Gas-phase and aerosol chemistry interactions in South Europe and the Mediterranean region

The atmospheric chemical composition is affected by the interaction mechanisms among gases and particulate matter through a wide range of chemical reactions that can occur with the aid of particulate matter (e.g. particles act as reacting or absorbing surfaces) or be influenced by the presence of particulate matter in the atmosphere (photochemical reactions). Physical and chemical processes are also bonded in an interactive way that often leads to the influence of the radiation budget, cloud physics and the warming or cooling of the lower atmospheric levels. The Euro-Mediterranean region is a key-sensitive area due to the unique climatic and air quality characteristics associated with the regional climatic patterns, geomorphology (land and water contrast) and coexistence of pollutants from different origin. Focusing on this region, the gas-aerosol interactions are studied using state-of-the-art atmospheric and chemical transport modeling tools following the necessary development in the chemical transport model CAMx. Sensitivity and large-scale simulations have shown significant responses of the modeling system to the inclusion of natural species emissions, the direct shading effect of dust particles on photochemical processes and the formation of new types of aerosols through heterogeneous uptake of gases on dust particles. Including such interactions in the chemical transport model often led to the improvement of the model performance compared with available measurements in the region.     

大气气溶胶研究新动向

本文概述了近年大气气溶胶研究的四个主要方面:大气气溶胶的表征、大气化学过程与气候变化、健康效应等的概况.阐明了当今大气气溶胶研究的趋向,主要着重于PM_(10)和PM_(2.5)细颗粒(可吸入颗粒物或二次颗粒物)的物理化学特性与环境行为、生态效应,更重视气溶胶的非均相化学反应过程;其研究范围,从平流层向对流层发展,并密切结合气候变化、健康影响等有关的一些实际问题,进行深层次的综合性研究.大气气溶胶化学已成为当今大气化学研究最前沿的领域.     

A comparison study of aerosol emissions sources in two receptor sites in Salvador (Brazil) city

Total suspended particles (TSP) and metal concentrations were determined in Salvador, Bahia, Brazil at two sites: a residential area and a residential‐commercial‐industrial neighborhood. The determined metals associated with atmospheric aerosols include Al, Ca, Cr, Cd, Fe, Mg, Mn, V, Zn and Na. Factor analysis was employed to identify the major atmospheric deposition sources. At one site the data were best represented by two sources: resuspended soil + marine aerosol and vehicular emissions, which represents 93% of the total system variance. In the second one the data were best represented by three sources: resuspended soil, metallurgy and building construction, which represents 79% of the total system variance.     

论城市室内环境中气溶胶污染问题

本文全面评述了室内环境中气溶胶的种类来源,化学组成,形成和自然清除机理。空气环境中气溶胶大致可分为：１．燃烧型气溶胶,主要包括各类燃料燃烧产生的烟雾和烟草烟雾等;２．矿物型气溶胶,包括粉尘,飞灰,石棉及其它天然纤维尘等;３．生物型气溶胶,包括植物生气溶胶,如动物皮屑及各类微生物等。     

World air particulate matter: sources,distribution and health effects

Particulate matter (PM) is both a major driver of climate change and a source of toxicity for health. In the upper atmosphere, particulate matter modifies the earth radiation budget, cloud formation and acts as a reaction center for air pollutants. In the lower atmosphere, particulate matter changes atmospheric visibility and alters biogeochemical cycles and meteorology. Most critical effects are observed in ambient air, where particulate matter degrades human health. Here we review the sources, spatial and temporal variability, and toxicity of PM₁₀, the particulate matter having particle sizes 10 micrometers or less in diameter, in world regions. For that we analyzed information from the world wide web and databases from government organizations after the year 2000. Findings show that PM₁₀ is a major risk in both developed and developing countries. This risk is more severe in Asian countries compared to Europe and USA, where decreasing trends are recorded during the last two decades. Meteorological factors modify particulate matter variations at local and regional levels. PM_2.5/PM₁₀ ratio provides information of particulate matter sources under different environment conditions. Crustal matter, road traffic and combustion of fuels are major sources of particulate matter pollution. Health studies indicate that long-term exposure to particulate matter has multiple health effects in people from all age groups. Identification of possible sources and their control with regular epidemiological monitoring could decrease the impact of particulate matter pollution.     

Homogeneous and heterogeneous photolysis of nitrate in the atmosphere: state of the science,current research needs,and future prospects

● Recent advances in the photolysis of nitrate/HNO₃ are reviewed. ● Mechanisms and key factors affecting the photolysis of nitrate/HNO₃ are summarized. ● Atmospheric implications and future research recommendations are provided. Nitrate is an important component of atmospheric particulate matter and affects air quality, climate, human health, and the ecosystem. Nitrate was previously considered a permanent sink for nitrogen oxides (NO_x). However, this viewpoint has been challenged in recent years because growing research evidence has shown the transformation of nitrate into NO_x (i.e., renoxification). The photolysis of nitrate/HNO₃, especially in the particulate phase or adsorbed on particles, can be a significant renoxification process in the atmosphere. The formation and photolysis of nitrate in aerosol not only change the diurnal variation of NO_x, but also provide long-distance transport of NO_x in the form of nitrate, which affects local and regional atmospheric chemistry and air quality. This review summarizes recent advances in the fundamental understanding of the photolysis of nitrate/HNO₃ under various atmospheric conditions, with a focus on mechanisms and key factors affecting the process. The atmospheric implications are discussed and future research is recommended.     

Study of atmospheric electrical conductivity,SO2, NO2, aerosols SPM (>10 μ) and RSPM (<10 μ) in Mysore city,India

It is well known that atmospheric electrical conductivity is mainly due to the presence of small ions. Near the surface of the earth, radon and its daughter products predominantly produce small ions. In the presence of aerosol particles, the small ion concentration is reduced due to attachment of small ions to aerosol particles which decreases mobility and conductivity in the atmosphere. The ion pair production rate is estimated from the measured radon and its progeny concentrations and correlated with electrical conductivity of the atmosphere. Measurement of concentrations of suspended particulate matter (SPM), SO₂, and NO₂ of air was also carried out. Data showed that reduced electrical conductivity was related to concentration of airborne SPM.     

Protein amino acids as markers for biological sources in urban aerosols

Biological aerosol particles are recently gaining increased attention, but global estimates of their emissions are unclear. Traditional organic tracers for biological particles have not been able to capture the diversity of biological sources such as residential wood burning. Here, we have analyzed protein content in air particulate matter over a year in a suburban area near Shibuya, in order to identify contributions from biological sources. Aerosols were separated into five size fractions using a high-volume cascade impactor. Amino acid profiles were obtained from acid hydrolysates by high-performance liquid chromatography and were subsequently used in a receptor model for source apportionment. Results show that protein content ranged from 0.5 to 2 % throughout the year in all size fractions. We observed contributions from seasonally variable emission sources such as pollen and fallen leaves in coarse particles, larger than 7 µm, at elevated concentrations during spring and winter. We also found contributions from pollen and fallen leaves in the smallest size fraction, lower than 1.1 µm, after spring. This finding indicates that sources are broken up to smaller particles in the urban environment. Overall, our findings demonstrate that protein content can be used as marker for biological aerosol particles, and that protein amino acid composition can distinguish multiple sources.     

Monitoring the transport of biomass burning emissions in South America

The atmospheric transport of biomass burning emissions in the South American and African continents is being monitored annually using a numerical simulation of air mass motions; we use a tracer transport capability developed within RAMS (Regional Atmospheric Modeling System) coupled to an emission model. Mass conservation equations are solved for carbon monoxide (CO) and particulate material (PM2.5). Source emissions of trace gases and particles associated with biomass burning activities in tropical forest, savanna and pasture have been parameterized and introduced into the model. The sources are distributed spatially and temporally and assimilated daily using the biomass burning locations detected by remote sensing. Advection effects (at grid scale) and turbulent transport (at sub-grid scale) are provided by the RAMS parameterizations. A sub-grid transport parameterization associated with moist deep and shallow convection, not explicitly resolved by the model due to its low spatial resolution, has also been introduced. Sinks associated with the process of wet and dry removal of aerosol particles and chemical transformation of gases are parameterized and introduced in the mass conservation equation. An operational system has been implemented which produces daily 48-h numerical simulations (including 24-h forecasts) of CO and PM2.5, in addition to traditional meteorological fields. The good prediction skills of the model are demonstrated by comparisons with time series of PM2.5 measured at the surface.     

Determining the carbon-to-chlorophyll ratio of natural phytoplankton

For field samples, regression analyses of plots of chemically determined particulate organic carbon on chlorophyll are often employed to estimate the algal carbon-to-chlorophyll ratio (F) in the presence of appreciable amounts of nonalgal particulate organic carbon. Spurious results will be obtained, however, if the temporal rate of change of the algae or the nonplant matter reverses its sign during the sampling interval and the samples cannot be ordered correctly in time or space. Previously recognized sources of bias inherent in the chemical approach are also discussed. The great uncertainty of our present knowledge of F is pointed out. It is shown that the concentration of microscopically visible, nonliving particles in the sea isnot known. Renewed studies are suggested as a means of improving on the chemical approach to determining F. The general argument holds for the ratios of nitrogen (particle volume, etc.)-to-chlorophyll, carbon (nitrogen, particle volume, etc.)-to-ATP, and similar conversion factors.Contribution No. 932 from the Department of Oceanography, University of Washington, Seattle, Washington 98195, USA. The article is a revised and expanded version of a paper contributed at the Joint Oceanographic Assembly, September 1976, at Edinburgh, Scotland, UK.     

气溶胶中正构烷烃的碳优先指数研究

本文研究了北京、广州两地不同季节气溶胶颗粒物上正构烷烃的碳优先指数值(CPI)随季节和颗粒物粒径的变化规律。结果表明,北京地区气溶胶中正构烷烃的CPI值:春>夏>秋>冬;广州地区为冬>春>夏,显示了不同的地区特征,而且随着气溶胶颗粒物粒径的减小,正构烷烃的CPI值亦减小。     

Distribution and retention of the copepodEurytemora affinis hirundoides in a turbid estuary

The spatial and temporal distribution of the copepodEurytemora affinis hirundoides (Nordquist, 1888) in the Gironde estuary, southwest France, was investigated in 1976, and between 1981 and 1983. The distribution pattern of the population bore a clear relationship to the patterns of water circulation and transport of particulate matter. Laboratory experiments suggested thatE. affinis hirundoides is incapable of autonomous displacement against the direction of general circulation and behaves as passive particles. A major problem faced by species living in estuaries is that of the maintenance of endemic populations. Some authors have suggested that behavioural responses may play an important role in minimising population losses. Our study indicated that hydrodynamic processes are sufficient to explain the distribution and retention ofE. affinis hirundoides, whose populations are retained in the estuary in the same manner as the suspended sediment. Since the outflow of particulate matter from the Gironde estuary to the sea is very sporadic, we hypothesize that most of the production ofE. affinis hirundoides remains within the estuary, and does not fertilize the continental shelf, at least not in the form of particulate organic matter.     

A study on major inorganic ion composition of atmospheric aerosols

Atmospheric aerosol samples were collected from Akola and Buldana region covering around 40 sqkm area during October-November 2002 and were analyzed for ten major inorganic ions namely F-, Cl-, NO3-, SO4(2-), PO4(2-), Na+, K+, Ca2+, Mg2+ and NH4+ using ion chromatographic technique. The average mass of aerosols was found to be 225.81 microg/m3 with standard deviation of 31.29 and average total water soluble load of total cations and anions was found to be 4.32 microg/m3. The concentration of ions in samples showed a general pattern as SO4(2-) > NO3- > Cl- > PO4(2-) > F- for anions and Na+ > Ca2+ > NH4+ > Mg2+ > K+ for cations. The overall composition of the aerosols was taken into account to identify the sources. The trend showed higher concentration of sodium followed by calcium, sulfate, nitrate, phosphate and ammoinum and found to be influenced by terrestrial sources. The presence of SO4(2-) and NO3- in aerosols may be due to re-suspension of soil particles. Ca2+, Mg2+ and Cl- are to be derived from soil materials. The presence of NH4+ may be attributed to the reaction of NH3 vapors with acidic gases may react or condense on an acidic particle surface of anthropogenic origin. The atmospheric aerosol is slightly acidic due to neutralization of basicity by SO2 and NO(x).     

Health risk of aerosols and toxic metals from incense and joss paper burning

We report for the first time the distribution and hazard potential of aerosol and metals resulting from joss paper burning. Burning joss paper and incense is a traditional custom in many Oriental countries. Large amounts of air pollutants, including particles, polycyclic aromatic hydrocarbons, toxic metals and other gaseous pollutants, are released into the environment during the burning stage. Many investigations have reported on the emission of pollutants from the incense burning. However, no work has been reported until now on the analysis of the released pollutants apart from polycyclic aromatic hydrocarbons. In this study, a micro-orifice uniform-deposit impactor and inductively coupled plasma optical emission spectrometry were, respectively, used to collect aerosols and characterize the toxic metals from joss paper burning. We studied two types of particulate matter (PM): PM_2.5 that are particles with a diameter smaller than 2.5 μm and PM₁₀ that are particles with a diameter smaller than 10 μm. PM_2.5 are the most potentially toxic particles. Our results showed that PM_2.5 are the major component of the pollutants and that the PM_2.5 to PM₁₀ ratio ranged from 62 to 99%. The metals Na, Ca, Mg, Al and K were the main species in the aerosol and in the bottom ash.     

Distribution and behaviour of polycyclic aromatic hydrocarbons in subtropical river estuary,Okinawa, Japan

Surface water samples were collected along the salinity gradient of Manko estuary in Okinawa, Japan, between January and November 2012, to examine spatial and temporal variability in the distribution, composition, behaviour, and sources of particulate polycyclic aromatic hydrocarbons (PAHs). Concentrations of total particulate PAHs ranged from 169.7?ng?g^?1 at riverine station (N1) in November 2012 to 922?ng?g^?1 at another riverine station (K3) in May 2012. Based on observed environmental behaviour, particularly relationships to organic matter, the PAHs appear divisible into two groups: group I (low molecular weight) PAHs were characterised by low particles affinity and strong correlations with a pool of autochthonous organic matter (e.g. high concentrations of polyunsaturated fatty acids), reflecting processes controlling their delivery to the estuary; and, in contrast, group II (high molecular weight) PAHs were characterised by high particles affinity and exhibited estuarine distribution primarily controlled by suspended solid load and inputs from terrigenous sources through river inflows. This relationship, coupled with isomer ratios indicative of combined mixed sources from petroleum and petroleum combustions, indicates that terrestrial run-off is the dominant mode of delivery of particulate PAHs in the estuary. The relationships between distinct groups of PAHs and lipid biomarkers demonstrated in this study suggest that very specific pools of particulate organic matter, as opposed to concentrations of particulate organic carbon alone, can be important in the transport and fate of hydrophobic contaminants.     

Aktuelle Aerosoltrends an der GAW Globalstation Hohenpeißenberg und ihre Relevanz für Luftreinhaltung und Klima

Aim and Scope

This study was aimed at representing current aerosol trends measured at the GAW global station and their relevance for the present fine dust discussion and a possible impact on climate.

Results and Discussion

1) The intensive GAW measuring program at Hohenpeissenberg covers numerous parameters for the characterization of the physical, optical and chemical characteristics of the atmospheric aerosol. The time series of the number concentration of ultra fine particles with diameters of about 0.004 to 3 μm shows an increase of about 50% since 1995. 2) The introduction of soot particle filters would lower the dust mass only slightly since soot particles from diesel cars only about 8–10% contribute to the dust mass, but about 90% to the number concentration of particles. 3) The single scattering albedo (SSA) is a key parameter determining whether the existing aerosol mixture causes a cooling (negative radiative forcing) or a warming (positive radiative forcing) in the atmosphere. At Hohenpeißenberg the SSA changed from 0.85 to 0.91 in the time period 1999 to 2005, i.e. the regional aerosol as a whole is dominated by scattering rather than absorbing particles.

Conclusion and Perspective

From current aerosol trends at the GAW global station Hohenpeißenberg it was possible to analyze their relevance for air pollution control and possible influences on climate. Dust mass is not a suitable parameter for accessing the contribution of diesel engined vehicles. Measuring the number concentration of particles much more reflects the influence of diesel engined vehicles and also shows, as expected, an upward trend due to a strong increase of the fraction of diesel vehicles in comparison to the total number of cars. Aerosol particles scatter and absorb solar radiation and thus cause a cooling or warming in the atmosphere. Calculated values of the single scattering albedo at Hohenpeissenberg show, that in the initial years the aerosol did not diminish the temperature rise, but rather caused it to increase. Only a data comparison from a global network like GAW can demonstrate, if the results are even representative for the large scale situation.     

Deposition and resorption of organic aerosol constituents in the respiratory tract as calculated from particle size distribution data

Data on the particle size distributions of organic aerosol constituents were used as input for a study, designed to calculate the fractions of the particulate concentrations of these compounds, deposited into the respiratory tract. The known relation between the deposition probability and the particle size as described by the ICRP‐model was used. The organic constituents were from the classes of the aliphatic hydrocarbons, carboxylic acids, polycyclic and aza‐heterocyclic aromatic hydrocarbons. Aerosol samples were obtained by Hi‐Vol cascade impactor sampling at suburban, rural and sea shore background stations as well as in an industrial emission site (coke oven).

Our approach uses the measured concentrations, being average values within each impactor particle size interval, as well as the integrated average deposition probabilities. This procedure was validated experimentally for eight model distributions from the literature, for which an infinitesimal calculation of the deposited fractions was possible.

Dilution reduces total particulate concentrations in the remote areas and predominantly determines the total deposited pollutant concentrations. Of these, pulmonary and nasopharyngeal deposition are most significant and, as a first approximation, correspond largely to the relative importance of the accumulation and dispersion modes of the sampled aerosol. A particle size distribution shift toward larger particles within the accumulation mode occurs upon ageing of the aerosol and reduces the pulmonary deposited fraction of the measured compounds in the background sites, compared to the one in the suburb. The total deposited fraction, however, increases. The contributions of biogenic higher odd n‐alkanes and, to a lesser extent, of even carboxylic acids to the dispersion mode of the aerosol result in an increased nasopharyngeal deposition at the background sites mainly during summer.

Since little information on the bio‐availability of organic aerosol constituents is available in the literature, the fractions of the particulate pollutant concentrations, resorbed in the tissues from the deposited material, were calculated, assuming an average efficiency of 70% for pulmonary and of 10% for nasopharyngeal and tracheobronchial resorption. A nearly constant total resorbed fraction of 20±2% resulted, independent of the sampling station or the season chosen, in contrast with the total deposited fractions, for which significant differences were observed. The predominant pulmonary resorption as well as compensating effects of the nasopharyngeal resorption level out the relatively small differences in particle size distributions observed. Based on these data, a first estimate in nanogram of the daily intake by inhalation of the organic pollutants studied can be formulated as four times the particulate pollutant concentration, expressed in ngm^‐3.     

西太平洋海域海水和雨水的化学特征

本工作测定了西太平洋海域中海水、海水悬浮物和海面上雨水的元素组成和浓度。通过富集因子的计算,探讨海面上雨水中微量元素的富集程度及其来源,讨论了海面上气溶胶粒子大小与洗出因子的关系,结果表明不同质量粒径大小的微量元素在公海上具有相似的洗出因子。     

Particle sedimentation in the ocean

Annual particle sedimentation is calculated for various ocean regions using an empirical equation based on studies published prior to 1980. Organic carbon sedimentation is predicted from annual phytoplankton production and water depth. Published data show that organic carbon (as weight percent) in sedimented material decreases with depth and independent of depth increases with phytoplankton production. A matrix of values of organic carbon in settled material over depth for three levels of primary production, generally consistent with published data, is derived and used to calculate dry matter sedimentation over depth for various ocean regions. Ranges of values overlap those reported since 1980 except near continental margins. Resuspension and lateral transport of particulate matter increase sedimentation in these regions above rates predicted for the open ocean.