Atmospheric Environment (v.44, #16)

Semipermeable membrane devices (SPMDs) were used for measurements in air of twelve polycyclic aromatic hydrocarbons (PAHs) in two Genoa locations, both on building roofs, distant 300 m from each other. The first, site A, was in front a dismissing steel complex and the second, site B, was in an urban area overlooking a busy thoroughfare. SPMDs were deployed contemporary at the two sites, in nine monthly samplings, from April 2007 to May 2008. The amount of sequestered PAHs, in sites A and B, ranged between 61–267 ng SPMD−1 d−1 and 50–535 ng SPMD−1 d−1, respectively.PAHs profiles highlighted seasonal differences and suggested the possible role of different PAHs sources in the two areas. In particular, the contribution of remediation works of the steel complex was observed in site A. Moreover, a naphthalene leak from a tank, into the former industrial area, and a fire broke out near site A, were registered by time-integrated measurements of SPMDs.However, the strong dependence between amount of sequestered PAHs and air temperature needs further studies to distinguish between uptake rate variability and seasonal contribution of different sources. Finally, to measure air concentrations with reasonable accuracy, it should be very important to have certified sampling rates for all individual PAHs.
Keywords: SPMDs; Passive sampling; PAHs; Air-monitoring;

The influence of aerosol dynamics on indoor exposure to airborne DEHP by Cong Liu; Bin Zhao; Yinping Zhang (1952-1959).
A mass-balance model was extended to investigate the influence of aerosol particles on the accumulation of indoor airborne DEHP, which allows the consideration of a variable particle concentration. The calculated gas-phase di-2-ethylhexyl phthalate (DEHP) concentration is consistent with those measured within residences in both the United States and Europe. Model predictions suggest that there are differences of more than 10% of particle-phase DEHP concentrations between the variable-particle-concentration case and the constant one for over half (578 days) within the calculation time of 1000 days. Airborne DEHP consists primarily of a particle phase. The exposure data indicate that the influence of particle dynamics remains significant throughout the calculation period, and the size fraction of 0–0.5 μm contributes the most, at 39.1%, to the total exposure to particle-phase DEHP as a result of a strong “source” effect which brings particles into the indoor air and a weak “sink” effect which removes particles from the indoor air. The sensitivity analysis indicates that deposition exhibits the most apparent influence, and particle emission from cooking is a significant factor, as cooking is the main source of particles in the size fraction of 0–0.5 μm. The sensitivity analysis also shows that particle penetration has a less obvious influence on the exposure to airborne DEHP because air exchange rate caused penetration introduces and removes particles simultaneously, thus having a limited influence on the airborne DEHP; while resuspension exhibits the weakest influence because it contributes little to the small particles which are the main component of aerosol particles indoors. Strategies for enhancing deposition and reducing particle emissions from cooking and penetration may be helpful to reduce residents’ exposure to airborne SVOCs.
Keywords: Semivolatile organic compounds (SVOCs); Aerosol particles; Indoor air quality (IAQ); Deposition; Resuspension; Penetration; Di-2-ethylhexyl phthalate (DEHP);

Using the Global Biosphere Emissions and Interactions System model (GloBEIS), 3 × 3 km gridded and hourly biogenic volatile organic compound (BVOC) emissions in the Pearl River Delta (PRD) were estimated for the year 2006. The study used newly available land cover database, observed meteorological data, and recent measurements of emission rates for tree species in China. The results show that the total BVOC emission in the PRD region in 2006 was 296 kt (2.2 × 1011 gC), of which isoprene contributes about 25% (73 kt, 6.4 × 1010 gC), monoterpenes about 34% (102 kt, 8.9 × 1010 gC), and other VOCs (OVOC) about 41% (121 kt, 6.8 × 1010 gC). BVOC emissions in the PRD region exhibit a marked seasonal pattern with the peak emission in July and the lowest emission in January, and are mainly distributed over the outlying areas of the PRD region, where the economy and land use are less developed. The uncertainties in BVOC emission estimates were quantified using Monte Carlo simulation; the results indicate high uncertainties in isoprene emission estimates, with a relative error of −82 to +177%, ranging from 12.4 to 186.4 kt; −41 to +58% uncertainty for monoterpenes emissions, ranging from 67.7 to 181.9 kt; and −26 to +30% uncertainty in OVOC emissions, ranging from 88.8 to 156.2 kt on the 95% confidence intervals. The key uncertainty sources include emission factors and the model empirical coefficients α, C T1, CL, and E opt for estimating isoprene emission, and emission factors and foliar density for estimating monoterpenes and OVOC emissions. This implies that determining these empirical coefficient values properly and conducting more field measurements of emission rates of tree species are key approaches for reducing uncertainties in BVOC emission estimates. Improving future BVOC emission inventory work in the PRD region requires giving priority to research on shrub land, coniferous forests, and irrigated cropland and pasture.
Keywords: Biogenic VOCs; Temporal and spatial characteristics; GloBEIS model; Uncertainty; Monte Carlo simulation;

During wintertime measurements in coastal southern California, organonitrate groups accounted for up to 10% of organic mass (OM) in submicron particles. In this study, we report the calibrated absorptivity, the uncertainties in the calibrations, the detection limits for 12 and 24 h ambient sampling, and the multipeak retrieval algorithm for the method developed. Organonitrate groups were observed when both submicron particle-phase nitrate and OM concentrations exceeded 1 μg m−3. These high concentrations were associated with a mixed urban fossil fuel combustion source type that had potential source regions near Riverside and the South Coast Air Basin. The high frequency of these organonitrate observations contrasts with a number of studies of aerosol particles in other regions with more humid conditions, in which organonitrate groups were not detected and submicron sulfate concentrations exceeded those of nitrate. Our results suggest both that organonitrates form and/or exist in significant concentrations during polluted urban conditions and that their lifetime may be limited by hydrolysis in the particle phase.
Keywords: Organonitrate; Organic nitrates; Aerosol; FTIR; PMF;

Airborne molds and mycotoxins associated with handling of corn silage and oilseed cakes in agricultural environment by Caroline Lanier; Estelle Richard; Natacha Heutte; Rachel Picquet; Valérie Bouchart; David Garon (1980-1986).
In agricultural areas, the contamination of feedstuffs with molds and mycotoxins presents major environmental and health concerns. During cattle feeding, fungi and mycotoxins were monitored in corn silage, oilseed cakes and bioaerosols collected in Normandy. Most of the corn silages were found to be contaminated by deoxynivalenol (mean concentration: 1883 μg kg−1) while a few of oilseed cakes were contaminated by alternariol, fumonisin B1 or gliotoxin. In ambient bioaerosols, the values for fungi per cubic meter of air varied from 4.3 × 102 to 6.2 × 105 cfu m−3. Seasonal variations were observed with some species like Aspergillus fumigatus which significantly decreased between the 2 seasons (P = 0.0186) while the Penicillium roqueforti group significantly increased during the second season (P = 0.0156). In the personal bioaerosols, the values for fungi per cubic meter of air varied from 3.3 103 to 1.7 106 cfu m−3 and the number of A. fumigatus spores significantly decreased between the 2 seasons (P = 0.0488). Gliotoxin, an immunosuppressive mycotoxin, was quantified in 3 personal filters at 3.73 μg m−3, 1.09 μg m−3 and 2.97 μg m−3.
Keywords: Agricultural environment; Bioaerosols; Molds; Mycotoxins;

Temperature and air velocity effects on ethanol emission from corn silage with the characteristics of an exposed silo face by Felipe Montes; Sasha D. Hafner; C. Alan Rotz; Frank M. Mitloehner (1987-1995).
Volatile organic compounds (VOCs) from agricultural sources are believed to be an important contributor to tropospheric ozone in some locations. Recent research suggests that silage is a major source of VOCs emitted from agriculture, but only limited data exist on silage emissions. Ethanol is the most abundant VOC emitted from corn silage; therefore, ethanol was used as a representative compound to characterize the pattern of emission over time and to quantify the effect of air velocity and temperature on emission rate. Ethanol emission was measured from corn silage samples removed intact from a bunker silo. Emission rate was monitored over 12 h for a range in air velocity (0.05, 0.5, and 5 m s−1) and temperature (5, 20, and 35 °C) using a wind tunnel system. Ethanol flux ranged from 0.47 to 210 g m−2 h−1 and 12 h cumulative emission ranged from 8.5 to 260 g m−2. Ethanol flux was highly dependent on exposure time, declining rapidly over the first hour and then continuing to decline more slowly over the duration of the 12 h trials. The 12 h cumulative emission increased by a factor of three with a 30 °C increase in temperature and by a factor of nine with a 100-fold increase in air velocity. Effects of air velocity, temperature, and air-filled porosity were generally consistent with a conceptual model of VOC emission from silage. Exposure duration, temperature, and air velocity should be taken into consideration when measuring emission rates of VOCs from silage, so emission rate data obtained from studies that utilize low air flow methods are not likely representative of field conditions.
Keywords: Volatile organic compounds; Ethanol; Ozone precursor; Silage; Farm emissions;

Characterization of polycyclic aromatic hydrocarbons deposition in PM2.5 and cloud/fog water at Mount Taishan (China) by Peng-hui Li; Yan Wang; Yu-hua Li; Zai-feng Wang; Hou-yong Zhang; Peng-ju Xu; Wen-xing Wang (1996-2003).
Polycyclic aromatic hydrocarbons (PAHs) in PM2.5 and cloud/fog water samples were collected at Mount Taishan in an autumn–winter period, and were analyzed by GS-MS. Higher molecular weight PAHs (4–6 rings) predominated in PM2.5 samples, whereas lighter PAH compounds contributed 61.71% of the total PAH concentration in cloud/fog samples. Particles tended to contain more PAHs and have a more intensive influence on the atmospheric environment on colder days. During cloud/fog events, the scavenging ratio based on PAHs associated with particles was estimated to be about 13.45%. PAHs in PM2.5 samples had a significant positive relationship with CO and SO2, suggesting that PAHs, SO2, and CO may originated from the same sources, such as residential coal combustion activities. Diagnostic ratio analysis and factor analysis indicated that the sources of PAHs were mainly from coal combustion during this period.
Keywords: Scavenging ratio; Diagnostic ratio; Factor analysis; Coal combustion;

Analysis of the air pollution climate at a central urban background site by Alessandro Bigi; Roy M. Harrison (2004-2012).
Measurements of air pollutants from a background site in central London are analysed. These comprise hourly data for CO, NO, NO2, O3, SO2 and PM10 from 1996 to 2008 and particle number count from 2001 to 2008. The data are analysed in terms of long-term trends, annual, weekly and diurnal cycles, and autocorrelation and cross-correlation functions. CO, NO and NO2 show a typical traffic-associated pattern with two daily peaks and lesser concentrations at the weekend. Particle number count and PM10 show a similar cycle, but with smaller amplitude. Ozone has an annual cycle with a maximum in May, influenced by the spring maximum in background ozone, but the diurnal and weekly cycles are dominated by losses through reaction with nitric oxide. Particle number count shows a minimum corresponding with maximum air temperatures in August, whereas the CO, NO NO2 and SO2 show a minimum in June/July. There is a lower particle count to NOx ratio at the background site compared to a central London kerbside site (Marylebone Road) and a seasonal pattern in particle count to NOx and PM10 ratios consistent with loss of nanoparticles by evaporation during atmospheric transport. Sulphur dioxide peaks in the morning in summer, but at midday in winter consistent with emissions from elevated sources mixing down from aloft as the diurnal mixed layer deepens. Implications for epidemiological studies of air quality and health are discussed. Sulphur dioxide, carbon monoxide, nitric oxide and nitrogen dioxide show clear downward trends over the measurement period, PM10 declines initially before levels stabilised, and ozone concentrations increased.
Keywords: Urban background; Pollution climates; London; Air pollution; Nanoparticles;

Urban–rural differences in atmospheric mercury speciation by Bian Liu; Gerald J. Keeler; J. Timothy Dvonch; James A. Barres; Mary M. Lynam; Frank J. Marsik; Joy Taylor Morgan (2013-2023).
Measurements of gaseous elemental mercury (GEM), particulate mercury (Hgp), and reactive gaseous mercury (RGM) were concurrently recorded at an urban site in Detroit and a rural site in Dexter, both in Michigan for the calendar year 2004. Their average concentrations (±standard deviation) for the urban area were 2.5 ± 1.4 ng m−3, 18.1 ± 61.0 pg m−3, and 15.5 ± 54.9 pg m−3, respectively, while their rural counterparts were 1.6 ± 0.6 ng m−3, 6.1 ± 5.5 pg m−3, and 3.8 ± 6.6 pg m−3, respectively. The medians of urban-to-rural ratios of Hg concentrations indicate approximately 1-fold, 2-fold, and 3-fold gradients between Detroit and Dexter for GEM, Hgp, and RGM, respectively. The urban–rural differences in Hg also varied considerably on different temporal scales and with wind flow patterns, which was most evident in RGM. Our results show that while Hg at both sites was impacted by regional sources, meteorological conditions, and photochemical transformations, the extent of variations in the observed urban-to-rural gradients, particularly in RGM, cannot be fully accounted for by these processes. Both analyses of the annual data and case studies indicate that the more variable and episodic nature of Hg, particularly RGM, seen in Detroit compared with Dexter, was the result of direct impact from local anthropogenic sources.
Keywords: Gaseous elemental mercury (GEM); Reactive gaseous mercury (RGM); Particulate phase mercury (Hgp); Local sources; Photochemistry;

Dealing with disjunct concentration measurements in eddy covariance applications: A comparison of available approaches by Lukas Hörtnagl; Robert Clement; Martin Graus; Albin Hammerle; Armin Hansel; Georg Wohlfahrt (2024-2032).
Using proton transfer reaction mass spectrometry equipped with a quadrupol mass analyser to quantify the biosphere-atmosphere exchange of volatile organic compounds (VOC), concentrations of different VOC are measured sequentially. Depending on how many VOC species are targeted and their respective integration times, each VOC is measured at repeat rates on the order of a few seconds. This represents an order of magnitude longer sample interval compared to the standard eddy covariance (EC) method (5–20 Hz sampling rates). Here we simulate the effect of disjunct sampling on EC flux estimates by decreasing the time resolution of CO2 and H2O concentrations measured at 20 Hz above a temperate mountain grassland in the Austrian Alps. Fluxes for one month are calculated with the standard EC method and compared to fluxes calculated based on the disjunct data (1, 3 and 5 s sampling rates) using the following approaches: i) imputation of missing concentrations based on the nearest neighbouring samples (iDECnn), ii) imputation by linear interpolation (iDECli), and iii) virtual disjunct EC (vDEC), i.e. flux calculation based solely on the disjunct concentrations. It is shown that the two imputation methods result in additional low-pass filtering, longer lag times (as determined with the maximum cross-correlation method) and a flux loss of 3–30% as compared to the standard EC method. A novel procedure, based on a transfer function approach, which specifically corrects for the effect of data treatment, was developed, resulting in improved correspondence (to within 2%). The vDEC method yields fluxes which approximate the true (20 Hz) fluxes to within 3–7% and it is this approach we recommend because it involves no additional empirical corrections. The only drawback of the vDEC method is the noisy nature of the cross-correlations, which poses problems with lag determination – practical approaches to overcome this limitation are discussed.
Keywords: Proton transfer reaction mass spectrometer (PTR-MS); Disjunct eddy covariance; Low-pass filtering; Grassland; Cross-correlation; Lag time;

We investigate the effects of anthropogenic and biogenic sources on tropospheric CO enhancements and outflow over North America and the Atlantic during July–August 2006, the 3rd warmest summer on record. The analysis is performed using the 3D Regional chEmical trAnsport Model (REAM), satellite data from TES on the Aura satellite, MOPITT on the Terra satellite and surface monitor data from the SEARCH network. The satellite measurements of CO provide insight into the location of regional CO enhancements along with the ability to resolve vertical features. Satellite and surface monitor data are used to compare with REAM, illustrating model's ability to reproduce observed CO concentrations. The REAM model used in this study features CO emissions reduced by 50% from the 1999 EPA NEI and biogenic VOC emissions scaled by EPA-observed isoprene concentrations (20% reduction). The REAM simulations show large variations in surface CO, lower tropospheric CO and column CO, which are also observed by the surface observations and satellite data. Over the US, during July–August 2006, the model estimates monthly CO production from anthropogenic sources (5.3 and 5.1 Tg CO) is generally larger than biogenic sources (4.3 and 3.5 Tg CO). However, the model shows that for very warm days, biogenic sources produce as much CO as anthropogenic sources, a result of increased biogenic production due to warmer temperatures. The satellite data show CO outflow occurs along the East Coast of the US and Canada in July and is more broadly distributed over the Atlantic in August. REAM results show the longitudinally exported CO enhancements from anthropogenic sources (3.3 and 3.9 Tg CO) are larger than biogenic sources (2.8 and 2.7 Tg CO) along the eastern boundary of REAM for July–August 2006. We show that when compared with the impacts of both sources on increasing tropospheric CO exports, the relative impacts in August are greater than in July because of preferable outflow transport.
Keywords: CO; Biogenic source; Anthropogenic source; Convective outflow;

Multi-year hourly PM2.5 carbon measurements in New York: Diurnal, day of week and seasonal patterns by Oliver V. Rattigan; H. Dirk Felton; Min-Suk Bae; James J. Schwab; Kenneth L. Demerjian (2043-2053).
Multi-year hourly measurements of PM2.5 elemental carbon (EC) and organic carbon (OC) from a site in the South Bronx, New York were used to examine diurnal, day of week and seasonal patterns. The hourly carbon measurements also provided temporally resolved information on sporadic EC spikes observed predominantly in winter. Furthermore, hourly EC and OC data were used to provide information on secondary organic aerosol formation. Average monthly EC concentrations ranged from 0.5 to 1.4 μg m−3 with peak hourly values of several μg m−3 typically observed from November to March. Mean EC concentrations were lower on weekends (approximately 27% lower on Saturday and 38% lower on Sunday) than on weekdays (Monday to Friday). The weekday/weekend difference was more pronounced during summer months and less noticeable during winter. Throughout the year EC exhibited a similar diurnal pattern to NO x showing a pronounced peak during the morning commute period (7–10 AM EST). These patterns suggest that EC was impacted by local mobile emissions and in addition by emissions from space heating sources during winter months. Although EC was highly correlated with black carbon (BC) there was a pronounced seasonal BC/EC gradient with summer BC concentrations approximately a factor of 2 higher than EC. Average monthly OC concentrations ranged from 1.0 to 4.1 μg m−3 with maximum hourly concentrations of 7–11 μg m−3 predominantly in summer or winter months. OC concentrations generally correlated with PM2.5 total mass and aerosol sulfate and with NO x during winter months. OC showed no particular day of week pattern. The OC diurnal pattern was typically different than EC except in winter when OC tracked EC and NO x indicating local primary emissions contributed significantly to OC during winter at the urban location. On average secondary organic aerosol was estimated to account for 40–50% of OC during winter and up to 63–73% during summer months.
Keywords: Organic carbon; Elemental carbon; Black carbon; Diurnal patterns; Secondary organic aerosol;

Gross fluxes of methyl chloride and methyl bromide in a California oak-savanna woodland by Robert C. Rhew; Christopher Chen; Yit Arn Teh; Dennis Baldocchi (2054-2061).
Temperate woodland ecosystems are believed to be both a source and sink for atmospheric methyl bromide and methyl chloride. To separate the gross production and consumption fluxes in this ecosystem, we applied a stable isotope tracer technique in field and laboratory-based experiments. Flux measurements were conducted in a California oak-savanna woodland ecosystem at several intervals throughout the day during the wet and dry seasons to observe the diurnal and seasonal variability of fluxes. While gross production was small and variable, gross consumption showed a clear difference between seasons, with much larger rates during the wet season and negligible rates during the dry season. Laboratory incubations confirmed that fluxes were strongly affected by soil moisture. Consumption rates of methyl bromide, however, are less than half of the previous estimates of temperate woodland soil uptake rates during the growing season. Nevertheless, woodlands cover a significant portion of the world's land surface area and may still be an important component of the soil sink for these methyl halides.
Keywords: Methyl halide; Gross flux; Chloromethane; Bromomethane; Woodlands; Stable isotope tracer;

Association of size-resolved airborne particles with foot traffic inside a carpeted hallway by Kai-Chung Cheng; Marian D. Goebes; Lynn M. Hildemann (2062-2066).
The effect of foot traffic on indoor particle resuspension was evaluated by associating non-prescribed foot traffic with simultaneous size-resolved airborne particulate matter (PM) concentrations in a northern California hospital. Foot traffic and PM were measured every 15 min in a carpeted hallway over two 27-h periods. The PM concentration in the hallway was modeled based on the foot traffic intensity, including the previous PM concentration via an autocorrelation regression method based on the well-mixed box model. All 5 size ranges of PM, ranging from 0.75–1 μm to 5–7.5 μm, were highly correlated with foot traffic measurements for both monitoring periods (p < 0.001, R 2 = 0.87–0.90). However, correlations during daytime hours were less significant than nighttime. Coefficients found via this autoregressive analysis can be interpreted to reveal (i) time-independent contributions of walking activities on PM levels for a specific location; and (ii) size-specific characteristics of the resuspended PM.
Keywords: Foot traffic; Aerosol; Hospital; Autocorrelation; Box model;