影响羟基自由基在O3/UV体系中生成规律的因素

臭氧紫外光（O₃/UV）法是将臭氧与紫外光辐射相结合的一种高级氧化技术。在紫外光的辐射下臭氧显著地加速了分解速率,在溶液中形成具有强氧化特性的羟基自由基。通过高效液相色谱法和荧光检测器测定O₃/UV体系中羟基自由基攻击水杨酸的产物2,5-二羟基苯甲酸（2,5-DHBA）,从而间接测定了捕捉到的羟基自由基的量。结果表明,反应时间、水相温度、初始pH值的增加明显有利于羟基自由基的生成,紫外光波长的减小和水杨酸浓度的增加也会对生成羟基自由基的量产生积极的影响。     

主要铁氧化物催化H2O2 氧化地下水中硝基苯实验

实验研究了含水层介质中主要铁氧化物催化H2O2 氧化地下水中硝基苯的机理和主要影响因素,为硝基苯污染地下水的原位化学修复技术提供了一定的理论依据。实验模拟在地下环境温度8 ℃ ～ 10 ℃条件下,利用动力学方程对硝基苯的衰减进行拟合,结果表明,其衰减系数K = 0. 044 3 min － 1 ; 硝基苯与H2O2 的最佳摩尔比为1∶200; 主要铁氧化物催化H2O2 氧化硝基苯能力依次为: 磁铁矿＞ 针铁矿＞ 氢氧化铁＞ 赤铁矿。     

流动CO2—H2O系统中方解石溶解动力学机制：扩散边界层效应和CO2转？…

利用旋转盘实验装置和高分子生物催化剂技术,笔者研究了流动ＣＯ２－Ｈ２Ｏ系统中方解石溶解动力学及其控制机制。实验发现,方解石的溶解既受到固－液界面间扩散边界层（ＤＢＬ）的控制,还受到扩散边界层内ＣＯ２慢速转换反应（ＣＯ２＋Ｈ２Ｏ←→Ｈ＾＋＋ＨＣＯ＾）的控制。然而,高ＣＯ２分压（Ｐｃｏ２〉０．０１ａｔｍ）时,溶解主要为ＣＯ２慢速转换控制,而低ＣＯ２分压（Ｐｃｏ２〈０．０１ａｔｍ）时,溶解主要为扩散为边     

H2O Content Measurement in Phengite by Secondary Ion Mass Spectrometry: A New Set of Reference Materials

Five new natural white mica reference materials (RMs) were developed for in situ H₂O content analyses by secondary ion mass spectrometry at the SwissSIMS laboratory of Lausanne University, Switzerland. The white mica reference materials cover a large part of the natural muscovite–phengite compositional range and are therefore suitable as reference materials for the analysis of natural rocks as well as individual minerals. The independent H₂O content of the reference materials UNIL_WM1 to UNIL_WM5 was obtained by thermal conversion elemental analyser and corresponds to 4.35 ± 0.02, 4.33 ± 0.03, 4.30 ± 0.07, 4.50 ± 0.02 and 4.42 ± 0.11 (% m/m, ± 1s), respectively. SIMS determinations of H₂O content revealed a matrix effect correlated to the FeO content of white mica. The compositional range in FeO of the reference materials that were calibrated for H₂O determination is from 1.13% to 3.67% m/m. No crystallographic orientation dependency was observed at the level of homogeneity of these reference materials. An analytical precision of 0.02% to 0.08% m/m (1SE) is expected for the final uncertainty on measurements of unknown white micas in natural samples.     

The orientation and vibrational states of H2O in synthetic alkali-free beryl

 The polarized single-crystal Raman spectra of synthetic H₂O-containing alkali-free beryl were recorded at room and low temperatures, and the polarized single-crystal IR spectra at room temperature. The H₂O molecule in the channel cavities is characterized by a Raman-active symmetric stretching vibration (ν₁) at 3607 cm⁻¹ and an IR-active asymmetric stretch (ν₃) at 3700 cm⁻¹ at room temperature. At low temperatures this ν₃ mode is observed in the Raman. Weak ν₁ and ν₃ modes of a second type of H₂O are also observed in the Raman spectra but only at 5 K. The H⋯·H vector of the most abundant type of H₂O is parallel to the channel axis of beryl along [0 0 0 1]. The components of the polarizability tensor of the ν₁ mode of H₂O are similar to, but not exactly the same as, those of a free H₂O molecule. The Raman measurements indicate that the H₂O molecule is rotationally disordered around [0 0 0 1]. External translation and librational modes of H₂O could be observed as overtones with the internal H₂O-stretching modes. In the case of the librational motions, normal modes could also be observed directly in the Raman spectra at ∼200 cm⁻¹. The energies of the translational modes can be determined from an analysis of the overtones and are about 9 cm⁻¹ in energy (i.e., T_z). The energies of the librational modes are about 210 cm⁻¹ for R_x and 190 cm⁻¹ for R_y. Received: 8 April 1999 / Accepted: 5 April 2000     

紫外/氯工艺对水中微囊藻毒素的去除

水体富营养化导致藻类的爆发进而引起藻毒素的释放。微囊藻毒素(MCLR)是最为常见的藻毒素,具有很强的毒性,对人类健康具有潜在危害。本文采用紫外/氯组合工艺,研究其对水中微囊藻毒素的控制效果。结果表明：紫外/氯共同作用下能够产生·Cl、·OH等活性自由基,具有协同降解MCLR的作用,30 min即可实现MCLR的完全去除,其降解效率随着氯投加质量浓度的增加而升高。在酸性及中性条件下,pH的变化对紫外/氯降解MCLR没有影响;在碱性条件下,MCLR的降解效率随pH的升高显著降低,pH升高至9时,30 min MCLR的降解效率仅为41.3%。此外,不同的水样来源和水质特点对紫外/氯联合降解MCLR的效率具有显著影响,纯水、西湖水及水厂滤后水的30 min去除率分别为99.5%,40.2%及63.3%。MCLR 的降解效率随腐殖酸质量浓度增大而降低,在60 min作用时间内,不含腐殖酸水样的MCLR去除率高达99.5%,当腐殖酸质量浓度增加到10 mg/L时,MCLR去除率仅为45.3%。     

MnO2-UV联用光化学降解苯酚废水的初步研究

探讨了人工合成的高价锰氧化物与紫外光(UV)联用时降解苯酚废水的特性。结果表明,氧化锰矿物在无UV时对苯酚的降解能力差异大,1 g/L的氧化锰4 h对200 mg/L苯酚废水的降解率和COD去除率分别为:锰钾矿97.51%、酸性水钠锰矿89.07%、碱性水钠锰矿11.36%、钙锰矿9.67%;锰钾矿87.79%、酸性水钠锰矿53.11%、碱性水钠锰矿6.42%、钙锰矿1.43%。UV光照下,氧化锰矿物对苯酚的降解率有不同程度的提高,且表现出显著的表面光催化性质,增加了苯酚的深度降解,COD去除率显著提高。UV下氧化锰4 h对苯酚的降解率分别为:锰钾矿99.48%、酸性水钠锰矿91.86%、碱性水钠锰矿40.15%、钙锰矿35.95%);COD的去除率分别为:锰钾矿98.11%、酸性水钠锰矿68.45%、钙锰矿27.57%、碱性水钠锰矿24.27%。MnO2-UV联用时降解苯酚可能包括两种主要作用机制:氧化锰矿物的直接化学氧化降解和UV下MnO2的表面光催化降解。     

Efficiency removal of phenol, lead and cadmium by means of UV/TiO2/H2O2 processes

A variety of processes can be used in treatment of industrial wastewaters. The relatively newest of which is photo catalysis with titanium dioxide which may also be used plus hydrogen peroxide to improve the treatment rate. In this study, photo catalysis/ hydrogen peroxide processes had been employed for the removal of phenol, lead and cadmium by three different pHs of 3.5, 7 and 11. The treatment tests were also accomplished without UV irradiation. In both experiments, the variables were pH and concentrations of reagent chemicals, but the detention time was kept constant (180 min). Results indicated that the optimum efficiencies of phenol and Cd removal were 76 % and 97.7 % at pH=11, respectively, and for lead, it was 98.8% in all pHs. In other words, no pH dependency was regarded for lead treatment. These results were all obtained by simultaneous use of UV irradiation with 3 mL/L H₂O₂ and 0.8 g/L TiO₂. Finally, the best pH for treatment, when all the three contaminants are presented is considered to be at 11. These results should be regarded by all industrial treatment plants which have experienced the problem of these three special contaminants in their effluents.     

钙钛矿镧钛酸钾电子结构的第一性原理研究

采用赝势法的第一性原理,计算了K2La2Ti3O10的电子密度分布和能带结构等基态物理性质.结果表明,K2La2Ti3O10属间接带隙半导体,理论带隙为3.2 eV,其导带主要由Ti的3d轨道构成,价带主要由氧的2p轨道构成.钛原子的d电子与镧原子的d电子和氧原子的2p电子之间的轨道杂化对K2La2Ti3O10的能带结构和光催化活性有着重要的意义.     

高岭土/胡敏酸复合体对重金属离子吸附解吸实验研究

本文利用高岭土对胡敏酸吸附形成稳定的有机一无机络合物,研究了高岭土／胡敏酸复合体对Cu^2＋、Cd^2＋和Cr^2＋的吸附。结果表明,胡敏酸对高岭土改性后能提高上述三种重金属离子的吸附性能,高岭土／胡敏酸复合体对三种重金属离子的吸附量都随pH值的升高而增加,随离子强度的增加而减小。本文还研究了高岭土／胡敏酸复合体对上述三种重金属离子的吸附动力学,发现吸附过程可用Elovich方程和一级动力学方程进行较好的拟合。     

温泉水中H2S对游离C02检测的影响

在实验室条件下模拟温泉水中H2S和游离C02来研究温泉水中H2S对游离C02现场检测的影响,以及现场检测时如何消除H2s的影响。实验结果证明：温泉水中H2S对游离C02的测定存在影响,其影响结果随H2S含量的不同而不同;采用扣除法可以很好的消除温泉水中H2S对游离CO2测定的影响。     

Blueschist‐facies metapelites from the Malpica–Tui Unit (NW Iberian Massif): phase equilibria modelling and H2O and Fe2O3 influence in high‐pressure assemblages

The Malpica–Tui Unit (Galicia, NW Spain) records eclogite‐ and blueschist‐facies metamorphism during the onset of the Variscan orogeny in Europe. Petrological analysis involving pseudosections calculated using thermocalc shows that the Upper Sheet of this unit, the Ceán Schists, recorded a three‐stage metamorphic evolution involving (i) Early subduction‐related medium‐pressure/low‐temperature metamorphism (M₁) constrained at ～350–380 °C, 12–14 kbar, which is only recorded in the basal part (lower metapelites, LM) of the Ceán Schists. (ii) Subduction‐related blueschist facies prograde metamorphism (M₂) going from ～19 kbar, 420 °C to 21 kbar, 460 °C in the LM, and from 16 kbar 430 °C to 21–22 kbar, 520 °C in the structurally upper metapelites (UM). (iii) Exhumation‐related metamorphism (M₃) is characterized by a decompression to 8–10 kbar, 470–490 °C in the LM. This decompression is also recorded in the UM, but it was not possible to estimate precise P–T conditions. The calculations indicate that (i) the prograde evolution in subduction zones may occur in fluid‐undersaturated conditions due to the crystallization of lawsonite, even in metapelitic rocks. This significantly influences phase equilibria and hence the P–T estimates. (ii) The proportion of ferric iron also has a strong influence on phase equilibria, even in metapelites. However, the analysed values of Fe₂O₃ may not reflect the oxidation state during the main metamorphic evolution and are probably easily modified by superficial alteration even in apparently fresh samples. The use of P–T–X(Fe₂O₃) pseudosections together with petrographic observations is then necessary to estimate the real oxidation state of the rocks and correctly evaluate the P–T conditions.