Infrared spectroscopic probing of dimethylamine clusters in an Ar matrix

Amines have many atmospheric sources and their clusters play an important role in aerosol nucleation processes. Clusters of a typical amine, dimethylamine (DMA), of different sizes were measured with matrix isolation IR (infrared) and NIR (near infrared) spectroscopy. The NIR vibrations are more separated and therefore it is easier to distinguish different sizes of clusters in this region. The DMA clusters, up to DMA tetramer, have been optimized using density functional methods, and the geometries, binding energies and thermodynamic properties of DMA clusters were obtained. The computed frequencies and intensities of NH-stretching vibrations in the DMA clusters were used to interpret the experimental spectra. We have identified the fundamental transitions of the bonded NH-stretching vibration and the first overtone transitions of the bonded and free NH-stretching vibration in the DMA clusters. Based on the changes in vibrational intensities during the annealing processes, the growth of clusters was clearly observed. The results of annealing processes indicate that DMA molecules tend to form larger clusters with lower energies under matrix temperatures, which is also supported by the calculated reaction energies of cluster formation.     

Experimental study of NO2 reduction in N2/Ar and O2/Ar mixtures by pulsed corona discharge

Non-thermal plasma technology has been regarded as a promising alternative technology for NOx removal. The understanding of NO2 reduction characteristics is extremely important since NO2 reduction could lower the total NO oxidation rate in the plasma atmosphere. In this study, NO2 reduction was experimentally investigated using a non-thermal plasma reactor driven by a pulsed power supply for different simulated gas compositions and operating parameters. The NO2 reduction was promoted by increasing the specific energy density （SED）, and the highest conversion rates were 33.7%, 42.1% and 25.7% for Ar, N2/Ar and O2/Ar, respectively. For a given SED, the NO2 conversion rate had the order N2/Ar 〉 Ar 〉 02/Ar. The highest energy yield of 3.31 g/kWh was obtained in N2/Ar plasma and decreased with increasing SED; the same trends were also found in the other two gas compositions. The conversion rate decreased with increasing initial NO2 concentration. Furthermore, the presence of N2 or O2 led to different reaction pathways for NO2 conversion due to the formation of different dominating reactive radicals.     

云南维西大宝山铜矿~(40)Ar/~(39)Ar年代学及成矿物质来源

云南大宝山铜矿是雪龙山成矿带规模较大的浅成中低温热液型铜矿床。文章通过对该矿区黄铜矿+石英+方解石+菱铁矿矿脉中白云母进行~(40)Ar/~(39)Ar定年,获得白云母~(40)Ar/~(39)Ar法年龄为26±2.5 Ma,代表大宝山铜矿的年龄;H、O同位素分析结果表明成矿流体是以大气降水为主并含有部分岩浆水的建造水;S同位素分析结果表明,主要金属矿物的δ34S值为-5.4‰~+1.3‰,表明成矿物质主要来源于深部岩浆;C同位素分析结果表明成矿流体主要来源于岩浆—地幔,并受大气降水影响。根据围岩蚀变及围岩中Cu丰度等特征,推断大宝山铜矿成矿物质主要来源于深部岩浆,成矿流体为岩浆水与大气降水的混合物。     

湖南大义山花岗岩南体黑云母40Ar-39Ar定年及地质意义

大义山岩体是一个多时代形成的复式岩体,习惯有大义山南体和北体之分.岩体内外接触带产有较多的W、Sn、Cu、Pb、Zn等多金属矿产.长期以来对南体主体形成的时代归属存在较大的差异,一部分人认为是印支期的产物,另一部人认为是燕山期的产物,这种结果对该区成矿作用的研究和指导找矿都带来很大的不利.本次研究通过对岩体的解体以及精确的黑云母氩氩法定年,确切地将大义山南体归属于两个不同的时代,即南体的北部为中侏罗世,南部为晚三叠世.这一成果对该岩体和成矿作用的研究都具有重要的现实意义.     

湖南骑田岭岩体北东部角闪石黑云母二长花岗岩的40Ar-39Ar定年及其意义

对骑田岭岩体主体仰天湖单元粗中粒斑状角闪石黑云母二长花岗岩进行了黑云母40Ar-39Ar年龄测定,获得坪年龄为(155.1±1.8)Ma,等时线年龄为(154.7±1.8)Ma.该年龄样品提高了骑田岭岩体形成时代的面上控制程度,与前人有关高精度年代资料一起说明骑田岭序列为中侏罗世末-晚侏罗世初形成的大岩基,基本排除其内部有其它时代成分的可能.结合骑田岭地区锡矿与花岗岩的关系,认为江口一带具有寻找锡矿的前景.     

利用膜进样质谱连续走航测定表层海水O2/Ar比值和pCO2

利用HIDEN公司HPR40溶解气体质谱分析仪,通过实验探索和实际应用,建立了连续走航高频率同时测定海水中O₂、Ar和CO₂等多种气体的分析方法。通过选择硅树脂膜的循环水取样器、进样流量为220 mL/min、进样平衡温度低于海水2℃等实验条件,建立了船载连续走航系统,实现了利用膜进样质谱仪（MIMS）连续走航测定表层海水O₂/Ar比值和pCO₂。所用仪器稳定性良好,连续测定12 h大气鼓泡48 h后的海水样品获得O₂、Ar和CO₂的精密度分别为1.57%、3.75%和2.21%,O₂/Ar的精密度为2.61%;该方法的重复性好,10 d内绘制7条CO₂工作曲线斜率的相对标准偏差RSD=4.18%。应用该方法在南海北部陆坡19.8°N～20.8°N,114.7°E～115°E断面进行调查并取得了很好的效果,结果表明:该调查断面的生物氧过饱和量Δ（O₂/Ar）为0.56%±1.02%,其变化范围为-2.52%至3.34%,调查断面的pCO₂值为361.53±40.46μatm。该方法具有直接、快速、高时空分辨率测定多种溶解气体的优点,为认识多组分气体的高分辨时空分布格局,深入开展我国陆架边缘海生物过饱和氧、海洋群落净生产力和pCO₂动力学研究提供了新方法。     

N_2:Ar法直接测定水体反硝化产物溶解N_2

为了深入开展水体反硝化过程及机理研究,利用HIDEN公司生产的HPR40溶解气体质谱分析仪,通过仪器配置和条件摸索,建立了基于N2:Ar原理直接测定水体反硝化产物溶解N2的分析方法,并总结了采样技术要点.实验结果表明,膜进样质谱仪(MIMS)在长时间(10h)连续测定情况下仍能保持良好的信号稳定性,盐度为0和2%的标样的N2/Ar(物质的量比)变异系数(CV)分别0.53%和0.17%;在最佳实验条件下(恒温槽温度设为18～25℃,磁搅拌气液平衡52h,仪器信号平稳),15d内绘制了5条校准工作曲线,其斜率的相对标准偏差为3.03%,说明该方法的重复性较好;平行水样的标准偏差小于2μmol·L-1.将N2:Ar法应用于福建省九龙江表层水样的连续观测,可观察到明显的反硝化过程,表明所建立的N2:Ar法在今后各种水体反硝化过程和机理研究中具有良好的应用前景.