Validation and Scenario Analysis of a Soil Organic Carbon Model

A model developed by the authors was validated against independent data sets. The data sets were obtained from field experiments of crop residue decomposition and a 7-year soil improvement in Yixing City, Jiangsu Province. Model validation indicated that soil organic carbon dynamics can be simulated from the weather variables of temperature, sunlight and precipitation, soil clay content and bulk density, grain yield of previous crops, qualities and quantities of the added organic matter. Model simulation in general agreed with the measurements. The comparison between computed and measured resulted in correlation coefficient γ2 values of 0.9291 * * * (n = 48) and 0. 6431 * * (n = 65) for the two experiments, respectively. Model prediction under three scenarios of no additional organic matter input, with an annual incorporation of rice and wheat straw at rates of 6.75t/ha and 9.0t/ha suggested that the soil organic carbon in Wanshi Township of Yixing City would be from an initial value of 7.85g/kg in 1983 to 6.30g/kg, 11.42g/kg and 13g/kg in 2014, respectively. Consequently, total nitrogen content of the soil was predicted to be respectively 0.49g/kg,0.89g/kg and 1.01g/kg under the three scenarios.     

腐殖酸的光化学行为研究进展

腐殖酸作为一种大分子有机物质受到越来越多的关注,尤其是腐殖酸的光化学行为。对腐殖酸光化学特性的研究进展与发展趋势进行了综述和探讨,主要包括腐殖酸自身的光降解,腐殖酸的间接光降解,腐殖酸的光敏化反应,腐殖酸光化学研究的前景与展望等。     

Inclusion systems of organic molecules in restacked single-layer molybdenum disulfide

Novel materials have been obtained by restacking single-layer molybdenum disulfide (MoS(2)) with organic molecules included between the layers. A large variety of organic molecules can be included between layers of MoS(2) and other transition-metal dichalcogenides. The films with the included organics are formed at the interface between an aqueous suspension of the MoS(2) and a water-immiscible organic liquid. The organic molecules are not necessarily electron donors. A highly oriented, conducting film of restacked MoS(2) containing ferrocene is presented as an example.     

Evidence for Photochemical Formation of H2O2 and Oxidation of SO2 in Authentic Fog Water

When samples of rain and fog water were exposed to ultraviolet and visible light, reactive transients such as hydrogen peroxide were formed and dissolved organic matter and sulfur dioxide were depleted. These results, in conjunction with those from previous studies, imply that dissolved organic compounds and transition metals such as iron ions are involved in the photochemical formation of hydrogen peroxide and other photooxidants in atmospheric waters.     

Photochemical reactions as a tool in organic syntheses

This article represents only a brief glimpse into one of the fascinating aspects of the chemistry of electronically excited molecules. More exhaustive coverage of synthetic applications of photochemical reactions may be found in texts and reviews. We summarize here by noting that classification of reliable photoreactions is possible, but that the most effective application of the classification scheme requires a familiarity with some of the special features of the chemistry of electronically excited states. Thus, knowledge of the properties of singlet and triplet states, the factors which determine photochemical efficiency and reactivity, and the special technical aspects of photochemical procedures such as selective direct and phtosensitized excitation and photoexcitation at low temperatures or solid matrices make photochemistry a useful tool for the construction of organic molecules. It is our hope that the material and flavor of this article will whet the intellectual and experimental appetites of researchers who are concerned with various aspects of the synthesis of oganic molecules.     

Urban ozone control and atmospheric reactivity of organic gases

Control strategies for urban ozone traditionally have been based on mass reductions in volatile organic compounds (VOCs). Studies show, however, that some organic gas species (such as alkanes and alcohols) form an order of magnitude less ozone than equal mass emissions of others (such as alkenes and aldehydes). Chemically detailed photochemical models are used to assess uncertainty and variability in reactivity quantification. VOC control strategies based on relative reactivity appear to be robust with respect to nationwide variations in environmental conditions and uncertainties in the atmospheric chemistry. Control of selective organic gas species on the basis of reactivity can offer cost savings over traditional strategies.     

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.     

1,2,4-三氯苯和萘对水稻抽穗期叶片光合特性的影响

 研究了1,2,4-三氯苯(TCB)和萘（NAP）对抽穗期水稻叶片光合特性的影响。结果表明，随TCB和NAP胁迫浓度的增加，叶绿素含量、净光合速率（Pn）、气孔导度( Gs)、细胞间隙CO2浓度(Ci)、蒸腾速率(Tr)、原初光能转换效率( Fv/Fm) 、PSⅡ潜在活性（Fv/Fo）、光合电子传递量子效率(ΦPSII)、光化学猝灭系数(qP)、非光化学猝灭系数(qN) 均呈下降趋势；而且TCB对以上指标的影响明显大于NAP的影响，汕优63的敏感性要大于武运粳7号；有机污染胁迫下，光合速率下降的原因，在低浓度时主要由于气孔限制引起，而在较高浓度下由气孔限制和非气孔限制共同引起。较高浓度的有机污染物使光合作用受到明显抑制，最终导致水稻产量显著降低。在各叶绿素荧光动力学参数中，以PSⅡ潜在活性（Fv/Fo）和非光化学猝灭系数(qN)对有机污染胁迫最为敏感。建议将这两个参数作为衡量水稻发生有机污染伤害的参考指标。     

有机污染物在腐殖酸作用下的光降解研究进展

腐殖酸是广泛存在于水体、土壤中的天然吸光物质,其光化学行为受到越来越多的关注。鉴于此,综述了近年来腐殖酸对不同种类的有机污染物包括除草剂、杀虫剂、抗生素、染料和有毒化学原料光降解的影响,并就腐殖酸对污染物光降解影响今后的研究方向进行了展望。     

Sulfur Dioxide Sensitized Photochemical Oxidation of Hydrocarbons

Near-ultraviolet sunlight is absorbed by sulfur dioxide to produce electronically excited molecules, which react with n-butane in the presence of wet or dry air to produce an aerosol and eventually a liquid precipitate. The product is a heavily oxidized, sulfur-containing, organic strong acid. The possible role of these reactions in photochemical air pollution is discussed.     

三唑酮的光化学降解研究

以太阳光和高压汞灯为光源研究了三唑酮在溶液相中的光化学降解。结果表明,在太阳光下,三唑酮在正己烷、甲醇、丙酮和纯水中均能较稳定存在;高压汞灯下熏三唑酮光降解速度很快,有机溶剂中降解快慢顺序是丙酮>甲醇>正己烷,水溶液中三唑酮的光解率与其初始浓度呈负相关关系,各种类型水中光降解速率顺序为纯水>井水>河水>池塘水。     

Exciplexes and electron transfer reactions

Electronically excited molecules, being better electron donors and acceptors than their ground states, form charge-transfer complexes (exciplexes) which can lead to radical ions. Exciplex emission is widely used to probe polymers and organized media such as membranes and micelles. Exciplexes are also intermediates in photoreactions that lead to unique products. Photochemical electron-transfer processes, which are the basis of silver halide photography and electrophotography, are involved in many reactions of wide scope. Recent studies have led to the discovery of several electron-transfer photooxygenations with a diversity that will probably rival that of singlet oxygen. Both exciplex emission and photochemical electron transfer play important roles in organic photochemistry.     

Photochemical Production of Formaldehyde in Earth's Primitive Atmosphere

Formaldehyde could have been produced by photochemical reactions in Earth's primitive atmosphere, at a time when it consisted mainly of molecular nitrogen, water vapor, carbon dioxide, and trace amounts of molecular hydrogen and carbon monoxide. Removal of formaldehyde from the atmosphere by precipitation can provide a source of organic carbon to the oceans at the rate of 10(11) moles per year. Subsequent reactions of formaldehyde in primeval aquatic environments would have implications for the abiotic synthesis of complex organic molecules and the origin of life.     

Creating favorable geometries for directing organic photoreactions in alkanethiolate monolayers

The products of photoreactions of conjugated organic molecules may be allowed by selection rules but not observed in solution reactions because of unfavorable reaction geometries. We have used defect sites in self-assembled alkanethiolate monolayers on gold surfaces to direct geometrically unfavorable photochemical reactions between individual organic molecules. High conductivity and stochastic switching of anthracene-terminated phenylethynylthiolates within alkanethiolate monolayers, as well as in situ photochemical transformations, have been observed and distinguished with the scanning tunneling microscope (STM). Ultraviolet light absorbed during imaging increases the apparent heights of excited molecules in STM images, a direct manifestation of probing electronically excited states.     

The hydrogen atom and its reactions in solution

Hydrogen atoms have been generated in solution by photolysis of thiols in solutions of organic compounds, and the relative rate constants, k(H), have been measured for the reaction H* + QH --> H(2) + Q*, where QH is any organic compound which contains hydrogen. This represents the first kinetic study of the hydrogen atom in which it is generated in solution by a technique not involving ionizing radiation. The relative values of k(H) are in agreement with the values from radiolysis for most of the substances studied; however, for some compounds significantly different results have been obtained.     

Irreversible organic crystalline chemistry monitored in real time

Because multiple laser shots are typically required to monitor ultrafast photochemical reaction dynamics, sample depletion and product accumulation have greatly restricted the range of substrates and structural environments amenable to study. By implementing a two-dimensional spatial delay gradient across the profile of a femtosecond probe pulse, we can monitor in a single laser shot organic crystalline reaction dynamics despite the formation of permanent photoproducts that cannot be conveniently removed. We monitored the photolysis of the triiodide anion, I3-, and subsequent recombination or relaxation of its reaction products, in three very different pure organic molecular crystals. The experimental results and associated molecular dynamics simulations illustrate the intimate connection between lattice structure and reaction dynamics, highlighting the role of lattice constraints in directing phase-coherent geminate recombination of photofragments within a crystalline reaction cage.     

天然土壤对菲吸附行为的动态变化

选择8种有机质含量各异的土壤,考察其对菲吸附行为的动态变化特征,并利用Freundlich模型描述1、48和720h条件下菲的相分配关系。结果表明,在不同接触时间条件下,Freundlich吸附系数KF与土壤有机质含量呈显著的线性关系,8种土样吸附行为的非线性指数n随时间逐渐减小,经土壤有机碳含量校正的单点Koc*值也随时间上升。这些结果指示土壤有机质是有机污染物土壤吸附的主要汇,土壤有机质吸附位点的位能表现为非均匀分布,颗粒内部有机质吸附位点的容量更大。此外,利用差减方式得到吸附过程后段的相分配关系的非线性明显强于吸附过程前段,说明慢吸附阶段中结构致密的土壤有机质组分的影响更趋强烈疏水性有机污染物在致密有机质组份中的扩散过程很可能是慢反应发生的主要原因。     

Direct Detection of C4H2 Photochemical Products: Possible Routes to Complex Hydrocarbons in Planetary Atmospheres

The photochemistry of diacetylene (C4H2), the largest hydrocarbon to be unambiguously identified in planetary atmospheres, is of considerable importance to understanding the mechanisms by which complex molecules are formed in the solar system. In this work, the primary products of C4H2's ultraviolet photochemistry were determined in a two-laser pump-probe scheme in which the products of C4H2 photoexcitation are detected by vacuum ultraviolet photoionization in a time-of-flight mass spectrometer. Three larger hydrocarbon primary products were observed with good yield in the C4H2* + C4H2 reaction: C6H2, C812, and C8H3. Neither C6H2 nor C8H3 is anticipated by current photochemical models of the atmospheres of Titan, Uranus, Neptune, Pluto, and Triton. The free hydrogen atoms that are released during the formation of the C8H3 and C8H2 products also may partially offset the role of C4H2 in catalysing the recombination of free hydrogen atoms in the planetary atmospheres.     

Lightning on jupiter: rate, energetics, and effects

Voyager data on the optical and radio-frequency detection of lightning discharges in the atmosphere of Jupiter suggest a stroke rate significantly lower than on the earth. The efficiency of conversion of atmospheric convective energy flux into lightning is almost certainly less than on the earth, probably near 10(-7) rather than the terrestrial value of 10(-4). At this level the rate of production of complex organic molecules by lightning and by thunder shock waves is negligible compared to the rates of known photochemical processes for forming colored inorganic solids.     

Carbon monoxide in rainwater

Concentrations of carbon monoxide in rainwater collected at widely diverse locations show up to a 200-fold supersaturation relative to the partial pressure of the gas in the atmosphere. These results indicate the existence of an additional natural source of carbon monoxide not heretofore considered. Production of carbon monoxide in clouds is tentatively attributed to the photochemical oxidation of organic matter or the slight dissociation of carbon dioxide induced by electrical discharges, or both. Methane concentrations measured in the same rainwater show that the partitioning of this gas, unlike that of carbon monoxide, is very close to a state of equilibrium.