Field Experimental Investigations on the Fe(II)- and Fe(III)-Content in Cloudwater Samples

The Fe(II)/Fe(III)-partition in cloudwater samples collected during two field campaigns is evaluated. It turned out that the simultaneous occurrence of complexing and reducing substances in the atmosphere and the cloud processing increase the solubility of iron compounds present in aerosol particles. A correlation between the concentration of iron(II) in the liquid phase and the intensity of the solar irradiation was observed for most of the cloudwater samples. This could be due to the fact that both the photochemical reduction of the iron(III) complexes and the photochemical reductive dissolution of iron(III)(hydr)oxides are depending on the pH-value. Iron(II) seems to be oxidised back to iron(III) preferably by hydrogen peroxide during the night. Positive correlations were received e.g. between the concentration of dissolved iron and the concentration of oxalate and between the percentage of iron(III) and the concentration of hydrogen peroxide. A negative correlation was found e.g. between the concentration of dissolved iron and the pH-value. The uncertainty of the whole process of sampling and analysis was investigated and the conformity of the results was satisfying considering the sometimes difficult conditions during a field campaign.     

S(IV) Autoxidation in Atmospheric Liquid Water: The Role of Fe(II) and the Effect of Oxalate

The reactivity of dissolved iron compounds towards different pollutants and photooxidants in atmospheric liquid water depends upon the oxidation state and speciation of iron. Our measurements of the oxidation state of dissolved iron eluted from aerosol particles (Dae: 0.4–1.6 m) collected in the urban atmosphere of Ljubljana showed that a large fraction of the iron content is present as Fe(II). The concentration ratio [Fe(II)]/[Fe(III)] varied between 0.9 and 3.1. The kinetics of S(IV) autoxidation catalyzed by Fe(II) under the conditions representative for acidified atmospheric liquid water and the influence of oxalate on this reaction under dark conditions was investigated. The reaction rate is the same if Fe(II) or Fe(III) is used as a catalyst under the condition that Fe(II) can be oxidized in Fe(III), which is the catalytically active species. Oxalate has a strong inhibiting effect on the S(IV) autoxidation in the presence of Fe(II). The reaction is autocatalytic with an induction period, that increases with higher concentrations of oxalate. The inhibiting effect of oxalate differs according to whether iron is initially in the Fe(II) or Fe(III) state. However, in both cases the inhibition by oxalate is a result of the formation of complexes with the catalyst.     

Speciation and role of iron in cloud droplets at the puy de Dôme station

Iron is the most abundant transition metal in the atmosphere and can play a significant role in cloudwater chemistry where its reactivity is closely related to the partitioning between Fe(II) and Fe(III). The objective of this work is to determine the total iron content and the iron speciation in a free tropospheric site, and to understand which factors influence these parameters. We collected 147 samples of cloudwater during 34 cloud events over a period of four years at the puy de Dôme summit. Besides iron we measured other chemical compounds, solar radiation, physico-chemical and meteorological parameters potentially connected with iron reactivity. The total iron concentrations ranged from 0.1 to 9.1 μM with the major frequency occurring at low levels. The pH and presence of organic complexants seem to be the most significant factors connected with total dissolved iron; while the iron oxidation state seems to be an independent factor. Light intensity, presence of complexants or oxidants (H₂O₂) do not influence the Fe(II)/Fe(Total) ratio, that was quite constant at about 0.75. This could be due to the potential redox that forces the Fe(II)-Fe(III) couple to the reduced form or, more probably to the complexation by Natural Organic Matter, that can stabilize iron in its reduced form and prevent further oxidation. Our field measurements did not show the diurnal cycle observed in surface water and predicted by models of atmospheric chemistry. This result prompts a more careful review of the role of iron and, by analogy, all the transition metals in atmospheric liquid phase, often over-estimated in the literature.     

The Great Dun Fell Experiment 1995: an overview

During March and April of 1995 a major international field project was conducted at the UMIST field station site on Great Dun Fell in Cumbria, Northern England. The hill cap cloud which frequently envelopes this site was used as a natural flow through reactor to examine the sensitivity of the cloud microphysics to the aerosol entering the cloud and also to investigate the effects of the cloud in changing the aerosol size distribution, chemical composition and associated optical properties. To investigate these processes, detailed measurements of the cloud water chemistry (including the chemistry of sulphur compounds, organic and inorganic oxidised nitrogen and ammonia), cloud microphysics and properties of the aerosol and trace gas concentrations upwind and downwind of the cap cloud were undertaken. It was found that the cloud droplet number was generally strongly correlated to aerosol number concentration, with up to 2000 activated droplets cm⁻³ being observed in the most polluted conditions. In such conditions it was inferred that hygroscopic organic compounds were important in the activation process. Often, the size distribution of the aerosol was substantially modified by the cloud processing, largely due to the aqueous phase oxidation of S(IV) to sulphate by hydrogen peroxide, but also through the uptake and fixing of gas phase nitric acid as nitrate, increasing the calculated optical scattering of the aerosol substantially (by up to 24%). New particle formation was also observed in the ultrafine aerosol mode (at about 5 nm) downwind of the cap cloud, particularly in conditions of low total aerosol surface area and in the presence of ammonia and HCl gases. This was seen to occur at night as well as during the day via a mechanism which is not yet understood. The implications of these results for parameterising aerosol growth in Global Climate Models are explored.     

The occurrence of bisulfite-aldehyde addition products in fog- and cloudwater

Elevated concentrations of S(IV) and formaldehyde were observed in fog- and cloudwater at sites in California. The highest concentrations (up to 3 mM S(IV) and 0.7 mM CH₂O) were measured at Bakersfield, during a prolonged period of repeated fog. In Bakersfield [S(IV)] generally exceeded [CH₂O], while in the Los Angeles area the reverse was observed. The lowest concentrations of both species were observed at marine and high altitude sites away from local emissions. Equilibrium computations indicate that high concentrations of S(IV) cannot be achieved without the formation of S(IV)-RCHO adducts.     

The Drop Size-Dependence of Iron and Manganese Concentrations in Clouds and Fogs: Implications for Sulfate Production

Differences in total iron and manganese concentrations between large (d > 23 m) and small (4 < d < 23 m) cloud and fog drops were investigated at four locations in the United States. The study examined coastal stratus and stratocumulus clouds in southern California and northern Oregon, frontal and orographic clouds at Mt. Mitchell, North Carolina, and radiation fogs in California's San Joaquin Valley. The speciation of iron as a function of drop size was also examined in some fog samples from the San Joaquin Valley. Total iron and manganese concentrations were generally higher in large drops than in small drops in clouds sampled at Mt. Mitchell and along the southern California coast. These species were typically enriched in small drops at the Oregon coast and San Joaquin Valley sites. Ratios of dissolved Fe(III) to total dissolved Fe ranged from 0.88 to 0.93 in small fog drops. Non-uniform distributions of iron and manganese across the drop size spectrum can influence rates of metal catalyzed S(IV) autooxidation. Approximately 50% of the sampled clouds were calculated to experience autooxidation rate enhancements greater than 30% due to variations in drop acidity and catalyst concentrations with drop size.     

Modelling of the nighttime nitrogen and sulfur chemistry in size resolved droplets of an orographic cloud

A chemistry module has been incorporated into a Lagrangian type model that computes the dynamics and microphysics of an orographical cloud formed in moist air flowing over the summit of Great Dun Fell (GDF) in England. The cloud droplets grow on a maritime aerosol which is assumed to be an external mixture of sea-salt particles and ammonium-sulfate particles. The dry particle radii are in the range 10 nm<r<1 µm. The gas-phase chemical reaction scheme considers reactions of nitrogen compounds that are important at night. The treatment of scavenging of gases into the aqueous phase in the model takes into account the different solubilities and accommodation coefficients. The chemistry in the aqueous phase focusses on the oxidation of S(IV) via different pathways.Sensitivity analyses have been performed to investigate deviations from gas-liquid equilibria according to Henry's law and also to study the influence of iron and of nitrogen compounds on the aqueous-phase oxidation of dissolved SO₂. When addressing these questions, special attention has been given to the dependence on the droplet size distribution and on the chemical composition of the cloud condensation nuclei on which the droplets have formed. It was found that the oxidation of S(IV) via a chain reaction of sulfur radicals can be important under conditions where H₂O₂ is low. However, major uncertainties remain with respect to the interaction of iron with the radical chain. It was shown that mixing of individual cloud droplets, which are not in equilibrium according to Henry's law, can result in a bulk sample in equilibrium with the ambient air. The dependence of the aqueous-phase concentrations on the size of the cloud droplets is discussed for iron, chloride and NO₃.     

In-cloud scavenging of gases and aerosols at a mountain site in Central Switzerland

An in-cloud scavenging case study of the major ions (NH₄ ⁺, SO₄ ^2- and NO₃ ^-) determining the cloudwater composition at a mountain site (1620 m.a.s.l.) is presented. A comparison between in-cloud measurements of the cloudwater composition, liquid water content, gas concentrations and aerosol concentrations and pre-cloud gas and aerosol concentrations yields the following results. Cloudwater concentrations resulted from scavenging of about half of the available NH₃, aerosol NH₄ ⁺, aerosol NO₃ ^-, and aerosol SO₄ ^2-. Approximately a third of the SO₂ was scavenged by the cloudwater and oxidized to SO₄ ^2-. Cloud acidity during the first two hours of cloud interception (pH 3.24) was determined mostly by the scavenged gases (NH₃, SO₂, and HNO₃); aerosol contributions to the acidity were found to be small. Observations of gas and aerosol concentrations at three elevations prior to several winter precipitation events indicated that NH₃ concentrations are typically half (12–80 %) of the total (gas and aerosol) N (-III) concentrations. HNO₃ typically is present at much lower concentrations (1–55 %) than aerosol NO₃ ^-. Concentrations of SO₂ are a substantial component of total sulfur, with concentrations averaging 60 % (14–76 %) of the total S (IV and VI).     

Effects of Rainwater Iron and Hydrogen Peroxide on Iron Speciation and Phytoplankton Growth in Seawater near Bermuda

Rainwater is a major source of dissolved iron to much of the world's oceans, including regions where iron may be a limiting nutrient for marine phytoplankton primary production. Rainwater iron is therefore potentially important in regulating global photosynthetic uptake of CO₂, and hence climate. Two rainwater addition bioassay experiments (2% rain) conducted at the Bermuda Atlantic Time-series Station (BATS) during March 2000 using 50 or 100 nM FeCl₂ or FeCl₃ in synthetic rain (pH 4.5 H₂SO₄) showed an increase in chlorophyll a 50% greater than controls after three days. Addition of 20 μM hydrogen peroxide, a typical rainwater concentration at BATS, completely removed the chlorophyll a increase with both forms of iron additions, suggesting stimulation of phytoplankton growth by rainwater iron can be limited by rainwater H₂O₂. In laboratory experiments using Gulf Stream seawater, iron-enriched (100 nM Fe(III)) synthetic rain was mixed with seawater in a 5% rain 95% seawater ratio. Dissolved iron concentrations increased two times above concentrations predicted based on dilution alone. The increase in soluble iron probably resulted from release from seawater particles and was maintained for more than 24 hours. No increase was observed in controls that did not have iron added to the synthetic rain, or with synthetic rainwater containing both added iron and H₂O₂. The increase in iron concentration above that predicted by dilution indicates rain may have a larger effect on seawater iron concentrations than that calculated for rainwater iron addition alone.     

The Effect of Atmospheric Organic Compounds on the Fe-Catalyzed S(IV) Autoxidation in Aqueous Solution

Laboratory experiments were conducted with real atmospheric aerosol particles as well as with synthetic solutions under dark conditions, to simulate some of the chemical features of aerosols. In solutions obtained by the leaching of aerosols (size range >D _ae: 0.4–1.6 m) that contained sufficient amounts of transition metal ions (e.g. Fe) and organic species (e.g. oxalate), S(IV) oxidation rates were significantly lower than those expected from the Fe-catalyzed S(IV) autoxidation in Milli-Q water. The results suggest that oxalate is responsible for much of the observed inhibition. Acetate and formate also inhibit the reaction, but to a much lesser extent. Oxalate has a strong inhibiting effect on the Fe-catalyzed S(IV) autoxidation at all investigated pH values (2.8, 3.7 and 4.5). It was established that Fe(III)-oxalato complexes affect the redox cycling of Fe(II)/Fe(III) and that the observed decrease of the reaction rate is caused by the reduced amount of catalytically active Fe(III) due to the complexation with oxalate. For the system Fe-S(IV)-O₂-oxalate at initial pH 3.7 the reaction rate was calculated using exponential simplification to account for oxalate influence on the amount of free Fe(III) by the following equation:–r_S(IV) = k · [S(IV)] · [Fe(III))] · e ^-b·[Ox]     

NUMERICAL SIMULATION OF ACIDIFICATION PROCESSES IN COLD CUMULUS CLOUDS

In this paper, a 1-D time dependent cold cumulus chemistry model is presented. In the coldcumulus model, 4 categories of hydrometeors: cloud drops, raindrops, cloud ice crystals, graupelparticles, and 18 microphysical interactions are considered, In the chemical model, the source andsink terms for pollutants include: the complicated interactions between pollutants (gases andaerosol particles) and the hydrometeors (especially ice crystals and graupel particles), the ex-changes of chemical compounds between two hydrometeors accompanying microphysical processesand the aqueous oxidations of S (IV) to S (VI). The two models are combined to study the acidifi-cation processes in cold cumulus clouds.     

Biogenic and anthropogenic organic matter in aerosol over continental Europe: source characterization in the east Baltic region

An Aerodyne quadruple aerosol mass spectrometer (Q-AMS) has been used to provide on-line measurements of size dependent chemical composition of fine aerosol particles (PM₁) at the Air Pollution Research Station in Preila, Lithuania, representing the east Baltic region. The size dependent chemical composition measurements by AMS have revealed that in marine air masses 118?nm mode organics-containing particles were fresher compared to sulfate-containing particles (295?nm), likely originated as secondary aerosol from forest emissions or produced by primary sea spray over the Baltic Sea. In polluted continental air masses sulfate and organics were highly internally mixed and aged. The mass spectral results indicated that the major components of organic compounds were oxygenated organic species with strong signals at m/z 18, 43, 44 with several specific features. Positive matrix factorization (PMF) of AMS organic mass spectral data has identified three factors: aged oxygenated low-volatility organic aerosol (LV-OOA), less oxygenated semi-volatile organic aerosol (SV-OOA), and biogenic organic aerosol (BGOA) of either terrestrial or marine origin. The measurements were compared with a real-time particulate matter Beta Absorption Monitor (Thermo ESM Andersen) and Micro Orifice Uniform Deposit Impactor (MOUDI) data. The intercomparison showed a good correlation and a stable ratio between PM₁ and PM_2.5 concentrations. A comparison of the on-line Q-AMS data and the off-line MOUDI fine particle (<1???m) data yielded a reasonable agreement in size distributions but not the absolute mass concentrations due to sampling conditions, evaporation of acidic species from sampling substrates and bounce of the particles in the MOUDI.     

新疆乌鲁木齐地区冬季降水与云水酸度及其化学成分的初步观测分析

分析了乌鲁木齐地区冬季降雪和云水的pH值与化学成分。降雪pH值平均为5.7。云水pH值为4.0左右，与采集云水同时段观测的地面降雪pH值为6.0。气团内部生成的低云云水的离子浓度比系统性降水云高约两个量级。初步分析结果表明，雪增长的微物理过程和雪粒下降过程中所捕集的大气气溶胶粒子特性可能对降雪雪水酸度有重要影响。     

Single Particle Characterisation of the Aerosol in the Marine Boundary Layer and Free Troposphere over Tenerife, NE Atlantic, during ACE-2

In the framework of the 2nd Aerosol Characterization Experiment (ACE-2), in June and July 1997, size segregated samples were collected for single particle analysis on the island of Tenerife, in both the marine boundary layer (MBL) and the free troposphere (FT), to study the characteristics of the North Atlantic aerosol. A systematic assessment was made of the aerosol under background conditions and when the environment was perturbed by European emissions and/or Saharan dust. The aerosol particles were analysed by automated and manual SEM-EDX, followed by cluster analysis to identify the different particle types and their abundance. Basing on back trajectory calculations, particle numbers and volume concentrations, different periods can be identified regarding the origin of the sampled air masses. In the FT, the air masses were classified as clean Atlantic, Saharan dust from Africa or pollution from Europe. In the MBL, air masses were classified as clean, polluted or perturbed by emissions from Europe. For both the FT and MBL samples, the main changes in chemical composition were observed between the fine and coarse mode aerosol. The FT fine mode aerosol is dominated by S-poor aluminosilicates (62%) in the event of the dust samples or sulphates, carbonaceous particles (20%) and S-rich aluminosilicates (46%) in the polluted samples. For the larger fractions, a strong decreasing trend was observed for the sulphates (less than 20%) and carbonaceous particles (10%) in the polluted samples. The MBL fine mode was completely dominated by S-rich particles (polluted 55% and perturbed 59%), and to a lesser extent, carbonaceous and aged sea salt particles. In the coarse mode, the polluted air mass is dominated by sea salt particles (62%). Contrary to the fine fraction, the polluted air mass in the coarse fraction contained 5.3% of S-rich particles. The combined interpretation of the data from the analysis of size-fractioned particles and the calculated backward trajectories for air masses coming from Europe, Africa and the Atlantic, results in better insights on aerosol chemistry, especially for the comparison of the particle composition in the FT and the MBL.     

北京和邢台新粒子生成的差别及其对CCN活性的影响

基于2016年冬季和2017年夏季在北京、2016年夏季在邢台的三次气溶胶外场观测实验,选取三次观测期间典型的新粒子生成事件,分析其对气溶胶吸湿和云凝结核（CCN）活化特性的影响。两地分别位于华北平原北部超大城市区域和中南部工业化区域,两地不同季节新粒子形成机制不同,对应的凝结汇、生长速率以及气溶胶化学组分也不同。北京站点新粒子生成事件的发生以有机物的生成主导,而邢台站点新粒子生成事件的发生则以硫酸盐和有机物的生成共同主导。邢台站点新粒子生成过程中气溶胶吸湿性及云凝结核活化能力明显强于北京站点,此特点在核模态尺度粒子中表现尤为明显。以上结果表明,在估算新粒子生成对CCN数浓度的影响时,应充分考虑气溶胶吸湿和活化特性的差异。     

Numerical quantification of sources and phase partitioning of chemical species in cloud: application to wintertime anthropogenic air masses at the Puy de Dôme station

The Model of Multiphase Cloud Chemistry M2C2 has recently been extended to account for nucleation scavenging of aerosol particles in the cloud water chemical composition. This extended version has been applied to multiphase measurements available at the Puy de Dôme station for typical wintertime anthropogenic air masses. The simulated ion concentrations in cloud water are in reasonable agreement with the experimental data. The analysis of the sources of the chemical species in cloud water shows an important contribution from nucleation scavenging of particles which prevails for nitrate, sulphate and ammonium. Moreover, the simulation shows that iron, which comes only from the dissolution of aerosol particles in cloud water, has a significant contribution in the hydroxyl radical production. Finally, the simulated phase partitioning of chemical species in cloud are compared with measurements. Numerical results show an underestimation of interstitial particulate phase fraction with respect to the measurements, which could be due to an overestimation of activated mass by the model. However, the simulated number scavenging efficiency of particles agrees well with the measured value of 40% of total number of aerosol particles activated in cloud droplets. Concerning the origin of chemical species in cloud water, the model reproduces quite well the contribution of gas and aerosol scavenging estimated from measurements. In addition, the simulation provides the contribution of in-cloud chemical reactivity to cloud water concentrations.     

我国西南地区云水化学的某些基本特征

本文介绍了1989年9—10月份在成都、重庆和贵阳地区进行的一次酸雨综合观测中得到的以这些地区为代表的西南地区云水化学的一些基本特征.结果说明,该地区云水已酸化.从云水酸度和化学组分时空分布规律及其变化,云水和雨水化学组分对比分析表明,该地区云下过程对雨水酸化起重要作用.     

Size Distributions of Aerosol Sulfates and Nitrates in Beijing during the 2008 Olympic Games: Impacts of Pollution Control Measures and Regional Transport

For the 2008 Olympic Games, drastic control measures were implemented on industrial and urban emissions of sulfur dioxide (SO₂), nitrogen oxides (NO_x) and other pollutants to address the issues of poor air quality in Beijing. To investigate the effects of SO₂ and NO_x reductions on the particulate sulfate and nitrate concentrations as well as their size distributions, size-segregated aerosol samples were collected using micro-orifice uniform deposit impactors (MOUDIs) at urban and downwind rural sites in Beijing before and after full-scale controls. During the sampling period, the mass concentrations of fine particles (PM_1.8) at the urban and rural sites were 94.0 and 85.9 μg m^-3, respectively. More than 90% of the sulfates and ～60% of nitrates formed as fine particles. Benefiting from the advantageous meteorological conditions and the source controls, sulfates were observed in rather low concentrations and primarily in condensation mode during the Olympics. The effects of the control measures were separately analyzed for the northerly and the southerly air-mass-dominated days to account for any bias. After the control measures were implemented, PM, sulfates, and nitrates were significantly reduced when the northerly air masses prevailed, with a higher percentage of reduction in larger particles. The droplet mode particles, which dominated the sulfates and nitrates before the controls were implemented, were remarkably reduced in mass concentration after the control measures were implemented. Nevertheless, when the polluted southerly air masses prevailed, the local source control measures in Beijing did not effectively reduce the ambient sulfate concentration due to the enormous regional contribution from the North China Plain.     

污染气溶胶对山西一次降水过程影响的数值模拟

利用耦合Morrision双参数物理方案的WRF(Weather Research and Forecasting)中尺度数值模式,对发生在2007年6月13日山西地区的一次强降水过程进行了模拟,并对清洁和污染背景下气溶胶对云微物理结构和降水变化的影响进行了敏感性试验和对比分析.结果显示:污染背景下,降水区域没有明显变...     

Source apportionment of visibility‐degrading aerosols in the lower fraser valley,B.C.

Abstract

The Lower Fraser Valley of British Columbia (LFV) is currently experiencing rapid population growth and is perceived to suffer from reduced air quality, specifically, elevated ozone concentrations and impaired visibility. It is necessary to identify the sources of visibility‐degrading aerosols in order to develop strategies to prevent further degradation and to institute measures to improve air quality in this region. Although chemical mass balance analyses have typically been used in such studies, herein, a P‐mode principal component analysis (PCA) is performed upon the ambient aerosol species at one polluted site in the LFV, and source profiles are inferred from the resulting component loadings. The loading coefficients on the five significant components (which account for over 70% of the variance in the fine aerosol speciation dataset) are used to assess the contribution of these sources to paniculate light scattering (b_sp) Automobile emissions and wood burning are found to contribute most to b_sp at this site.