Ca~(2+)对煤中含氮活性基团阻化效应研究

为揭示CaCl2抑制煤炭自燃发生的机理,提高阻化效果,采用Gaussian03软件包,对Ca2+与煤中含N活性基团形成的配位体的结构及分子前沿轨道、稳定化能、自然键轨道和净电荷布居、电荷转移进行系统研究。结果表明,Ca2+能够与煤中含N活性基团形成二配体、三配体及四配体配合物,形成四配体的稳定化能与前沿轨道能级能隙差较大,说明四配体配合物最为稳定,而且形成配合物后,煤含N活性结构中的-NH2基团对前沿轨道的贡献大大减少,同时轨道能级大幅增加,增加了煤活性结构的稳定性,提高了煤活性结构的抗氧化性。     

三种铜缓蚀剂抗H2S腐蚀性能研究

研究了BTA,MBI,MBT等3种铜缓蚀剂在H2S环境中的缓蚀性能,采用量子化学研究方法对实验结果进行了分析,研究了苯三唑在铜表面所形成的配合物保护膜的稳定性。结果表明,MBT抗H2S腐蚀性能较差,BTA是铜及其合金在H2S环境中理想的接触缓蚀剂和气相缓蚀剂。     

雅鲁藏布江河水氢氧同位素时空变化特征

为揭示流域内水汽循环过程变化规律、揭示河水稳定同位素与气象要素及海拔之间的关系,2018年先后采集雅鲁藏布江干流丰、平、枯,水期水样90个,对河水的氢氧同位素组成进行了分析.结果表明：利用δ¹⁸O与纬度和海拔定量关系模型研究了雅江流域降水氢氧同位素空间变化特征,发现降水中δ¹⁸O值变化呈现东西部（雅江上、下游）高中部（雅江中游）低的趋势;建立了雅江丰、平、枯水期河水氢氧同位素方程,研究发现δD与δ¹⁸O的线性方程斜率低于中国大气降水线,河水δD与δ¹⁸O有一定的季节性特征,其受大气降水的影响较大,且丰水期较平水期以及枯水期相比更为明显;雅江河水中δ¹⁸O空间特征表现为,从上游至下游整体表现出先降低再升高的变化趋势.南北空间上表现为河水δD-δ¹⁸O从南至北逐步增高的趋势.δD-δ¹⁸O值与海拔高度具有较弱的负相关关系;受地表蒸发分馏、降水云团迁移以及流域岩石风化的影响,雅江河水d值季节性、空间性变化明显.     

黄土区典型小流域矿物化学风化及碳汇效应

黄土中蕴含了巨大的碳库,黄土中碳的转移对区域乃至全球碳循环具有重要影响。本文选择山西省临县一典型黄土小流域青凉寺沟流域进行调查分析,研究黄土水的化学特征及离子来源,分析黄土矿物的溶蚀过程及碳汇效应,并利用正演模型和水化学方法估算不同矿物的离子贡献比例及流域碳汇通量。结果发现,研究区黄土化学成分的含量由高到低依次为SiO_2、Al_2O_3、CaO、Fe_2O_3、MgO、K_2O、Na_2O,表现出贫SiO_2、Fe_2O_3,富CaO、MgO的特点;黄土水的pH呈中性偏碱,阴离子主要以HCO_3~-为主,阳离子以Na~+为主,水化学类型为重碳酸-钠型(HCO_3~--Na~+),水化学组成与黄土的化学组成相对应;流域内不同端元离子来源贡献计算结果表明,大气沉降、人类输入、蒸发盐矿物、硅酸盐矿物和碳酸盐矿物化学风化贡献的溶解物质分别占总溶解物质的1. 66%、6. 32%、10. 38%、62. 23%、19. 31%;黄土区长时间的水-矿物作用是硅酸盐矿物溶解贡献占主导的主要原因,阳离子置换反应、土壤-盐分浸出与蒸发以及人类输入对硅酸盐矿物溶解也有一定的贡献;受黄土区相对低温少雨的影响,黄土矿物的平均化学风化速率较低,为9. 31 t/(km~2·a),低于全球岩石的化学风化速率平均值36 t/(km~2·a),但是其消耗大气CO_2的速率较高,约为6. 34 t CO_2/(km2·a),明显高于同纬度三川河岩溶流域的碳汇速率(5. 28 t CO_2/(km~2·a));利用水化学径流法计算的青凉寺沟黄土小流域的矿物化学风化的大气CO_2消耗量为0. 18×10~4t/a,为中国黄土区大气CO_2消耗量的估算提供基础数据。     

2014年北京地区云内云下的降水化学分析

为了解现阶段北京地区降水的化学特征和云下/云内的清除作用,于2014年采用分段采样的方式针对25场降水进行收集,分析了降水中各离子组分浓度.结果发现,2014年北京地区降水中NH₄⁺、SO₄^2-、NO₃^-和Ca²⁺浓度最高,雨量加权平均离子浓度分别为240、162、91和65 μeq·L^-1,与早期研究相比均有所下降.SO₄^2-/NO₃^-比值为1.8,NO₃^-和NH₄⁺的比重显著增加.综合利用相关性分析、主因子分析及后向轨迹等方法,探讨了北京地区降水中各离子组分的来源.结果表明,东南气团中主要离子NO₃^-、SO₄^2-及NH₄⁺的浓度较高,主要受人为活动排放的影响.总体上各离子的云下冲刷作用略大于云内清除,其中,Na⁺、Ca²⁺及NO₃^-云下冲刷的贡献大于SO₄^2-和NH₄⁺.与其他城市相比,北京地区云内清除的贡献略大,表明长距离输送的影响不可忽视.     

南方典型农田区浅层地下水污染特征

为分析我国南方农田生态系统浅层地下水污染特征及主要污染物的地球化学行为,以太湖流域典型农田区域为对象,联合常规水质分析方法、荧光光谱技术和多元统计分析手段,研究了浅层地下水的水化学特性、溶解性有机物和重金属分布特征及其成因.结果表明,研究区水体呈还原态,浅层地下水的水化学类型为HCO3-Ca·Na,三氮含量中硝态氮最高,氨氮、亚硝态氮次之.类腐殖酸、类色氨酸和类酪氨酸为浅层地下水中溶解性有机物的主要组分,由陆源与生物内源双重贡献.影响地下水中溶解性有机物分布的主要因素为地表水补给及地下水流方向.所检测的9种重金属元素,Fe和Cr平均浓度高于国家地下水环境质量Ⅲ类标准,且部分点位的Fe、Cr、Mn、Zn含量存在超标.相关性分析结果显示,荧光性有机物变化特征可较好反映浅层地下水的污染状况,其中类蛋白物质与氨氮密切相关;Cu、Ni分布与DOC相关,且主要络合于小分子荧光性有机物上.     

Susceptibility of Eucalyptus globulus to Mnesampela privata defoliation in relation to a specific foliar wax compound

Summary. Increased abundance of several aliphatic benzyl and phenylethyl alkanoates were previously associated with reduced defoliation of Eucalyptus globulus Labill. by the autumn gum moth (Mnesampela privata Guenée) in two clonally replicated F₂ families. We examine the robustness of this association by comparing the abundance of the implicated foliar wax compounds with defoliation levels in three plantation sites and a genetics trial in northern Tasmania. At all locations, the aliphatic alkanoate, benzyl n-tetracosanoate (C₂₄), was found in significantly higher abundance in the foliar wax of E. globulus trees that had displayed low M. privata damage (designated resistant) compared to trees that had displayed high damage (designated susceptible). Further, when sites were combined, benzyl n-tetracosanoate (C₂₄) accounted for 16 % of variation in field defoliation. Field defoliation was also positively correlated to M. privata oviposition both in the field and on foliage sprigs in a cage. In the cage bioassay, oviposition accounted for 20 % of variation in field defoliation making it a better predictor of tree defoliation in the field than either field oviposition, which accounted for 9 % of variation, or screening foliage for the abundance of benzyl n-tetracosanoate (C₂₄). Despite both benzyl n-tetracosanoate (C₂₄) and oviposition being related to field defoliation, there was no statistically significant relationship between the abundance of benzyl n-tetracosanoate (C₂₄) and oviposition in the field or cage bioassay. Further work is therefore required to determine if increased levels of this compound in the foliar wax operates as a direct deterrent to M. privataoviposition.     

VARIATION IN ADIRONDACK,NEW YORK,LAKEWATER CHEMISTRY AS FUNCTION OF SURFACE AREA1

ABSTRACT: Data from a recent survey conducted by the Adirondack Lake Survey Corporation were used to evaluate the influence of lake surface area on the acid-base status of lakes in Adirondack State Park, New York. Acid neutralizing capacity (ANC) in the small lakes (< 4 ha) occurred more frequently at extreme values (> 200, < 0 μeq L^?1), whereas larger lakes tended to be intermediate in ANC. Consequently, acidic (ANC ≤ 0) and low-pH lakes were typically small. The small lakes also exhibited lower Ca²⁺ concentration and higher dissolved organic carbon than did larger lakes. Lakes ≥ 4 ha were only half as likely to be acidic as were lakes ≥ 1 ha in area. These data illustrate the dependence of lake chemistry on lake surface area and the importance of the lower lake area limit for a statistical survey of lake water chemistry.     

Energy futures and green chemistry: competing for carbon

Global energy demand is expected to increase from the current 400 ExaJ per year to as much as 700–1,000 ExaJ per year by the middle of this century. If fossil carbon resources continue to make up the bulk of the energy supply, not only will atmospheric carbon dioxide increase to levels not seen for the past 30–35 million years, but depleting fossil carbon resources will become increasingly less available for other purposes, particularly the production of chemicals on which society now depends. The chemical process industries are heavily dependent on the availability of low-price petroleum as a feedstock. Recent life-cycle analyses suggest that pursuing both strategies of renewable energy sources and renewable feedstocks (i.e. biomass) will be required to meet these competing demands. Reducing the global use of both energy and manufactured chemicals will be a challenge for sustainable development. Education of the next generation of chemists and chemical engineers will have to change significantly from its current emphasis on petrochemical-based manufacturing to include a much greater emphasis on renewable resources and bio-based processes.Brief accounts of this work were presented at the 7th International Symposium on Green Chemistry in China (Zhuhai, People’s Republic of China, May 2005) and at the Joint US–China Green Chemistry Workshop (Beijing, People’s Republic of China, May 2005; this workshop was supported by US National Science Foundation grant CHE-0522369).     

The State of Components of the Biota as an Indicator of Disturbances in Natural Ecosystems Exposed to Petrochemical Pollution

Russian Journal of Ecology -