A Modified Technique for the Preparation of SO2 from Sulphates and Sulphides for Sulphur Isotope Analyses

Abstract

A modified technique for the conversion of sulphates and sulphides to SO₂ with the mixture of V₂O₅—SiO₂ for sulphur isotopic analyses is described. This technique is more suitable for routine analysis of large number of samples. Modification of the reaction vessel and using manifold inlet system allows to analyse up to 24 samples every day. The modified technique assures the complete yield of SO₂, consistent oxygen isotope composition of the SO₂ gas and reproducibility of δ³⁴S measurements being within 0.10‰. It is observed, however, oxygen in SO₂ produced from sulphides differs in δ¹⁸O with respect to that produced from sulphates.     

Synthese und Qualitätskontrolle 15N-markierter Stickoxide mit hoher 15N-Häufigkeit für umweltrelevante Tracer-Untersuchungen

Für die Untersuchung ausgewählter Probleme des Verhaltens und der Wirkung der Stickoxide NO _x (NO + NO₂) in Ökosystemen, z.B. die Aufnahme und Freisetzung von NOx durch das System “Boden-Pflanze”, bietet sich der Einsatz ¹⁵N-markierter Stickoxide an. Die dazu benötigten ¹⁵N-markierten Gasgemische hoher Reinheit werden aus eigens dafür synthetisiertem [¹⁵N]Stickstoffmonoxid oder [¹⁵N]Stickstoffdioxid mit hoher ¹⁵N-Häufigkeit hergestellt. Beide Synthesen gehen jeweils von der kostengünstig kommerziell erhältlichen [¹⁵N]Salpetersäure aus.

Im Falle des [¹⁵N]Stickstoffdioxids erfolgt die Herstellung über die Präparation von Bleinitrat und dessen thermische Zersetzung. Die Ausbeute liegt bei 70–75% bezogen auf eingesetzte [¹⁵N]Salpetersäure.

Die Herstellung von [¹⁵N]Stickstoffmonoxid erfolgt durch Reduktion von [¹⁵N]Salpetersäure mit Eisen-II-sulfat in stark saurer Lösung. Die Ausbeute beträgt 60–70%, bezogen auf eingesetzte Salpetersäure.

The application of ¹⁵N is very useful for the investigation of the behavior and the effect of the nitrogen oxides NO _x (nitric oxide + nitrogen dioxide) in ecosystems, e.g. the uptake and release of NO _x by the soil-plant system. The ¹⁵N labelled gas mixture needed for that purpose has to be prepared from synthesized highly enriched [¹⁵N]nitric oxide and [¹⁵N]nitrogen dioxide. These two syntheses both use the commercially available and reasonable [¹⁵N]nitric acid.

In the case of [¹⁵N]nitrogen dioxide the synthesis is carried out via [¹⁵N]lead nitrate and its decomposition with increasing temperature. The yield is 70–75% related to the [¹⁵N]nitric acid input. The preparation of [¹⁵N]nitric oxide is done by reduction of [¹⁵N]nitric acid by means of FeSO₄ in strong acid solution. The yield amounts to 60–70%.     

15N-Werte als Mittel zur Analyse der Stickstoffernährung bei insektivoren Pflanzen

The study presents a new serial pooling method of shifted tree ring blocks for the building of isotope chronologies. This method combines the advantages of traditional ‘serial’ and ‘intertree’ pooling, and can be recommended for the construction of sub-regional long isotope chronologies with sufficient replication, and on annual resolution, especially for the case of extremely narrow tree rings. For Scots pines (Pinus sylvestris L., Khibiny Low Mountains, NW Russia) and Silver firs (Abies alba Mill., Franconia, Southern Germany), serial pooling of five consecutive tree rings seems appropriate because the species- and site-specific particularities lead to blurs of climate linkages in their tree rings for the period up to ca. five years back. An equivalent to a five-year running means that curve gained on the base annual data sets of single trees can be derived from the analysis of yearly shifted five-year blocks of consecutive tree rings, and therefore, with approximately 20% of the expense. Good coherence of δ¹³C- and δ¹⁸O-values between calculated means of annual total rings or late wood data and means of five-year blocks of consecutive total tree rings analysed experimentally on most similar material confirms this assumption.     

GC-R-CF-MS method to determine the 13C abundance of gaseous combustion products in cigarette smoke

To determine the ¹³C abundance of combustion and break down products formed in cigarette smoke, especially CO and CO₂, a simple and fast analytical method is needed. Taking into account the knowledge about the determination of the natural ¹³C abundance in air, an online method—based on gas chromatography-reaction-continuous flow mass spectrometry (GC-R-CF-MS)—has been developed, which enables the determination of the ¹³C abundance of CO and CO₂ in the vapour phase of cigarette smoke with a relative standard deviation of≤0.5% in one analytical run. Additionally, in a second step, the ¹³C abundance of total volatile carbon can be determined.     

Sauna,sweat and science II – do we sweat what we drink?

ABSTRACT

Inspired by a previous ‘Sauna, sweat and science’ study [Zech et al. Isot Environ Health Stud. 2015;51(3):439–447] and out of curiosity and enthusiasm for stable isotope and sauna research we aimed at answering the question ‘do we sweat (isotopically) what we drink’? We, therefore, pulse-labelled five test persons in a sauna experiment with beverages that were ²H-enriched at about +25,600?‰. Sweat samples were collected during six sauna rounds and the hydrogen isotope composition δ²H_sweat was determined using an isotope ratio mass spectrometer. Before pulse labelling, δ²H_sweat – reflecting by approximation body water – ranged from –32 to –22?‰. This is ～35?‰ enriched compared to usual mid-European drinking water and can be explained with hydrogen-bearing food as well as with the respiratory loss of ²H-depleted vapour. The absence of a clearly detectable ²H pulse in sweat after pulse labelling and δ²H_sweat results of ≤+250?‰ due to a fast ²H equilibration with body water are moreover a clearly negative answer to our research question also in a short-term consideration. Given that the recovery of the tracer based on an isotope mass balance calculation is clearly below 100?%, we finally answer the question ‘where did the rest of the tracer go?’     

Development of non-lethal sampling of carbon and nitrogen stable isotope ratios in salmonids: effects of lipid and inorganic components of fins

The preferred tissue for analyses of fish stable isotope ratios for most researchers is muscle, the sampling of which typically requires the specimen to be sacrificed. The use of non-destructive methods in fish isotopic research has been increasing recently, but as yet is not a standard procedure. Previous studies have reported varying levels of success regarding the utility of non-lethally obtained stable isotope materials, e.g. fins, but none have accounted for the potential compounding effects of inorganic components of fin rays or lipids. Comparisons of carbon (δ¹³C) and nitrogen (δ¹⁵N) stable isotope ratios of muscle with adipose and caudal fin of two salmonids, Atlantic salmon (Salmo salar L.) and brown trout (Salmo trutta L.), revealed that caudal fin can be used as a non-destructive surrogate for muscle in stable isotope analysis, but that adipose fin, where available, is a better proxy. The use of a published model to inexpensively counteract the confounding effect of lipids, which are depleted in ¹³C, greatly improved the relationship between fish muscle and fins. However, efforts to account for the inorganic components of fin rays were counterproductive and required twice the biomass of fins clipped from each fish. As this experiment was conducted on wild fish, controlled laboratory studies are required to confirm these field observations.     

Assessing the authenticity of commercial deep-sea drinking water by chemical and isotopic approaches

This study combines stable isotopes and chemical elements with statistical principal component analysis (PCA) to assess the authenticity of bottled commercial drinking water desalinized from deep seawater in the Taiwan market. Isotopic results indicate that true bottled deep-sea drinking water (DSDW) exhibits about 0?‰ for both δ²H and δ¹⁸O values, which are values similar to those of open seawater. By comparison, suspected counterfeit DSDW products display δ²H and δ¹⁸O values of around ?51?‰ and ?8?‰, respectively. These values are representative of terrestrial freshwater. In addition, suspected counterfeit DSDWs have δ and electrical conductivity values similar to a mixed water (MW) product that was manufactured by purifying terrestrial freshwater and adulterating this with small amounts of brine. Furthermore, PCA results indicate the chemical constitution of suspected DSDW products to be similar to the MW product which falls between purified terrestrial freshwater and desalinized open seawater. These similarities imply that suspected counterfeit DSDW products are manufactured in a similar manner to the declared MW product. This study demonstrates how combining knowledge of stable water isotopes and PCA can be used in assessing the authenticity of commercial DSDW products. The method should be of great interest to similar investigations elsewhere.     

GPS/LEO掩星正则变换反演方法

利用无线电全息方法, 如正则变换方法或全谱反演方法, 可以有效地解决大气多路径条件下GPS掩星信号的反演问题. 本文采用正则变换方法反演掩星资料, 模拟仿真反演结果显示正则变换方法可以准确地反演包含大气多路径效应的信号. 在模拟信号的相位中加入不同程度的高斯相位噪声后, 正则变换方法的反演结果会受到不同程度的影响. 用正则变换方法对2007年第71天至73天共约4500个COSMIC数据进行处理. 将其折射率反演结果和atmPrf资料 (利用全谱反演方法计算得到) 一起, 与对应的ECMWF 分析场资料进行统计比较, 结果表明: 在5 km以下, 正则变换方法计算的折射率的相对误差的平均值普遍大于atmPrf资料. 其原因可能为: 正则变换方法将信号从LEO轨迹后传播至辅助屏, 造成孔径缩小, 精度下降. 同时也讨论了信号截断对低对流层中反演精度和掩星个数的影响. 关键词： 无线电掩星 大气多路径 多相位屏技术 正则变换方法     

基于背景光调制的复合光傅里叶变换轮廓术

提出一种基于背景光调制的用于傅里叶变换轮廓术测量范围的复合光栅,该光栅通过调制一正弦条纹和不含任何相位信息的背景光来抑制零频,较基于相移技术的复合光栅有更大的优势:背景光只含直流分量,使得复合光栅的频谱更加简单,有利于滤出载波信息,提高测量精度;对从复合光栅中解调出来的背景光只涉及平均值校准,校准过程更为简单;解调出的背景光与物体表面的反射率成正比,具有潜在的应用价值。采用Matlab程序对该复合光栅进行了数值模拟,并对该光栅实用性进行了实验研究,结果证实了该光栅用于抑制零频、扩大傅里叶变换轮廓术测量范围的有效性,且提高了测量精度。     

基于斯托克斯矢量的偏振成像仪器及其进展

偏振成像技术将景物的偏振信息转化为二维图像信息,从而可以和灰度图像一样对目标景物进行场景特征分析。介绍了基于斯托克斯矢量的偏振成像原理。按照获取斯托克斯矢量方法的不同,分别介绍了偏振片起偏、偏振棱镜分光和可变延迟波片调制三类分时偏振成像方式,分振幅、分孔径、分焦平面三种同时偏振成像方式。结合我国的制造水平,设计了双CCD渥拉斯顿棱镜同时偏振成像实验系统,并采集了实验图像。分析了各种偏振成像方式的优缺点。指出了偏振激光照明主动偏振成像、光谱偏振成像是偏振成像仪器进一步的发展方向。