戊基磷酸二戊酯萃取色层分离-电感耦合等离子体质谱法测定铀产品中9种杂质元素

铀产品中杂质元素的含量测定在核法证学溯源分析或燃料元件厂质量检验中具有重要应用价值,保证测量的准确度主要在于控制流程空白、提高杂质元素的回收率。本文建立了戊基磷酸二戊酯(UTEVA)树脂快速分离铀与杂质元素、电感耦合等离子体质谱法(ICP-MS)测定杂质元素含量的系统流程。结果表明,UTEVA树脂对铀的吸附能力强,铀样品取样量为16.43 mg时,全流程对铀的去污因子大于3×105,9种杂质元素(锰钼镍铜铬铝钛钒镉)的回收率为95.1%~105.1%,国家标准物质GBW04205中杂质元素的分析结果与参考值在不确定度(k=2)范围内一致。本工作建立的分离流程对铀的去污效果好,特别适用于样品量少的情况下铀中杂质元素的分析,为核法证分析最终的归因溯源或燃料质量检验提供了技术支持。     

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.     

Anthropogenic iodine-129 in seawater along a transect from the Norwegian coastal current to the North Pole

Variation in the concentrations of iodine-129 (129I, T1/2=15.7 Myr), a low-level radioactive component of nuclear fuel waste, is documented in surface waters and depth profiles collected during 2001 along a transect from the Norwegian Coastal Current to the North Pole. The surface waters near the Norwegian coast are found to have 20 times higher 129I concentration than the surface waters of the Arctic Ocean. The depth profiles of 129I taken in the Arctic Ocean reveal a sharp decline in the concentration to a depth of about 300-500 m followed by a weaker gradient extending down to the bottom. A twofold increase in the 129I concentration is observed in the upper 1000 m since 1996. Based on known estimates of marine transient time from the release sources (the nuclear reprocessing facilities at La Hague, France, and Sellafield, UK), a doubling in the 129I inventory of the top 1000 m of the Arctic Ocean is expected to occur between the years 2001 and 2006. As 129I of polar mixed layer and Atlantic layer of the Arctic Ocean is ventilated by the East Greenland Current into the Nordic Seas and North Atlantic Ocean, further dispersal and increase of the isotope concentration in these regions will be encountered in the near future.     

气袋采样法对还原硫化物测定的影响因素分析及机理研究

还原硫化物是一Z类典型的恶臭物质,其特点是活性高、不易储存,因此适宜的储存条件对还原硫化物的准确测定具有重要意义。本文使用气相色谱-质谱联用技术,从气袋材质、还原硫化物初始浓度、还原硫化物性质和储存时间四个因素探究袋采样法储存还原硫化物过程的损失情况。以Tedlar~? PVF和Teflon~? FEP为目标采样袋,使用5个初始浓度(0. 001、0. 010、0. 100、1. 000和10. 000μg/m L)的混合还原硫化物,选择0、2、6、12、24、48以及72h的储存时间,以响应因子和相对回收率作为评价因子,并使用配对t检验法和吸附动力学,研究影响储存效果的主要因素、物质损失机理以及两种采样袋的储存能力。结果表明,储存时间越长、物质初始浓度越高,物质活性越强,损失情况越严重;在环境温度达到60℃时,Tedlar~? PVF的基质背景较Teflon~? FEP更复杂;相同条件下,还原硫化物在Teflon~? FEP储存过程中损失更严重。依据研究结果建议:(1)样品采集后避光保存;(2)低浓度含硫样品的测定在采样后8h内完成,高浓度含硫样品的测定在2h内完成;(3)若待测样品气体温度较高,优先选择Teflon~? FEP采样袋,气体温度较低条件下选择Tedlar~? PVF采样袋,可最大限度保持样品的原始状态。本研究成果有利于确保还原硫化物样品的储存稳定性,最大限度还原恶臭污染现场情况,为恶臭污染的分析测试以及后续的恶臭污染控制与治理提供技术支持。     

原子荧光光谱测定土壤和水系沉积物中硒的干扰来源及消除方法

原子荧光光谱法(AFS)具有灵敏度高、结构简单、容易操作等优点,但目前测定土壤和沉积物中的硒等元素的标准方法所采用的消解过程繁琐,易产生干扰。沸水浴可以把土壤和水系沉积物中硒提取完全,本文根据样品中元素丰度和仪器性能,将AFS测定Se的干扰分为Cu和Pb两大类,根据实验提出在水浴消解液加入浓盐酸(不宜加入硫脲-抗坏血酸),通过增加溶液酸度和Cl~-浓度,即保持样品中盐酸浓度高于23%,可抑制Cu~(2+)还原为Cu~0和Pb~(4+)生成PbH_4,有效降低了Cu的负干扰和Pb的正干扰,提高了AFS测定Se的精密度和准确度。本方法测定Se的检出限为0.008mg/kg,测试标准物质的相对标准偏差为0.5%～11%,相对误差为-16.3%～9.5%;比行业标准HJ 680—2013的检出限(0.01mg/kg)、精密度(0.79%～23.1%)和准确度等技术指标更佳。     

基于TIE方程的空间域相位恢复迭代算法

利用同步辐射X射线同轴显微层析(CT)方法对页岩进行扫描成像是一种无损的,对研究页岩孔裂隙大小、形态、三维结构及连通性等微观结构特征有重要意义的方法.同步辐射的引入将在物理上为提高页岩成像的分辨率提供了可能,在相位-吸收二重性假设下利用光强传递TIE(transport-of-intensity)方程可以较好地抑制由于相位信息带来的"边缘增强"效应,但该问题本质上是不适定的反演问题.本文根据实际问题构造模型,提出了一种与传统基于频域方法不同的,基于空间域的相位恢复迭代算法,并采用迭代Tikhonov正则化在数值上解决了噪声干扰下的不稳定性·问题.研究结果表明,新方法的残差仅为频域方法的1%左右,该方法可用于未来实际数据的处理.     

Characterisation of Fulvic Acids and Glycyrrhizic Acid by Time‐of‐Flight Secondary Ion Mass Spectrometry

Fulvic acids of different origin, spray deposited on polished silicon after dissolution in high‐purity water without any additives, were analysed by time‐of‐flight secondary ion mass spectrometry (TOF‐SIMS) in combination with oblique 24...36 keV SF₅⁺ ion bombardment. The observed, highly reproducible mass spectra cover more than five orders of magnitude in dynamic range, without background subtraction. Apart from lines due to atomic ions and low‐mass ion fragments, the mass spectra exhibit broad maxima between m/z 200...350, mainly due to a beat‐like superposition of lines at every single mass number, up to at least m/z 400. In the negative ion spectra the beats have a spacing of m/z 14, corresponding to a CH₂‐unit. The high‐mass tails of the spectra extend well beyond m/z 5000, with similar slopes in the positive and the negative ion mass spectra. The negative spectra appear to be less affected by fragmentation products than the positive spectra. Fulvic acids (FAs) of different origin show distinctly different spectra, with mean masses ranging between m/z ≈ 450 and 580 (for a low‐mass cut‐off m/z 150). To further verify the ability of TOF‐SIMS to detect molecules and clusters with masses significantly above the maxima of the FA spectra, samples of glycyrrhizic acid (GA, as GA ammonium salt with molecular weight 840) were also analysed. Parent ions as well as multimers (GA)_n were observed as positive and negative ions, up to n = 4 (m/z 3320). The results are compared with spectra recently obtained by other mass spectrometric techniques.     

Sorption and Chemical Reactions of PAHs with Dissolved Humic Substances and Related Model Polymers

Sorption coefficients measured for PAHs on dissolved humic substances by SPME and FQT were found to be inevitably different and method‐dependent – SPME provides activity‐based and FQT concentration‐based sorption coefficients. Poly(acrylic acid) esters as well‐defined model polymers were used in sorption experiments, leading to the conclusion that short aliphatic chains are more effective in binding PAHs than aromatic moieties. FQT was inappropriate to measure sorption coefficients for the interaction of pyrene with poly(acrylic acid) esters but the experiments revealed a characteristic shift in the fluorescence spectrum. Using pyrene as a probe for the molecular environment in the sorbed state, the observed spectral shift indicated a highly hydrophobic microenvironment. The empirical relationships between lg K_DOC and lg K_OW were generalized on the basis of a modified Flory‐Huggins concept. Introducing only one sorbent‐specific parameter, the solubility parameter δ_DOM, the calculation of sorption coefficients became possible for a wide range of HOCs using fundamental data readily available from the literature. Long‐term experiments showed that reactive PAHs (such as acenaphthylene and 9‐methylanthracene) are able to react with HAs under strictly abiotic and anoxic conditions, whereas less reactive PAHs (such as naphthalene and dihydroanthracene) do not form bound residues. The HA reveals two functions in the interaction, behaving as a reaction partner and as a protecting ligand.     

Time-resolved Fluorescence Measurements of Aquatic Natural Organic Matter (NOM)

The fluorescence decay of aquatic natural organic matter (NOM) samples was investigated using the time-correlated single photon counting technique (TCSPC). Two different approaches for the data analysis are presented: the discrete component approach (DCA) and the exponential series method (ESM). The parameter set obtained in the DCA is discussed in terms of characterization for NOM of different origins. However, the obtained parameter set can only be interpreted as operationally defined. Using the ESM for a fluorescence decay time distribution analysis no a priori assumption about the number of fluorescing components was introduced into the data analysis. The interpretation of fluorescence decay time data for samples before and after ozonation is in good agreement with results of other analytical methods.     

Untersuchungen zum Abbau von Pharmaka in kommunalen Kläranlagen mit HPLC-Electrospray-Massenspektrometrie

Examination of the Degradation of Drugs in Municipal Sewage Plants Using Liquid Chromatography-Electrospray Mass Spectrometry Numerous drugs can be identified in the secondary effluent of municipal sewage plants. In order to obtain information about the degree of elimination (adsorption, aerobic degradation) of these compounds, a batch reactor containing different drugs in environmentally relevant concentrations and a suspension of activated sludge was coupled to a HPLC-MS-MS system. During a testing period of three days concentration-time-curves were recorded. For most of the examined drugs (acetamidoantipyrine, crotamiton, diclofenac, primidone, propyphenazone) solely a strong decrease of the initial concentration within the first 15 minutes was observed, which was interpreted primarily as adsorption to the activated sludge. For acetaminophenol and pentoxifyllin an additional slower decrease in concentration within several hours was observed. This slower elimination was interpreted to be caused mainly by primary degradation. It could be shown that dihydrocodeine is oxidized to hydrocodone in the batch reactor. The conjugate acetaminophen glucuronide was cleaved.