高能偏振能量色散X射线荧光光谱仪应用现状和进展

对高能偏振能量色散X射线荧光光谱仪基本特点及其用于环境、生物、地质样品中痕量元素的分析和RoSH检测等领域的应用现状予以介绍,并对二次靶与滤光片在痕量元素分析中的应用作了探讨。     

Optical spectrum based measurement of flotation slurry contents

Monitoring and control of a flotation circuit is mainly based on the information gained by assaying the process slurry lines. In flotation plants, usually an X-ray fluorescence analyzer is used to obtain the on-line assays. This article introduces the visual and near-infrared reflectance spectroscopic analysis of the process slurries as a supplementary method which complements the on-line assay information available from an X-ray fluorescence analyzer. It is shown that the spectral information can be used to accurately predict the element contents in the slurry in between successive XRF analyses. Since the spectral measurements can be taken with high frequency as opposed to the sparse X-ray fluorescence analysis, a practically continuous on-line estimate of the slurry contents is reached. These estimates can be used in the plant control to improve the overall performance of the circuits and to yield also economical savings. Additionally, the frequent monitoring of the grades can provide means to eliminate rapid disturbances in the circuits, thus improving the stability of the process.     

基于荧光原理的叶绿素a传感器校准方法研究

利用传感器对水体叶绿素a 浓度进行原位测量是获取实时、连续、长时间序列数据的重要手段。本文在对RBR 传感器和ECO（Environmental Characterization Optics）传感器进行原理分析和线性度、稳定性、重复性等基本性能测试的基础上，利用单一藻种培养液和2020年南海北部海域现场数据校准传感器，并对新的传感器校准系数进行验证。结果表明：两台传感器使用新系数比原出厂系数的叶绿素a 浓度测量准确度有明显提高。RBR 传感器现场数据校准系数的计算结果与叶绿素a 标准值误差最小，平均绝对误差从1.93 μg/L 减小到0.35 μg/L，平均相对误差从55.1%减小到10.9%；ECO 传感器藻液系数明显优于出厂系数和现场数据校准系数的计算结果，平均绝对误差从1.76 μg/L 减小到0.59 μg/L，平均相对误差从50.3%减小到15.1%。传感器测量准确度的提高，可为海洋环境监测、海洋生态灾害预警等工作获取真实可靠数据提供支撑。     

On the pH-dependent formation constants of iron(III)-sulfur(IV) transient complexes

An experimental study is described of Fe(III)-S(IV) formation constants measured as a function of pH (1–3), ionic strength (0.2–0.5 M) and [Fe(III)] _T (2.5–5.0×10^–4 M) using a continuous-flow spectrophotometric technique to make observations 160 ms after mixing. Preliminary experiments using pulse-accelerated-flow (PAF) spectrophotometry to measure rate constants on a microsecond timescale are also described. The conditional formation constant at 25 °C can be modeled with the following equation: {ie307-1} where {ie307-2}K ₇ andK ₈ can be interpreted as intrinsic constants for the coordination of HSO ₃ ^– by FeOH²⁺ and Fe³⁺, respectively, but until further evidence is obtained they should be regarded as fitting constants. PAF spectrophotometry showed that the initial reaction of Fe(III) with S(IV) (pH 2.0) is characterized by a second-order rate constant of 4×10⁶ M^–1 s^–1 which is comparable to rate of reaction of FeOH²⁺ with SO ₄ ^2– . However, the PAF results should be regarded as preliminary since unexpected features in the initial data indicate that the reaction may be more complex than expected.     

Micro-spectroscopic investigations of highly heterogeneous waste repository materials

Assuring safe disposal and long-term storage of radioactive and toxic wastes corresponds to a primary environmental task of present societies. To improve any technical limitation, a mechanistic understanding of the processes governing the binding of heavy metals and radionuclides is required. In this study, the significance of synchrotron-based X-ray microprobes for elucidating the spatial distribution and the speciation of radionuclides in highly heterogeneous waste repository materials will be outlined. A case study on the uptake process of Co in cementitious engineered barrier materials exposed to microbial degradation will be presented.     

Origin and three-dimensional fluorescence spectrum of the chromophoric dissolved organic matter in Yangtze estuary, East China

Dissolved organic matter （DOM） is an important chemical component in natural water. Chromophoric dissolved organic matter （CDOM）, a fraction of optical properties, plays art important role in the biogeochemical cycle of nutrients in aquatic environment. People realized that DOM cycle is crucial in the global carbon and nitrogen flux, and also is inherently related to nutrients and trace metal elements. Therefore, CDOM was concerned by scientists in global oceanography and limnology fields. Water samples were collected from three sections （North Channel, South Channel and Zhuyuan） of the Yangtze （Changjiang River） estuary in March 2006 Three-dimensional excitation emission matrix （3-DEEM） fluorescence spectra were analyzed for those filtrates through Whatman GF/F filters. Dissolved organic carbon （DOC） was also measured by TOC analyzer. The tidal variety was also taken into account. The 3-D EEM fluorescence scans suggested the fluorescence characteristics of humic acid （Ex=332-344 nm, Em=439-451 nm） and fulvic acid （Ex=250-254 nm, Em=472-478 nm） were obvious, and the fluorescence group of protein-like and tyrosine （Ex=230 nm, Em=283 nm） was also found. They are mainly composed of CDOM in the Yangtze estuary. Further data analysis, especially the fluorescence index （f 450/500）, showed that terrestrial signal was rather strong （1.41-1.65） in the surface water, however, some terrestrial CDOM signals of bottom water showed excursions （1.28-1.39）. On the other hand, anthropogenic sign was impressed in the waters of Zhuyuan, which is one of the main drain outlets of Shanghai Metropolis. DOC concentrations ranged from 2.2 mg/L to 3.4 mg/L in Zhuyuan and South Channel, and from 2.0 mg/L to 2.4 mg/L in North Channel. The tide effect played a role in the composition of the CDOM measured by 3-D fluorescence scan technology.     

邻苯二酚螯合树脂的合成及水样中铝的测定

合成并表征了新螯合树脂———邻苯二酚螯合树脂(XAD-2-Catechol),研究了XAD-2-Catechol吸附铝的特性和茜素红-铝的显色反应,在pH4.5的HAc-NaAc缓冲介质中,茜素红和铝(Ⅲ)反应生成红色络合物,λm ax=500 nm,铝的含量在0-50μg/25 mL内符合比耳定律。建立了邻苯二酚螯合树脂分离/富集-茜素红分光光度法测定天然水样中铝的新方法,对水样中铝形态进行测定,结果满意。     

原子荧光光谱法测定化探样品时有机质对As,Sb,Bi的干扰

通过研究黑龙江省森林沼泽景观区有机水系沉积物（泥炭）、土壤中As,Sb,Bi的测定结果，发现样品中的有机质对王水消解氢化物原子荧光法测定上述元素存在极大的干扰，提出采用低温（＜450℃）灰化处理可完全消除干扰。对比研究还发现，过去森林沼泽景观区的区域化探扫面资料中的As,Sb,Bi数据存在问题，应专门对其进行评价研究。     

Advances in energy-dispersive X-ray fluorescence

Recently, two new instruments for X-ray fluorescence analysis (XRF) with interesting features for geochemical applications came to the market. Both instruments were designed to improve the peak to background ratio, the principal factor limiting the sensitivity of XRF. Total reflection XRF (TXRF) was designed to analyse extremely small sample amounts. An instrument, using polarised X-rays (P-XRF) for excitation, is designed to reduce scattered background in spectra of bulk samples. The performance of both instruments was compared with conventional XRF-methods and ICP/MS. Results for GXR-1, GXR-2, GXR-3, GXR-4 and GXR-6 obtained with TXRF and P-XRF are in good agreement with literature data. The effective amount of sample, analysed by TXRF was 200 μg only and detection limits of ~ l μg/g were achieved. P-XRF shows considerable improved detection limits (0.25–0.5 μg/g) for bulk samples for elements with atomic numbers 42–51 (Mo-Sb) compared with conventional XRF-methods.     

催化褪色光度法测定痕量锰的研究及应用

本研究了在ＰＨ＝４．０醋酸－醋酸钠缓冲溶液中，锰催化ＫＩＯ４氧化５－Ｂｒ－ＰＡＤＡＰ的褪色反应及其动力学条件，建立了一个痕量锰的高灵敏度新方法，方法灵敏度为１．３２×１０＾－１０ｇ／ｍｌ，测定范围Ｍｎ＾２＋浓度为０￣１．５μｇ／ｍｌ，用于测定人发，自来水，茶叶中痕量锰，结果满意。