CS自由基与O2的反应研究

采用CS2 在 1 85nm光照下产生CS自由基的方法 ,研究了CS自由基与O2 的反应 .在纯CS2 和CS2 O2 体系 ,光解产生的CS自由基中 ,CS2 的量子产额分别为Φ表观 =0 6 2和Φ′表观 =2 0 5、表观速率常数分别为k表观 =8 0 6× 1 0 - 4s- 1和k′表观 =2 72×1 0 - 3 s- 1,并讨论了CS自由基与O2 反应的机理 .研究表明 ,CS自由基与O2 反应的主要产物为COS,SO2 和SO3 ,N2 的加入不影响CS自由基与O2 的反应 .     

氮肥对土壤氧化大气甲烷影响的机制

综合评述了氮氧化甲烷的抑制机制。包括：（1）竞争甲烷单氧化酶的竞争抑制机制，（2）代谢产物的毒害抑制机制，（3）外源盐引起的微生物生理缺水抑制机制和（4）氮素周围作用引起的抑制机制。提出了氧化菌竞争利用土壤空气有限O2的竞争抑制机制，即氨氧化菌利用更多的土壤有限氧气→产生优势氨氧化菌→形成优势菌群→限制甲烷氧化菌繁殖和功能发挥的氨长期抑土壤化大气甲烷的机制，并认为这种抑制作用是不可逆的。     

Pd掺杂对Fe,Co系钙钛矿型三效催化剂性能的影响

用共沉淀法制备了LaFeO3，LaFe0.96Pd0.04O3，LaCoO3，LaCo0.96Pd0.04O3四种催化剂，用X－射线衍射仪（XRD）对催化剂进行了结构分析。程序升温还原（TPR）实验揭示催化剂中存在两种类型的氧种：α氧和β氧。活性评价和TPR实验表明，α氧是CO和C3H6氧化反应的活性氧种，而C3H8的氧化则由α氧和β氧共同来完成。Pd的掺杂可使ABO3中β氧的活性增强，从而使三效活性得以明显提高。     

生物覆盖层基质对垃圾填埋场甲烷氧化的影响

生物覆盖层甲烷氧化是填埋场甲烷减排的重要途径,覆盖层基质性能对其甲烷氧化能力影响较大。选用≤1mm堆肥物（1#基质）、≤1mm堆肥物＋陶粒（2^#基质）、≤1mm堆肥物＋陶粒（3#基质）、1～2mm堆肥物（4#基质）、2～3．2mm堆肥物（5#基质）等5种不同类型的生物覆盖层基质,在实验室内模拟研究填埋场生物覆盖层的甲烷生物氧化状况,旨在为筛选垃圾填埋场甲烷高效氧化的生物覆盖材料提供科学依据。试验结果表明：粒径对基质氧气传输能力的影响不明显;不同基质的甲烷氧化能力存在显著差异,纯堆肥物基质（1#、4#和5#基质）几乎没有甲烷氧化能力,堆肥物＋陶粒（1：1（v：v）的复合基质（2#、3#基质）的甲烷氧化效率高达100％。堆肥物一陶粒复合基质为甲烷氧化细菌营造了良好的环境,改善了生物覆盖层内的气体传输性能,是一种适宜的填埋场生物覆盖层基质材料。     

水稻土中半胱氨酸分解产生含硫气体的研究^1）

在室内培养条件下，测定了水稻土中含硫气体的释放，结果表明，该土壤中有硫化氢（H2S），羧基硫（COS），二甲基硫（DMS）三种气体释放，当土壤中加入半胱氨酸后，COS和H2S气体的浓度有了明显增加，并有CS2和CH3SH测出，而DMS的浓度变化不大，这些结果表明法胱氨酸的分解可能是COS，H2S，CS2和CH3SH的产生源之一，在好氧（正常大气）条件下，H2S，COS，CS2和CH3SH的释放量低于氧（氮气氛围）条件下的释放量，DMS则高于厌氧条件下，这表明水稻土中半胱氨酸分解产生H2S，COS，CS2和CH3SH需较强的还原条件，产生这四种气体的微生物需要严格的厌氧条件，产生DMS的微生物则比前者需要高一些的含氧量，在光照条件下，各含硫气体的释放量普遍高于无光照条件下的释放量，释放含硫气体的大多数微生物适宜的含水率为50％且对土壤的pH值有一定要求。     

不同溶剂对提取原煤中PAHs种类、含量与分布的影响

以淮北煤田的煤样为研究对象,选取二硫化碳（CS2）、二氯甲烷（CH2Cl2）、正己烷（C6H14）三种溶剂,采用索氏提取法对原煤中的多环芳烃进行提取．利用气相色谱-质谱联用仪对提取液中的多环芳烃进行定量分析,研究了不同溶剂对原煤中多环芳烃种类、含量和分布的影响,通过研究发现,C6H14的提取能力显著低于CS2和CH2Cl2,CS2容易提取低环数的PAHs,CH2Cl2更容易提取高环数的PAHs．     

稀土离子对超氧阴离子自由基生成的抑制作用

利用肾上腺素在碱性条件下自氧化产生超氧阴离子自由基（O^.-2）的性质，研究了稀土硝酸盐对生成O^.-2的抑制作用。稀土硝酸盐与超氧化物歧化酶（SOD）具有相似的性质，对肾上腺素自氧化生成的O^.-2有明显的抑制作用。抑制率在16．3％－78．4％之间，而且体系中稀土硝酸盐的浓度与其对O^.-2的抑制率之间有明显的剂量效应关系。     

互花米草入侵盐沼湿地CH4和N2O排放日变化特征研究

甲烷（CH4）和氧化亚氮（N2O）是导致全球气候变暖的2种重要温室气体,探索其源汇及地域排放特征一直是全球变化研究领域的核心内容。CH4和N2O通量的日变化研究是正确估算大时间尺度下CH4和N2O排放量的基础。利用静态箱法原位观测了江苏沿海芦苇（Phragmites australis）、盐蒿（Suada salsa）、光滩、水面以及互花米草（Spartina alterniflora）入侵湿地CH4和N2O排放的日变化特征。结果表明,1）互花米草湿地地上部生物量为1.70 kg·m^-2,土壤有机碳质量分数为13.55 g·kg^-1;分别是芦苇和盐蒿湿地的2.50-3.43和2.15-4.15倍。2）互花米草和芦苇湿地土壤10 cm处氧化还原电位（Eh）有明显日变化,最低值出现在3：00,最高值出现在12：00;光滩和盐蒿湿地没有明显的日变化。3）互花米草湿地 CH4日平均排放通量为0.52 mg·m^-2·h^-1,是其他湿地的2.12-6.40倍;N2O日平均通量为-3.24μg·m^-2·h^-1,显著低于盐蒿湿地、光滩和水面（P＜0.05）。互花米草和芦苇湿地CH4排放通量最高值（0.73 mg·m^-2·h^-1和0.30 mg·m^-2·h^-1）出现在15：00,最低值（0.37 mg·m^-2·h^-1和0.17 mg·m^-2·h^-1）出现在3：00,均与土壤孔隙水中CH4浓度呈显著负相关（P＜0.05）。互花米草湿地CH4排放通量与10 cm土温、Eh和生态系统CO2净交换量（NEE）显著正相关（P＜0.05）。互花米草和芦苇湿地N2O通量9：00-18：00为负值,21：00—6：00为正值,均与NEE呈显著负相关（P＜0.05）。盐蒿湿地、光滩和水面CH4和N2O排放通量没有明显日变化特征。互花米草入侵提高了沿海湿地CH4排放,但降低了N2O排放,植物对CH4传输作用以及向根际传输O2和易分解有机物是导致互花米草和芦苇湿地CH4和N2O排放表现出日变化特征的原因。     

羰基硫(COS)紫外光解动力学的研究

在185nm紫外光照射下,研究了COS体系、COS-O2体系以及COS-空气体系中COS的转化反应,并考察了光照时间、O2分压和水气对COS光解的影响．推导了COS光解速率方程,并计算了其表观量子产率,据此提出了185nm紫外光作用下COS在不同体系中的反应机理．实验表明,平流层紫外光解是COS的重要汇,也是平流层含硫气溶胶的主要来源之一．     

碘铈共掺杂纳米TiO_2的制备及可见光光催化性能

采用溶胶凝胶法制备了不同原料比例碘铈共掺杂纳米TiO2催化剂,运用X射线光电子能谱（XPS）,X射线衍射（XRD）,透射电镜（TEM）等检测手段对催化剂进行了初步表征.结果表明,经过450℃煅烧处理得到的TiO2、铈掺杂TiO2以及碘铈共掺杂TiO2催化剂均为锐钛矿相,掺杂的Ce和I原子可能以I—Ce—O及O—Ti—I等键合方式进入TiO2晶格内部,此外,I-Ce离子共掺杂能有效降低TiO2表面的电子-空穴对的复合.以染料罗丹明B（Rhodamine B,RhB）和无色小分子水杨酸（Salicylic acid,SA）为降解的目标化合物,发现碘铈共掺杂的最佳物质的量之比为nCe∶nI∶nTi=0.04∶0.05∶1,即I0.05Ce0.04TiO2催化剂在可见光照射下（λ〉420 nm）降解目标化合物其光化学活性明显优于单掺铈的TiO2催化剂和未掺杂的TiO2.该催化反应涉及到空穴氧化,并伴有羟基自由基（.OH）、超氧自由基（O2.-）及H2O2等氧化物种的产生.     

活性炭及活性炭纤维对CS2的吸附行为研究及其方法探讨

以活性炭纤维(ACF)对水中CS:的吸附处理作为研究对象,并与另外两种活性炭(颗粒活性炭GAC和粉末活性炭PAC)进行对比研究,展示了ACF对CS:的优异吸附性能与处理效果,即吸附容量大,吸附低浓度效果好.同时运用新的宽平衡浓度吸附试验方法,测试了ACF、GAC、PAC对CS2的吸附平衡曲线,并对几种常见的吸附等温方程...     

Singlet molecular oxygen—mediated photooxidation of monochloro and mononitrophenols. A kinetic study

A kinetic and mechanistic study on the aerobic dye sensitized photooxidation of the mono—nitro and chlorophenols was carried out. A singlet molecular oxygen mechanism operates in the photooxidation. Solvent and substituent effects, suggest the intermediacy of a complex with partial charge transfer character, as has been postulated for other phenols.

Chemical (reactive) and physical interactions of the substrates with singlet molecular oxygen were discriminated. Quantum yields for photooxidation (higher for the chlorophenols) range from 3 × 10^‐2 to 2 × 10^‐3, as measured by substrate or oxygen consumption. These values indicate the viability of a singlet molecular oxygen photooxidation as a way for the degradation of nitro and chlorophenol environmental contaminants.     

硝酸根对罗丹明B光解的敏化作用

研究了紫外光照射下，KNO3对罗丹明B光解的敏化作用．结果表明，KNO3的加入可以显著提高罗丹明B的光降解率，反应液的酸度愈强愈有利于反应的进行，KNO3不仅对罗丹明B的降解有敏化作用，而且还能够直接提供氧化罗丹明B所需要的氧。     

Photolysis and photooxidation of typical gaseous VOCs by UV Irradiation: Removal performance and mechanisms

UV photodegradation of 27 typical VOCs was systematically investigated. Contribution of photolysis and photooxidation to VOCs removal was identified. Gaseous VOC could be partially converted to particles by 185/254 nm UV irradiation. The mineralization and conversion of 27 VOCs by UV irradiation were reported. Photodegradation by ultraviolet irradiation (UV) is increasingly applied in volatile organic compound (VOC) and odor gas treatments. In this study, 27 typical VOCs, including 11 hydrocarbons and 16 hydrocarbon derivatives, at 150–200 ppm in air and nitrogen gas were treated by a laboratory-scale UV reactor with 185/254 nm irradiation to systematically investigate their removal and conversion by UV irradiation. For the tested 27 VOCs, the VOC removal efficiencies in air were within the range of 13%–97% (with an average of 80%) at a retention time of 53 s, which showed a moderate positive correlation with the molecular weight of the VOCs (R = 0.53). The respective contributions of photolysis and photooxidation to VOC removal were identified for each VOC. According to the CO₂ results, the mineralization rate of the tested VOCs was within the range of 9%–90%, with an average of 41% and were negatively correlated to the molecular weight (R = -0.63). Many of the tested VOCs exhibited high concentration particulate matters in the off-gases with a 3–283 mg/m³ PM₁₀ range and a 2–40 mg/m³ PM_2.5 range. The carbon balance of each VOC during UV irradiation was analyzed based on the VOC, CO₂ and PM₁₀ concentrations. Certain organic intermediates and 23–218 ppm ozone were also identified in the off-gases. Although the UV technique exhibited a high VOC removal efficiency, its drawbacks, specifically low mineralization, particulate matters production, and ozone emission, must be considered prior to its application in VOC gas treatments.     

Effects of oxidizing environment on digestate humification and identification of substances governing the dissolved organic matter (DOM) transformation process

• Liquid digestate humification was investigated under different oxidizing environment. • Tryptophan-like substances dominated the transformation of the liquid digestate DOM. • The humification sequence of the liquid digestate DOM was identified. • UV₃₂₅ was first identified as a pre-humus intermediate during humification reaction. The formation of humic-like acids (HLAs) is an essential process for converting liquid digestate into organic soil amendments to enhance agricultural sustainability. The aim of this study was to investigate the impact of oxygen and/or MnO₂ on the production of HLAs. Herein, abiotic humification performance of the digestate dissolved organic matter (DOM) is investigated with fluxes of air and N₂ in the absence and presence of MnO₂. Our results demonstrated that the fate of digestate DOM greatly depends on the oxidizing environment, the MnO₂ enhanced nitrogen involved in the formation of HLAs. The synergistic effects of MnO₂ and oxygen effectively improved the production of HLAs, and the corresponding component evolution was analyzed using spectroscopic evidence. The two-dimensional correlation spectroscopy results demonstrated that the reaction sequence of digestate DOM followed the order of protein-like substances, substances with an absorbance at 325 nm, substances with UV absorbance at 254 nm and HLAs. Additionally, excitation emission matrix fluorescence combined with parallel factor analysis (EEM-PARAFAC) showed that tryptophan-like C3 was more prone to transformation than tyrosine-like C2 and was responsible for the humification process. The substance with an absorbance at 325 nm was a reaction intermediate in the transformation process of protein-like substances to HLAs. The above findings can be used to promote the production of liquid fertilizer associated with carbon sequestration as well as the sustainable development of biogas production.     

三种典型纳米颗粒物造成的人体肺细胞氧化应激和炎症效应(Oxidative Stress and Inflammatory Effect on A549 Cell Line Induced by Three Typical Nano-Particles )

采用体外细胞暴露实验研究了人肺腺癌细胞系(A549)单层细胞暴露于50和500μg·mL-1两种浓度纳米氧化钛、纳米氧化硅、碳纳米管和晶体石英砂等四种颗粒物后产生的氧化应激和炎症反应.用细胞活度、细胞内活性氧总量和细胞上清液中白细胞介素8(IL-8)表达量表征暴露效应.研究结果表明,纳米氧化钛、纳米氧化硅和碳纳米管在体外暴露实验过程中均发生不同程度的聚集;细胞暴露48h后,三种纳米颗粒物均使A549细胞活度下降,诱导细胞产生过量活性氧,同时刺激细胞IL-8表达量增高;三种纳米颗粒物中,纳米氧化钛和纳米氧化硅对细胞活度影响较大,碳纳米管诱发的炎症效应较另两种纳米材料强.     

Artificial UV-B induced changes in pigmentation of marine diatom Coscinodiscus gigas

In vitro studies in marine diatom Coscinodiscus gigas revealed that artificial UV-B radiation (313 nm) at a dose level of 0.4W m(-2) for a continuous period of 3 hours in a UV treatment chamber caused disbursement of chromatophores from their normal loci and resulted in clumping / aggregation of chromatophores exhibiting a phenomenon called UV-B induced syntrophism. It is also understood that such clumping could cause only insignificant reduction in photosynthetic oxygen release.     

Preparation,characterization of sludge adsorbent and investigations on its removal of hydrogen sulfide under room temperature

To recycle the sludge resource from sewage treatment plants and solve the problem of odor pollution, the sludge was converted into an adsorbent by carbonized pyrolysis and the process was optimized by orthogonal experiments. The capability for odor removal as well as the structure of the adsorbent was studied with H₂S as a target pollutant. The results indicate that the main factor affecting the deodorization performance of the adsorbent is the activating time. The sludge adsorbent sample SAC1 prepared under optimum conditions exhibits the best deodorization performance with a H₂S breakthrough time of 58 min and an iodine value nearly that of the coal activated carbon. The breakthrough time of H₂S is much longer than that on the coal activated carbon. On the other hand, characterization results from X-ray diffractometer (XRD), X-ray photoelectron spectrometer (XPS) and scanning electron microscope (SEM) techniques show that SAC1 is composed of mainly graphite carbon with lower oxygen content on the surface. The bulk of SAC1 exhibits a honeycomb structure with well developed porosity and a high specific surface area of 120.47 m²·g^-1, with the average pore diameter being about 5 nm. Such a structure is in favor of H₂S adsorption. Moreover, SAC1 is detected to contain various metal elements such as Zn, Fe, Mg, etc., leading to a superior deodorization property to that of coal activated carbon.     

Acute nitrate poisoning in two cattle

Abstract

The rate and product composition during photooxidation of aromatic hydrocarbons (toluene, o‐, m‐, p‐xylene and cumene) dissolved in n‐hexane and spread as a liquid film on water is reported. The photo degradability of these chemicals is 10–20%. The products identified are oxygenated aromatic compounds. It is observed that the absorption bands of the compounds under investigation depend upon the partial pressure of dissolved oxygen and these bands extend up to 290 nm. The new absorption band around 290 nm is probably due to broadening of ¹L_b bands which is responsible for direct photolysis.

stream. We have been especially interested in investigating the rate of disappearance and distribution of main oxidation products in two phases. Besides that an attempt has been made to throw some light on the reaction mechanism.