominant local isotropic aerosol source, correlation in our case is high (about 0.8). Correlation mainly depends on the traffic intensity. During the working days concentration averages of 10 min – 1 h are good representatives of concentration variation in relatively large area of the city. The place for the sampling point must be chosen carefully.     

Predicting residential indoor concentrations of nitrogen dioxide,fine particulate matter,and elemental carbon using questionnaire and geographic information system based data

Previous studies have identified associations between traffic-related air pollution and adverse health effects. Most have used measurements from a few central ambient monitors and/or some measure of traffic as indicators of exposure, disregarding spatial variability and factors influencing personal exposure-ambient concentration relationships. This study seeks to utilize publicly available data (i.e., central site monitors, geographic information system, and property assessment data) and questionnaire responses to predict residential indoor concentrations of traffic-related air pollutants for lower socioeconomic status (SES) urban households.As part of a prospective birth cohort study in urban Boston, we collected indoor and outdoor 3–4 day samples of nitrogen dioxide (NO₂) and fine particulate matter (PM_2.5) in 43 low SES residences across multiple seasons from 2003 to 2005. Elemental carbon (EC) concentrations were determined via reflectance analysis. Multiple traffic indicators were derived using Massachusetts Highway Department data and traffic counts collected outside sampling homes. Home characteristics and occupant behaviors were collected via a standardized questionnaire. Additional housing information was collected through property tax records, and ambient concentrations were collected from a centrally located ambient monitor.The contributions of ambient concentrations, local traffic and indoor sources to indoor concentrations were quantified with regression analyses. PM_2.5 was influenced less by local traffic but had significant indoor sources, while EC was associated with traffic and NO₂ with both traffic and indoor sources. Comparing models based on covariate selection using p-values or a Bayesian approach yielded similar results, with traffic density within a 50 m buffer of a home and distance from a truck route as important contributors to indoor levels of NO₂ and EC, respectively. The Bayesian approach also highlighted the uncertanity in the models. We conclude that by utilizing public databases and focused questionnaire data we can identify important predictors of indoor concentrations for multiple air pollutants in a high-risk population.     

Urban atmospheric pollution: personal exposure versus fixed monitoring station measurements

We initiated the PETER (pedestrian environmental traffic pollutant exposure research) project to investigate pedestrians' exposure to traffic related atmospheric pollutants, based on data obtained with the collaboration of selected categories of pedestrian urban workers. We investigated relations between roadside personal exposure levels of volatile aromatic hydrocarbons (including benzene) and particulate matter <10 microm (PM10) among traffic police (n = 126) and parking wardens (n = 50) working in downtown Bologna, Italy. Data were collected from workshifts throughout four 1-week periods in different seasons of 2000-2001. For benzene and PM10, comparisons were made with measurements by fixed monitoring stations, and influence of localized traffic intensity and meteorological parameters was examined. Roadside personal exposure to benzene correlated more strongly with other volatile aromatic hydrocarbons (toluene, xylenes and ethylbenzene) than with PM10. Benzene and PM10 personal exposure levels were higher than fixed monitoring station values (both p<0.0001). At multivariate analysis, benzene and PM10 data from fixed monitoring stations both correlated with meteorological variables, and were also influenced by localized traffic intensity. Plausibly because of the downtown canyon-like streets, weather conditions (during a period of drought) only marginally affected benzene personal exposure, and moderately affected PM10 personal exposure. These findings reinforce the concept that urban atmospheric pollution data from fixed air monitoring stations cannot automatically be taken as indications of roadside exposures.     

A mobile pollutant measurement laboratory—measuring gas phase and aerosol ambient concentrations with high spatial and temporal resolution

A mobile pollutant measurement laboratory was designed and built at the Paul Scherrer Institute (Switzerland) for the measurement of on-road ambient concentrations of a large set of trace gases and aerosol parameters with high time resolution (<15 s for most instruments), along with geographical and meteorological information. This approach allowed for pollutant level measurements both near traffic (e.g. in urban areas or on freeways/main roads) and at rural locations far away from traffic, within short periods of time and at different times of day and year. Such measurements were performed on a regular base during the project year of gas phase and aerosol measurements (YOGAM). This paper presents data measured in the Zürich (Switzerland) area on a late autumn day (6 November) in 2001. The local urban particle background easily reached 50 000 cm⁻³, with additional peak particle number concentrations of up to 400 000 cm⁻³. The regional background of the total particle number concentration was not found to significantly correlate with the distance to traffic and anthropogenic emissions of carbon monoxide and nitrogen oxides. On the other hand, this correlation was significant for the number concentration of particles in the size range 50–150 nm, indicating that the particle number concentration in this size range is a better traffic indicator than the total number concentration. Particle number size distribution measurements showed that daytime urban ambient air is dominated by high number concentrations of ultrafine particles (nanoparticles) with diameters <50 nm, which are immediately formed by traffic exhaust and thus belong to the primary emissions. However, significant variation of the nanoparticle mode was also observed in number size distributions measured in rural areas both at daytime and nighttime, suggesting that nanoparticles are not exclusively formed by primary traffic emissions. While urban daytime total number concentrations were increased by a factor of 10 compared to the nighttime background, corresponding factors for total surface area and total volume concentrations were 2 and 1.5, respectively.     

Application of a Lagrangian particle model to assess the impact of harbour,industrial and urban activities on air quality in the Taranto area,Italy

This paper evaluates the relative impact on air quality of harbour emissions, with respect to other emission sources located in the same area. The impact assessment study was conducted in the city of Taranto, Italy. This area was considered as representative of a typical Mediterranean harbour region, where shipping, industries and urban activities co-exist at a short distance, producing an ideal case to study the interaction among these different sources. Chemical and meteorological field campaigns were carried out to provide data to this study. An emission inventory has been developed taking into account industrial sources, traffic, domestic heating, fugitive and harbour emissions. A 3D Lagrangian particle dispersion model (SPRAY) has then been applied to the study area using reconstructed meteorological fields calculated by the diagnostic meteorological model MINERVE. 3D short term hourly concentrations have been computed for both all and specific sources. Industrial activities are found to be the main contributor to SO₂. Industry and traffic emissions are mainly responsible for NO_x simulated concentrations. CO concentrations are found to be mainly related to traffic emissions, while primary PM₁₀ simulated concentrations tend to be linked to industrial and fugitive emissions. Contributions of harbour activities to the seasonal average concentrations of SO₂ and NO_x are predicted to be up to 5 and 30 μg m⁻³, respectively to be compared to a overall peak values of 60 μg m⁻³ for SO₂ and 70 μg m⁻³ for NO_x. At selected urban monitoring stations, SO₂ and NO_x average source contributions are predicted to be both of about 9% from harbour activities, while 87% and 41% respectively of total concentrations are predicted to be of industrial origin.     

Exposure to cadmium in male urban and rural workers and effects on FSH,LH and testosterone

ObjectiveThis cross-sectional study was conducted to assess the relationship between exposure to cadmium and circulating reproductive hormone levels in urban and rural male workers.Materials and MethodsUrinary cadmium, blood cadmium, luteinizing hormone (LH), follicle stimulating hormone (FSH) and testosterone were obtained from 86 non-smoking traffic policemen and 86 subjects working as roadmen in a rural area. All subjects were monitored to evaluate airborne exposure to cadmium.ResultsThe mean value of exposure to cadmium was 1.3 ng m^?3 in traffic policemen, while the mean value was less than 0.5 ng m^?3 in roadmen. The mean concentrations of urinary cadmium (1.4 vs. 0.9 μg g^?1 creatinine; p = 0.001), blood cadmium (1.1 vs. 0.7 μg l^?1; p = 0.000), FSH (2.6 vs. 3.2 μlU ml^?1; p = 0.02) and LH (2.6 vs. 3.1 μlU ml^?1; p = 0.03) were significantly different between traffic policemen and roadmen. No differences were found in the mean values of testosterone between the two groups. Multiple linear regression models showed associations between (a) urinary cadmium, airborne cadmium, working life, job category and consumption of water from water supply (b) blood cadmium, airborne cadmium and job category (c) the values of FSH and age, working life, job category, urinary cadmium and blood cadmium (d) the values of LH and both the age and working life.ConclusionThe above results must be confirmed by further studies, but they indicate the influence of exposure to the cadmium present in urban air on the circulating FSH, even at low doses.     

In situ measurements of volatile aromatic hydrocarbon biodegradation rates in groundwater

Benzene and alkylbenzene biodegradation rates and patterns were measured using an in situ microcosm in a crude-oil contaminated aquifer near Bemidji, Minnesota. Benzene-D6, toluene, ethylbenzene, o-, m- and p-xylenes and four pairs of C₃- and C₄-benzenes were added to an in situ microcosm and studied over a 3-year period. The microcosm allowed for a mass-balance approach and quantification of hydrocarbon biodegradation rates within a well-defined iron-reducing zone of the anoxic plume. Among the BTEX compounds, the apparent order of persistence is ethylbenzene > benzene > m,p-xylenes > o-xylene ≥ toluene. Threshold concentrations were observed for several compounds in the in situ microcosm, below which degradation was not observed, even after hundreds of days. In addition, long lag times were observed before the onset of degradation of benzene or ethylbenzene. The isomer-specific degradation patterns were compared to observations from a multi-year study conducted using data collected from monitoring wells along a flowpath in the contaminant plume. The data were fit with both first-order and Michaelis-Menten models. First-order kinetics provided a good fit for hydrocarbons with starting concentrations below 1 mg/L and Michaelis-Menten kinetics were a better fit when starting concentrations were above 1 mg/L, as was the case for benzene. The biodegradation rate data from this study were also compared to rates from other investigations reported in the literature.