Fine Particle (PM25) Measurement Methodology,Quality Assurance Procedures,and Pilot Results of the EXPOLIS Study

ABSTRACT

EXPOLIS is a European multicenter (Athens, Basel, Grenoble, Helsinki, Milan, and Prague) air pollution exposure study. It is the first international, population-based, large-scale study, where personal exposures to PM_{2 5} aerosol particles (together with volatile organic compounds and carbon monoxide) are being monitored. EXPOLIS is performed in six different centers across Europe, the sampled aerosol concentrations vary greatly, and the mi-croenvironmental samples are not collected with the same equipment as the personal samples. Therefore careful equipment selection, methods development and testing, and thorough quality assurance and quality control (QA & QC) procedures are essential for producing reliable and comparable PM_2.5 data. This paper introduces the equipment, the laboratory test results, the pilot results, the standard operating procedures, and the QA & QC procedures of EXPOLIS. Test results show good comparability and repeatability between personal and microenvironmen-tal monitors for PM2.5 at different concentration levels measured across Europe in EXPOLIS centers.     

Comparison of micrometeorological and two-film estimates of air–water gas exchange for alpha-hexachlorocyclohexane in the Canadian archipelago

The air-sea gas exchange of alpha-hexachlorocyclohexane (α-HCH) in the Canadian Arctic was estimated using a micrometeorological approach and the commonly used Whitman two-film model. Concurrent shipboard measurements of α-HCH in air at two heights (1 and 15 m) and in surface seawater were conducted during the Circumpolar Flaw Lead study in 2008. Sampling was carried out during eight events in the early summer time when open water was encountered. The micrometeorological technique employed the vertical gradient in air concentration and the wind speed to estimate the flux; results were corrected for atmospheric stability using the Monin-Obukhov stability parameter. The Whitman two-film model used the concentrations of α-HCH in surface seawater, in bulk air at 1 and 15 m above the surface, and the Henry's law constant adjusted for temperature and salinity to derive the flux. Both approaches showed that the overall net flux of α-HCH was from water to air. Mean fluxes calculated using the micrometeorological technique ranged from -3.5 to 18 ng m(-2) day(-1) (mean 7.4), compared to 3.5 to 14 ng m(-2) day(-1) (mean 7.5) using the Whitman two-film model. Flux estimates for individual events agreed in direction and within a factor of two in magnitude for six of eight events. For two events, fluxes estimated by micrometeorology were zero or negative, while fluxes estimated with the two-film model were positive, and the reasons for these discrepancies are unclear. Improvements are needed to shorten air sampling times to ensure that stationarity of meteorological conditions is not compromised over the measurement periods. The micrometeorological technique could be particularly useful to estimate fluxes of organic chemicals over water in situations where no water samples are available.     

Residential indoor,outdoor, and workplace concentrations of carbonyl compounds: relationships with personal exposure concentrations and correlation with sources

Personal 48-hr exposures of 15 randomly selected participants as well as microenvironment concentrations in each participant's residence and workplace were measured for 16 carbonyl compounds during summer-fall 1997 as a part of the Air Pollution Exposure Distributions within Adult Urban Populations in Europe (EXPOLIS) study in Helsinki, Finland. When formaldehyde and acetaldehyde were excluded, geometric mean ambient air concentrations outside each participant's residence were less than 1 ppb for all target compounds. Geometric mean residential indoor concentrations of carbonyls were systematically higher than geometric mean personal exposures and indoor workplace concentrations. Additionally, residential indoor/outdoor ratios indicated substantial indoor sources for most target compounds. Carbonyls in residential indoor air correlated significantly, suggesting similar mechanisms of entry into indoor environments. Overall, this study demonstrated the important role of non-traffic-related emissions in the personal exposures of participants in Helsinki and that comprehensive apportionment of population risk to air toxics should include exposure concentrations derived from product emissions and chemical formation in indoor air.     

Personal exposure levels and microenvironmental concentrations of formaldehyde and acetaldehyde in the Helsinki metropolitan area, Finland

Personal 48-hr exposures to formaldehyde and acetaldehyde of 15 randomly selected participants were measured during the summer/autumn of 1997 using Sep-Pak DNPH-Silica cartridges as a part of the EXPOLIS study in Helsinki, Finland. In addition to personal exposures, simultaneous measurements of microenvironmental concentrations were conducted at each participant's residence (indoor and outdoor) and workplace. Mean personal exposure levels were 21.4 ppb for formaldehyde and 7.9 ppb for acetaldehyde. Personal exposures were systematically lower than indoor residential concentrations for both compounds, and ambient air concentrations were lower than both indoor residential concentrations and personal exposure levels. Mean workplace concentrations of both compounds were lower than mean indoor residential concentrations. Correlation between personal exposures and indoor residential concentrations was statistically significant for both compounds. This indicated that indoor residential concentrations of formaldehyde and acetaldehyde are a better estimate of personal exposures than are concentrations in ambient air. In addition, a time-weighted exposure model did not improve the estimation of personal exposures above that obtained using indoor residential concentrations as a surrogate for personal exposures. Correlation between formaldehyde and acetaldehyde was statistically significant in outdoor microenvironments, suggesting that both compounds have similar sources and sinks in ambient urban air.     

Modeling polychlorinated biphenyl sorption isotherms for soot and coal

Sorption isotherms (pg-ng/L) were measured for 11 polychlorinated biphenyls (PCBs) of varying molecular planarity from aqueous solution to two carbonaceous geosorbents, anthracite coal and traffic soot. All isotherms were reasonably log-log-linear, but smooth for traffic soot and staircase-shaped for coal, to which sorption was stronger and more nonlinear. The isotherms were modeled using seven sorption models, including Freundlich, (dual) Langmuir, and Polanyi-Dubinin-Manes (PDM). PDM provided the best combination of reliability and mechanistically-interpretable parameters. The PDM normalizing factor Z appeared to correlate negatively with sorbate molecular volume, dependent on the degree of molecular planarity. The modeling results supported the hypothesis that maximum adsorption capacities (Q_max) correlate positively with the sorbent’s specific surface area. Q_max did not decrease with increasing sorbate molecular size, and adsorption affinities clearly differed between the sorbents. Sorption was consistently stronger but not less linear for planar than for nonplanar PCBs, suggesting surface rather than pore sorption.     

Integrated Ambient and Microenvironment Model for Estimation of PM10 Exposures of Children in Annual and Episode Settings

Particulate matter air pollution is estimated to cause in the order of 350,000 excess deaths in the European Union calling for policy development and evaluation tools. In the current work, a model for PM₁₀ exposures of children is developed using microenvironment time activities and infiltration of ambient pollution indoors, both evaluated against observations earlier and integrated with city-wide air quality models in the current work. The model is demonstrated using data from two cities in Italy. High-end short-term exposures are characterized by an episode-day situation in Turin, and annual mean exposures in downtown Bologna. The air quality model was unable to capture the highest levels during the episode, and therefore, the exposure model was adjusted using observed–modeled ratio from a monitoring station. Air quality model performance for the annual levels was significantly better. Annual exposure variability within the target population was 1.5-fold in the downtown area Bologna and tenfold during the episode day in Turin.     

Characterization of Air Quality Problems in Five Finnish Indoor Ice Arenas

ABSTRACT

The air quality in five Finnish ice arenas with different volumes, ventilation systems, and resurfacer power sources (propane, gasoline, electric) was monitored during a usual training evening and a standardized, simulated ice hockey game. The measurements included continuous recording of carbon monoxide (CO), nitric oxide (NO), and nitrogen dioxide (NO₂) concentrations, and sampling and analysis of volatile organic compounds (VOCs). Emissions from the ice resurfacers with combustion engines caused indoor air quality problems in all ice arenas. The highest 1-hour average CO and NO₂ concentrations ranged from 20 to 33 mg/m³ (17 to 29 ppm) and 270 to 7440 µg/m³ (0.14 to 3.96 ppm), respectively. The 3-hour total VOC concentrations ranged from 150 to 1200 µg/m³. The highest CO and VOC levels were measured in the arena in which a gasoline-fueled resurfacer was used. The highest NO₂ levels were measured in small ice arenas with propane-fueled ice resurfacers and insufficient ventilation.

In these arenas, the indoor NO₂ levels were about 100 times the levels measured in ambient outdoor air, and the highest 1-hour concentrations were about 20 times the national and World Health Organization (WHO) health-based air quality guidelines. The air quality was fully acceptable only in the arena with an electric resurfacer. The present study showed that the air quality problems of indoor ice arenas may vary with the fuel type of resurfacer and the volume and ventilation of arena building. It also confirmed that there are severe air quality problems in Finnish ice arenas similar to those previously described in North America.     

Personal carbon monoxide exposures of preschool children in Helsinki, Finland—comparison to ambient air concentrations

The associations of personal carbon monoxide (CO) exposures with ambient air CO concentrations measured at fixed monitoring sites, were studied among 194 children aged 3–6 yr in four downtown and four suburban day-care centers in Helsinki, Finland. Each child carried a personal CO exposure monitor between 1 and 4 times for a time period of between 20 and 24 h. CO concentrations at two fixed monitoring sites were measured simultaneously. The CO concentrations measured at the fixed monitoring sites were usually lower (mean maximum 8-h concentration: 0.9 and 2.6 mg m⁻³) than the personal CO exposure concentrations (mean maximum 8-h concentration: 3.3 mg m⁻³). The fixed site CO concentrations were poor predictors of the personal CO exposure concentrations. However, the correlations between the personal CO exposure and the fixed monitoring site CO concentrations increased (−0.03–−0.12 to 0.13–0.16) with increasing averaging times from 1 to 8 h. Also, the fixed monitoring site CO concentrations explained the mean daily or weekly personal CO exposures of a group of simultaneously measured children better than individual exposure CO concentrations. This study suggests that the short-term CO personal exposure of children cannot be meaningfully assessed using fixed monitoring sites.     

Evaluation of VOC measurments in the EXPOLIS study. Air Pollution Exposure Distributions within Adult Urban Urban Populations in Europe

Personal exposures and microenvironment concentrations of 30 target VOCs were measured for 401 participants living in five European cities as a part of the EXPOLIS (Air Pollution Exposure Distributions within Adult Urban Populations in Europe) study. Measurements in Basel used an active charcoal (Carbotech) adsorbent as opposed to the Tenax TA used in the other study centres. In addition, within each centre, personal and microenvironment VOC sampling required different sampling pumps and, because of different sampling durations, different sampling flow rates. Thus, careful testing of the sampling and analysis procedures was required to ensure accuracy and comparability of collected data. Monitor comparison tests using Tenax TA showed a mean VOC concentration ratio of 0.95 between the personal and microenvironment monitors. The LODs for the target VOCs using Tenax TA ranged from 0.7 to 5.2 microg m(-3). The LODs for the 14 target compounds quantifiable using Carbotech ranged from 0.9 to 3.2 microg m(-3). Tenax TA field blanks showed no remarkable contamination with the target VOCs, except benzaldehyde, a known artefact with this adsorbent. Thus, the diffusion barrier system used prevented contamination of Tenax TA samples by passive diffusion during non-sampling periods. Duplicate and parallel evaluations of the Tenax TA and Carbotech showed an average difference of < 17% in VOC concentrations within the sampling methods, but a systematic difference between the methods (Tenax TA: Carbotech concentration ratio = 1.18-2.36). These field evaluations and quality assurance tests showed that interpretation and comparison of the results in any VOC monitoring exercise should be done on a compound by compound basis. It is also apparent that carefully planned and realised QA and QC (QA/QC) procedures are needed in multi-centre studies, where a common sampling method and laboratory analysis technique are not used, to strengthen and simplify the interpretation of observed VOC levels between participating centres.