Mass-independent oxygen isotope fractionation in atmospheric CO as a result of the reaction CO + OH

Atmospheric carbon monoxide (CO) exhibits mass-independent fractionation in the oxygen isotopes. An 17O excess up to 7.5 per mil was observed in summer at high northern latitudes. The major source of this puzzling fractionation in this important trace gas is its dominant atmospheric removal reaction, CO + OH --> CO2 + H, in which the surviving CO gains excess 17O. The occurrence of mass-independent fractionation in the reaction of CO with OH raises fundamental questions about kinetic processes. At the same time the effect is a useful marker for the degree to which CO in the atmosphere has been reacting with OH.     

Carbon monoxide and nitric oxide consumption in polluted air: the carbon monoxide-hydroperoxyl reaction

A recent laboratory measurement of the ratio of the rate constant for the reaction CO + HO (2) --> C0(2) + OH relative to that for H + HO(2) --> 2OH indicates that the former reaction is probably faster than CO + OH --> CO(2) + H. On this basis a simple analysis is given showing that the calculated lifetime of nitric oxide in polluted atmospheres would be appreciably longer than that estimated on the assumption that the carbon monoxide-hydroperoxyl reaction may be neglected. A fast carbon monoxide-hydroperoxyl reaction implies that the cyclic consumption of carbon monoxide (an atmospheric sink) could occur even with no nitric oxide present.     

Chemical cartography: finding the keys to the kinetic labyrinth

Very high resolution lasers allow spectroscopic pictures to be taken following a collision between two molecular reactants. The features of these "pictures" are the electronic, vibrational, rotational, and translational motions of the atomic particles, which relate the quantum states of the reactants to the quantum states of the products. Such state-to-state kinetic information can be used to test the shape and nature of the interaction potential that controls the collision process. The potential itself is akin to a map of the terrain through mountains and valleys where elevation is a measure of energy instead of height. Accurate mapping of this potential surface leads to an understanding of the forces which control rates and mechanisms of chemical reactions. The application of four different advanced laser techniques to the study of collisions between "hot" hydrogen(H) atoms and carbon dioxide(CO(2)) molecules has provided a wealth of information about both reactive and nonreactive collisions for this system. The availability of data for rotationally, vibrationally, and translationally inelastic excitation of CO(2) by H atoms, when compared with data for reactive events producing OH + CO, provides insights into the dynamics of collisions between H and CO(2), and illustrates the future promise of these powerful techniques for elucidating features of potential energy surfaces.     

添加有机物料后红壤CO2释放特征与微生物生物量动态

 【目的】对不同有机物料施入红壤后CO2释放特征及几种形态碳、氮变化进行了观测,并分析其相互关系,以阐明添加有机物料后红壤中CO2释放量及几种碳、氮形态的变化特征。【方法】采用室内恒温培养试验,向红壤中添加5种有机物料（猪粪、牛粪、鸡粪、玉米秸秆和小麦秸秆）,培养期间定期采样分析红壤CO2释放量及土壤微生物量碳、氮（SMBC、SMBN）的动态变化。【结果】添加有机物料后,各处理CO2释放速率在培养前期较高,在培养18-20 d后基本趋于稳定。整个培养期间,土壤CO2-C的累积过程符合一级反应动力学方程。添加不同有机物料后红壤CO2潜在释放量从高到低顺序为：小麦秸秆（1.51 g•kg-1）＞玉米秸秆（1.38 g•kg-1）＞猪粪（0.89 g•kg-1）＞鸡粪（0.78 g•kg-1）＞牛粪（0.50 g•kg-1）。添加几种有机物料后红壤CO2释放量存在显著差异,秸秆类有机物料分解释放CO2量相当于动物有机肥的2倍以上,其中小麦秸秆最高,牛粪最低,且有机物料分解释放CO2量与SMBC、SMBN、土壤可溶性有机碳（WSOC）和有机物料C/N呈显著相关。【结论】等碳量的有机物料施入红壤后能显著提高土壤CO2的释放速率和释放量,且土壤CO2释放量与土壤微生物量、可溶性碳和有机物料的C/N紧密相关。添加有机物料处理,土壤微生物生物量和碳源、氮源的有效性较高,有利于土壤养分的转化和释放。     

The hydroperoxyl radical in atmospheric chemical dynamics: reaction with carbon monoxide

From measurements of the photochemical rate of production of CO(2)(16,18) and CO(2)(16,16), produced from the low intensity photolysis of mixtures of CO, H(2)O, Ar, and O(2)(18,18), the rate constant for the reaction HO(2) + CO --> CO(2) + OH has been determined at 300 degrees K to be less than or equal to 10(-20) cubic centimeter per molecule per second. These measurements indicate that the reaction of thermalized HO(2) is of negligible importance as a sink mechanism for converting CO to CO(2) in either the troposphere or the stratosphere.     

The oceanic sink for anthropogenic CO2

Using inorganic carbon measurements from an international survey effort in the 1990s and a tracer-based separation technique, we estimate a global oceanic anthropogenic carbon dioxide (CO2) sink for the period from 1800 to 1994 of 118 +/- 19 petagrams of carbon. The oceanic sink accounts for approximately 48% of the total fossil-fuel and cement-manufacturing emissions, implying that the terrestrial biosphere was a net source of CO2 to the atmosphere of about 39 +/- 28 petagrams of carbon for this period. The current fraction of total anthropogenic CO2 emissions stored in the ocean appears to be about one-third of the long-term potential.     

The roaming atom: straying from the reaction path in formaldehyde decomposition

We present a combined experimental and theoretical investigation of formaldehyde (H2CO) dissociation to H2 and CO at energies just above the threshold for competing H elimination. High-resolution state-resolved imaging measurements of the CO velocity distributions reveal two dissociation pathways. The first proceeds through a well-established transition state to produce rotationally excited CO and vibrationally cold H2. The second dissociation pathway yields rotationally cold CO in conjunction with highly vibrationally excited H2. Quasi-classical trajectory calculations performed on a global potential energy surface for H2CO suggest that this second channel represents an intramolecular hydrogen abstraction mechanism: One hydrogen atom explores large regions of the potential energy surface before bonding with the second H atom, bypassing the saddle point entirely.     

The role of Mg2+ as an impurity in calcite growth

Magnesium is a key determinant in CaCO3 mineralization; however, macroscopic observations have failed to provide a clear physical understanding of how magnesium modifies carbonate growth. Atomic force microscopy was used to resolve the mechanism of calcite inhibition by magnesium through molecular-scale determination of the thermodynamic and kinetic controls of magnesium on calcite formation. Comparison of directly measured step velocities to standard impurity models demonstrated that enhanced mineral solubility through magnesium incorporation inhibited calcite growth. Terrace width measurements on calcite growth spirals were consistent with a decrease in effective supersaturation due to magnesium incorporation. Ca(1-x)Mg(x)CO3 solubilities determined from microscopic observations of step dynamics can thus be linked to macroscopic measurements.     

Visualizing gas molecules interacting with supported nanoparticulate catalysts at reaction conditions

Understanding how molecules can restructure the surfaces of heterogeneous catalysts under reaction conditions requires methods that can visualize atoms in real space and time. We applied a newly developed aberration-corrected environmental transmission electron microscopy to show that adsorbed carbon monoxide (CO) molecules caused the {100} facets of a gold nanoparticle to reconstruct during CO oxidation at room temperature. The CO molecules adsorbed at the on-top sites of gold atoms in the reconstructed surface, and the energetic favorability of this reconstructed structure was confirmed by ab initio calculations and image simulations. This atomic-scale visualizing method can be applied to help elucidate reaction mechanisms in heterogeneous catalysis.     

Experimental test of self-shielding in vacuum ultraviolet photodissociation of CO

Self-shielding of carbon monoxide (CO) within the nebular disk has been proposed as the source of isotopically anomalous oxygen in the solar reservoir and the source of meteoritic oxygen isotopic compositions. A series of CO photodissociation experiments at the Advanced Light Source show that vacuum ultraviolet (VUV) photodissociation of CO produces large wavelength-dependent isotopic fractionation. An anomalously enriched atomic oxygen reservoir can thus be generated through CO photodissociation without self-shielding. In the presence of optical self-shielding of VUV light, the fractionation associated with CO dissociation dominates over self-shielding. These results indicate the potential role of photochemistry in early solar system formation and may help in the understanding of oxygen isotopic variations in Genesis solar-wind samples.     

长白山阔叶红松林碳收支特征

植被-大气间CO2交换研究对准确评价陆地生态系统碳收支有重要意义．该研究采用开路式涡动相关系统对长白山阔叶红松林的C O2交换特征进行了整年连续监测．结果表明,该森林生态系统的碳交换季节变化明显,2003年森林净生态系统碳交换量(NEE)变化范围在-6.37～2.13 g/(m2·d)之间,5—9月均表现为碳汇,其余月份为碳源,其中净碳吸收量与释放量最大的月份分别为6和10月;全年森林净吸收的碳量为-191.3 g/m2,整体表现为一定强度的碳汇．影响NEE的环境因子主要是光合有效辐射(PAR)和土壤温度等,白天NEE对PAR 的响应符合直角双曲线方程,夜间的NEE与5 cm深土壤温度有较好的指数关系．生态系统呼吸释放对温度响应的敏感性(Ｑ10)为3.17．      

Annual heat balance of martian polar caps: viking observations

The Infrared Thermal Mappers aboard the two Viking orbiters obtained solar reflectance and infrared emission measurements of the Martian north and south polar regions during an entire Mars year. The observations were used to determine annual radiation budgets, infer annual carbon dioxide frost budgets, and constrain spring season surface and atmospheric properties with the aid of a polar radiative model. The results provide further confirmation of the presence of permanent CO(2)frost deposits near the south pole and show that the stability of these deposits can be explained by their high reflectivities. In the north, the observed absence of solid CO(2) during summer was primarily the result of enhanced CO(2) sublimation rates due to lower frost reflectivities during spring. The results suggest that the present asymmetric behavior of CO(2)frost at the Martian poles is caused by preferential contamination of the north seasonal polar cap by atmospheric dust.     

Carbon dioxide supersaturation in the surface waters of lakes

Data on the partial pressure of carbon dioxide (CO(2)) in the surface waters from a large number of lakes (1835) with a worldwide distribution show that only a small proportion of the 4665 samples analyzed (less than 10 percent) were within +/-20 percent of equilibrium with the atmosphere and that most samples (87 percent) were supersaturated. The mean partial pressure of CO(2) averaged 1036 microatmospheres, about three times the value in the overlying atmosphere, indicating that lakes are sources rather than sinks of atmospheric CO(2). On a global scale, the potential efflux of CO(2) from lakes (about 0.14 x 10(15) grams of carbon per year) is about half as large as riverine transport of organic plus inorganic carbon to the ocean. Lakes are a small but potentially important conduit for carbon from terrestrial sources to the atmospheric sink.     

Venus upper atmosphere neutral gas composition: first observations of the diurnal variations

Measurements of the composition, temperature, and diurnal variations of the major neutral constituents in the thermosphere of Venus are being made with a quadrupole mass spectrometer on the Pioneer Venus orbiter. Concentrations of carbon dioxide, carbon monoxide, molecular nitrogen, atomic oxygen, and helium are presented, in addition to an empirical model of the data. The concentrations of the heavy gases, carbon dioxide, carbon monoxide, and molecular nitrogen, rapidly decrease from the evening terminator toward the nightside; the concentration of atomic oxygen remains nearly constant and the helium concentration increases, an indication of a nightside bulge. The kinetic temperature inferred from scale heights drops rapidly from 230 K at the terminator to 130 K at a solar zenith angle of 120 degrees , and to 112 K at the antisolar point.     

二恶英和二氧化碳排放量与GDP关系初探

[目的]探讨二恶英排放量与二氧化碳排放量及GDP的关系。[方法]利用公式“源强=排放因子ב活动率’”估算出二恶英和二氧化碳的排放量,进而研究二恶英排放量与二氧化碳排放量及GDP的关系。[结果]根据二恶英（PCDD／Fs）排放量与二氧化碳排放量做出log（PCDD／Fs）-log（CO2）曲线,log（PCDD／Fs）和log（CO2）呈现出良好的线性关系,说明二恶英排放量和二氧化碳排放量具有正相关关系。根据二恶英排放量与GDP做出log（PCDD／Fs）-log（GDP）曲线,log（PCDD／Fs）和log（GDP）呈现出良好的线性关系。二恶英排放量与二氧化碳排放量及GDP存在相关性。log（PCDD／Fs）-log（CO2）和log（PCDD／Fs）-log（GDP）曲线都显示出良好的相关性。[结论]该研究表明高GDP地区也是二氧化碳和二恶英排放量较高的地区,技术水平的地区差别没有导致二氧化碳和二恶英排放量的明显差异。     

溶解CO_2对原料乳中主要腐败微生物生长参数的影响

研究了4℃下在原料乳中溶解CO2对其中主要腐败微生物生长参数的影响。试验以未处理的原料乳作对照组,CO2处理组的原料乳中CO2浓度分别为11.9、28.54、42.27 mmol.L-1。分别对各组中的假单胞菌、肠杆菌科细菌、乳酸菌和细菌总数的生长过程进行动态监测,并由此建立Gompertz数学模型、计算生长参数。结果表明,原料乳中溶解的CO2浓度越高,对3类主要腐败菌的抑制作用越大;CO2对革兰氏阴性菌的抑制作用大于革兰氏阳性菌;4℃下溶解42.27 mmol.L-1 CO2可以使原料乳的保质期延长1倍。     

Rocket ultraviolet spectrophotometry of comet kohoutek (1973f)

Observations of Comet Kohoutek (1973f) in the spectral region between 1200 and 3200 angstroms were made from an Aerobee rocket on 5.1 January 1974 universal time. The strongest features observed were the Lyman alpha line of neutral atomic hydrogen at 1216 angstroms and the hydroxyl (OH) bands at 3090 and 3142 angstroms. Atomic oxygen and atomic carbon were also detected, and their luminosity implies a production rate (of carbon monoxide or carbon dioxide) commensurate with that of water vapor.     

The impact of agricultural soil erosion on the global carbon cycle

Agricultural soil erosion is thought to perturb the global carbon cycle, but estimates of its effect range from a source of 1 petagram per year(-1) to a sink of the same magnitude. By using caesium-137 and carbon inventory measurements from a large-scale survey, we found consistent evidence for an erosion-induced sink of atmospheric carbon equivalent to approximately 26% of the carbon transported by erosion. Based on this relationship, we estimated a global carbon sink of 0.12 (range 0.06 to 0.27) petagrams of carbon per year(-1) resulting from erosion in the world's agricultural landscapes. Our analysis directly challenges the view that agricultural erosion represents an important source or sink for atmospheric CO2.     

Atomic hydrogen on Mars: measurements at solar minimum

The Copernicus Orbiting Astronomical Observatory was used to obtain measurements of Mars Lyman-alpha (1215.671-angstrom) emission at the solar minimum, which has resulted in the first information on atomic hydrogen concentrations in the upper atmosphere of Mars at the solar minimum. The Copernicus measurements, coupled with the Viking in situ measurements of the temperature (170 degrees +/- 30 degrees K) of the upper atmosphere of Mars, indicate that the atomic hydrogen number density at the exobase of Mars (250 kilometers) is about 60 times greater than that deduced from Mariner 6 and 7 Lyman-alpha measurements obtained during a period of high solar activity. The Copernicus results are consistent with Hunten's hypothesis of the diffusion-limited escape of atomic hydrogen from Mars.     

冬小麦夏玉米农田土壤呼吸与碳平衡的研究

为探讨不同农作措施下的农田碳平衡规律,研究农田对大气CO2的“源”、“汇”特征,2000年至2003年连续测定了不同秸秆管理、灌溉和氮肥施用等种植措施下华北冬小麦、夏玉米生长季的土壤呼吸。结果表明,农田CO2释放主要受气温、土壤水分状况和有机物投入量等因素的影响。秸秆还田与优化灌溉增加了土壤呼吸的强度,不同农作措施间土壤呼吸的差异主要发生在冬小麦生长季。对农田碳平衡研究的计算结果显示,农田系统在常规种植措施下表现为大气CO2的“汇”。在传统农作措施下,华北冬小麦、夏玉米生长季植物碳净固定量(NPP)与土壤碳排放量(Rm)的比值分别为1.16、1.21。