Reduction of soil carbon formation by tropospheric ozone under increased carbon dioxide levels

In the Northern Hemisphere, ozone levels in the troposphere have increased by 35 per cent over the past century, with detrimental impacts on forest and agricultural productivity, even when forest productivity has been stimulated by increased carbon dioxide levels. In addition to reducing productivity, increased tropospheric ozone levels could alter terrestrial carbon cycling by lowering the quantity and quality of carbon inputs to soils. However, the influence of elevated ozone levels on soil carbon formation and decomposition are unknown. Here we examine the effects of elevated ozone levels on the formation rates of total and decay-resistant acid-insoluble soil carbon under conditions of elevated carbon dioxide levels in experimental aspen (Populus tremuloides) stands and mixed aspen-birch (Betula papyrifera) stands. With ambient concentrations of ozone and carbon dioxide both raised by 50 per cent, we find that the formation rates of total and acid-insoluble soil carbon are reduced by 50 per cent relative to the amounts entering the soil when the forests were exposed to increased carbon dioxide alone. Our results suggest that, in a world with elevated atmospheric carbon dioxide concentrations, global-scale reductions in plant productivity due to elevated ozone levels will also lower soil carbon formation rates significantly.     

Indirect radiative forcing of climate change through ozone effects on the land-carbon sink

The evolution of the Earth's climate over the twenty-first century depends on the rate at which anthropogenic carbon dioxide emissions are removed from the atmosphere by the ocean and land carbon cycles. Coupled climate-carbon cycle models suggest that global warming will act to limit the land-carbon sink, but these first generation models neglected the impacts of changing atmospheric chemistry. Emissions associated with fossil fuel and biomass burning have acted to approximately double the global mean tropospheric ozone concentration, and further increases are expected over the twenty-first century. Tropospheric ozone is known to damage plants, reducing plant primary productivity and crop yields, yet increasing atmospheric carbon dioxide concentrations are thought to stimulate plant primary productivity. Increased carbon dioxide and ozone levels can both lead to stomatal closure, which reduces the uptake of either gas, and in turn limits the damaging effect of ozone and the carbon dioxide fertilization of photosynthesis. Here we estimate the impact of projected changes in ozone levels on the land-carbon sink, using a global land carbon cycle model modified to include the effect of ozone deposition on photosynthesis and to account for interactions between ozone and carbon dioxide through stomatal closure. For a range of sensitivity parameters based on manipulative field experiments, we find a significant suppression of the global land-carbon sink as increases in ozone concentrations affect plant productivity. In consequence, more carbon dioxide accumulates in the atmosphere. We suggest that the resulting indirect radiative forcing by ozone effects on plants could contribute more to global warming than the direct radiative forcing due to tropospheric ozone increases.     

Extensive halogen-mediated ozone destruction over the tropical Atlantic Ocean

Increasing tropospheric ozone levels over the past 150 years have led to a significant climate perturbation; the prediction of future trends in tropospheric ozone will require a full understanding of both its precursor emissions and its destruction processes. A large proportion of tropospheric ozone loss occurs in the tropical marine boundary layer and is thought to be driven primarily by high ozone photolysis rates in the presence of high concentrations of water vapour. A further reduction in the tropospheric ozone burden through bromine and iodine emitted from open-ocean marine sources has been postulated by numerical models, but thus far has not been verified by observations. Here we report eight months of spectroscopic measurements at the Cape Verde Observatory indicative of the ubiquitous daytime presence of bromine monoxide and iodine monoxide in the tropical marine boundary layer. A year-round data set of co-located in situ surface trace gas measurements made in conjunction with low-level aircraft observations shows that the mean daily observed ozone loss is approximately 50 per cent greater than that simulated by a global chemistry model using a classical photochemistry scheme that excludes halogen chemistry. We perform box model calculations that indicate that the observed halogen concentrations induce the extra ozone loss required for the models to match observations. Our results show that halogen chemistry has a significant and extensive influence on photochemical ozone loss in the tropical Atlantic Ocean boundary layer. The omission of halogen sources and their chemistry in atmospheric models may lead to significant errors in calculations of global ozone budgets, tropospheric oxidizing capacity and methane oxidation rates, both historically and in the future.     

A possible nitrogen crisis for Archaean life due to reduced nitrogen fixation by lightning.

Nitrogen is an essential element for life and is often the limiting nutrient for terrestrial ecosystems. As most nitrogen is locked in the kinetically stable form, N2, in the Earth's atmosphere, processes that can fix N2 into biologically available forms-such as nitrate and ammonia-control the supply of nitrogen for organisms. On the early Earth, nitrogen is thought to have been fixed abiotically, as nitric oxide formed during lightning discharge. The advent of biological nitrogen fixation suggests that at some point the demand for fixed nitrogen exceeded the supply from abiotic sources, but the timing and causes of the onset of biological nitrogen fixation remain unclear. Here we report an experimental simulation of nitrogen fixation by lightning over a range of Hadean (4.5-3.8 Gyr ago) and Archaean (3.8-2.5 Gyr ago) atmospheric compositions, from predominantly carbon dioxide to predominantly dinitrogen (but always without oxygen). We infer that, as atmospheric CO2 decreased over the Archaean period, the production of nitric oxide from lightning discharge decreased by two orders of magnitude until about 2.2 Gyr. After this time, the rise in oxygen (or methane) concentrations probably initiated other abiotic sources of nitrogen. Although the temporary reduction in nitric oxide production may have lasted for only 100 Myr or less, this was potentially long enough to cause an ecological crisis that triggered the development of biological nitrogen fixation.     

高炉处理烧结烟气脱硫脱硝理论分析

对利用高炉处理烧结烟气同时脱硫脱硝脱二噁英技术的可行性进行了理论探讨,分析高炉内部还原二氧化硫和氮氧化物,以及分解二噁英的热力学条件,探讨烧结烟气代替空气鼓风对理论燃烧温度、风量、炉缸煤气、炉顶煤气和铁水硫含量的影响.结果表明：二氧化硫、一氧化氮和二氧化氮的最低平衡体积分数分别为1.84×10-13%、3.08×10-11%和3.72×10-21%,高炉内部还原二氧化硫和氮氧化物是可行的;高炉具有分解二噁英的有利热力学条件;烟气中二氧化硫和一氧化碳对理论燃烧温度的影响可忽略,氮氧化物能略微提高理论燃烧温度,二氧化碳体积分数增加1%,理论燃烧温度降低大约40.5℃,但通过降低鼓风湿度和提高富氧率等措施,能达到高炉正常生产时的炉缸热状态水平;随着烟气中二氧化碳含量的增加,风量、炉缸和炉顶煤气量都逐渐降低,炉缸煤气一氧化碳和氢气含量增加,炉顶煤气中一氧化碳、氢气、二氧化碳和水含量都增加,氮气含量显著降低;铁水硫含量与烟气二氧化硫含量成正比,但当二氧化硫质量浓度达到2000 mg·m-3,铁水中硫质量分数仅为0.025%,铁水质量仍合格.通过综合调节高炉操作参数,也可以实现烧结烟气代替空气鼓风进行高炉炼铁生产,达到脱硫脱硝脱二恶英的目的.     

碳键机制(CB-IV)模拟大气光化学反应的研究

通过单独求解碳键机制(CB-IV),对污染条件下VOCs和NOx的初始浓度比和排放比分别变化情况下的O3浓度变化进行了模拟．结果表明,VOCs的增加使得上午时段O3浓度的增长速率提高,O3浓度峰值出现的时间提前;而且随着VOCs的增加,O3的浓度峰值开始会有所增加,但达到某一最大值后其峰值将会下降．VOCs对O3浓度变化的影响主要是二种作用的综合结果：随着VOCs的增加,VOCs反应生成的过氧氢自由基以及OLE和ETH等活泼组分对O3的消耗作用逐渐增强;VOCs的增加使得整个反应体系中HO2和XO2的浓度增加,造成了NO的消耗,从而削弱了NO对O3的消耗作用．夜间O3浓度的衰减主要受NOx,HO2,OLE和ETH等物质的影响．研究结果还表明,NO/NO2排放比例的变化对O3浓度的影响很小．     

Global distribution of peroxyacetyl nitrate

Nitrogen oxides (NOx) have a central role in the chemistry of the atmosphere, especially in key processes relating to ozone, hydroxyl-radical (OH) and acid formation. High reactivity of NOx (lifetime of 0.5-2 days) precludes hemispheric-scale transport and it has been proposed that non-methane hydrocarbons present in the troposphere can transform NOx into its organic forms principally as peroxyacetyl nitrate (PAN). PAN is highly stable in the colder regions of the middle and upper troposphere and can provide a mechanism for NOx storage and transport. Once transported, PAN and its homologues can easily release free NOx in warmer atmospheric conditions. PAN is probably ubiquitous and its concentrations could exceed those of NOx in clean tropospheric conditions. Here we present the first view of the global distribution of PAN based on extensive shipboard and aircraft measurements. PAN is more abundant in the Northern than in the Southern Hemisphere and in the continental than in the marine troposphere. In contrast to its behaviour in polluted atmospheres, PAN mixing ratios in winter greatly exceed those in summer. These measurements provide a basis for assessing the significance of PAN as a reservoir of NOx and for extending and validating reactive nitrogen chemistry theory in the troposphere.     

Changes in tropospheric ozone levels over the Three Representative Regions of China observed from space by the Tropospheric Emission Spectrometer (TES), 2005–2010

Tropospheric ozone observations over China from 2005 to 2010 at three pressure levels (484,681 and 825 hPa) from the Tropospheric Emission Spectrometer on board the NASA Aura satellite have been analyzed.Fourier Transform analysis revealed the trends and seasonality of regionally-averaged,monthly-mean ozone concentrations over western,northern and southern China.Significant increases in ozone levels are found over all three regions at 464 hPa and the rate of increase is fastest over northern China,reaching 0.89±0.059 nL/(La).At 681 hPa,ozone shows increases over northern and western China,at a rate of 0.57± 0.065 nL/(La) and 0.41±0.041 nL/(La) respectively,but is constant over southern China.At 825 hPa,ozone increases at a rate of 0.36±0.074 nL/(La) over northern China,while decreasing over southern China at a rate of 0.21±0.061 nL/(La).Over the three regions,ozone levels are generally higher in summer and lower in winter.Over southern China at all three pressure levels and northern China at the 825 hPa level,ozone shows double peaks occurring in spring and autumn as a result of the combined effects of atmospheric chemistry and global transport.This work provides a useful observational dataset and tools for future analysis of changes in tropospheric ozone over China.     

大气中氮氧化物对生态环境的影响

造成大气污染的氮氧化物主要是一氧化氮和二氧化氮,氮氧化物的危害性如下:①形成光化学烟雾.②易与动物血液中血色素结合.③破坏平流层(同温层)中的臭氧层.④可生成毒性更大的硝酸或硝酸盐气溶胶,形成酸雨.大气中氮氧化物含量的确定是评价人类生存环境质量优劣的重要指标之一,而其测定方法的准确性又是至关重要的.本文通过实验同时介绍了盐酸萘乙二胺分光光度法测定大气中氮氧化物含量方法的改进.     

亚印太交汇区低纬上空不同层次大气臭氧的时空变化分析

 利用ECMWF 195709~200208共45a的多层臭氧质量混合比月平均资料,详细分析了亚印太交汇区(AIPO)低纬地带上空平流层、对流层各层次上臭氧浓度的分布特征.结果表明:①区域上空对流层、平流层及臭氧总量大尺度特征均显著,纬度带分布特征明显;②对流层和平流层臭氧各个季节变化趋势相反,平流层臭氧和臭氧总量各个季节变化趋势一致;同一层次夏季臭氧浓度变化趋势与其他3个季节变化趋势相反;③区域上空20~3hPa是臭氧浓度的高值区,50~30hPa臭氧平均变化幅度最大;④对流层臭氧距平变化在整个高度上较为一致,正、负距平随季节绕赤道做南、北半球摆动,且存在季节性突变;⑤赤道上空有明显从平流层上层随季节逐渐往较低层传播的臭氧正负距平现象.     

东亚和西太平洋地区Hadley环流对对流层臭氧分布的影响

 采用了后向轨迹方法,利用臭氧混合比ρ₃和风场资料,来探讨东亚和西太平洋地区上空Hadley 环流对对流层臭氧分布的影响,文中对所研究关键点上7月份对流层高、中、低三层的轨迹进行分向统计后,计算方向概率与ρ₃的相关系数,得出了东亚和西太平洋地区Hadley 环流水平平流作用对臭氧分布的影响.结果表明:①青藏高原地区上空对流层低层Hadley 环流水平平流作用将会使臭氧混合比减少,而对应的高层南半球Hadley环流下沉支,其总体效果则是使臭氧增加;②在西太平洋地区上空对流层低层,北半球Hadley环流上升支其作用是使臭氧混合比减少,对应的高层南半球Hadley环流下沉支,其影响较弱;③另外,东亚季风的水平平流作用似乎和臭氧的分布也有联系,这还有待于进一步研究.     

超临界CO_2与环氧丙烷和甲醇催化反应体系研究

以负载型氧化物为催化剂 ,研究了二氧化碳在超临界条件下 ,与甲醇和环氧丙烷一步合成碳酸二甲酯的反应性能 .发现反应中的DMC是由PO和二氧化碳环加成合成的PC与甲醇进行酯交换所生成的 ,甲醇对PO和二氧化碳合成PC具有促进作用 ,催化剂具有较好的催化活性和稳定性     

柴油机燃用二甲醚时采用排气再循环降低NOx排放

在单缸直喷柴油机上燃用二甲醚和采用排气再循环时,进行了发动机性能和排放的试验研究。结果表明：与燃用柴油相比,发动机燃用二甲醚可以实现无烟燃烧,ＮＯｘ降低３０％,未燃碳氢和ＣＯ２排放有所下降;     

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.     

氮气及氮气+二氧化碳在四丁基溴化铵水溶液中水合物相平衡研究

采用压力搜索法测量了四丁基溴化铵-氮气-水和四丁基溴化铵-氮气-二氧化碳-水体系水合物的相平衡数据。四丁基溴化铵水溶液的质量浓度范围为10%~30%,实验的温度和压力范围分别为283.25~288.65 K和1.98~5.89 MPa。在实验压力和温度范围内,添加四丁基溴化铵降低了氮气和氮气+二氧化碳体系水合物的形成压力;而且随着四丁基溴化铵溶液浓度的增加,水合物相平衡压力下降的幅度也增大,说明四丁基溴化铵是氮气和氮气+二氧化碳水合物形成的促进剂。实验结果还表明,在氮气中混入二氧化碳,水合物相平衡压力降低;随着二氧化碳含量的增大,水合物相平衡压力下降的幅度增大。     

关于大气臭氧问题的主要研究进展

大气臭氧是非常重要的温室气体,其在全球的分布具有不均匀性,受到人类活动的显著影响,近几十年来由于对流层臭氧增加造成正的辐射强迫会增加大气温室效应,而平流臭氧减少会使其吸收的紫外线辐射减少,为负的辐射强迫,使得平流层大气降温。因此关于大气臭氧浓度变化及其对气候的影响是非常复杂的,一直是科学界研究的热点和难点问题。自从20世纪50年代末到70年代就发现臭氧浓度有减少的趋势。1985年英国南极考察队在南纬60°地区观测发现存在大气臭氧层空洞;自此开始,大气臭氧问题引起了世界各国的极大关注,并给予很多研究。目前,平流层和对流层臭氧浓度的观测仍然是研究的重点。鉴于对流层臭氧浓度持续升高和平流层臭氧浓度的不断下降,以及他们在对流层和平流层大气温度中所起的不同作用,本文将主要针对近五年来大气臭氧相关的研究进展进行简要的综述,包括对流层和平流层臭氧浓度及其观测研究,和人类活动的影响等方面进行分述。最后给出目前研究工作的不足和未来工作展望。     

影响环境空气质量的PM2．5与相关因素的关系研究

上海地区空气中细颗粒物浓度与相关因素的研究表明,空气中臭氧、一氧化碳、二氧化硫浓度及温度与PM2.5指标值有着密切的关系,其中一氧化碳、二氧化氮、二氧化硫浓度与PM2.5指标值有很强的正相关关系。因子分析和回归分析表明,臭氧、一氧化碳、二氧化氮、二氧化硫浓度及温度的潜在内涵因子人类主动行为因素和自然因素,两个因子与空气中细颗粒物关系显著,尤其是第一主因子人类主动行为因素,治理环境空气污染可从人类主动行为因素突破。     

Impact of Flue Gas Species and Temperature on Mercury Oxidation

Systematic experimental research has been conducted in a fix-bed reactor system to determine the impact of coal-fired flue gas species and temperature on mercury oxidation. This work focuses on the temperatures range of 200°C to 800°C to demonstrate that temperature is a critical factor for the effect of the gas components on the mercury oxidation process. Among the investigated gases, hydrogen chloride is essential for oxidizing the elemental mercury. Nitrogen oxide was also found to have a positive correlation with the mercury oxidation when hydrogen chloride was present. Sulfur dioxide can either promote or inhibit the oxidation depending on the conditions; however, when nitrogen oxide is also present, sulfur dioxide has a negative impact. Ammonia exhibits an strong inhibitory effect. Several plausible mercury oxidation pathways are suggested in this paper.     

北京地区臭氧源识别个例研究

利用三维区域空气质量模式CAMx模拟京、津地区对流层大气光化学过程。运用臭氧源识别技术研究不同地区、不同种类污染源排放对北京市城近郊区臭氧浓度的影响,并统计分析这一地区的臭氧来源构成。结果表明,北京市城近郊区排放的污染物对本地及其下风地区的臭氧生成有显著影响;北京市城近郊区的各类源排放中,流动源对臭氧生成贡献最大,油品储运和溶剂使用与工业源的臭氧生成贡献也占有较高份额,天然源排放对臭氧生成的贡献很小。另外,研究表明,北京地区的臭氧生成具有区域特征,气象和源排放条件会对这一地区臭氧来源的构成产生较大影响,周边地区污染物排放的影响应予以关注。     

冬季Hadley环流活动与大气臭氧变化的关系研究

 利用1957年9月到2002年8月,共540个月的ECMWF的经向风和臭氧质量混合比资料,分析研究了冬季Hadley环流强弱特征的变化对臭氧变化的影响.分析指出在冬季伴随Hadley环流的增强,其中心南移,高度升高,臭氧在对流层增加,平流层减少,臭氧总量呈现出减少的趋势.Hadley环流的增强,中心南移,高度升高以及臭氧在对流层的增加对全球变暖是正反馈,而平流层臭氧减少,臭氧总量减少对全球变暖是负反馈.因此Hadley环流的强弱对臭氧的影响明显.