Heterogeneous atmospheric aerosol production by acid-catalyzed particle-phase reactions

According to evidence from our laboratory, acidic surfaces on atmospheric aerosols lead to potentially multifold increases in secondary organic aerosol (SOA) mass. Experimental observations using a multichannel flow reactor, Teflon (polytetrafluoroethylene) film bag batch reactors, and outdoor Teflon-film smog chambers strongly confirm that inorganic acids, such as sulfuric acid, catalyze particle-phase heterogeneous reactions of atmospheric organic carbonyl species. The net result is a large increase in SOA mass and stabilized organic layers as particles age. If acid-catalyzed heterogeneous reactions of SOA products are included in current models, the predicted SOA formation will be much greater and could have a much larger impact on climate forcing effects than we now predict.     

大气污染物中2-甲基丁四醇硫酸酯的质谱解析

利用液相色谱/负离子电喷雾质谱(LC/(-)ESI-MS)技术,对受到人类活动影响的上海崇明东平国家森林公园的大气样品进行了研究。成功分离到异戊二烯主要的光氧化产物,非对映异构体2-甲基丁四醇和大气中的SO2结合生成的有机硫酸酯类化合物。采用质谱解析法鉴定了2种构型(erythro-、threo-)-2-甲基丁四醇硫酸酯的结构。     

Pyrolysis mass spectrometry of complex organic materials

Pyrolysis mass spectrometry in combination with computerized multivariate statistical analysis enables qualitative and quantitative analysis of nonvolatile organic materials containing molecular assemblies of a complexity and size far beyond the capabilities of direct mass spectrometry. The state of the art in pyrolysis mass spectrometry techniques is illustrated through specific applications, including structural determination and quality control of synthetic polymers, quantitative analysis of polymer mixtures, classification and structural characterization of fossil organic matter, and nonsupervised numerical extraction of component patterns from complex biological samples.     

In situ measurements of organics, meteoritic material, mercury, and other elements in aerosols at 5 to 19 kilometers

In situ measurements of the chemical composition of individual aerosol particles at altitudes between 5 and 19 kilometers reveal that upper tropospheric aerosols often contained more organic material than sulfate. Although stratospheric aerosols primarily consisted of sulfuric acid and water, many also contained meteoritic material. Just above the tropopause, small amounts of mercury were found in over half of the aerosol particles that were analyzed. Overall, there was tremendous variety in aerosol composition. One measure of this diversity is that at least 45 elements were detected in aerosol particles. These results have wide implications for the complexity of aerosol sources and chemistry. They also offer possibilities for understanding the transport of atmospheric aerosols.     

In situ observations of aerosol and chlorine monoxide after the 1991 eruption of mount pinatubo: effect of reactions on sulfate aerosol

Highly resolved aerosol size distributions measured from high-altitude aircraft can be used to describe the effect of the 1991 eruption of Mount Pinatubo on the stratospheric aerosol. In some air masses, aerosol mass mixing ratios increased by factors exceeding 100 and aerosol surface area concentrations increased by factors of 30 or more. Increases in aerosol surface area concentration were accompanied by increases in chlorine monoxide at mid-latitudes when confounding factors were controlled. This observation supports the assertion that reactions occurring on the aerosol can increase the fraction of stratospheric chlorine that occurs in ozone-destroying forms.     

Organic aerosol growth mechanisms and their climate-forcing implications

Surface- and volume-limited chemical reactions on and in atmospheric aerosol particles cause growth while changing organic composition by 13 to 24% per day. Many of these particles contain carbonaceous components from mineral dust and combustion emissions in Africa, Asia, and North America and reveal reaction rates that are three times slower than those typically used in climate models. These slower rates for converting from volatile or hydrophobic to condensed and hygroscopic organic compounds increase carbonaceous particle burdens in climate models by 70%, producing organic aerosol climate forcings of as much as -0.8 watt per square meter cooling and +0.3 watt per square meter warming.     

Evidence for NO(x) control over nighttime SOA formation

Laboratory studies have established a number of chemical pathways by which nitrogen oxides (NO(x)) affect atmospheric organic aerosol (OA) production. However, these effects have not been directly observed in ambient OA. We report measurements of particulate organic nitrates in Bakersfield, California, the nighttime formation of which increases with NO(x) and is suppressed by high concentrations of organic molecules that rapidly react with nitrate radical (NO(3))--evidence that multigenerational chemistry is responsible for organic nitrate aerosol production. This class of molecules represents about a third of the nighttime increase in OA, suggesting that most nighttime secondary OA is due to the NO(3) product of anthropogenic NO(x) emissions. Consequently, reductions in NO(x) emissions should reduce the concentration of organic aerosol in Bakersfield and the surrounding region.     

Smog aerosol: infrared spectra

Infrared spectra of smog aerosol are similar to those of sulfuric acid aerosol, but they do not show the prominent CH and carbonyl bands of organic aerosols from terpenes. Some features of the smog aerosol spectra are not present in the spectra from either type of synthetic aerosol.     

High natural aerosol loading over boreal forests

Aerosols play a key role in the radiation balance of the atmosphere. Here, we present evidence that the European boreal region is a substantial source of both aerosol mass and aerosol number. The investigation supplies a straightforward relation between emissions of monoterpenes and gas-to-particle formation over regions substantially lacking in anthropogenic aerosol sources. Our results show that the forest provides an aerosol population of 1000 to 2000 particles of climatically active sizes per cubic centimeter during the late spring to early fall period. This has important implications for radiation budget estimates and relevancy for the evaluation of feedback loops believed to determine our future climate.     

Phytoplankton and cloudiness in the Southern Ocean

The effect of ocean biological productivity on marine clouds is explored over a large phytoplankton bloom in the Southern Ocean with the use of remotely sensed data. Cloud droplet number concentration over the bloom was twice what it was away from the bloom, and cloud effective radius was reduced by 30%. The resulting change in the short-wave radiative flux at the top of the atmosphere was -15 watts per square meter, comparable to the aerosol indirect effect over highly polluted regions. This observed impact of phytoplankton on clouds is attributed to changes in the size distribution and chemical composition of cloud condensation nuclei. We propose that secondary organic aerosol, formed from the oxidation of phytoplankton-produced isoprene, can affect chemical composition of marine cloud condensation nuclei and influence cloud droplet number. Model simulations support this hypothesis, indicating that 100% of the observed changes in cloud properties can be attributed to the isoprene secondary organic aerosol.     

Characterization of aerosols from eruptions of mount st. Helens

Measurements of mass concentration and size distribution of aerosols from eruptions of Mount St. Helens as well as morphological and elemental analyses were obtained between 7 April and 7 August 1980. In situ measurements were made in early phreatic and later, minor phreatomagmatic eruption clouds near the vent of the volcano and in plumes injected into the stratosphere from the major eruptions of 18 and 25 May. The phreatic aerosol was characterized by an essentially monomodal size distribution dominated by silicate particles larger than 10 micrometers in diameter. The phreatomagmatic eruption cloud was multimodal; the large size mode consisted of silicate particles and the small size modes were made up of mixtures of sulfuric acid and silicate particles. The stratospheric aerosol from the main eruption exhibited a characteristic narrow single mode with particles less than 1 micrometer in diameter and nearly all of the mass made up of sulfuric acid droplets.     

Organic aerosol formation downwind from the Deepwater Horizon oil spill

A large fraction of atmospheric aerosols are derived from organic compounds with various volatilities. A National Oceanic and Atmospheric Administration (NOAA) WP-3D research aircraft made airborne measurements of the gaseous and aerosol composition of air over the Deepwater Horizon (DWH) oil spill in the Gulf of Mexico that occurred from April to August 2010. A narrow plume of hydrocarbons was observed downwind of DWH that is attributed to the evaporation of fresh oil on the sea surface. A much wider plume with high concentrations of organic aerosol (>25 micrograms per cubic meter) was attributed to the formation of secondary organic aerosol (SOA) from unmeasured, less volatile hydrocarbons that were emitted from a wider area around DWH. These observations provide direct and compelling evidence for the importance of formation of SOA from less volatile hydrocarbons.     

Formation of secondary organic aerosols through photooxidation of isoprene

Detailed organic analysis of natural aerosols from the Amazonian rain forest showed considerable quantities of previously unobserved polar organic compounds, which were identified as a mixture of two diastereoisomeric 2-methyltetrols: 2-methylthreitol and 2-methylerythritol. These polyols, which have the isoprene skeleton, can be explained by OH radical-initiated photooxidation of isoprene. They have low vapor pressure, allowing them to condense onto preexisting particles. It is estimated that photooxidation of isoprene results in an annual global production of about 2 teragrams of the polyols, a substantial fraction of the Intergovernmental Panel on Climate Change estimate of between 8 and 40 teragrams per year of secondary organic aerosol from biogenic sources.     

Synthesis of two-dimensional polymers

A synthetic pathway is described to construct "in bulk" two-dimensional (2D) polymers shaped as molecular sheets. A chiral oligomeric precursor is used that contains two reactive sites, a polymerizable group at one terminus and a reactive stereogenic center near the middle of the molecule. The bulk reaction yields bilayer 2D polymers of molecular weight in the order of millions and a monodisperse thickness of 50.2 angstroms. The 2D molecular objects form through molecular recognition by the oligomers, which self-organize into layers that place the reactive groups within specific planes. The oligomers become catenated by two different stitching reactions involving the reactive sites. At room temperature, stacks of these molecular objects can organize as single crystals and at higher temperatures melt into smectic liquid crystals. Nonlinear optical experiments reveal that solid films containing the 2D polymers form structures that are thermally and temporally more stable than those containing analogous 1D polymers. This observation suggests that the transformation of common polymers from a 1D to a 2D architecture may produce generations of organic materials with improved properties.     

枣麦间作生态系统土壤养分的时空异质性

通过研究枣麦间作生态系统土壤养分的时空异质性,为系统内科学的肥料管理技术提供参考。基于枣麦间作生态系统(JIE)内部的异质性,在冬小麦不同生育期,对不同位点取样调查。结果表明:土壤有机质质量分数随冬小麦生育进程呈递增趋势,水平分布上表现出距枣树越远其土壤有机质质量分数越低,并且0~20cm土层有机质质量分数高于20~40cm土层。土壤速效N、P、K质量分数表现出明显的时空分布特性。土壤速效N、P、K质量分数随冬小麦生育进程基本呈下降趋势;水平分布上,土壤速效N、P、K质量分数随距枣树距离的增加而逐渐下降;而在垂直分布则表现出随土层深度的增加,土壤速效N、P、K质量分数呈逐渐降低。因此,在枣麦间作生态系统中,应适当增加20~40cm土层和距树体150~200cm的氮肥、磷肥施用量,以缓和枣树和小麦养分竞争。     

Rethinking organic aerosols: semivolatile emissions and photochemical aging

Most primary organic-particulate emissions are semivolatile; thus, they partially evaporate with atmospheric dilution, creating substantial amounts of low-volatility gas-phase material. Laboratory experiments show that photo-oxidation of diesel emissions rapidly generates organic aerosol, greatly exceeding the contribution from known secondary organic-aerosol precursors. We attribute this unexplained secondary organic-aerosol production to the oxidation of low-volatility gas-phase species. Accounting for partitioning and photochemical processing of primary emissions creates a more regionally distributed aerosol and brings model predictions into better agreement with observations. Controlling organic particulate-matter concentrations will require substantial changes in the approaches that are currently used to measure and regulate emissions.     

Biogenic potassium salt particles as seeds for secondary organic aerosol in the Amazon

The fine particles serving as cloud condensation nuclei in pristine Amazonian rainforest air consist mostly of secondary organic aerosol. Their origin is enigmatic, however, because new particle formation in the atmosphere is not observed. Here, we show that the growth of organic aerosol particles can be initiated by potassium-salt-rich particles emitted by biota in the rainforest. These particles act as seeds for the condensation of low- or semi-volatile organic compounds from the atmospheric gas phase or multiphase oxidation of isoprene and terpenes. Our findings suggest that the primary emission of biogenic salt particles directly influences the number concentration of cloud condensation nuclei and affects the microphysics of cloud formation and precipitation over the rainforest.     

2006年9～10月常德市太阳山大气中PM10气溶胶变化特征

对常德市太阳山大气成分站GRIMM-180颗粒物监测仪2006年9～10月PM10质量浓度资料进行分析,结果得出非降水天气下质量浓度日变化呈双峰分布。主要影响因子为人类生产活动直接产生和排放的气溶胶以及影响气溶胶扩散的气象条件大气湍流,非降水有雾天气质量浓度明显比无雾天气偏高;降水天气过程对大气中气溶胶有明显湿清除作用;对比常德市环境监测站PM10观测采样资料,两者具有很高的相关性,常德市环境监测站的PM10浓度要略高于太阳山大气成分站,说明太阳山受到人为影响更弱一些,具有更加充分的区域代表性。     

Dispersion polymerizations in supercritical carbon dioxide

Conventional heterogeneous dispersion polymerizations of unsaturated monomers are performed in either aqueous or organic dispersing media with the addition of interfacially active agents to stabilize the colloidal dispersion that forms. Successful stabilization of the polymer colloid during polymerization results in the formation of high molar mass polymers with high rates of polymerization. An environmentally responsible alternative to aqueous and organic dispersing media for heterogeneous dispersion polymerizations is described in which supercritical carbon dioxide (CO(2)) is used in conjunction with molecularly engineered free radical initiators and amphipathic molecules that are specifically designed to be interfacially active in CO(2). Conventional lipophilic monomers, exemplified by methyl methacrylate, can be quantitatively (>90 percent) polymerized heterogeneously to very high degrees of polymerization (>3000) in supercritical CO(2) in the presence of an added stabilizer to form kinetically stable dispersions that result in micrometer-sized particles with a narrow size distribution.     

Coordination polymers of osmium: the nature of osmium black

The design of cytochemical reagents that yield osmiophilic products from which an osmium black may be derived on exposure to osmium tetroxide has resulted in new methods described previously for the ultrastructural demonstration of enzyme activity and functional groups of macromolecules with the electron microscope. Attempts to determine the nature of the osmium black end products have been frustrated by their insolubility. The preparation of watersoluble analogs and their characterization as polymers suggest that the insoluble osmium blacks are coordination polymers. This is consonant with the unusually favorable properties of osmium black in electron microscopy. Although polymers of osmium have frequently been postulated as the end products of reaction of osmium tetroxide with tissue conistituents or with other organic compounds, this is the first example of their characterization.