Multivariate analysis of fluorescence and source identification of dissolved organic matter in Jiaozhou Bay, China

Hierarchical clustering analysis and principal component analysis (PCA) methods were used to assess the similarities and dissimilarities of the entire Excitation-emission matrix spectroscopy (EEMs) data sets of samples collected from Jiaozhou Bay, China. The results demonstrate that multivariate analysis facilitates the complex data treatment and spectral sorting processes, and also enhances the probability to reveal otherwise hidden information concerning the chemical characteristics of the dissolved organic matter (DOM). The distribution of different water samples as revealed by multivariate results has been used to track the movement of DOM material in the study area, and the interpretation is supported by the results obtained from the numerical simulation model of substance tracing technique, which show that the substance discharged by Haibo River can be distributed in Jiaozhou Bay.     

X射线荧光光谱法测定重晶石中的硫酸钡方法研究

应用XRF可快速测定重晶石中钡元素的总量,但当测定硫酸钡含量时,由于样品中的碳酸钡计入钡量造成硫酸钡的测定结果不准确,铜、铅、锌等有色金属元素对熔样坩埚会造成损害,需要进行酸处理除去碳酸钡、铅等干扰。而样品经酸处理后不同样品的剩余量不同,造成熔剂与样品的比例不确定,也不能准确测定硫酸钡的含量,因此保证熔剂与样品比例一致是解决该问题的关键。本文优化了样品前处理、熔片制样和仪器工作条件,将一定量样品以10%盐酸和10%硝酸溶解,过滤除去碳酸钡、硫酸钙及铜、铅、锌等有色金属元素,未溶解样品在700℃下灼烧后以氧化铝补充到原取样量,实现了熔剂与样品比例一致,再以硝酸铵作氧化剂,溴化锂和碘化铵作脱模剂,1075℃熔融制片,即可用XRF准确测定硫酸钡的含量。本方法的相对标准偏差(RSD)小于0.4%,检出限为72μg/g,较ICP-OES等方法的检测周期短、干扰元素少,提高了测试效率和分析质量。     

Isothermal annealing of partially metamict zircon: evidence for a three-stage recovery process

 Raman spectroscopy and the powder diffraction technique have been used to monitor the recovery process of two partially metamict zircons (2.6 and 4.8 × 10¹⁸ α-decays g⁻¹) from Sri Lanka during a series of isothermal annealing experiments in the temperature range from 870 to 1622 K. These experiments show for the first time that structural recovery in partially metamict zircon proceeds via three distinct recovery stages, each of which occurs within a distinct time-temperature regime. Whereas the first two stages have previously been recognized (recovery of damaged crystalline remnants and epitaxial recrystallization), the third stage has not yet been identified as a single activated process. It is suggested that anisotropic defect annealing during the first stage at low temperatures, where the structure recovers preferentially along the a(b) plane, produces a geometrical situation where large structural rearrangements are necessary to remove the remaining defects inside the crystalline material. This situation is approximately reached when the amorphous domains start to recrystallize. The reason for anisotropic annealing can be found in a different connectivity between polyhedral linkages in both directions of the zircon lattice. High apparent activation energies, in the range of 6.4 to 7.9 eV, were determined for the third recovery stage from the Raman data, which are interpreted to reflect large structural rearrangements (i.e. polyhedral tilting) associated with the final recovery of the c axis. This explains the occurrence of a distinct recrystallization stage without defect annealing. Finally, it should be mentioned that the first recovery stage is not necessarily expected to occur in less damaged zircon crystals (<∼2 × 10¹⁸ α-decays g⁻¹), since less stable defects along the basal plane might have already been self-annealed during radiation damage accumulation under ambient temperatures. Received: 6 September 2001 / Accepted: 25 February 2002     

CHARACTERIZATION OF THE EFFECT OF PEAK SHIFTS ON THE PERFORMANCE OF THE KALMAN FILTER IN MULTICOMPONENT ANALYSES

The effect of peak shifts on the performance of a Kalman filter multicomponent analysis algorithm hasbeen investigated.A series of Gaussian test systems were employed to characterize the concentrationestimation errors and the morphology of the on-line residuals(the innovations sequence).Both forwardand reverse filters were used in the generation of the innovations sequences.It was found that thedifference between the forward and reverse innovations sequences gave an accurate indication of thedirection and magnitude of the peak shift.A series of overlapped two-component systems were alsoinvestigated.Again,a correlation between the difference innovations and the degree of the responseshift was observed.The behavior of the Katman filter in fitting the shifted fluorescence emissionspectrum of benzo[a]pyrene was also examined.The response for henzo[a]pyrene in cyclohexanesolution was compared to that obtained on the surface of a reversed phase thin layer chromatographyplate.A red shift of 4 nm was detected for the surface spectrum by observing the difference innovationssequence.This approach holds promise for correction of response shifts in multicomponent systems.     

巯基改性蒙脱石对中国北方中碱性农田土壤镉钝化效果研究

农田土壤重金属污染是影响中国农产品环境质量安全的主要因素。钝化材料是修复农田重金属污染土壤的关键材料,研究开发出高效土壤重金属钝化材料,对于修复重金属污染农田和保障农产品食用安全非常重要。本文以蒙脱石为原材料,将巯基基团负载在其表面或层间制备巯基改性蒙脱石,借助X射线衍射(XRD)、扫描电镜(SEM)、透射电镜(TEM)和傅里叶红外光谱(FTIR)等技术表征巯基改性蒙脱石的特性,并开展室内土培试验,采用二乙三胺五乙酸浸提-火焰原子吸收分光光度法分析土壤镉的有效态,通过Tessier修正顺序七步提取法分析土壤镉的赋存形态。结果表明：蒙脱石经巯基改性后不仅新增了C−H、S−H共价键,而且增强了−OH和C=O化学键的活性,能与Cd2+发生巯基及羟基配位吸附。供试土壤添加巯基改性蒙脱石后,由于巯基配位吸附作用使土壤离子交换态镉转化为铁锰氧化物结合态,而增强的羟基配位吸附作用使其转化为碳酸盐结合态,结果使土壤中镉的赋存形态发生显著改变,离子交换态大幅减少,作物根系可吸收的土壤有效镉显著降低。添加1%、3%、5%巯基改性蒙脱石后,土壤有效镉分别降低21.92%、69.11%、82.90%;而作为对照组添加1%、3%、5%蒙脱石仅分别降低3.37%、1.80%、6.71%。蒙脱石经巯基改性后对土壤镉的钝化效果得到显著提升,土壤有效镉的降低幅度有随巯基改性蒙脱石添加量增加而提高的趋势。巯基改性蒙脱石对中国北方中碱性农田土壤镉的钝化效果显著,具有一定的参考应用价值。     

Al hematites prepared by homogeneous precipitation of oxinates: material characterization and determination of the Morin transition

A novel method for synthesis of aluminium hematites, based upon the homogeneous precipitation of Fe and Al oxinates in various proportions, is presented. The precursor precipitates are heated in air at 700?°C. X-ray diffraction, thermal analyses, BET, FTIR, optical reflection analysis, TEM and Mössbauer spectroscopy at room temperature and 80?K of the resulting products indicate that single-phase hematites are formed with structural Al substitution of up to 10 at%. Interestingly, the particle size (>100?nm) is not substantially reduced by the Al content. Although it remains difficult to obtain a homogeneously distributed Al substitution in the final hematite, this processing line offers a unique opportunity to separate the effects of grain size and Al substitution on the Morin transition temperature (T _M) of Al hematite. From the comparison between the present hematites and a series of Al-substituted hematites with lepidocrocite as precursor, it could be shown that the effect on T _M, associated with a change of a factor 10 in grain size, is about 1/3 of the effect caused by a change of 10 in the degree of substitution. Finally, it is suggested that proper thermal treatments under different conditions of the same precursors are likely to produce spinel phases.     

Premelting and calcium mobility in gehlenite (Ca2Al2SiO7) and pseudowollastonite (CaSiO3)

 Premelting effects in gehlenite (Ca₂Al₂SiO₇) have been studied by Raman spectroscopy and calorimetry, and in gehlenite and pseudowollastonite (CaSiO₃) by electrical conductivity. The enthalpy of premelting of gehlenite is 17.3 kJ mol⁻¹ and represents 9% of the reported enthalpy of fusion, which is in the range of the reported fraction of other minerals. The Raman and electrical conductivity experiments at high temperatures, for gehlenite and pseudowollastonite, show that the premelting effects of both compositions are associated with enhanced dynamics of calcium atoms near the melting point. This conclusion agrees with the results obtained for other minerals like diopside, but contrasts with those found for sodium metasilicate in which the weaker bonding of sodium allows the silicate framework to distort near the melting temperature and deform in such a way to prefigure the silicate entities present in the melt. Received: 30 April 2002 / Accepted: 7 August 2002 Acknowledgements We thank Y. Linard for help with DSC measurements and two anonymous reviewers for their constructive comments. This work has been partly supported by the EU Marie-Curie fellowship contract no. HPMF-CT-1999-00329, the CNRS-Carnegie Institution of Washington program PICS no.192, and the NSF grants EAR-9614432 and EAR-9901886 to B.O.M.     

Ultra-Deep Optical Spectroscopy with PMAS. Using the Nod-and-Shuffle Technique

PMAS, the Potsdam Multi-Aperture Spectrophotometer, is a new integral field spectrograph in the optical, which is optimized for good transmission and high image quality from 350 nm to 1 μm. We present our plan to implement a CCD charge-shuffle mode to allow for beam switching with a very high degree of sky subtraction accuracy for faint object 3-D spectroscopy. This revised version was published online in July 2006 with corrections to the Cover Date.     

添加纳米TiO2的氯醚树脂的XPS分析

在紫外线老化前后,利用光电子能谱(XPS)研究了分别添加金红石型和锐钛型纳米TiO2的氯醚树脂。研究发现,氯醚树脂中氯、氧元素具有表面富积现象——趋肤效应,而钛和碳元素在内层聚集;添加颜料粒子越小,在表面含量越大;金红石型纳米二氧化钛紫外屏蔽性好,减缓树脂老化;而锐钛型纳米二氧化钛具有显著的光催化活性,加速树脂老化。因此,金红石型纳米二氧化钛将是一种有前途的紫外线吸收剂。     

反射光谱技术:研究南极企鹅古生态演化的一种新方法

为探求快速、廉价、无损和同步的光谱技术在南极生态环境研究中的可能性,本文利用南极阿德雷岛的四根企鹅粪土沉积柱样品的反射光谱,通过逐步多元线性回归和主成分回归两种数学运算方法,建立了反射光谱数据与企鹅粪九种标型元素浓度之间的关系,并探讨了南极企鹅粪土沉积物光谱数据的古生态意义。结果表明:南极粪土沉积样品反射率光谱与企鹅粪九种标型元素(P、Ca、Cu、F、Ba、S、Zn、Sr、Se)含量之间存在良好的相关性,预测值与实测值之间的相关系数R都达到了0.9以上,在深度剖面上预测浓度与实测浓度具有非常一致的变化趋势;南极粪土沉积物光谱数据包含有明确的古生态变化信息,可利用主成分分析快速恢复历史时期企鹅数量演化过程。本研究结果为在偏远的南极地区开展古生态环境研究提供了一种新的快捷方法和技术途径。