A larger pool of ozone-forming carbon compounds in urban atmospheres

Volatile organic compounds play a central role in the processes that generate both urban photochemical smog and tropospheric ozone. For successful and accurate prediction of these pollution episodes, identification of the dominant reactive species within the volatile organic carbon pool is needed. At present, lack of resolution inherent in single-column chromatographic analysis limits such a detailed chemical characterization of the complex urban atmosphere. Here we present an improved method of peak deconvolution from double-column (orthogonal) gas chromatography. This has enabled us to isolate and classify more than 500 chemical species of volatile organic compounds in urban air, including over 100 multi-substituted monoaromatic and volatile oxygenated hydrocarbons. We suggest that previous assessments of reactive carbon species may therefore have underestimated the contribution made by volatile organic compounds to urban pollution, particularly for compounds with more than six carbon atoms. Incorporating these species in predictive models should greatly improve our understanding of photochemical ozone yields and the formation of harmful secondary organic aerosols.     

苏州市大气VOCs特征及来源解析

基于苏州市2020年7—10月VOCs离线采样数据, 探讨苏州市VOCs的时空分布特征、来源及其臭氧生成潜势(OFP), 并与国内其他研究进行对比。结果表明, 苏州市夏季VOCs平均浓度为47.1 nL/L, OFP平均贡献为334.7 μg/m³, 芳香烃和含氧挥发性有机物(OVOCs)是VOCs 的重要组分, 对臭氧生成贡献较大, 其浓度和组分与上海市趋势相似。PMF结果表明, VOCs的6个主要浓度来源排序为液化石油气挥发源(20.7%)>有机溶剂使用源(19.5%)>工业源(17.5%)>机动车尾气排放源>其他源>燃烧源, 苏州市液化石油气挥发源高于长三角地区普遍水平。长三角地区芳香烃浓度较高, 与较高的工业和溶剂使用源贡献相关。总体来说, 芳香烃和OVOCs对苏州市大气环境影响较大, 贡献较大的是表面涂层源、加油站、道路移动源、石化与化工源, 应重点管控。     

Ubiquitous occurrence of 2-nitrofluoranthene and 2-nitropyrene in air

Several nitrated polycyclic aromatic hydrocarbons (nitro-PAH) are direct-acting mutagens and/or carcinogens, and are important constituents of combustion emissions and ambient air. These nitro-PAH are emitted from various combustion sources including gasoline and diesel engine exhaust, aluminium smelting effluent, coal fly ash, wood smoke, and cigarette smoke condensates. Of these, diesel engine exhaust is the best characterized, more than 50 nitrated polycyclic aromatic compounds having been identified by Paputa-Peck et al., including 1-nitropyrene (1-NP) as the single most abundant nitro-PAH. However, nitro-PAH may also be formed during source-receptor transport by atmospheric reactions of adsorbed or gas-phase PAH with oxides of nitrogen, nitric acid and other atmospherically important species such as the OH radical. Evidence for the atmospheric formation of nitro-PAH has come only recently, from observations that 2-nitropyrene (2-NP) and 2-nitrofluoranthene (2-NF) neither of which has been reported to be emitted from combustion sources, are among the major nitro-PAH present in ambient air. We present here data from several locations which demonstrate that these two atmospherically formed nitro-PAH are ubiquitous in tropospheric ambient air.     

Halocarbons produced by natural oxidation processes during degradation of organic matter

Volatile halogenated organic compounds (VHOC) play an important role in atmospheric chemical processes-contributing, for example, to stratospheric ozone depletion. For anthropogenic VHOC whose sources are well known, the global atmospheric input can be estimated from industrial production data. Halogenated compounds of natural origin can also contribute significantly to the levels of VHOC in the atmosphere. The oceans have been implicated as one of the main natural sources, where organisms such as macroalgae and microalgae can release large quantities of VHOC to the atmosphere. Some terrestrial sources have also been identified, such as wood-rotting fungi, biomass burning and volcanic emissions. Here we report the identification of a different terrestrial source of naturally occurring VHOC. We find that, in soils and sediments, halide ions can be alkylated during the oxidation of organic matter by an electron acceptor such as Fe(III): sunlight or microbial mediation are not required for these reactions. When the available halide ion is chloride, the reaction products are CH3Cl, C2H5Cl, C3H7Cl and C4H9Cl. (The corresponding alkyl bromides or alkyl iodides are produced when bromide or iodide are present.) Such abiotic processes could make a significant contribution to the budget of the important atmospheric compounds CH3Cl, CH3Br and CH3I.     

大气中二羰基化合物及其生成的二次有机气溶胶

二次有机气溶胶(secondary organic aerosol, SOA)对大气灰霾的贡献是当前大气化学研究的热点. 二羰基化合物(乙二醛和甲基乙二醛)是大气光化学反应的中间产物, 可以通过多种途径形成SOA, 对SOA的形成和总量增加有重要的贡献. 大气中二羰基化合物主要来源于生物源(如异戊二烯)和人为源(如乙炔)等挥发性有机物的氧化. 二羰基化合物可通过气粒分配(可逆过程)形成SOA, 也可被云、雾或水相气溶胶吸收, 发生水合、聚合、氧化等反应,生成的低挥发性产物留在颗粒相中生成SOA(不可逆过程). 目前常用的二羰基化合物检测方法是利用衍生化试剂与二羰基化合物反应生成衍生物, 经溶剂洗脱后再用气相色谱-质谱(gas chromatography-mass spectrometry, GC/MS)仪进行分析.     

城市大气中甲醛来源分析的示踪技术

甲醛是城市大气中浓度水平最高的含氧挥发性有机物。甲醛在城市地区主要来自机动车尾气排放等一次来源及大气光化学反应二次来源。然而,目前识别甲醛一次和二次来源的研究开展得较少。基于大气一次污染和二次污染示踪物的统计分析方法,是大气甲醛来源分析的新进展。作者介绍了采用示踪物估算城市大气甲醛来源贡献的技术方法和初步结果,并针对示踪物的特点讨论了该方法的适用性。     

在超临界相条件下由合成气合成C2含氧化合物反应的研究

首次把超临界相引入到合成气合成C2含氧化合物反应中。结果表明，在超临界相中进行反应可大幅度提高C2含氧化合物的选择性，尤其是提高产物乙醇的选择性，抑制了高碳数含氧化合物和烃类的生成。     

神府和胜利煤液化残渣CS_2萃取物的组成分析

以CS2作为溶剂,对神府和胜利煤液化残渣进行了常温萃取,利用GC/MS对萃取物进行分析,考察产物中各族组分的分布规律,进而比较两种煤液化残渣的分子结构特征.结果表明:在神府和胜利煤液化残渣的萃取物中分别检测到33和22种化合物,主要由大分子的芳烃、脂肪烃和含杂原子有机化合物组成.芳烃包括4-7环的稠环芳烃及其烷基取代衍生物,其中6环的苯并[ghi]苝含量最高,脂肪烃主要为正构烷烃和取代烷烃,含杂原子有机化合物主要以含氧和含硫元素的化合物为主.     

夏季石家庄高新区VOCs污染特征及来源解析

对2019年夏季臭氧高峰期石家庄市高新区进行环境大气挥发性有机物(VOCs)罐采样及组分分析,开展VOCs污染特征、臭氧生成潜势(OFP)和来源解析研究.结果表明,观测期间VOCs体积分数为51.52×10^-9,占比最高的为OVOCs,其次为烷烃、卤代烃,烯炔烃和芳香烃占比较小.首要物种以醛酮类和低碳烷烃为主.观测期间各类VOCs均有明显的周末效应,人类活动对VOCs排放有重要的影响.各类VOCs中,臭氧生成潜势最大的为OVOCs,占58%,烯炔烃占16%,芳香烃和烷烃分别占14%、11%.臭氧生成潜势最大组分为甲醛.利用正交矩阵因子法(PMF)源解析模型对VOCs来源进行解析,机动车尾气排放、区域背景源贡献均为24%,生物质燃烧贡献18%,溶剂使用贡献17%,工业排放源贡献9%,植物排放贡献8%.     

大气压化学电离质谱法分析润滑基础油的结构组成

利用大气压固体分析探针技术对两种合成航空润滑油的结构组成进行了分析表征,考察了两种润滑基础油中有机物的分子量分布范围及种类.结果显示:在合成航空润滑基础油中,检测到的化合物主要有烃类、酯类和含杂原子化合物(N,O和S).其中大气压化学电离源对烃类化合物的响应值较好,对酯类则相对较弱.检测到的含氮化合物的含量不高,但种类较多,有C6H16N,C6H10N3,C27H41N10,C6H13N6O3,C20H33N6O2,C21H35N6O2,C22H37N6O2和C24H41N6O3,含氮化合物特别是碱性含氮化合物对润滑基础油的热氧化安定性能影响较大.     

Carbon isotope composition of low molecular weight hydrocarbons and monocarboxylic acids from Murchison meteorite

The origin of the organic matter in carbonaceous meteorites remains controversial despite extensive study over the past 20 yr. Motivated by the expectation that the patterns of isotopic variation with molecular structure among the organic compounds would contain important clues to their origin, we have measured the carbon isotopic compositions for individual hydrocarbons and monocarboxylic acids from Murchison meteorite, a C2 carbonaceous chondrite which fell in Australia in 1969. With few exceptions, notably benzene, the volatile products are substantially isotopically heavier than their terrestrial counterparts, signifying their extraterrestrial origin. For both classes of compounds, the ratio of 13C to 12C decreases with increasing carbon number in a roughly parallel manner, and each carboxylic acid exhibits a higher isotopic ratio than the hydrocarbon containing the same number of carbon atoms. These trends are consistent with the kinetically controlled synthesis of higher homologues from lower ones. The results suggest the possibility that the production mechanisms for hydrocarbons and carboxylic acids may be similar; they also impose constraints on the identity of the reactant species.     

Recent decreases in fossil-fuel emissions of ethane and methane derived from firn air

Methane and ethane are the most abundant hydrocarbons in the atmosphere and they affect both atmospheric chemistry and climate. Both gases are emitted from fossil fuels and biomass burning, whereas methane (CH(4)) alone has large sources from wetlands, agriculture, landfills and waste water. Here we use measurements in firn (perennial snowpack) air from Greenland and Antarctica to reconstruct the atmospheric variability of ethane (C(2)H(6)) during the twentieth century. Ethane levels rose from early in the century until the 1980s, when the trend reversed, with a period of decline over the next 20?years. We find that this variability was primarily driven by changes in ethane emissions from fossil fuels; these emissions peaked in the 1960s and 1970s at 14-16 teragrams per year (1?Tg = 10(12)?g) and dropped to 8-10?Tg yr(-1) by the turn of the century. The reduction in fossil-fuel sources is probably related to changes in light hydrocarbon emissions associated with petroleum production and use. The ethane-based fossil-fuel emission history is strikingly different from bottom-up estimates of methane emissions from fossil-fuel use, and implies that the fossil-fuel source of methane started to decline in the 1980s and probably caused the late twentieth century slow-down in the growth rate of atmospheric methane.     

北京市局部大气沉降颗粒表面成分分析

采用X射线光电子能谱（XPS）对大气沉降颗粒表面元素组成和元素的存在形式进行分析,发现其表面含有Al、Ca、Si等地壳元素和C、N、O等轻元素。Al、Si、Ca等地壳元素的原子数分数总和高达16.4%,表明大气颗粒物的沉降过程伴随着地壳元素的累积;元素S与N的原子数分数比值接近1,表明没有足够的碱性物质NH₃中和酸性物质SO₄^2-,沉降颗粒表面呈现酸性。结合高分辨率XPS图谱分析,发现沉降颗粒物表面的含碳物质以有机含碳化合物为主,同时存在少量的无定型碳;而氮元素则主要来源于以NO_x、NH₄⁺为主的无机氮和以吡啶氮为主的有机氮。     

Reassessing the first appearance of eukaryotes and cyanobacteria

The evolution of oxygenic photosynthesis had a profound impact on the Earth's surface chemistry, leading to a sharp rise in atmospheric oxygen between 2.45 and 2.32 billion years (Gyr) ago and the onset of extreme ice ages. The oldest widely accepted evidence for oxygenic photosynthesis has come from hydrocarbons extracted from approximately 2.7-Gyr-old shales in the Pilbara Craton, Australia, which contain traces of biomarkers (molecular fossils) indicative of eukaryotes and suggestive of oxygen-producing cyanobacteria. The soluble hydrocarbons were interpreted to be indigenous and syngenetic despite metamorphic alteration and extreme enrichment (10-20 per thousand) of (13)C relative to bulk sedimentary organic matter. Here we present micrometre-scale, in situ (13)C/(12)C measurements of pyrobitumen (thermally altered petroleum) and kerogen from these metamorphosed shales, including samples that originally yielded biomarkers. Our results show that both kerogen and pyrobitumen are strongly depleted in (13)C, indicating that indigenous petroleum is 10-20 per thousand lighter than the extracted hydrocarbons. These results are inconsistent with an indigenous origin for the biomarkers. Whatever their origin, the biomarkers must have entered the rock after peak metamorphism approximately 2.2 Gyr ago and thus do not provide evidence for the existence of eukaryotes and cyanobacteria in the Archaean eon. The oldest fossil evidence for eukaryotes and cyanobacteria therefore reverts to 1.78-1.68 Gyr ago and approximately 2.15 Gyr ago, respectively. Our results eliminate the evidence for oxygenic photosynthesis approximately 2.7 Gyr ago and exclude previous biomarker evidence for a long delay (approximately 300 million years) between the appearance of oxygen-producing cyanobacteria and the rise in atmospheric oxygen 2.45-2.32 Gyr ago.     

Interhemispheric climate links revealed by late-glacial cooling episode in southern Chile

Understanding the relative timings of climate events in the Northern and Southern hemispheres is a prerequisite for determining the causes of abrupt climate changes. But climate records from the Patagonian Andes and New Zealand for the period of transition from glacial to interglacial conditions--about 14.6-10 kyr before present, as determined by radiocarbon dating--show varying degrees of correlation with similar records from the Northern Hemisphere. It is necessary to resolve these apparent discrepancies in order to be able to assess the relative roles of Northern Hemisphere ice sheets and oceanic, atmospheric and astronomical influences in initiating climate change in the late-glacial period. Here we report pollen records from three sites in the Lake District of southern Chile (41 degrees S) from which we infer conditions similar to modern climate between about 13 and 12.2 14C kyr before present (BP), followed by cooling events at about 12.2 and 11.4 14C kyr BP, and then by a warming at about 9.8 14C kyr BP. These events were nearly synchronous with important palaeoclimate changes recorded in the North Atlantic region, supporting the idea that interhemispheric linkage through the atmosphere was the primary control on climate during the last deglaciation. In other regions of the Southern Hemisphere, where climate events are not in phase with those in the Northern Hemisphere, local oceanic influences may have counteracted the effects that propagated through the atmosphere.     

兰州市大气中NMHCs的稳定碳同位素组成及来源

利用Tenax TA吸附管采集了兰州市污染源和主要功能区冬季及夏季大气样品, 利用热解析-气相色谱-同位素质谱联用仪分析了样品中非甲烷烃的稳定碳同位素组成。结果表明: 不同源排放的 NMHCs 的稳定碳同位素组成不同, 交通相关源中NMHCs的δC平均值为 - 28. 7‰, 显著低于燃煤烟气(-24.1‰); 夏季各功能区NMHCs 的δ¹³C值相差不大, 平均值在 - 29. 5‰ ～- 27. 4‰之间, 冬季西固工业区的 δ¹³C平均值(-25. 5‰)大于盘旋路(-28. 8‰) 和二电厂(-31. 2‰)。同位素来源分析结果显示: 盘旋路冬夏两季 NMHCs主要来源于交通相关源; 西固工业区冬季 NMHCs 主要来源于燃煤烟气, 夏季正烷烃和苯主要来源于交通相关源;二电厂冬季正戊烷、正己烷和苯等主要来源于交通相关源; 居民区夏季 NMHCs 则受到交通相关源排放的影响较大, 其他未知源也有贡献。冬夏两季大气中均检测出苯的存在, 且主要来源于交通相关源, 因此控制交通相关源的排放是降低致癌物质苯污染的关键。     

Changes in carbon dioxide during an oceanic anoxic event linked to intrusion into Gondwana coals

The marine sedimentary record exhibits evidence for episodes of enhanced organic carbon burial known as 'oceanic anoxic events' (OAEs). They are characterized by carbon-isotope excursions in marine and terrestrial reservoirs and mass extinction of marine faunas. Causal mechanisms for the enhancement of organic carbon burial during OAEs are still debated, but it is thought that such events should draw down significant quantities of atmospheric carbon dioxide. In the case of the Toarcian OAE (approximately 183 million years ago), a short-lived negative carbon-isotope excursion in oceanic and terrestrial reservoirs has been interpreted to indicate raised atmospheric carbon dioxide caused by oxidation of methane catastrophically released from either marine gas hydrates or magma-intruded organic-rich rocks. Here we test these two leading hypotheses for a negative carbon isotopic excursion marking the initiation of the Toarcian OAE using a high-resolution atmospheric carbon dioxide record obtained from fossil leaf stomatal frequency. We find that coincident with the negative carbon-isotope excursion carbon dioxide is first drawn down by 350 +/- 100 p.p.m.v. and then abruptly elevated by 1,200 +/- 400 p.p.m.v, and infer a global cooling and greenhouse warming of 2.5 +/- 0.1 degrees C and 6.5 +/- 1 degrees C, respectively. The pattern and magnitude of carbon dioxide change are difficult to reconcile with catastrophic input of isotopically light methane from hydrates as the cause of the negative isotopic signal. Our carbon dioxide record better supports a magma-intrusion hypothesis, and suggests that injection of isotopically light carbon from the release of thermogenic methane occurred owing to the intrusion of Gondwana coals by Toarcian-aged Karoo-Ferrar dolerites.     

用Ni2B还原法研究富硫原油沥青质中的含硫结构单元

采用新型的脱硫试剂 (Ni2 B)对富硫原油沥青质中含硫结构单元的研究结果表明 ,沥青质脱硫产物以饱和烃为主 ,包括丰富的正构烷烃系列和环状生标系列。沥青质脱硫产物类似于原油饱和烃的分布。通过计算得到了沥青质脱硫饱和烃及其环状生标的参数 ,这些参数与原油饱和烃的相应参数比较接近 ,这表明沥青质中的含硫结构单元可能是原油饱和烃的先质。     

The Southern Ocean biogeochemical divide

Modelling studies have demonstrated that the nutrient and carbon cycles in the Southern Ocean play a central role in setting the air-sea balance of CO(2) and global biological production. Box model studies first pointed out that an increase in nutrient utilization in the high latitudes results in a strong decrease in the atmospheric carbon dioxide partial pressure (pCO2). This early research led to two important ideas: high latitude regions are more important in determining atmospheric pCO2 than low latitudes, despite their much smaller area, and nutrient utilization and atmospheric pCO2 are tightly linked. Subsequent general circulation model simulations show that the Southern Ocean is the most important high latitude region in controlling pre-industrial atmospheric CO(2) because it serves as a lid to a larger volume of the deep ocean. Other studies point out the crucial role of the Southern Ocean in the uptake and storage of anthropogenic carbon dioxide and in controlling global biological production. Here we probe the system to determine whether certain regions of the Southern Ocean are more critical than others for air-sea CO(2) balance and the biological export production, by increasing surface nutrient drawdown in an ocean general circulation model. We demonstrate that atmospheric CO(2) and global biological export production are controlled by different regions of the Southern Ocean. The air-sea balance of carbon dioxide is controlled mainly by the biological pump and circulation in the Antarctic deep-water formation region, whereas global export production is controlled mainly by the biological pump and circulation in the Subantarctic intermediate and mode water formation region. The existence of this biogeochemical divide separating the Antarctic from the Subantarctic suggests that it may be possible for climate change or human intervention to modify one of these without greatly altering the other.     

大气二次有机气溶胶研究进展

 大气二次有机气溶胶（SOA）严重影响着空气质量、大气辐射平衡和人体健康等,对SOA生成和控制的研究对于揭示颗粒物污染成因、为打赢蓝天保卫战提供决策依据都具有重要意义。但由于SOA的组成成分和生成过程复杂、来源繁多、具体机理难以识别,有关SOA的研究仍然面临着众多挑战。在调研近2年表在环境及大气化学等领域的国际重要学术期刊上的研究成果的基础上,总结了在SOA的分子组成、污染特征、前体物或来源、生成与老化过程的机理、关键影响因素、对大气光学性质和人体健康的影响等方面的研究进展。