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.     

THE WAVELENGTH COMPONENT VECTORGRAM: A TOOL FOR RESOLVING TWO-COMPONENT FLUORESCENT MIXTURES

We consider the problem of resolving the total luminescence spectra of two-component mixtures.Non-negativity of the constituent spectra is commonly used as a criterion to accomplish this resolution,but its application seldom leads to unique answers. Sometimes, the condition must be relaxed because nosolution satisfying non-negativity exists. In these cases judgments must be made concerning which partsof the spectra will be allowed to go negative and by how much. The wavelength component vectorgramn (WCV) is presented here as a tool for assisting theexperimenter in making these judgments. Even when non-negative resolutions exist, it may happen thatresolutions with slight negative elements will more closely match the spectra of the pure constituents.The WCV can also be used as a tool for detecting these cases. The methodology is illustrated with realdata from a two-component mixture.     

A portable remote methane detector using an InGaAsP DFB laser

A portable remote methane detector based on infrared-absorption spectroscopy using an InGaAsP distributed-feedback laser is described. This equipment transmits a laser beam and detects a fraction of the backscatter reflected from the target. From this, the detector thereby measures the integrated methane concentration between the detector and the target. The equipment operator can easily detect methane clouds at a distance by hand-scanning the laser beam. To achieve a high sensitivity of detection, wavelength-modulation spectroscopy is applied to the infrared-absorption measurement for methane. The wavelength of the light source is modulated at a frequency of 10 kHz, and the center wavelength is stabilized at the center of the 2₃ band R(3) line of methane (1.65372 m). When used with typical targets at distances up to 10 m, the detector has a detection limit of less than 5 ppm-m. To the best of the authors knowledge, the detector is the only hand-held product capable of remote methane detection. Recently, this novel equipment was commercially introduced into the Japanese market as a product named the Portable Remote Methane Detector (PRMD). Some PRMD units were in research use for detecting methane emissions from garbage landfills, although the PRMD was mainly developed for remote detection of leaks from natural gas pipelines. The author expects that the PRMD could become the standard equipment for field measurements of methane emissions from land.     

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.     

超细固体悬浮液进样-电感耦合等离子体质谱法测定土壤中的微量元素

固体进样技术应用于土壤样品测量领域,一直受制于样品粒径的限制,无法应用在配有气动雾化器的分析仪器上。本文系统研究了土壤样品超细粉碎技术,在乙醇介质下,数分钟内将其粉碎至微米级,经此制成的固体悬浮液直接进行电感耦合等离子体质谱法(ICP-MS)测定,可以避免气动雾化器的堵塞。标准物质测定表明,样品粒径为6.8μm时,固体悬浮液进样仍然存在干扰,通过在固体悬浮液中加入少量氢氟酸和硝酸,对固体悬浮液进行改性,减小了固体悬浮液中固体颗粒粒径,从而减少了样品粒径的影响,可用ICP-MS测定土壤中锂铍钒铬镍铜锌铷锶镉铯钡铅等13个微量元素。经国家一级标准物质验证,本方法的最大相对误差在10.5%左右,多数元素的相对误差小于5%,相对标准偏差(RSD)小于5.4%(镉元素除外),满足了DZ/G 0130—2006质量控制要求。     

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LWPC和IRI模型的NWC台站信号传播幅度建模分析

频率为3~30 kHz的甚低频（VLF,Very Low Frequency）电磁波具有波长长、传播距离远的特点,能够沿地面-低电离层波导进行传播,在通信、导航等许多领域都被广泛应用.基于波导模理论的长波传播模型（LWPC,Long-Wavelength Propagation Capability）能够用于计算甚低频波的传播路径及幅度,进而研究耀斑、磁暴、地震等事件对电离层的扰动.本文利用国际电离层参考模型（IRI,International Reference Ionosphere）对LWPC中电子密度和碰撞频率进行改进,并将模拟结果与武汉大学VLF接收机实际观测到的NWC （North West Cape）台站信号幅度进行比较分析,结果表明改进后LWPC模型得到的幅度及变化趋势与实际值更加接近.LWPC模型给出的电子密度与IRI模型得到的电子密度在日间基本一致,但是在夜间存在差异,造成夜间部分区域NWC台站信号幅度的差异性,验证了电离层电子密度对于VLF信号传播具有的重要影响.传播路径上的晨昏变化也可以引起VLF信号幅度分布的突变,在日出和日落时间段内存在明显的过渡区域.基于IRI模型的LWPC,改善了VLF电波传播过程的预测分析效果,提供了一种长波导航通信质量的评估方法.     

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.