Influence of Baltimore's Urban Atmosphere on Organic Contaminants over the Northern Chesapeake Bay

ABSTRACT

Air and precipitation samples were collected along an urban to over-water to rural transect across the northern Chesapeake Bay as a preliminary investigation into the spatial extent of elevated atmospheric concentrations of urban-derived persistent organic pollutants. Air samples were collected daily from June 3–9, 1996, along the transect as part of the Atmospheric Exchange over Lakes and Oceans project. Total (gas + particle bound) atmospheric polycy-clic aromatic hydrocarbon concentrations [∑-PAH] ranged from 0.4 to 114 ng/m³, and gas phase polychlorinated bi-phenyl concentrations [∑-PCB] ranged from 0.02 to 3.4 ng/m³. Strong concentration gradients were found for both PAHs and PCBs, with the highest concentrations in the city and the lowest at the downwind rural site. Gas and particle bound PAHs varied independently in the city, possibly due to strong but geographically separated emission sources. A precipitation event collected during westerly winds contained fourfold higher ∑-PAH and twelvefold higher ∑-PCB concentrations at the over-water site than at the rural background location, further indicating that the urban plume extends from Baltimore, MD, over the northern Chesapeake Bay over a spatial scale of approximately 30 km.     

Emission and Fate Assessment of Methyl Tertiary Butyl Ether in the Boston Area Airshed Using a Simple Multimedia Box Model: Comparison with Urban Air Measurements

Abstract

Expected urban air concentrations of the gasoline additive methyl tertiary butyl ether (MTBE) were calculated using volatile emissions estimates and screening transport models, and these predictions were compared with Boston, MA, area urban air measurements. The total volatile flux of MTBE into the Boston primary metropolitan statistical area (PMSA) airshed was calculated based on estimated automobile nontailpipe emissions and the Universal Quasi-Chemical Functional-Group Activity Coefficient computed abundance of MTBE in gasoline vapor. The fate of MTBE in the Boston PMSA was assessed using both the European Union System for the Evaluation of Substances, which is a steady-state multimedia box model, and a simple airshed box model. Both models were parameterized based on the meteorological conditions observed during air sampling in the Boston area. Measured average urban air concentrations of 0.1 and 1 [H9262]g/m³ MTBE during February and September of 2000, respectively, were comparable to corresponding model predictions of 0.3 and 1 μg/m³ and could be essentially explained from estimated temperature-dependent volatile emissions rates, observed average wind speed (the airshed flushing rate), and reaction with ambient tropospheric hydroxyl radical (.OH), within model uncertainty. These findings support the proposition that one can estimate gasoline component source fluxes and use simple multimedia models to screen the potential impact of future proposed gasoline additives on urban airsheds.     

Seasonal variation of heavy metals in ambient air and precipitation at a single site in Washington, DC

Atmospheric samples of precipitation and ambient air were collected at a single site in Washington, DC, for 7 months (for ambient air samples) and 1 year (for wet deposition samples) and analyzed for arsenic, cadmium, chromium and lead. The ranges of heavy metal concentrations for 6-day wet deposition samples collected over the 1-year period were 0.20-1.3 microg/l, 0.060-5.1 microg/l, 0.062-4.6 microg/l and 0.11-3.2 microg/l for arsenic, cadmium, chromium and lead, respectively, with a precision better than 5% for more than 95% of the measurements. The ranges of heavy metal concentrations for the 6-day ambient air samples were 0.800-15.7 ng/m(3), 1.50-30.0 ng/m(3), 16.8-112 ng/m(3), and 2.90-137 ng/m(3) for arsenic, cadmium, chromium and lead, respectively, with a precision better than 10%. The spread in the heavy metal concentration over the observation period suggests a high seasonal variability for heavy metal content in both ambient air and wet deposition samples.     

Sources, distribution and behaviour of methyl tert-butyl ether (MTBE) in the Tamar Estuary, UK

Negligible information is currently available concerning levels of the fuel additive methyl tert-butyl ether (MTBE) in European estuaries or coastal environments. MTBE was measured at selected potentially contaminated harbours and marinas, and throughout an axial transect of the Tamar Estuary, UK. Headspace solid-phase microextraction was used in combination with GC-MS for its determination. MTBE was detected in water samples from all stations at concentrations ranging from a few ng/l to a maximum of 194 ng/l (in a semi-enclosed harbour). Elevated levels were generally associated with motor vehicle and boating activities. The Tamar road and rail bridges provided a major input to the lower estuary, downstream of which conservative mixing appeared depressed, probably through volatilisation and possibly through salting-out. The selected analytical system (using a Carboxen/PDMS fiber) proved both rapid and highly sensitive (with a detection limit of 6 ng/l). During method development, salinity was shown to have a major influence in controlling the extraction efficiency and it was found necessary to adjust salinity in all samples (to 75% saturation) prior to extraction. From these tests, we (for the first time) estimated the Setschenow ("salting-out") constant of MTBE to be 0.11 l/mol.     

Pesticides in precipitation in the Gdańsk region (Poland)

Selected organonitrogen, organophosphorus and organochlorine pesticides have been determined in precipitation samples collected at 10 sites in the Gdańsk region (northern Poland) over a period of one year (1998). Compounds which were detected most often included simazine (0.11-5.80 ng/l), fenitrothion (0.1-2.10 ng/l), chlorfenvinfos (0.1-1.30 ng/l), gamma-HCH (0.012-5.06 ng/l), heptachlor epoxide (0.05-3.28 ng/l) and aldrin (0.02-3.28 ng/l). The pesticide concentrations in precipitation samples revealed seasonal fluctuations, with higher concentrations observed during the application periods (June and July). The concentrations observed were also affected by the inflow of polluted air masses from the southwest. The total pesticide concentration in the precipitation samples was strongly related to the abundance of green areas in the vicinity of the sampling sites. A weak correlation was also found between the total concentration of organonitrogen and organophosphorus pesticides, and the total concentration of organochlorine pesticides in the samples collected.     

Urban and rural ultrafine (PM0.1) particles in the Helsinki area

In June 1996–June 1997 Berner low-pressure impactors were used at an urban and at a rural site in the Helsinki area for sampling ultrafine particles (UFP, PM_0.1). Ten sample pairs, each pair measured simultaneously, were collected in the size range of 0.03–15 μm of particle aerodynamic diameter. More than 40 chemical components were measured. Surprisingly, the average UFP mass concentration was higher at the rural site (520 ng/m³) than at the urban site (490 ng/m³). The average chemical composition of UFP was similar at the two sites. The most abundant of the measured components were sulphate (32 and 40 ng/m³ for the urban and rural sites, respectively), ammonium (22 and 25 ng/m³), nitrate (4 and 11 ng/m³) and the Ca²⁺ ion (5 and 7 ng/m³). The most important metals at both sites were Ca, Na, Fe, K and Zn with concentrations between 0.7 and 5 ng/m³. Of the heavy metals, Ni, V, Cu, and Pb were important with average ultrafine concentrations between about 0.1 and 0.2 ng/m³. Also the organic anions oxalate (urban 2.1 ng/m³ and rural 1.9 ng/m³) and methanesulphonate (1.3 and 1.7 ng/m³) contributed similarly at both sites. The measured species accounted for only about 15–20% of the total ultrafine mass. The fraction that was not measured includes mainly carbonaceous material and water. It was estimated that the amount of water was about 10% (50 ng/m³) and that of carbonaceous material about 70% (350 ng/m³) at both sites. Aitken modes were observed for most components with the average mass mean mode diameters being between about 0.06 and 0.12 μm. The average concentrations in the Aitken mode differed clearly from those in the UFP for several components.The average contribution of ultrafine mass to the fine particle mass (PM_2.5) was about 7% at the urban site and 8.5% at the rural site. At both sites the contribution of ultrafine to fine was especially high for Se, Ag, B, and Ni (10–20%) and at the rural site also for Co (20%), Ca²⁺ (16%) and Mo (11%). Enrichment in the ultrafine particles suggests that local sources may exist for these elements.Aitken modes turned out to be useful indicators of local sources for several components. The Aitken modes of Ba, Ca, Mg and Sr were similar in several samples, suggesting a common local combustion source for these elements, possibly traffic exhaust. Co, Fe, Mo and Ni formed another group of elements often having similar Aitken modes, the likely source being combustion of heavy fuel oil.     

Determination of MTBE in a recreational harbor using solid-phase microextraction

Discovery of the fuel additive methyl tert-butyl ether (MTBE) in groundwater, surface water, and stormwater has prompted studies of its sources, transport and fate. More limited data, however, is available on the extent of contamination of coastal waters, as well as the persistence of MTBE in the marine environment. We apply here the combination of solid phase microextraction and gas chromatography-mass spectrometry to the detection of sub-to-low microgram/l concentrations of MTBE in seawater samples. Analysis of samples collected at the Marina del Rey harbor, a shallow recreational harbor near Los Angeles, CA, show MTBE contamination in the low microgram/l level. MTBE measurements were made at different depths, from the surface to the bottom, at five sites within the harbor during months showing no measurable precipitation. The highest concentration of MTBE (18 microgram/l) was found at the boat launching ramp, and the lowest (0.2 microgram/l) near the harbor entrance, approximately 2.3 km from the ramp. The levels of MTBE measured, as well as their variation over the study period, are fully consistent with recreational boating as the primary source of contamination. No evidence for MTBE contamination from the adjacent stormwater control channel was noted.     

Seasonal and spatial variation of solvent extractable organic compounds in fine suspended particulate matter in Hong Kong

The results of a 12-month study of more than 100 solvent extractable organic compounds (SEOC) in particulate matter (PM) less than or equal to 2.5 microm (PM2.5) collected at three air monitoring stations located at roadside, urban, and rural sites in Hong Kong are reported. The total yield of SEOC that accounts for approximately 8-18% of organic carbon (OC) determined by a thermal optical transmittance method was 125-2060 ng/m3, which included 14.6-128 ng/m3 resolved aliphatic hydrocarbons, 39.4-1380 ng/m3 unresolved complex mixtures, 0.6-17.2 ng/m3 polycyclic aromatic hydrocarbons, 41.6-520 ng/m3 fatty acids, and < 0.1-12.1 ng/m3 alkanols. Distinct seasonal variations (summer/winter differences) were observed with higher concentrations of the total and each class of SEOC in the winter and lower concentrations in the summer. Spatial variations are also obvious, with the roadside samples having the highest concentrations of SEOC and the rural samples having the lowest concentrations in all seasons. Characteristic ratios of petroleum hydrocarbons, such as carbon preference index, unresolved to resolved components, and carbon number with maximum concentration, suggest that PM2.5 carbon in Hong Kong originates from both biogenic and anthropogenic sources. The proportion of SEOC in PM2.5 from anthropogenic sources is estimated.     

Screening of human health risk to infants associated with the polychlorinated biphenyl (PCB) levels in human milk from Punjab Province,Pakistan

This study assessed the polychlorinated biphenyl (PCB) levels in human milk and its associated health risk to infants from rural and urban settings of five districts of Punjab Province, Pakistan. The ∑₃₄PCB concentrations ranged from 30.9 to 68.3 ng g^?1 on lipid weight (l.w.) basis. The ∑₈DL-PCB concentrations were ranged from 0.29 to 1.35 ng g^?1 l.w., (mean 6.2 ± 8.7 ng g^?1 l.w.), with toxicity equivalent to polychlorinated dibenzodioxins (PCDDs) ranging from 8.58 × 10^?6 to 0.05 ng TEQ g^?1 l.w. The spatial trend of PCB levels in human milk revealed higher bioaccumulative levels for urban mothers as compared with rural counterparts. The estimated daily intake (EDI) values of DL-PCBs to infants through trans-mammary transfer were considerably higher than tolerable daily intake limits established by WHO (i.e., 1–4 pg TEQ kg^?1 bw) and other globally recognized organizations. Similarly, the hazard quotient values for TEQ ∑₈DL-PCBs (range 1.21 to 79.87) were far above the benchmark value of 1 at all the sampling sites, indicating the high levels of adverse health risks to infants in the region through breast milk consumption. The ∑₃₄PCB levels were found to be negatively correlated with mother’ age (r = ?0.31; p = 0.02), parity (r = ? 0.85; p = 0.001), and infant’ birth weight (r = ? 0.73; p = 0.01). The present study suggests undertaking comprehensive public health risk assessment studies and firm regulatory measures to safeguard human health risks.

     

Methyl tert-butyl ether (MTBE) in finished drinking water in Germany

In the present study 83 finished drinking water samples from 50 cities in Germany were analyzed for methyl tert-butyl ether (MTBE) content with a detection limit of 10 ng/L. The detection frequency was 46% and the concentrations ranged between 17 and 712 ng/L. Highest concentrations were found in the community water systems (CWSs) of Leuna and Spergau in Saxony-Anhalt. These CWSs are supplied with water possibly affected by MTBE contaminated groundwater. MTBE was detected at concentrations lower than 100 ng/L in drinking water supplied by CWSs using bank filtered water from Rhine and Main Rivers. The results from Leuna and Spergau show that large groundwater contaminations in the vicinity of CWSs pose the highest risk for MTBE contamination in drinking water. CWSs using bank filtered water from Rhine and Main Rivers are susceptible to low MTBE contaminations in finished drinking water. All measured MTBE concentrations were below proposed limit values for drinking water.     

Time trends in the concentrations of lead in wet precipitation from rural and urban sites in Austria

Trend and time series analysis of concentrations of lead in wet precipitation at different rural and urban sampling sites in Austria, collected during intervals of 6-12 years (between 1984 and 1995) is performed. A substantial decrease of the lead concentrations for all sites in consideration is observed similar to observations in Germany, Sweden and North sea and western Atlantic regions. Reductions in rural sites between 60 and 80% in 10 years and around 90% in 10 years in urban areas are found. This trend correlates with the reduction of lead emissions from combustion of gasoline. The seasonal deconvolution model of the data set reveals a typical seasonality with lead concentration peaks in summer and spring for the rural sites and winter peaks for urban sites. The average annual lead concentration in the rural region for 1995 was 1.25 micrograms/l, in the urban region 2.25 micrograms/l.     

MTBE in California Drinking Water: An Analysis of Patterns and Trends

Over the past decade, there has been much publicity surrounding the impact of Methyl tert -butyl ether (MTBE) on drinking water supplies in the United States. In California, the presence of MTBE in groundwater and drinking water has led to a ban on the future use of MTBE in gasoline. Other states, such as those in the northeast, are also seeking ways to reduce or eliminate the use of MTBE due to perceived threats to the environment and public health. Despite claims about the incidence of MTBE in drinking water, no comprehensive characterization has been conducted on the available drinking water monitoring data. This paper provides a detailed analysis of the MTBE drinking water data compiled by the California Department of Health Services (CDHS) from 1995 to 2000. We find that MTBE was detected in about 1.3% of all drinking water samples, 2.5% of drinking water sources, and 3.7% of drinking water systems in California over this 6-year period. Our analysis reveals that many drinking water sources are not sampled routinely for MTBE, and in those sources that appear to be affected by MTBE, the compound is not consistently detected. The majority of MTBE detections are also concentrated in several geographic areas, which contain about 9–21% of the total California population. Average detected MTBE concentrations have decreased significantly since 1995 and 1996, ranging from 5 to 15 ppb over the last 3 years depending on the outcome of interest. Of the samples in which MTBE was present above the analytical detection limit, the concentrations in approximately 73% of drinking water samples and 86% of drinking water sources and systems were below the State's primary health-based standard of 13 ppb. Our findings suggest that, although some drinking water supplies in California have been affected by MTBE, the majority of drinking water sources and systems either have not been affected at all or contain MTBE at concentrations below levels that are likely to be of health concern.     

Indoor air quality differences between urban and rural preschools in Korea

Background, aims, and scope

Preschool indoor air quality (IAQ) is believed to be different from elementary school or higher school IAQ and preschool is the first place for social activity. Younger children are more susceptible than higher-grade children and spend more time indoors. The purpose of this study was to compare the indoor air quality by investigating the concentrations of airborne particulates and gaseous materials at preschools in urban and rural locations in Korea.

Methods

We investigated the concentrations of airborne particulates and gaseous materials in 71 classrooms at 17 Korean preschools. For comparison, outdoor air was sampled simultaneously with indoor air samples. Airborne concentrations of total suspended particulates, respirable particulates, lead, asbestos, total volatile organic compounds and components, formaldehyde, and CO₂ were measured with National Institute for Occupational Safety and Health and/or Environmental Protection Agency analytical methods.

Results

The concentration profiles of the investigated pollutants in indoor and urban settings were higher than those in outdoor and rural areas, respectively. The ratios of indoor/outdoor concentrations (I/O) of particulates and gaseous pollutants were characterized in urban and rural preschools. Total dust concentration was highest in urban indoor settings followed by urban outdoor, rural indoor, and rural outdoor locations with an I/O ratio of 1.37 in urban and 1.35 in rural areas. Although I/O ratios of lead were close to 1, lead concentrations were much higher in urban than in rural areas. The I/O ratio of total VOCs was 2.29 in urban and 2.52 in rural areas, with the highest level in urban indoor settings. The I/O ratio of formaldehyde concentrations was higher in rural than in urban areas because the outdoor rural level was much lower than the urban concentration. Since an I/O ratio higher than 1 implies the presence of indoor sources, we concluded that there are many indoor sources in preschools.

Conclusions

We confirmed that pollutants in indoor and urban settings were higher than those in outdoor and rural areas, respectively. Preschool children are expected to spend more time inside preschool facilities and therefore to be more exposed to pollutants. As far as we know, preschool IAQ is different from elementary school or higher school IAQ. Also, they are more vulnerable than higher-grade children. We found that the indoor and urban concentration profiles of the studied pollutants in preschools were higher than those in outdoor and rural areas. We believe that our findings may be useful for understanding the potential health effects of exposure and intervention studies in preschools.     

Occurrence and fate of polycyclic musks in wastewater treatment plants in Kentucky and Georgia, USA

Wastewater treatment plants (WWTPs) are a potential of source of polycyclic musks in the aquatic environment. In this study, contamination profiles and mass flow of polycyclic musks, 1,3,4,6,7,8-hexahydro-4,6,6,7,8,8-hexamethylcyclopenta[gamma]-2-benzopyran (HHCB), 7-acetyl-1,1,3,4,4,6-hexamethyl-1,2,3,4-tetrahydronaphthalene (AHTN), and HHCB-lactone (oxidation product of HHCB), in two WWTPs, one located in Kentucky (Plant A, rural area) and the other in Georgia (Plant B, urban), USA, were determined. HHCB, AHTN and HHCB-lactone were detected in the influent, effluent, and sludge samples analyzed. The concentrations in wastewater samples varied widely, from 10 to 7,030 ng/l, 13 to 5,400 ng/l, and 66 to 790 ng/l, for HHCB, AHTN, and HHCB-lactone, respectively. Sludge samples contained HHCB at <0.02-36 microg/g dry weight, AHTN at <0.02-7.2 microg/g dry weight, and HHCB-lactone at <0.05-17 microg/g dry weight. Based on the daily flow rates and mean concentrations of polycyclic musks, the estimated discharge of total polycyclic musks to the rivers was 21 g/day from Plant A and 31 g/day from Plant B. Mass balance analysis suggested that only 30% of HHCB and AHTN entering the plants was accounted for in the effluent and the sludge. Removal efficiencies of HHCB and AHTN in the two WWTPs ranged from 72% to 98%. In contrast, HHCB-lactone concentrations increased following the treatment. Concentrations of polycyclic musks in sludge were on the order of several parts per million. Incineration of sludge at one plant reduced the concentration of polycyclic musks.     

MTBE in California Drinking Water: An Analysis of Patterns and Trends

Over the past decade, there has been much publicity surrounding the impact of Methyl tert -butyl ether (MTBE) on drinking water supplies in the United States. In California, the presence of MTBE in groundwater and drinking water has led to a ban on the future use of MTBE in gasoline. Other states, such as those in the northeast, are also seeking ways to reduce or eliminate the use of MTBE due to perceived threats to the environment and public health. Despite claims about the incidence of MTBE in drinking water, no comprehensive characterization has been conducted on the available drinking water monitoring data. This paper provides a detailed analysis of the MTBE drinking water data compiled by the California Department of Health Services (CDHS) from 1995 to 2000. We find that MTBE was detected in about 1.3% of all drinking water samples, 2.5% of drinking water sources, and 3.7% of drinking water systems in California over this 6-year period. Our analysis reveals that many drinking water sources are not sampled routinely for MTBE, and in those sources that appear to be affected by MTBE, the compound is not consistently detected. The majority of MTBE detections are also concentrated in several geographic areas, which contain about 9-21% of the total California population. Average detected MTBE concentrations have decreased significantly since 1995 and 1996, ranging from 5 to 15 ppb over the last 3 years depending on the outcome of interest. Of the samples in which MTBE was present above the analytical detection limit, the concentrations in approximately 73% of drinking water samples and 86% of drinking water sources and systems were below the State's primary health-based standard of 13 ppb. Our findings suggest that, although some drinking water supplies in California have been affected by MTBE, the majority of drinking water sources and systems either have not been affected at all or contain MTBE at concentrations below levels that are likely to be of health concern.     

Organochlorine pesticides and polychlorinated biphenyls in air and soil across Azerbaijan

Concentrations of selected organochlorine pesticides (OCPs) and polychlorinated biphenyls (PCBs) are reported in air and surface soil in an extensive spatial survey across Azerbaijan, a country bordering the Caspian Sea with a history of OCP production and extensive use. Polyurethane foam disc passive air samplers (PAS) were deployed during October-November 2008 with soil samples collected in July 2009. Levels of Σ(7)PCB in ambient air were generally low (mean of 0.046 ng m(-3), n?=?13) and comparable to concentrations reported in countries within Eastern Europe and similar to or lower than concentrations reported in urban air in the UK and other western countries. Surprisingly, PCB concentrations in rural/background soil fell below the method detection limits at most sites, although concentrations were 0.209 and 0.071 ng Σ(7)PCB g(-1) dry weight (dw) for two urban sites, again comparable to PCB levels measured at background sites in Europe. Levels of α-HCH, β-HCH, γ-HCH and p,p'-DDT/E were elevated in ambient air across Azerbaijan in comparison to PAS-derived concentrations reported elsewhere, with concentrations of α-HCH in air ranging from 0.085 to 2.699 ng m(-3) and p,p'-DDE, 0.037-2.290 ng m(-3). High concentrations of OCPs occurred at several of the urban sites and at sites in proximity to old pesticide storage facilities with concentrations in soil >0.1 μg g(-1) dw for p,p'-DDE and p,p'-DDT at several sites. The ratio of p,p'-DDT/p,p'-DDE was close to unity in the soil at these sites, but elsewhere, the ratio was <1, indicating a weathered DDT pattern, which was also reflected in the air at all sites. A fugacity approach revealed the strong likelihood of net soil-to-air transfer at the majority of sites for all OCPs. The calculated annual fluxes or loading to the atmosphere from a rural/agricultural area (representing land as vineyards and cotton cultivation) were estimated to be on the order of ≈10-100 kg year(-1) for the HCH isomers (including the β -isomer) and p,p'-DDE. The high levels of OCPs in soils, particularly in the vicinity of obsolete-pesticide storage facilities and at select urban sites are of concern and warrant regular monitoring activities and the development of containment or mitigation strategies.     

Concentrations of two organic contaminants in precipitation, soils and plants in the Essex region of Southern Ontario

Recent research has indicated that the atmosphere is an important pathway by which pollutants enter terrestrial and aquatic ecosystems. We report here concentrations of PCBs and octachlorostyrene (OCS) in precipitation, soils and plants in Essex County, Ontario. The average PCB concentration in urban precipitation (23 ng litre(-1)) was lower than that previously reported for urban areas in the Great Lakes basin. Differences between sites and with varying wind directions were not significant. OCS concentrations in precipitation averaged 1.6 ng litre(-1). Concentrations of PCBs in soils were 2-3 orders of magnitude greater than in precipitation. Concentrations of these pollutants in city soils and plant roots were consistently higher than those from suburban and rural sites. Ratios of urban to suburban concentrations in soils and precipitation were approximately 5:1 for PCBs. However, concentrations of OCS were similar in urban and suburban samples of precipitation, soils and plant tissues. These comparisons suggest an urban source for PCBs, but not OCS. Concentrations of all contaminants in plant leaves, unlike those in precipitation, roots and soils, were relatively similar in urban and suburban areas. That similarity suggests that direct foliar uptake is not an important pathway for pollutant uptake in plants.     

Emission and fate assessment of methyl tertiary butyl ether in the Boston area airshed using a simple multimedia box model: comparison with urban air measurements

Expected urban air concentrations of the gasoline additive methyl tertiary butyl ether (MTBE) were calculated using volatile emissions estimates and screening transport models, and these predictions were compared with Boston, MA, area urban air measurements. The total volatile flux of MTBE into the Boston primary metropolitan statistical area (PMSA) airshed was calculated based on estimated automobile nontailpipe emissions and the Universal Quasi-Chemical Functional-Group Activity Coefficient computed abundance of MTBE in gasoline vapor. The fate of MTBE in the Boston PMSA was assessed using both the European Union System for the Evaluation of Substances, which is a steady-state multimedia box model, and a simple airshed box model. Both models were parameterized based on the meteorological conditions observed during air sampling in the Boston area. Measured average urban air concentrations of 0.1 and 1 microg/m3 MTBE during February and September of 2000, respectively, were comparable to corresponding model predictions of 0.3 and 1 microg/m3 and could be essentially explained from estimated temperature-dependent volatile emissions rates, observed average wind speed (the airshed flushing rate), and reaction with ambient tropospheric hydroxyl radical (*OH), within model uncertainty. These findings support the proposition that one can estimate gasoline component source fluxes and use simple multimedia models to screen the potential impact of future proposed gasoline additives on urban airsheds.     

Atmospheric mercury levels in the Slovak Republic.

Total mercury concentrations (as a sum of vapor and particulate mercury) were measured in 24-h samples of ambient air in 20 different localities of the Slovak Republic eight times during the period 1996-1997. Vapor mercury was analyzed on site by atomic fluorescence with amalgamation technique. Particulate mercury was determined by vapor hydride atomic absorption spectrometry after wet digestion of filters with particulate air samples. The results showed that 34% of the 160 individual total mercury concentrations exceeded 5 ng/m3--the ambient air quality guideline value recommended by the WHO. The range of total mercury concentrations in the ambient air of Slovakia was: 1.13-3.98 ng/m3 (geom. mean 2.63) in the background area; 2.25-5.27 ng/m3 (geom. mean 3.64) in the agricultural areas; 1.73-20.53 ng/m3 (geom. mean 4.57) in the urban areas; and 1.53-39.85 ng/m3 (geom. mean 5.28) in the industrial areas. The highest mercury levels occurred in areas with metallurgical industry and coal combustion. The predominant form of mercury present in air was vapor mercury. The particulate fraction of mercury in ambient air (as a percentage of total mercury) varied widely from 0.4% to 42.1% (geom. mean = 4.4%). This fraction was lower in agricultural areas (2.3%) than in urban areas (5.3%). Although the atmospheric vapor mercury concentrations were slightly higher in summer than in winter, a direct correlation of vapor mercury concentrations and ambient air temperature was not found. Furthermore, the particulate mercury concentrations did not correlate with total particulate levels.     

Airborne polycyclic aromatic hydrocarbons in a medium-sized city affected by preharvest sugarcane burning and inhalation risk for human health

Polycyclic aromatic hydrocarbons (PAHs) in air were measured in a municipality where sugarcane plantations are extensive, at three sites, one in the city center and two in rural localities. Twenty-four-hour sampling was done using PS1 PUF samplers from Andersen Instruments Inc., at least 1 day per month per site, from June 2009 to October 2009. The chemical analyses were performed by gas chromatography–mass spectrometry (GC/MS) for the 16 most toxic PAHs. The incremental lifetime cancer risk (ILTR) by inhalation was determined by the Monte Carlo method for the urban population using Crystal Ball software. The total concentration of the 16 PAHs at all sites varied from 6.2 to 65.7 ng m^?3, with an average of 25.9 ± 18.2 ng m^?3. The average concentrations per site were 14.1 ± 13.0 ng m^?3 at rural site B, 20.7 ± 11.5 ng m^?3 at rural site A, and 36.1 ± 22.7 ng m^?3 at the central site. The cancer risk for infants, children, and adults was approximately 14%, 25%, and 61% of the total IRLT, respectively. The mean (95% upper probability limit [95% UPL]) values were 1.2 × 10^?7 (2.2 × 10^?7) for infants, 2.2 × 10^?7 (4.1 × 10^?7) for children, and 8.9 × 10^?7 (1.1 × 10^?6) for adults. Although the three most abundant PAHs found were phenanthrene, fluoranthene, and pyrene, the three most important contributions to the incremental risk of cancer came from benzo[a]pyrene, benzo[b]fluoranthene, and naphthalene. Compared with the risks in big cities such as São Paulo, this would be low, but not negligible. Analysis of ratios of PAHs according to the literature showed that vehicle exhaust and biomass burning, including sugarcane burning, seem to be the most important contributors to PAH concentrations in the central area of Araraquara City.

Implications:The growth of biofuel use worldwide, especially ethanol, together with preharvesting burning practice, is cause of concern with regard to possible health effects, due to increased air pollution levels in cities in regions where sugarcane plantation and processing are intensive. This paper shows that the risk of cancer from PAH inhalation in an urban area surrounded by sugarcane agriculture was of the same order of magnitude as the tolerable risk value of 10^?6. As other classical and hazardous pollutants are also present, care should be taken to keep pollution as low as possible to protect human health.