Laboratory study of the rates and products of the phototransformations of naphthalene adsorbed on samples of titanium dioxide,ferric oxide,muscovite, and fly ash

The photodegradation of naphthalene (NPH), chosen as a model of polynuclear aromatic pollutants, has been studied in the presence of a layer of four water-insoluble inorganic solids which can be found in the troposphere (TiO₂, Fe₂O₃, muscovite, and a fly ash sample). Direct photolysis of NPH is negligible at >340 nm. Dark adsorption of NPH on TiO₂ (mainly anatase, nonporous, 50 m² g^–1) at 293 K corresponds to a surface coverage ofca. 50% at equilibrium. Under these conditions (saturated surface), the stationary-state photocatalytic degradation reaches 0.4 molecule nm^–2 h^–1 (>340 nm, radiant fluxca. 22 mW cm^–2). Dioxygen is required and its partial pressure in air is such that the degradation is zero order in O₂. Water vapor markedly increases the rate. The other particulates have also an effect, less important than that of TiO₂, however quite noticeable with respect to surface area unit for the fly ash sample which contains 3.2% Fe₂O₃. Apart from 1,4-naphthoquinone, which is the main intermediate product in all cases, 2-naphthol, phthalide, phthaldialdehyde, phthalic acid, acetophenone, benzaldehyde, benzoic acid are also formed on dry TiO₂. Depending on their volatility, these compounds are transferred to the gas phase or remain principally adsorbed on the solid particles where they are further transformed. For instance, phthalic acid (or anhydride) and benzoic acid are generated from 1,4-naphthoquinone. Degradation mechanisms are briefly discussed.     

A photoelectric detector for the measurement of photolysis frequencies of ozone and other atmospheric molecules

Photoelectric detectors for the measurement of photolysis frequencies of different trace gases in the atmosphere are described. They exhibit uniform response characteristics over one hemisphere (2 sr) and wavelength characteristics closely matched to those of the photolysis frequencies J _O1D, J _NO2, and J _NO3, respectively. Absolute calibration of the J _O1D detector was performed by chemical actinometry with an accuracy of ±16 percent. Simultaneous measurements of J _NO2 and J _O1D are presented.     

Numerical study of the oxidation process of dimethylsulfide in the marine atmosphere

A box model, involving simple heterogeneous reaction processes associated with the production of non-sea-salt sulfate (nss-SO ₄ ^2– ) particles, is used to investigate the oxidation processes of dimethylsulfide (DMS or CH₃SCH₃) in the marine atmosphere. The model is applied to chemical reactions in the atmospheric surface mixing layer, at intervals of 15 degrees latitude between 60° N and 60° S. Given that the addition reaction of the hydroxyl radical (OH) to the sulfur atom in the DMS molecule is faster at lower temperature than at higher temperature and that it is the predominant pathway for the production of methanesulfonic acid (MSA or CH₃SO₃H), the results can well explain both the increasing tendency of the molar ratio of MSA to nss-SO ₄ ^2– toward higher latitudes and the uniform distribution with latitude of sulfur dioxide (SO₂). The predicted production rate of MSA increases with increasing latitude due to the elevated rate constant of the addition reaction at lower temperature. Since latitudinal distributions of OH concentration and DMS reaction rate with OH are opposite, a uniform production rate of SO₂ is realized over the globe. The primary sink of DMS in unpolluted air is caused by the reaction with OH. Reaction of DMS with the nitrate radical (NO₃) also reduces DMS concentration but it is less important compared with that of OH. Concentrations of SO₂, MSA, and nss-SO ₄ ^2– are almost independent of NO _x concentration and radiation field. If dimethylsulfoxide (DMSO or CH₃S(O)CH₃) is produced by the addition reaction and further converted to sulfuric acid (H₂SO₄) in an aqueous solution of cloud droplets, the oxidation process of DMSO might be important for the production of aerosol particles containing nss-SO ₄ ^2– at high latitudes.     

中国二氧化碳地区间排放差异分析及减排政策建议

利用统计数据,参照政府间气候变化专门委员会（IPCC）的方法,对2008年我国各省区CO₂的排放情况进行了计算分析,并对东西部地区进行对比得出：东部发达地区在人均排放量和排放密度等方面均高于西部欠发达地区,但东部地区的排放强度却明显低于西部地区。国家经济战略,东、西部地区技术、经济社会发展水平差异是造成这一趋势的主要原因。提出了我国实现温室气体减排目标、分解减排任务的建议。     

近地层O3和CO2浓度变化对冬小麦影响的数值模拟：Ⅱ模拟结果和分析

针对CO2和O3浓度变化对冬小麦影响,改进了农田生态系统碳氮生物化学模型(DNDC),并利用模型模拟了O3和CO2浓度变化对冬小麦生长发育和产量的影响,检验了模型的模拟效果.通过对原DNDC模型适用性的调整,使之适用于固城站,为进一步改进作物模型打下了可靠的基础.通过试验资料验证表明,模型较好地反映了O3和CO2浓度变化对冬小麦生长发育和产量形成的影响.通过敏感性分析得出,模型对温度变化反映灵敏;在CO2浓度倍增情况下,O3浓度变化对冬小麦的复合影响分析看出,一定浓度范围内,CO2可缓解O3对作物影响的负效应,O3对CO2带来的正效应有削弱作用.     

Inter-annual and seasonal variations in the air–sea CO2 balance in the central Baltic Sea and the Kattegat

We estimated the net annual air–sea exchange of carbon dioxide (CO₂) using monitoring data from the East Gotland Sea, Bornholm Sea, and Kattegat for the 1993–2009 period. Wind speed and the sea surface partial pressure of CO₂ (pCO₂^w), calculated from pH, total alkalinity, temperature, and salinity, were used for the flux calculations. We demonstrate that regions in the central Baltic Sea and the Kattegat alternate between being sinks (−) and sources (+) of CO₂ within the −4.2 to +5.2 mol m⁻² yr⁻¹ range. On average, for the 1994–2008 period, the East Gotland Sea was a source of CO₂ (1.64 mol m⁻² yr⁻¹), the Bornholm Sea was a source (2.34 mol m⁻² yr⁻¹), and the Kattegat was a sink (−1.16 mol m⁻² yr⁻¹). Large inter-annual and regional variations in the air–sea balance were observed. We used two parameterizations for the gas transfer velocity (k) and the choice varied the air–sea exchange by a factor of two. Inter-annual variations in pCO₂^w between summers were controlled by the maximum concentration of phosphate in winter. Inter-annual variations in the CO₂ flux and gas transfer velocity were larger between winters than between summers. This indicates that the inter-annual variability in the total flux was controlled by winter conditions. The large differences between the central Baltic Sea and Kattegat were considered to depend partly on the differences in the mixed layer depth.     

碳糊电极循环伏安法测定γ－和β－二氧化锰物相

利用碳糊电极循环伏安法对γ－ＭｎＯ＿２和β－ＭｎＯ＿２进行了定量分析，相对于２００．０ｍｇ碳粉的线性范围分别为γ－ＭｎＯ＿２９．１３～４５，６ｍｇ；β－ＭｎＯ＿２４．５６～３６．５ｍｇ，在线性范围内测量７次，其ＲＳＤ分别为０．５９％～５．２８％和Ｏ％～５．７２％。同时对γ－ＭｎＯ＿２和β－ＭｎＯ＿２的混合试样及湘潭电解二氧化锰也进行了定量测定，其平均相对误差分别为２．０１％～１２．４％和１．９６％～７．５２％。该方法进行物相分析，具有简便、快速、灵敏、经济和不经化学分离等特点。     

Supercritical Carbon Dioxide Extraction of Organic Matter from Petroleum Source Rocks and Its Implications

Organic matter was experimentally extracted by supercritical fluids(CO2 1% isopropanol)from petroleum source rocks of different thermo-maturities at different buried depths in the same stratigraphic unit in the Dongying Basin.The results show that supercritical fluid extraction(SFE)is more effective than Soxhlet extraction(SE),with higher amounts and greater varieties of hydrocarbons and soluble organic matter becoming extractive.The supercritical CO2 extraction is therefore considered more valuable in evaluation of petroleum source rocks and oil resources,particularly those of immature types.     

苏北盆地油田封存二氧化碳潜力初探

油田二氧化碳封存是减少温室气体排放量最有效的途径之一,油藏中封存CO2 主要有构造地层储存、束缚气储存、 溶解储存和矿化储存等四种方式,CO2 在油藏中的地质储存容量采用国际上通用的资源储量金字塔理论来进行潜力评价。 本文通过分析油田CO2 封存机理,结合江苏省苏北盆地的地质和构造条件,对苏北盆地油田进行CO2 封存潜力研究。苏北 盆地油田多为低渗透和含水油藏,在储存CO2 的潜力上,东台坳陷优于盐阜坳陷,次级单元中又以高邮凹陷、金湖凹陷封 存CO2 潜力最大,一系列小型构造单元比较适合于CO2 封存,并有利于后期的保存。在封盖能力上,苏北盆地在垂向上有 明显的两分性,下部上白垩系和古新统盖层相对上部始新统盖层对CO2 封盖性更好。估算得到苏北盆地油田埋存CO2 的理 论储存容量为1.5054×108 t,有效储存容量为0.0828×108 t~0.4421×108 t,表明苏北油田封存CO2 的潜力较大。     

澳大利亚Otway盆地二氧化碳地质封存示范工程介绍

澳大利亚Otway盆地二氧化碳地质封存示范工程是澳大利亚第一个完整的从源到汇的碳封存研究项目,也是碳封存领导论坛（CSLF）和国际能源总署（IEA）认可的二氧化碳地质封存国际合作项目,由澳大利亚CO2CRC牵头开展相关研究。项目封存场地位于澳大利亚维多利亚州的Otway盆地,分两个阶段进行。第一阶段,2004~2010年开展衰竭气田的二氧化碳地质封存研究,已向位于地下深处2000m的晚白垩系Waarre C粗砂岩地层灌注二氧化碳混合气体65000多吨,并成功实现构造圈闭封存,同时开展了地下水、土壤气体、大气、地球化学、地球物理等综合监测;第二阶段,2010 ~2015年开展地下咸水层封存二氧化碳的研究,将向位于地下1500m深处的晚白垩系Paaratte细砂岩咸水含水层注入10000t二氧化碳,实现二氧化碳毛细滞留圈闭封存,目前正在开展前期抽注试验。