Variability of tropospheric hydroperoxides at a coastal surface site in Antarctica

The annual cycles of hydrogen peroxide (H₂O₂) and methylhydroperoxide (MHP) have been investigated at a remote site in Antarctica in order to study seasonal variations as well as chemical processes in the troposphere. The measurements have been performed from March 1997 to January 1998 and in February 1999 at the German Antarctic research station Neumayer which is located at 70°39′S, 8°15′W. The obtained time series for hydrogen peroxide and methylhydroperoxide in near-surface air represents the first all-year measurements in Antarctica and indicates clearly the occurrence of seasonal variations. During polar night mean values of 0.054±0.046 ppbv (range<0.03–0.11 ppbv) for hydrogen peroxide and 0.089±0.052 ppbv (range<0.05–0.14 ppbv) for methylhydroperoxide were detected. At the sunlit period higher Mixing ratios were found, 0.20±0.13 ppbv (range<0.03–0.91 ppbv) for hydrogen peroxide and 0.19±0.10 ppbv (range<0.05–0.89 ppbv) for methylhydroperoxide. Occasional long-range transport of air masses from mid-latitudes caused enhanced peroxide concentrations at polar night. During the period of stratospheric ozone depletion we observed peroxide mixing ratios comparable to typical winter levels.     

Particle formation events measured at a semirural background site in Denmark

The particle formation and growth events observed at a semirural background site in Denmark were analyzed based on particle number size distribution data collected during the period from February 2005 to December 2010. The new particle formation (NPF) events have been classified visually in detail according to 3D daily plots in combination with an automatic routine. A clear seasonal variation was found in the way that events occurred more frequently during the warm season from May to September and especially in June. The mean values of the apparent 6 nm particle formation rates, the growth rate and the condensation sink were about 0.36 cm^?3 s^?1, 2.6 nm h^?1, 4.3?×?10^?3 s^?1, respectively. A positive relationship of oxidation capacity (O_X?=?O₃?+?NO₂) of the atmosphere and the appearance of NPF events was found indicating that the oxidation of the atmosphere was linked to the formation of new particles. An analysis of a 3-day backward trajectories revealed that NW air masses from the North Sea were giving the highest probability of NPF events, namely between 20 and 40 %.     

Seasonal variations in atmospheric SOx and NOy species in the adirondacks

This paper reports the results of over 2 years of measurements of several of the species comprising atmospheric SO_x (=SO₂+SO₄²⁻) and NO_y (=NO+NO₂ + PAN + HNO₃+NO₃⁻+ organicnitrates + HONO + 2N₂O₅ …) at Whiteface Mountain, New York. Continuous real-time measurements of SO₂ and total gaseous NO_y provided data for about 50% and 65% of the period, respectively, and 122 filter pack samples were obtained for HNO₃, SO₂ and aerosol SO₄²⁻, NO₃⁻, H⁺ and NH₄⁺. Concentrations of SO₂ and NO_y were greatest in winter, whereas concentrations of the reaction products SO₄²⁻ and HNO₃were greatest in summer. The seasonal variation in SO₄²⁻ was considerably more pronounced than that of HNO₃and the high concentrations of SO₄²⁻ aerosol present in summer were also relatively more acidic than SO₄²⁻ aerosol in other seasons. As a result, SO₄²⁻ aerosol was the predominant acidic species present in summer, HNO₃was predominant in other seasons. Aerosol NO₃⁻ concentrations were low in all seasons and appeared unrelated to simultaneous NO_y and HNO₃concentrations. These data are consistent with seasonal variations in photochemical oxidation rates and with existing data on seasonal variations in precipitation composition. The results of this study suggest that emission reductions targeted at the summer season might be a cost-effective way to reduce deposition of S species, but would not be similarly cost-effective in reducing deposition of N species. kwAcid deposition, seasonal variation, sulfate, nitrate, nitric acid, sulfur dioxide, oxides of nitrogen, hydrogen peroxide, ozone, air pollution, Adirondack Mountains     

Diurnal cycles of short-lived tropospheric alkenes at a north Atlantic coastal site

Observation of diurnal cycles in atmospheric concentrations of reactive alkenes are reported from measurements performed at a North Atlantic coastal site (Mace Head, Eire 53°19′34″N; 9°54′14″W). Species seen to exhibit distinct cycles included isoprene, ethene, propene, 1-butene, iso-butene and a substituted C₆ alkene. Five hundred and thirty air mass classified measurements were performed over a 4 week period at approximately hourly frequency and demonstrate that during periods when air flow resulted from unpolluted oceanic regions a clear daily cycle in concentrations existed, peaking at around solar noon for all species. These observations support the proposed mechanism of production via photochemical degradation of organic carbon in sea water. The observed concentrations showed strong correlation (propene R²>0.75) with solar flux, with little relationship to other meteorological or chemical parameters. The species’ short atmospheric lifetimes indicate that the source of emission was from local coastal waters within close proximity of the sampling site. At solar noon concentrations of reactive alkenes from oceanic sources were responsible for up to 88% of non-methane hydrocarbon reaction with the hydroxyl radical at this coastal marine site.     

Diurnal variations in major rainwater components at a coastal site in North Carolina

Concentrations of several major rainwater components were determined in rain events occurring during the early morning hours (12:00 midnight to 6:00 a.m.) and during the afternoon (12:00 noon to 6:00 p.m.) to examine possible diurnal variations. Generally, rainwater components with gas phase origins (H⁺, NO₃⁻, formaldehyde, H₂O₂, formic acid, acetic acid, pyruvic acid, oxalic acid, and lactic acid) had higher concentrations during p.m. rain events compared to a.m. events. Although source strengths of both biogenic and anthropogenic rainwater components are generally higher during the daytime, nocturnal removal of a wide variety of components in similar proportions (approximately 2–3× less at night) indicates a physical rather than a chemical process affecting diurnal variations. Rainwater components with aerosol origins (Cl⁻, and SO₄²⁻) displayed the opposite diurnal pattern or showed no diurnal variation. Possible reasons for these variations include one or both of the following scenarios: (1) the formation of dew at night removes gas phase atmospheric gasses but not aerosols or (2) during the night, a marine air mass containing lower concentrations of all analytes and higher concentrations of Cl⁻ is advected into the area.     

Formaldehyde in rainwater at Trombay, Mumbai: a coastal site in India

Formaldehyde was measured in rainwater samples collected at a residential area of Trombay, Mumbai (a coastal site in India). A mean concentration of 2.1 μmo1/1 and a range of 0.4-11.0 μmol/l were observed. The mean formaldehyde concentration in rainwater has increased from 1.2 μmol/l in 1979 by a factor of about two at this site.     

Characterisation of local and external contributions of atmospheric particulate matter at a background coastal site

This study applies a methodology for discriminating local and external contributions of atmospheric particulate matter (PM) at a rural background station in the North-western coast of Spain. The main inputs at the nearest scale have come from soil dust, marine aerosol and road traffic. At a larger scale, the highest contributions have come from fossil-fuel combustion sources, giving rise to relatively high ammonium sulphate background levels, mainly in summer. External contributions from long-range transport processes of African dust and nitrate have been detected. Morocco and Western Sahara have been identified as the main potential source regions of African dust, with a higher content of Al and Ti than other crustal components. Geographical areas from central and Eastern Europe have been identified as potential sources of particulate nitrate. The discrimination of the PM contribution from natural and anthropogenic sources at different geographical scales is a necessary information for establishing PM reduction strategies in specific areas.     

Mercury species measured atop the Moody Tower TRAMP site,Houston, Texas

Atmospheric mercury speciation was monitored within Houston, Texas, USA, August 6–October 14, 2006 as part of the TexAQS Radical and Aerosol Measurement Program (TRAMP). On average, all mercury levels were significantly elevated compared to a rural Gulf of Mexico coastal site. Concentrations varied from very clean to very dirty. Multi-day periods of stagnant or low-wind conditions brought elevated concentrations of all mercury species, whereas multi-day periods of strong winds, particularly southerly winds off the Gulf of Mexico, brought very low values of mercury species. Over the entire mercury measurement period, the daily averages of mercury species showed distinct and consistent relationships with the average planetary boundary layer dynamics, with gaseous elemental and particulate-bound mercury near-surface concentrations enhanced by a shallow nocturnal boundary layer, and reactive gaseous mercury concentration enhanced by midday convective boundary layer air entrainment transporting air aloft to the surface. Mercury concentrations were not significantly correlated with known products of combustion, likely indicating non-combustion mercury sources from the Houston area petrochemical complexes. On the morning of August 31, 2006 an observed emission event at a refinery complex on the Houston Ship Channel resulted in extremely high concentrations of aerosol mass and particulate-bound mercury at the TRAMP measurement site 20 km downwind.     

PM2.5–10, PM2.5 and associated water-soluble inorganic species at a coastal urban site in the metropolitan region of Rio de Janeiro

The concentrations of PM_2.5−10, PM_2.5 and associated water-soluble inorganic species (WSIS) were determined in a coastal site of the metropolitan region of Rio de Janeiro, Southeastern Brazil, from October 1998 to September 1999 (n=50). Samples were dissolved in water and analyzed for major inorganic ions. The mean (± standard deviation; median) concentrations of PM_2.5−10 and PM_2.5 were, respectively, 26 (± 16; 21) μg m⁻³ and 17 (± 13; 14) μg m⁻³. Their mean concentrations were 1.7–1.8 times higher in dry season (May–October) than in rainy season (November–April). The WSIS comprised, respectively, 34% and 28% of the PM_2.5−10 and PM_2.5 masses. Chloride, Na⁺ and Mg²⁺ were the predominant ions in PM_2.5−10, indicating a significant influence of sea-salt aerosols. In PM_2.5, SO₄²⁻ (∼97% nss-SO₄²⁻) and NH₄⁺ were the most abundant ions and their equivalent concentration ratio (SO₄²⁻/NH₄⁺ ∼1.0) suggests that they were present as (NH₄)₂SO₄ particles. The mean concentration of (NH₄)₂SO₄ was 3.4 μg m⁻³. The mean equivalent PM_2.5 NO₃⁻ concentration was eight times smaller than those of SO₄²⁻ and NH₄⁺. The PM_2.5 NO₃⁻ concentration in dry season was three times higher than in rainy season, probably due to reaction of NaCl (sea salt) with HNO₃ as a result of higher levels of NO_y during the dry season and/or reduced volatilization of NH₄NO₃ due to lower wintertime temperature. Chloride depletion was observed in both size ranges, although more pronouncely in PM_2.5.     

Estimation of source apportionment and potential source locations of PM2.5 at a west coastal IMPROVE site

Particle composition data for PM_2.5 samples collected at Kalmiopsis Interagency Monitoring of Protected Visual Environments (IMPROVE) site in southwestern Oregon from March 2000 to May 2004 were analyzed to provide source identification and apportionment. A total of 493 samples were collected and 32 species were analyzed by particle induced X-ray emission, proton elastic scattering analysis, photon-induced X-ray fluorescence, ion chromatography, and thermal optical reflectance methods. Positive matrix factorization (PMF) was used to estimate the source profiles and their mass contributions. The PMF modeling identified nine sources. In the Kalmiopsis site, the average mass was apportioned to wood/field burning (38.4%), secondary sulfate (26.9%), airborne soil including Asian dust (8.6 %), secondary nitrate (7.6%), fresh sea salt (5.8%), OP-rich sulfate (4.9%), aged sea salt (4.5 %), gasoline vehicle (1.9%), and diesel emission (1.4%). The potential source contribution function (PSCF) was then used to help identify likely locations of the regional sources of pollution. The PSCF map for wood/field burning indicates there is a major potential source area in the Siskiyou County and eastern Oregon. The potential source locations for secondary sulfate are found in western Washington, northwestern Oregon, and the near shore Pacific Ocean where there are extensive shipping lanes. It was not possible to extract a profile directly attributable to ship emissions, but indications of their influence are seen in the secondary sulfate and aged sea salt compositions.     

Sulphur dioxide,oxides of nitrogen and ozone measured continuously for 2 years at a rural site

Continuous specific measurements of sulphur dioxide, nitric oxide, nitrogen dioxide and ozone have been made for over 2y at Bottesford, a rural site in central England, 20 km away from town and industry sources and 1 km from traffic sources. Statistics of hourly, daily, monthly, seasonal and yearly values are given.On an annual basis, there was 50% more oxides of nitrogen (nitric oxide plus nitrogen dioxide) than sulphur dioxide, and more ozone than either. The nitric oxide and nitrogen dioxide were approximately equal. No other published annual values of nitric oxide, nitrogen dioxide and ozone at U.K. rural sites are known. The summer nitric oxide values were greater at this site than at three other rural sites in the British Isles for which summer nitric oxide values have been reported, but so was the sulphur dioxide, and the amounts of both these gases probably reflect the size and distance of combustion sources.Diurnal variations of the four gases during summer months at Bottesford were similar to those published for a site in southern England. The diurnal variations for winter months at Bottesford were somewhat different, especially for nitrogen dioxide. No other published winter patterns are known.Usually nitrogen dioxide and ozone concentrations were in opposition, both short and long term, but on rare occasions, for example in relatively clean winter air, the ozone concentration rose and fell directly with the nitrogen dioxide. Hourly ozone values exceeded 50 ppb (10⁻⁹, by volume) for several hours a month in 22 months out of 24. The World Health Organisation guideline for public health exposure limits is given as 50–100 ppb h⁻¹, not to be exceeded more than once per month.     

Comparison between measured and predicted CCN concentrations at Egbert,Ontario: Focus on the organic aerosol fraction at a semi-rural site

Aerosol–cloud condensation nuclei (CCN) closure was studied in a semi-rural location 80 km north of Toronto, Canada at the Centre for Atmospheric Research Experiments outside of Egbert, Ontario during the fall of 2005. This site is subject to both polluted air from southern Ontario and clean air from the north. The purpose of the investigation was to evaluate the degree to which closure is attained at a supersaturation of 0.32% when size-resolved aerosol compositions from an Aerodyne Quadrupole Aerosol Mass Spectrometer are made alongside measurements of CCN number density and aerosol size distribution. Attention was given to assessing the sensitivity of closure to assumptions made concerning the water solubility and surface tension of the organic fraction of the aerosol in the Köhler analysis. By assuming that the organics are insoluble and that the growing droplet has the surface tension of water, a good overall degree of closure is attained throughout the analysis time period, with the predicted numbers of CCN within 15% of the modelled numbers, which is within our estimated systematic uncertainties. However, for the specific periods during which the organic content of the aerosol is high, the degree of closure is significantly lower. Sensitivity analyses indicate that some degree of organic water solubility and/or surface tension reduction is necessary to achieve the best agreement and least variance between the modelled and measured numbers of CCN. A general conclusion is that significant uncertainties arise in predicting CCN levels only when the level of soluble inorganic species is below approximately 25% by mass.     

Flow patterns influencing the seasonal behavior of surface ozone and carbon monoxide at a coastal site near Hong Kong

Surface O₃ and CO were measured at Cape D’Aguilar, Hong Kong during the period of January 1994 to December1996 in order to understand the temporal variations of surface O₃ and CO in East Asia–West Pacific region. The isentropic backward trajectories were used to isolate different air masses reaching the site and to analyze the long-range transport and photochemical buildup of O₃ on a regional scale. The results show that the diurnal variation of surface O₃ was significant in all seasons with daily O₃ production being about 20 ppbv in fall and 10 ppbv in winter, indicating more active photochemical processes in the subtropical region. The distinct seasonal cycles of O₃ and CO were found with a summer minimum (16 ppbv)–fall maximum (41 ppbv) for O₃ and a summer minimum (116 ppbv)–winter maximum (489 ppbv) for CO. The isentropic backward trajectory cluster analyses suggest that the air masses (associated with regional characteristics) to the site can be categorized into five groups, which are governed by the movement of synoptic weather systems under the influence of the Asian monsoon. For marine-originated air masses (M-SW, M-SE and M-E, standing for marine-southwest, marine-southeast and marine-east, respectively) which always appear in summer and spring, the surface O₃ and CO have relatively lower mixing ratios (18, 16 and 30 ppbv for O₃, 127, 134 and 213 ppbv for CO), while the continental air masses (C-E and C-N, standing for continent-east and continent-north, respectively) usually arrive at the site in winter and fall seasons with higher O₃ (43 and 48 ppbv) and CO (286 and 329 ppbv). The 43 ppbv O₃ and 286 ppbv CO are representative of the regionally polluted continental outflow air mass due to the anthropogenic activity in East Asia, while 17 ppbv O₃ and 131 ppbv CO can be considered as the signature of the approximately clean marine background of South China Sea. The very high CO values (461–508 ppbv) during winter indicate that the long-range transport of air pollutants from China continent is important at the monitoring site. The fall maximum (35–46 ppbv) of surface O₃ was believed to be caused by the effects of the weak slowly moving high-pressure systems which underlie favorable photochemical production conditions and the long-range transport of aged air masses with higher O₃ and its precursors.     

Chemical composition of aerosol size fractions at a coastal site in southwestern Italy: seasonal variability and transport influence

The present study focuses on the elemental characterization of fine and coarse particles collected at a coastal site of southwestern Italy, in a suburban area of the Calabria region. A chemical tracer analysis was carried out to identify the major emission sources influencing on the atmospheric aerosol levels. Size-resolved particulate samples were collected during three 2-week seasonal sampling campaigns: autumn (19 October to 2 November 2003), winter (19 January to 2 February 2004) and spring (26 April to 10 May 2004). Ambient concentrations of selected elements (Fe, Mn, Mg, Ca, V, Cu, Cr, Ni, Zn, Pb, and Cd) associated to fine and coarse size fractions were determined using atomic absorption spectrometry (AAS). The enrichment factor method was applied, suggesting a prevailing anthropogenic component for all the detected elements, with Fe, Mg, Mn, and Ca as exceptions. Trajectory sector analysis was used in order to discriminate the influence of different air mass origins and paths. Long-range transport from both the continental Europe and the Saharan region proved to be the main influencing factors. African dust outbreaks, whose occurrence frequency was greater during the autumn and spring seasonal monitoring periods, gave rise to a total of eight exceedances of the European Commission (EC) PM10 daily limit value as well as an increase in values of the crustal-derived elements (Fe, Mg, and Ca). Long-range transport from the heavily industrialized area of Central/Eastern Europe contributed to the high levels of Zn, Cd, and Pb that were recorded during the winter sampling campaign. Seasonal trend and comparison with measurements previously performed across the Mediterranean basin were also presented and discussed.     

Aircraft observations of aerosols,O3 and NOy in a nighttime urban plume

Nighttime measurements of aerosol surface area, O₃, NO_y and moisture were made downwind of Portland, Oregon, as part of a study to characterize the chemistry in a nocturnal urban plume. Air parcels sampled within the urban plume soon after sunset had positive correlations between O₃, relative humidity, NO_y and aerosol number density. However, the air parcels sampled within the urban plume just before dawn had O₃ mixing ratios that were highly anti-correlated with aerosol number density, NO_y and relative humidity. Back-trajectories from a mesoscale model show that both the post-sunset and pre-dawn parcels came from a common maritime source to the northwest of Portland. The pre-dawn parcels with strong anti-correlations passed directly over Portland in contrast to the other parcels that were found to pass west of Portland. Several gas-phase mechanisms and a heterogeneous mechanism involving the loss of O₃ to the aerosol surface, are examined to explain the observed depletion in O₃ within the pre-dawn parcels that had passed over Portland.     

Overall dry deposition velocities of trace elements measured at harbor and traffic site in central Taiwan

For reasonable and convenient assessments of the characteristics of the dry deposition velocities between Taichung harbor site and Wuchi town site in central Taiwan, the overall dry deposition velocities of several metallic elements were calculated as the particulate diameter (D(p)) distributions of large particles (D(p) > 10 microm), coarse particles (10 microm < D(p) < 2.5 microm), and fine particles (D(p) < 2.5 microm) based on the ambient measurements during March-December of 2004. In this work, the dry deposition fluxes showed the higher correlation with coarse particle concentrations than large particle concentrations; however, the least well correlation was observed between the dry deposition fluxes and the fine particle concentrations. The calculated best-fit overall dry deposition velocities obtained using coarse particle concentrations varied from approximately 0.2 cm s(-1) for Cr to 1.5 cm s(-1) for Pb and 0.2 cm s(-1) for Fe to 2.6 cm s(-1) for Pb at Taichung harbor and Wuchi town site, respectively. In general, the crustal elements had higher deposition velocities than anthropogenic elements. In addition, overall dry deposition velocities for crustal elements were higher in Wuchi town site than in Taichung harbor site. The results identified the dry deposition flux was mainly contributed from large and coarse particles due to their high deposition velocities. The results also indicated that the best approach to estimate overall dry deposition was by depending on the characteristics of particles with diameters larger than 2.5 microm.     

Identification of a new Irgarol-1051 related s-triazine species in coastal waters

A previously unknown s-triazine species present in commercially available Irgarol-1051, a booster biocide additive in copper-based antifouling paints for the replacement of organotin-based antifoulants, has been identified in the coastal aquatic environment. After careful isolation, purification and characterization by high resolution MS-MS and (1)H NMR, the molecular structure of that unknown species is found to be N,N'-di-tert-butyl-6-methylthiol-s-triazine-2,4-diamine (designated as M3). Levels of Irgarol-1051, its major degradation product (M1) and the newly identified M3 in the coastal waters of Hong Kong, one of the world's busiest ports located in the southern coast of China, were monitored by SPME-GC-MS and SPME-GC-FID. Water samples from five locations within Hong Kong waters were analysed and the levels of Irgarol-1051, M1 and M3 were found to be 0.1-1.6 microg l(-1), 36.8-259.0 microg l(-1) and 0.03-0.39 microg l(-1), respectively. Our results indicate that M3 is relatively stable against photo- and bio-degradation and may pose considerable risk to primary producer communities in the coastal marine environment.     

Metal accumulation and performance of nestlings of passerine bird species at an urban brownfield site

The use of passerine species as bioindicators of metal bioaccumulation is often underutilized when examining the wildlife habitat value of polluted sites. In this study we tested feathers of nestlings of two common bird species (house wren and American robin) for accumulation of Pb, Zn, As, Cr, Cu, Fe in comparison of a polluted, urban brownfield with a rural, unpolluted site. House wren nestlings at the study site accumulated significantly greater concentrations of all target metals except Zn. At the polluted site we found significant species differences of metal concentrations in feathers, with house wrens accumulating greater concentrations of Pb, Fe, and Zn but slightly lesser accumulations of Cr and Cu than American robins. Although house wren nestlings demonstrated significant accumulation of metals, these concentrations showed little effect on size metrics or fledge rates during the breeding season compared to nestlings from the control site.     

Semivolatile behavior of dicarboxylic acids and other polar organic species at a rural background site (Nylsvley,RSA)

In this study aerosol samples from the South African savanna were analyzed for their polar organic constituents. Samples were collected with a front/back-up filter tandem system of quartz fiber filters (dual filter strategy). In all samples (n=15) dicarboxylic acids and a variety of phthalates, aldehydes and monocarboxylic acids were observed. Oxalic acid was the dominating compound with an average amount of 79.2 ng m⁻³ on the front filter and 11.3 ng m⁻³ on the back-up filter. The presence of significant concentrations of dicarboxylic acids on the back-up filter was rather unexpected. There are two possible sources to explain the presence of individual compounds on the back-up filter – particle penetration through the front filter or adsorption of compound parts from the gas phase. Interpretation of the data indicates that the dicarboxylic acid concentrations on the back-up filters appear to be caused by the adsorption of gaseous organic species. Dicarboxylic acids semivolatilic behavior is evident with this results. This conclusion refutes the commonly held view that dicarboxylic acids in the atmosphere were associated with the aerosol phase only. Additionally, it was found that the distribution of dicarboxylic acids between the gas and particle phase in the atmosphere is not only dependent on their vapor pressures. The actual gas phase concentration appears to be more determined by the chemical properties of the particles than by pure physical influences. Surprisingly, malonic acid exhibits an anomaly, as it does not show a semivolatile tendency.