Optical growth of highly viscous organic/sulfate particles

Light extinction by atmospheric particles is strongly dependent on their chemical composition and water content. Since light extinction directly impacts climate, optical measurements of atmospherically relevant aerosols at varying relative humidities (RH) are needed. Recent studies have highlighted the possibility that some atmospheric aerosols are glassy under ambient conditions. Here, the particle optical growth factor, fRH_ext, was measured for liquid and glassy particles using cavity ring-down aerosol extinction spectroscopy. The particles were composed of ammonium sulfate (AS), 1,2,6-hexanetriol, sucrose, raffinose, and mixed particles containing AS and either sucrose or raffinose. Both sucrose and raffinose can be glassy at room temperature. For the pure organics, the highly viscous sucrose and raffinose particles have similar optical growth curves to the liquid 1,2,6 hexanetriol particles. However, for particles composed of sucrose or raffinose mixed with AS, optical growth depends on the AS weight-percent, which in turn controls the phase state of the AS and ultimately the water uptake.     

Product study of the reaction of OH radicals with isoprene in the atmosphere simulation chamber SAPHIR

Atmospheric oxidation of isoprene and its oxidation products methacrolein (MACR) and methyl vinyl ketone (MVK) have an important impact on the photochemical activity in the boundary layer, in particular in forested areas. The oxidation of isoprene by OH radicals was investigated in chamber experiments conducted under tropospheric conditions in the atmosphere simulation chamber SAPHIR at the Research Center Jülich. The aim was to determine the product yield of MVK and MACR in the OH-induced isoprene oxidation and the rate constant of their reaction with OH under real atmospheric conditions. The recently published updated degradation scheme for isoprene from Geiger et al. (2003) was used to determine rate constants and product yields. The fractional yields in the isoprene peroxy radical reaction with NO were found to be 0.41±0.03 for MVK and 0.27±0.03 for MACR. The rate coefficient for MACR with OH was found to be in very good agreement with the recommended value of IUPAC Atkinson (Atkinson et al., 2005). while the rate coefficient for MVK with OH was 27% lower.     

Formation of carbonyls and hydroperoxyenals (HPALDs) from the OH radical reaction of isoprene for low-NOx conditions: influence of temperature and water vapour content

The formation of gas-phase products from the reaction of OH radicals with isoprene for low-NO_x conditions ([NO_x] ≤ 10¹⁰ molecule cm^?3) has been studied in an atmospheric pressure flow tube (Institute for Tropospheric Research-Laminar Flow Tube, IfT-LFT) operating in the temperature range of 293–343 K and a relative humidity of < 0.5 % up to 50 %. The photolysis of H₂O₂ or ozone photolysis in the presence of water vapour served as the NO_x-free OH radical sources. For dry conditions at 293 K, the measured yields of methyl vinyl ketone (MVK), 0.07?±?0.02, and methacrolein (MACR), 0.12?±?0.04, were in reasonable agreement with literature data. Beside the C₄-carbonyls, further product signals have been attributed tentatively to glycolaldehyde, methylglyoxal, hydroxyacetone, 3-methylfuran, C₅-hydroperoxyenals (HPALDs) and C₅-hydroxy-hydroperoxides. A simplified, “classical” reaction mechanism without efficient HPALD production describes well the observed yield for MVK and MACR. Unexpected high MVK and MACR yields of up to 0.65 in total were measured under conditions of a relative humidity of 50 % using both OH radical sources and two different measurement techniques for organics (proton transfer reaction mass spectrometry and gas chromatography with flame ionization detector). The reaction mechanism applied is not able to describe the strong increase of MVK and MACR yields with increasing water vapour content. The signal attributed to the HPALDs showed a distinct rise of about one order of magnitude increasing the temperature from 293 K to 343 K. A rough estimate leads to a HPALD yield of 0.32 at 343 K with an uncertainty of a factor of two. The results of this study do not support a predominant formation of HPALDs under atmospheric conditions in low-NO_x areas. The surprisingly high MVK and MACR yields measured for a relative humidity of 50 % and the formation of glycolaldehyde, methylglyoxal and hydroxyacetone necessitate further research.     

Carbonaceous Particle Hydration III

Previous soot hydration studies have been extended to compare the water uptake properties of soots from selected fuels (JP-8 Jet fuel, kerosene, diesel, and metal containing and S-containing synthetics) prepared under varying conditions with corresponding n-hexane model soots. Adsorption and desorption isotherms have yielded such adsorption parameters as the surface coverages at the limit of chemisorption and at 83% relative humidity (RH). These values increase with soot surface oxidation over the range 35–85% RH, while hydration levels at lower RH down to 22% are a function of fuel composition and combustion conditions, thus determining the extent of water uptake at higher RH. Both S- and metal-containing soots exhibit higher levels of hydration than those of the base fuel soots, a result with its origin in availability of sulfate and metal centers at the surface.     

Oligomerization of levoglucosan by Fenton chemistry in proxies of biomass burning aerosols

Reactions of levoglucosan with produced from Fenton chemistry were studied in solution serving as a proxy for biomass burning aerosols. Two modes of oligomerization (≤2000 u) were observed for reaction times between 1 and 7 days using matrix-assisted laser desorption time-of-flight mass spectrometry (MALDI-TOF-MS) and laser desorption ionization time-of-flight mass spectrometry (LDI-TOF-MS). Single-mass unit continuum mass distributions with dominant −2 u patterns were measured and superimposed by a +176/+162 u oligomer series. This latter oligomer pattern was attributed to a Criegee rearrangement (+14 u) of levoglucosan, initiated by , forming a lactone (176 u). The acid-catalyzed reaction of any ROH from levoglucosan (+162 u) forms an ester through transesterification of the lactone functionality, whereupon propagation forms polyesters. Proposed products and chemical mechanisms are suggested as sources and precursors of humic-like substances (HULIS), which are known to possess a large saccharic component and are possibly formed from biomass burning aerosols (Andreae, Global Biomass Burning, MIT Press, Cambridge, Massachusetts, 3–21, 1991).     

The Effect of Air/Fuel Ratio on Properties and Reactivity of Combustion Soots

The dependence of specific properties of black carbon (BC) soots on fuel type and combustion conditions has been studied, and the effects of these properties on soot particle hydration and reaction with ozone determined. Series of soots were prepared from n-hexane, diesel and JP8 aircraft fuels, utilizing a flow combustion system designed for accurate control of the air/fuel ratio in premixed flames. It has been shown that, for each of these, linear relationships exist between the state of soot surface oxidation, surface area, unpaired electron spin density, and air/fuel ratio. The interrelationship of these properties potentially enables the preparation of soots with pre-selected characteristics by establishing combustion conditions for each fuel type. Predictable variations in these soot characteristics have been demonstrated through preparations near sea level and at higher elevation. Soot hydration and its reactivity with ozone are quantitatively related to surface oxidation and, thus, the air/fuel combustion ratio for soot's formation in premixed flames. The effect of relative humidity (RH) on the soot-ozone reaction over the O₃ concentration and RH ranges 2–4.8 ppm and17–78%, respectively, is expressed by–d[O₃]/dt =k[O₃]²[H₂O]^0.2and is directly related to particle surface oxidation.     

Seasonal variability of air-sea fluxes in two contrasting basins of the North Indian Ocean

Latent Heat Flux (LHF) and Sensible Heat Flux (SHF) are the two important parameters in air-sea interactions and hence have significant implications for any coupled ocean-atmospheric model. These two fluxes are conventionally computed from met-ocean parameters using bulk aerodynamic formulations; or the Coupled Ocean Atmosphere Response Experiment (COARE) bulk flux algorithms. Here COARE 3.5 algorithm is used to estimate the heat flux from two Ocean Moored Buoy Network for northern Indian Ocean (OMNI) buoy met-ocean observations in Arabian Sea (AS) and the Bay of Bengal (BoB). The AS and BoB are two ocean basins which are situated in same latitudinal range, but experience drastically differing in their met-ocean conditions, especially during the monsoon seasons. In this study, we have computed and compared the LHF and SHF at two different buoy locations in the AS and BoB and analysed their variability during three different seasons from November 2012 to September 2013. Additionally, 20 years (1998–2017) of Objectively Analysed (OA) Flux data sets collocated with the OMNI buoy locations were also utilised to the analyse the long period seasonal variabilities. The flux terms show strong seasonal variability with several peaks during the monsoon seasons in both the ocean basins. LHF varies directly with wind speed (WS) and inversely with relative humidity (RH). The correlation of LHF with WS is greater than 0.7 and RH is nearly -0.6 with few exceptions during pre-monsoon season in the AS and southwest monsoon in the BoB. However, SHF is less correlated with WS (∼0.3 to 0.5). The difference of sea surface temperature and air temperature (denoted as SST-AT) plays a significant role in determining SHF with a correlation greater than 0.6 in both the basins.     

NaCl Aerosol Particle Hygroscopicity Dependence on Mixing with Organic Compounds

Organic compounds in the atmosphere can influence the activation, growth and lifetimes of haze, fog and cloud droplets by changing the condensation and evaporation rates of liquid water by these aqueous aerosol particles. Depending on the nature and properties of the organic compounds, the change can be to enhance or reduce these rates. In this paper we used a tandem differential mobility analyzer (TDMA) to examine the effect of tetracosane, octanoic acid, and lauric acid on the hygroscopic properties of NaCl aerosol particles at relative humidities (RH) between 30 and 95%. These organic compounds have been identified in ambient aerosol particle samples. A slight lowering of the deliquescence relative humidity (DRH) and suppression of hygroscopic growth for the NaCl-organic compound mixtures were observed when compared to pure NaCl particles. The growth of pure NaCl particles was 2.25 in diameter at 85% RH while the growth of the mixed particles was 1.3 to 1.7 in particle diameter at 85% RH with organic mass fraction of 30–50%. This shows that these organic compounds have to be present in rather large mass fractions to effect the hygroscopic behavior to a similar degree observed for ambient aerosol during field measurements. Despite the mixing of the organic material with NaCl, hysteresis was observed for decreasing RH histories, suggesting the formation of metastable droplets. These laboratory results are strikingly similar to ambient field results. For example, if the total organic mass fraction of the particles is between 0.30 and 0.50, the particle growth at 85% RH is about a factor of 1.4 for the laboratory and field measurements. Such reduction in growth compared to the pure inorganic salt is in contradiction to speculations concerning significant effects by organic compounds on cloud condensation nuclei and thus formation on clouds.     

Deuterium, Oxygen-18, and Tritium as Tracers for Water Vapour Transport in the Lower Stratosphere and Tropopause Region

Simultaneous measurements of the three rare isotopes Deuterium (D), Tritium (T), and Oxygen-18 (18O) in water vapour were made for the first time in the vicinity of the northern hemisphere tropopause. In contrast to expectation, high D/H and 18O/16O ratios, but relatively low T/H ratios, were found within the lowermost stratosphere. Since water vapour in the low-latitude upper troposphere shows a similar isotopic signature, we conclude that in the mid-latitudes considerable amounts of tropospheric water vapour are injected into the lowermost stratosphere, probably resulting in a hydration of the lower stratosphere. In addition, T can serve as tracer for precipitation of water containing stratospheric aerosol particles, because the T/H ratio in stratospheric water vapour is orders of magnitude higher than in the upper troposphere. Thus, even a small contribution of water of stratospheric origin should be detectable in the tropopause region. In our measurements performed in the Arctic we did not find isotopic evidence for sedimentation of PSC particles down to the tropopause. This may be caused by the low spatial and temporal coverage of our observations; however, it may also be due to the much weaker wintertime dehydration of the Arctic vortex compared to the Antarctic.     

Hygroscopic behavior of aerosol particles from biomass fires using environmental transmission electron microscopy

We used both a conventional transmission electron microscope and an environmental transmission electron microscope (ETEM) to determine morphology, composition, and water uptake of 80 individual aerosol particles collected from the young smoke of flaming and smoldering fires during SAFARI-2000, a comprehensive air quality campaign in southern Africa. Six representative carbonaceous particle types are described, including soot, tar balls, and heterogeneously internally mixed particles containing C with S-, K-, Mg- or Na-rich inorganic phases. The hygroscopic behavior of these particles over the range 0–100% relative humidity (RH) was studied in detail. Soot and tar balls did not take up water, whereas the mixed organic–inorganic particles took up water between 55 and 100% RH, the exact value depending on the composition of their water-soluble phases. The inorganic phase appeared to determine the hygroscopic properties of all mixed organic–inorganic particles. Thus, incorporation of inorganic plant material or reactions with inorganic atmospheric components can dramatically alter the hygroscopic properties of carbonaceous particles in smoke plumes. The fraction of these mixed organic–inorganic particles plausibly increases with time, which will modulate the effects of smoke on radiative budgets.     

Estimation of PM_(2.5) Mass Concentration from Visibility

Aerosols in the atmosphere not only degrade visibility, but are also detrimental to human health and transportation. In order to develop a method to estimate PM_(2.5) mass concentration from the widely measured visibility, a field campaign was conducted in Southwest China in January 2019. Visibility, ambient relative humidity(RH), PM_(2.5) mass concentrations and scattering coefficients of dry particles were measured. During the campaign, two pollution episodes, i.e., from 4-9 January and from 10-16 January, were encountered. Each of the two episodes could be divided into two periods. High aerosol hygroscopicity was found during the first period, when RH was higher than 80% at most of the time, and sometimes even approached 100%. The second period experienced a relatively dry but more polluted condition and aerosol hygroscopicity was lower than that during the first period. An empirical relationship between PM_(2.5) mass concentration and visibility(ambient aerosol extinction) under different RH conditions could thus be established. Based on the empirical relationship,PM_(2.5) mass concentration could be well estimated from visibility and RH. This method will be useful for remote sensing of PM_(2.5) mass concentration.     

基于加密探空资料的上海不同云天下AIRS/Aqua相对湿度廓线反演精度研究

目前云对卫星相对湿度廓线反演精度的影响研究大多是针对云量,对其他云属性的影响研究尚少,云高也是影响卫星相对湿度廓线反演精度的重要因素。利用上海宝山站L波段(1型)加密探空资料,分析了上海地区7—9月不同质量控制标识、云量和云顶高度条件下大气红外探测器AIRS/Aqua (Atmospheric Infrared Sounder)相对湿度廓线的反演精度,以期为今后开展AIRS等卫星资料的同化研究提供科学依据。结果表明：（1）AIRS相对湿度廓线反演误差随着云量的增加而逐渐增大,并且随着气压值的升高,少云与多云时的均方根误差(Root Mean Squared Error, RMSE)之差有逐渐增大的趋势;（2）云顶高度越高,AIRS相对湿度廓线反演精度越差,云顶以上湿度廓线反演精度更高,而云顶以下高度的反演误差较大;（3）高云且多云时,AIRS相对湿度廓线的反演精度最差,850 hPa处,AIRS相对湿度反演数据与探空资料绝对误差的下限达到了-63.51%;(4)虽然质量控制标识为0时,AIRS湿度廓线在对流层范围内的反演精度仍达不到无线电探空的水平,但是相对于质量控制标识1时,反演精度...     

Influence of High Relative Humidity on Secondary Organic Carbon: Observations at a Background Site in East China

To investigate the impacts of relative humidity(RH) on secondary organic aerosol(SOA) concentrations and chemical reactions, the carbonaceous aerosol components [i.e., organic carbon(OC) and element carbon(EC)] were quantified in daily PM2.5 samples collected at a background site in East China during summer 2015. Based on the method of EC-tracer, the concentration of secondary organic carbon(SOC) demonstrated an obvious negative relationship with RH higher than 60%. Moreover, the ratio of SOC/EC also exhibited obvious decreasing trends with increasing RH, indicating negative effects for chemical production of SOA under high RH conditions. Due to high RH,photochemistry was weakened, gaseous oxidant concentrations was lowered(e.g., significantly decreased O3 levels),and the production rates of SOA were relatively low. On the other hand, because of more water uptake under higher RH conditions, the aerosol droplet acidity was reduced and enhancement of SOA formation by acidity was accordingly absent. In addition, high RH also plays an important role in changing viscosity of pre-existing aerosol coatings,which can affect reactive uptake yield of SOA. Overall, the results from this study imply that SOA production may be more associated with photochemical processes, while aqueous-phase chemistry is not very important for some SOA formation in a moist ambient environment. In the ambient atmosphere, oxidant concentrations, reaction rates,airborne species, etc., are highly variable. How do these factors affect SOA yields under given ambient environment warrants further detailed investigations.     

利用MODIS大气廓线产品计算空气相对湿度的方法研究

森林火灾遍及全球,损失巨大。火险天气指数（FWI）是森林火灾预警和管理的有效工具。相对湿度（RH）是计算天气火险指数一个非常重要的参数。然而,由插值方法得到的RH在远离气象站点的地方往往存在很大的误差。因此,尝试利用MODIS遥感数据计算基于像元的高分辨率RH。MODIS的MOD07大气廓线产品,可以提供大气可降水量和地表气温数据。基于地面水汽压和大气可降水量的经验关系,利用MODIS数据计算了地表空气的相对湿度,平均绝对误差小于5％。结果表明,利用MODIS数据能简单而有效地计算地表空气的相对湿度,拓展了遥感技术在森林火险管理中的应用。     

On convection and static stability during the AMMA SOP3 campaign

Using radiosonde dataset from 15 weather stations over West Africa, this paper investigates the contribution of the couple convection-static stability in the framework of the African monsoon multidisciplinary analyses Special Observing Period 3 (AMMA SOP3) experiment. Within this 31-day period, the boundary layer-winds depictions have revealed the West African monsoon’s (WAM) depth (around 1500 m) is not thick enough to trigger intense convection. However, the midlevel winds distribution (700–600 hPa) has shown the average African easterly jet core strength (15 m s^?1) is sufficient to allow the development of African easterly waves (AEWs) necessary for squall lines activities. In return, in the upper levels (200–100 hPa), the speed (below 18 m s^?1) of the mean Tropical easterly jet (TEJ) core cannot favor midlevel updrafts. The free tropospheric humidity (FTH) depiction has indicated convective events are more likely in the western Sahel where the highest FTH (FTH >50 %) are recorded. The static stability analysis has testified that convection is stronger in the semi-arid (SA) area during night time (0000 GMT). However, convective activities are inhibited in the wet equatorial (WE) region due to mean low-level stability. We used METEOSAT Second Generation (MSG) infrared (IR10.8) imagery of the 8th September 2006 to confirm that result. Furthermore, a maximum midtropospheric static stability combined with maximum relative humidity (RH) was found on the fringe of the Saharan air layer’s (SAL) top (altitude around 5.3 km) in the WE region.     

Mass spectrometric study of aged benzene secondary organic aerosol in the presence of dry ammonium sulfate

Inorganic seed particles have relatively large surface area, and play an important role in the formation and aging of secondary organic aerosol (SOA). The effects of dry (NH₄)₂SO₄ which is the most commonly found in urban atmosphere on the aged benzene SOA were qualitatively studied utilizing aerosol laser time-of-flight mass spectrometer (ALTOFMS) coupled with Fuzzy C-Means (FCM) clustering algorithm in this study. Experimental results indicated that nitrophenol, oxocarboxylic acid, epoxide products are the predominant components in the aged benzene SOA in the presence of low concentration (about 10 μg m^?3) of dry (NH₄)₂SO₄. These aged products are the same as the previously obtained aged benzene SOA without (NH₄)₂SO₄ seed aerosol, indicating that low concentration of dry (NH₄)₂SO₄ acts just as the nucleation or condensation center of the SOA, and do not affect the chemical composition of SOA. However, 1 H-imidazole, 1 H-imidazole-2-carbaldehyde, hydrated 1 H-imidazole-2-carbaldehyde, 2,2′-biimidazole, hydrated N-glyoxal substituted 1 H-imidazole, N-glyoxal substituted hydrated 1 H-imidazole-2- carbaldehyde, hydrated mono glyoxal substituted hydrated 1 H-imidazole-2-carboxaldehyde, mono glyoxal substituted 2,2-biimidazole and hydrated glyoxal dimer substituted imidazole which are formed from ammonium ion reaction with glyoxal are the major particulate products in the aged benzene SOA in the presence of high concentration (about 100 μg m^?3) of dry (NH₄)₂SO₄. The retention of water on the dry (NH₄)₂SO₄ particles creates ammonium ion, which can promote the formation of high-molecular-weight (HMW) products through multiphase reactions such as hydration and polymerization of aldehydes form from OH-initiated oxidation of benzene.     

Evaluation of Surface Relative Humidity in China from the CRA-40 and Current Reanalyses

Recently, the China Meteorological Administration (CMA) released a new Global Atmospheric Reanalysis (CRA-40) dataset for the period 1979-2018. In this study, surface relative humidity (RH) from CRA-40 and other current reanalyses (e.g., CFSR, ERA5, ERA-Interim, JRA-55, and MERRA-2) is comprehensively evaluated against homogenized observations over China. The results suggest that most reanalyses overestimate the observations by 15％-30％ (absolute difference) over the Tibetan Plateau but underestimate the observations by 5％-10％ over most of northern China. The CRA-40 performs relatively well in describing the long-term change and variance seen in the observed surface RH over China. Most of the reanalyses reproduce the observed surface RH climatology and interannual variations well, while few reanalyses can capture the observed long-term RH trends over China. Among these reanalyses, the CFSR does poorly in describing the interannual changes in the observed RH, especially in Southwest China. An empirical orthogonal function (EOF) analysis also suggests that the CRA-40 performs better than other reanalyses to capture the first two leading EOF modes revealed by the observations. The results of this study are expected to improve understanding of the strengths and weaknesses of the current reanalysis products and thus facilitate their application.     

State of mixing, shape factor, number size distribution, and hygroscopic growth of the Saharan anthropogenic and mineral dust aerosol at Tinfou, Morocco

The Saharan Mineral Dust Experiment (SAMUM) was conducted in May and June 2006 in Tinfou, Morocco. A H-TDMA system and a H-DMA-APS system were used to obtain hygroscopic properties of mineral dust particles at 85% RH. Dynamic shape factors of 1.11, 1.19 and 1.25 were determined for the volume equivalent diameters 720, 840 and 960 nm, respectively.
During a dust event, the hydrophobic number fraction of 250 and 350 nm particles increased significantly from 30 and 65% to 53 and 75%, respectively, indicating that mineral dust particles can be as small as 200 nm in diameter. Log-normal functions for mineral dust number size distributions were obtained from total particle number size distributions and fractions of hydrophobic particles. The geometric mean diameter for Saharan dust particles was 715 nm during the dust event and 570 nm for the Saharan background aerosol.
Measurements of hygroscopic growth showed that the Saharan aerosol consists of an anthropogenic fraction (predominantly non natural sulphate and carbonaceous particles) and of mineral dust particles. Hygroscopic growth and hysteresis curve measurements of the 'more' hygroscopic particle fraction indicated ammonium sulphate as a main component of the anthropogenic aerosol. Particles larger than 720 nm in diameter were completely hydrophobic meaning that mineral dust particles are not hygroscopic.     

基于新一代天气雷达产品闽西南强对流天气临近预报方法研究

利用2003—2008年福建龙岩新一代天气雷达资料和常规探空资料,对闽西南历史冰雹及闽西雷雨大风天气发生的环境条件进行统计分析,建立历史冰雹和雷雨大风天气过程对应的新一代天气雷达产品判别指标。利用判别方程、新一代天气雷达产品和探空资料联合开展强对流天气临近预报预警方法研究：首先利用Fisher判别分析方法建立冰雹天气的判别方程,主要用于冰雹天气的判断,再利用雷雨大风的判别指标对雷雨大风和强雷暴天气进行第二次判别。通过历史过程的回报和2009年的试报表明：该系统对闽西南冰雹天气预报准确率较高,雷雨大风准确率次之。同时,利用风暴单体识别与跟踪的预测方法对冰雹预报结果和实况进行统计,表明风暴单体识别和跟踪算法（SCIT）预报准确率较高,可以用于风暴未来移速移向的预报。     

新一代天气雷达负仰角探测能力分析

由于地球曲率的影响,当CINRAD.SA新一代天气雷达使用目前最低仰角同定为0.5°的模式探测时,探测肓区较大,对低层降水回波的探测能力严重不足.在实地展开试验的基础上,推导了负仰角探测时雷达最低探测高度计算公式,计算出仰角为0.5°、0°、-0.3°、-0.5°时不同探测距离上的雷达最低探测高度,对比分析不同仰角观测模式的主要雷达产品特点,探讨新一代天气雷达使用负仰角观测模式的局限性,提出了新一代天气雷达使用负仰角观测的建议.