Monitoring of sources and atmospheric processes controlling air quality in an urban Mediterranean environment

Different monitoring parameters (PM mass concentrations, number–size distribution, black carbon, gaseous pollutants, and chemical composition, among others) are currently used in air quality studies. Urban aerosols are the result of several sources and atmospheric processes, which suggests that a single monitoring technique is insufficient to quantitatively evaluate all of them.This study assesses the suitability of a number of monitoring techniques (PM mass concentrations, number and size distribution of ultra-fine particles, levels of gaseous pollutants, and a complete chemical characterization of PM₁₀ and PM_2.5) by examining the response of those techniques to the different emission sources and/or atmospheric processes affecting an urban Mediterranean area (Barcelona, NE Spain).The results of this work reveal that the PM mass, the number concentration and the chemical composition give different, but complementary, information. Whereas the mineral matter, a key atmospheric aerosol component across the Mediterranean, is not properly quantitatively assessed by measuring sub-micrometric particles, the monitoring of the number concentration is indispensable to interpret the origin of specific aerosol episodes. Furthermore, the chemical composition yields very relevant information to deduce the causes of specific pollution episodes.The number concentration of ultra-fine particles in urban areas is strongly dependent upon vehicle exhaust emissions, which may cause adverse health impacts. Moreover, urban Mediterranean environments are favourable to produce nucleation-mode particles (<20 nm) with photochemical origin. In those cases, these particles are expected to be of high solubility and consequently their toxicity may differ from that of traffic-generated ultra-fine particles. Thus, the use of a single monitoring parameter to evaluate the health effects seems to be not enough.     

The role of a changing Arctic Ocean and climate for the biogeochemical cycling of dimethyl sulphide and carbon monoxide

Dimethyl sulphide (DMS) and carbon monoxide (CO) are climate-relevant trace gases that play key roles in the radiative budget of the Arctic atmosphere. Under global warming, Arctic sea ice retreats at an unprecedented rate, altering light penetration and biological communities, and potentially affect DMS and CO cycling in the Arctic Ocean. This could have socio-economic implications in and beyond the Arctic region. However, little is known about CO production pathways and emissions in this region and the future development of DMS and CO cycling. Here we summarize the current understanding and assess potential future changes of DMS and CO cycling in relation to changes in sea ice coverage, light penetration, bacterial and microalgal communities, pH and physical properties. We suggest that production of DMS and CO might increase with ice melting, increasing light availability and shifting phytoplankton community. Among others, policy measures should facilitate large-scale process studies, coordinated long term observations and modelling efforts to improve our current understanding of the cycling and emissions of DMS and CO in the Arctic Ocean and of global consequences.     

大气汞的来源及其浓度分布特征研究进展

大气汞是全球性的污染物,其来源有自然源和人为源,亚洲地区是最大的人为大气汞排放源,占全球人为排汞量的67％(质量分数),其中又以中国为最.燃煤和有色金属冶炼对中国大气汞排放的贡献最大.环境界面的释汞通量是全球大气汞预算的重要组成部分,也是目前的研究热点之一.综述了不同环境界面的释汞通量及其影响因素,并比较了不同地区大气...     

The effect of aniline on photochemical reactions in atmospheric and synthetic air samples

The inhibitory effect of aniline in photochemical smog reactions was studied using actual Toronto air samples. An aniline concentration of 0.81 pphm had negligible effect in a light traffic air sample containing negligible NO, whereas 20 pphm in a heavy traffic sample caused a 70% decrease in the oxidant dosage, a 50% decrease in the NO₂ peak and a four-fold increase in the NO half-life. In experiments with propylene in synthetic mixtures, the half-life of propylene was increased from 144 min. to 192 min. by the present of 20 pphm of aniline. In addition, a thirty-fold increase in condensation nuclei was produced following a one hour induction period. A chemical mechanism is proposed which is consistent with these results. Although the condensation nuclei detected may be too small to produce light scattering, they may be retained in the lung. In addition they may grow in size. These consequences do not favour the use of aniline as an inhibitor in photochemical smog.     

Simultaneous use of relaxed eddy accumulation and gradient flux techniques for the measurement of sea-to-air exchange of dimethyl sulphide

The sea-to-air flux of the biogenic volatile sulphur compound dimethyl sulphide was assessed with the relaxed eddy accumulation (REA) and the gradient flux (GF) techniques from a stationary platform in the coastal Atlantic Ocean. Fluxes varied between 2 and 16 μmol m⁻² d⁻¹. Fluxes derived from REA were on average 7.1±5.03 μmol m⁻² d⁻¹, not significantly different from the average flux of 5.3±2.3 μmol m⁻² d⁻¹ derived from GF measurements. Gas transfer velocities were calculated from the fluxes and seawater DMS concentrations. They were within the range of gas transfer rates derived from the commonly used parameterizations that relate gas transfer to wind speed.     

河北廊坊地区大气污染物变化特征与来源追踪

为了解河北省廊坊地区大气污染水平、变化特征以及污染物来源,2009年7月—2010年6月对该地区大气中NO、NO_x（NO_x=NO+NO₂）、O₃、SO₂和PM₁₀进行了连续在线观测,并用统计方法和后向轨迹模拟对所获数据进行分析。结果表明,一次污染物NO、NO_x、SO₂和PM₁₀浓度具有相似的季变化和日变化,冬季浓度最高,季节日均值分别为（57±53）、（127±84）、（69±340）和（181±129）μg/m³;二次污染物O₃夏季浓度最高,日小时均值最高值季节日平均为（99±39）μg/m³。一次污染物浓度日变化呈早晚双峰型,冬季,变化幅度最大;二次污染物日变化为单峰型,最大值出现在夏季午后。夏季受东南气流影响,往往造成该地区O₃超标;冬季,廊坊和天津污染具有较高一致性,出现区域性大气复合污染。廊坊地区大气污染除受本地排放影响,还受到周边地区污染物输送的影响,其在京津两大城市间对大气污染的缓冲作用也不可小觑。     

Computation of uncertainty for atmospheric emission projections from key pollutant sources in Spain

Emission projections are important for environmental policy, both to evaluate the effectiveness of abatement strategies and to determine legislation compliance in the future. Moreover, including uncertainty is an essential added value for decision makers. In this work, projection values and their associated uncertainty are computed for pollutant emissions corresponding to the most significant activities from the national atmospheric emission inventory in Spain. Till now, projections had been calculated under three main scenarios: “without measures” (WoM), “with measures” (WM) and “with additional measures” (WAM). For the first one, regression techniques had been applied, which are inadequate for time-dependent data. For the other scenarios, values had been computed taking into account expected activity growth, as well as policies and measures. However, only point forecasts had been computed. In this work statistical methodology has been applied for: a) Inclusion of projection intervals for future time points, where the width of the intervals is a measure of uncertainty. b) For the WoM scenario, ARIMA models are applied to model the dynamics of the processes. c) In the WM scenario, bootstrap is applied as an additional non-parametric tool, which does not rely on distributional assumptions and is thus more general. The advantages of using ARIMA models for the WoM scenario including uncertainty are shown. Moreover, presenting the WM scenario allows observing if projected emission values fall within the intervals, thus showing if the measures to be taken to reach the scenario imply a significant improvement. Results also show how bootstrap techniques incorporate stochastic modelling to produce forecast intervals for the WM scenario.     

杭州市大气降尘重金属污染特征及来源研究

于2006年6月至2009年6月期间,在杭州市主城区7个采样点对大气降尘进行采集,并对10种重金属元素含量进行了分析。结果表明:重金属元素Cu、Cd、Mn、Ni、Pb、Zn、Co、Al、Fe、Mo质量浓度分别为223.6、15.6、741.1、27.8、363.7、1 820.4、7.0、8 982.4、21 149.0、13.4mg/kg;各功能区差异较大,半山(工业区)Fe、Mn、Pb、Zn浓度较高,江城立交(交通枢纽)Cu、Cd浓度较高。富集因子评价结果表明,Cd、Mo、Pb、Zn、Cu富集程度较高,受到不同程度人为污染。主因子分析结果显示,Mn、Fe可能来自钢铁冶炼及机械制造;Cu、Cd可能来自交通源;Zn、Mo可能来自相关的冶炼加工及合金工业;Ni、Co可能由煤和石油等化石燃料燃烧排放;Pb来自工业排放;Al主要来自地壳。     

Measurements of the aerosol concentrations of methanesulphonic acid,dimethyl sulphoxide and dimethyl sulphone in the marine atmosphere of the British Isles

Aerosol concentrations of methanesulphonic acid (MSA), dimethyl sulphoxide (DMSO) and dimethyl sulphone (DMSO₂) have been measured from landbased stations at Plymouth (Devon, U.K.), Galway (EIRE), and from various shipboard stations in the North Sea and the North Atlantic Ocean. MSA, DMSO and DMSO₂ all show seasonal cycles with spring/summer maxima and winter minima. The summer concentrations of MSA are approximately an order of magnitude higher than in winter. The general levels of MSA (July 1985 mean = 9.27 × 10⁻⁹ mol m⁻³, December 1986 mean = 1.14 × 10⁻⁹ mol m⁻³) are comparable to those reported from Cape Grim, Tasmania. Modelling indicates that neither MSA nor DMSO₂ are present in sufficient quantity to represent major oxidation pathways for dimethyl sulphide (DMS). Rate constant ratios for both the reactions of DMS and DMSO with OH and IO have been estimated. Hydroxyl radical does not appear to be reactive enough for it to be the major sink of atmospheric DMS. It is also shown that the rate constants for the destruction of DMSO (the main reaction product of the DMS/IO system) with either IO or OH are likely to be slow. Thus low tropospheric concentrations of DMSO tend to indicate that it also is not a major product of DMS oxidation.     

The sources and forms of phosphorus in marine aerosol particles and rain from Northern New Zealand

Various forms of phosphorus were measured in marine aerosol particles and rain samples collected from the northern tip of the North Island of New Zealand. Approximately 58 % of the total phosphorus in the aerosol particles was organic and 7 % was soluble in deionized water. The remaining 35 % was not released by treatment with potassium persulfate, and it was defined as a refractory fraction. Stepwise regression analyses suggested that (1) the concentrations of organic phosphorus in the aerosol particles were related to those of sodium, which was regarded as sea salt tracer, (2) the concentrations of water soluble phosphorus were correlated with those of aluminum, which was considered an indicator of crustal material and (3) total phosphorus was derived from the ocean and from the earth's crust. The mass particle-size distribution of the refractory and organic phosphorus combined was similar to that of sodium and aluminum. However, on submicrometer particles the concentrations of all forms of phosphorus appeared to increase relative to those of sodium, suggesting that small particle phosphorus may be derived from a non-marine source, possibly weathered crustal material or wind blown fertilizer. The wet deposition rates for water soluble and organic phosphorus were calculated to be 0.30 and 0.61 μg cm ⁻² y ⁻¹, respectively. The dry deposition of these two forms of phosphorus combined (0.14 μg cm ⁻² y ⁻¹ ) was clearly lower than the wet deposition rate. Total deposition of phosphorus to the site was estimated to be 1.5μgcm⁻²y⁻¹.     

Evaluation of atmospheric sources of PCDD/Fs, PCBs and PBDEs around a steel industrial complex in northeast China using passive air samplers

The concern about emissions of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) polychlorinated biphenyls (PCBs), and polybrominated diphenyl ethers (PBDEs) from steel industrial parks has increased in the past decades. In this study, polyurethane foam (PUF)-disk based passive air samples were collected in and around a big steel industrial park of Anshan, Northeast China from June 2008 to March 2009. The levels, seasonal variations and potential sources of PCDD/Fs, PCBs and PBDEs in the atmosphere around the steel industrial complex were investigated, and potential contribution of these three groups of persistent organic pollutants (POPs) from iron and steel production was also assessed. The air concentrations of ∑₁₇PCDD/Fs (summer: 0.02-2.77 pg m⁻³; winter: 0.20-9.79 pg m⁻³), ∑₁₉PCBs (summer: 23.5-155.8 pg m⁻³; winter: 14.6-81.3 pg m⁻³) and ∑₁₃PBDEs (summer: 2.91-10.7 pg m⁻³; winter: 1.10-3.89 pg m⁻³) in this targeted industrial park were relatively low in comparison to other studies, which implied that the industrial activities of iron and steel had not resulted in serious contamination to the ambient air in this area. On the whole, the air concentrations of PCDD/Fs in winter were higher than those of summer, whereas the concentrations of PCBs and PBDEs showed opposite trends. The result from principal component analysis indicated that coal combustion might be the main contributor of PCDD/F sources in this area.     

Identification and quantification of methyl halide sources in a lowland tropical rainforest

In conjunction with the OP3 campaign in Danum Valley, Malaysian Borneo, flux measurements of methyl chloride (CH₃Cl) and methyl bromide (CH₃Br) were performed from both tropical plant branches and leaf litter in June and July 2008. Live plants were mainly from the Dipterocarpaceae family whilst leaf litter samples were representative mixtures of different plant species. Environmental parameters, including photosynthetically-active radiation, total solar radiation and air temperature, were also recorded. The dominant factor determining magnitude of methyl halide fluxes from living plants was plant species, with specimens of the genus Shorea showing persistent high emissions of both gases, e.g. Shorea pilosa: 65 ± 17 ng CH₃Cl h^?1 g^?1 (dry weight foliage) and 2.7 ± 0.6 ng CH₃Br h^?1 g^?1 (dry weight foliage). Mean CH₃Cl and CH₃Br emissions across 18 species of plant were 19 (range, <LOD ?76) and 0.4 (<LOD ?2.9) ng h^?1 g^?1 respectively; fluxes from leaf litter were 1–2 orders of magnitude smaller per dry mass. CH₃Cl and CH₃Br fluxes were weakly correlated. Overall, the findings suggest that tropical rainforests make an important contribution to global terrestrial emissions of CH₃Cl, but less so for CH₃Br.     

Temperature-dependent rate coefficients for the reactions of Cl atoms with methyl methacrylate,methyl acrylate and butyl methacrylate at atmospheric pressure

Rate coefficients for the gas-phase reactions of Cl atoms with a series of unsaturated esters CH₂C(CH₃)C(O)OCH₃ (MMA), CH₂CHC(O)OCH₃ (MAC) and CH₂C(CH₃)C(O)O(CH₂)₃CH₃ (BMA) have been measured as a function of temperature by the relative technique in an environmental chamber with in situ FTIR detection of reactants. The rate coefficients obtained at 298 K in one atmosphere of nitrogen or synthetic air using propene, isobutene and 1,3-butadiene as reference hydrocarbons were (in units of 10^?10 cm³ molecule^?1 s^?1) as follows: k_(Cl+MMA) = 2.82 ± 0.93, k_(Cl+MAC) = 2.04 ± 0.54 and k_(Cl+BMA) = 3.60 ± 0.87. The kinetic data obtained over the temperature range 287–313 K were used to derive the following Arrhenius expressions (in units of cm³ molecule^?1 s^?1): k_(Cl+MMA) = (13.9 ± 7.8) × 10^?15 exp[(2904 ± 420)/T], k_(Cl+MAC) = (0.4 ± 0.2) × 10^?15 exp[(3884 ± 879)/T], k_(Cl+BMA) = (0.98 ± 0.42) × 10^?15 exp[(3779 ± 850)/T]. All the rate coefficients display a slight negative temperature dependence which points to the importance of the reversibility of the addition mechanism for these reactions. This work constitutes the first kinetic and temperature dependence study of the reactions cited above.An analysis of the available rates of addition of Cl atoms and OH radicals to the double bond of alkenes and unsaturated and oxygenated volatile organic compounds (VOCs) at 298 K has shown that they can be related by the expression: log k_OH = 1.09 log k_Cl ? 0.10. In addition, a correlation between the reactivity of unsaturated VOCs toward OH radicals and Cl atoms and the HOMO of the unsaturated VOC is presented. Tropospheric implications of the results are also discussed.     

The distribution of atmospheric sulphates in Canada and its relationship to long-range transport of air pollutants

Analyses of the distribution of airborne sulphates in Canada have been carried out using data obtained during April-May 1975. The present observations indicate that atmospheric sulphate loadings were relatively low ( < 5 μg m⁻³) in the Western Provinces while high values ( > 15 μg, m⁻³) were frequently observed in eastern Canada. The natural background level of ambient sulphates appeared to be less than 1.5 μg m⁻³ in Canada. However, maximum values ( > 20 μg m⁻³) were found to occur in southern Ontario. Generally, values recorded in the Atlantic Provinces were lower than the values observed in Ontario.The analyses indicate that the observed levels of sulphates could be associated with 3 types of typical weather situations : (a) extratropical cyclones, or on the forward sides of anticyclones with cold northerly flows (low sulphates); (b) on the rear sides of anticyclones (high sulphates); (c) quasi-stationary fronts (mixed). Air-parcel trajectory analyses of the low-level atmosphere show that high sulphate levels were often associated with S-SW airflows on the rear side of a warm moist air mass. The results suggest the long-range transport of airborne sulphur pollutants, mainly from several industrial areas in the U.S.A.     

A method for determination of methyl chloride concentration in air trapped in ice cores

A method for measuring the concentration of methyl chloride (CH3Cl) in air trapped in an ice core was developed. The method combines the air extraction by milling the ice core samples under vacuum and the analysis of the extracted air with a cryogenic preconcentration/gas chromatograph/mass spectrometry system. The method was applied to air from Antarctic ice core samples estimated to have been formed in the pre-industrial and/or early industrial periods. The overall precision of the method deduced from duplicate ice core analyses was estimated to be better than +/-20 pptv. The measured CH3Cl concentration of 528+/-26 pptv was similar to the present-day concentration in the remote atmosphere as well as the CH3Cl concentration over the past 300 years obtained from Antarctic firn air and ice core analyses.