The aim of this study is to determine the content of selected metals (As, Ba, Cd, Co, Cr, Cu, Mn, Mo, Ni, Se, Sn, Sr, Pb, V, Zn) in samples of leaves and grapes produced by ecologic agriculture and compare to results with leaves and grapes produced by integrated agriculture. The measured results used to assess the impact of agricultural technology on the quality of vines and grapes. The amount of elements was analysed using inductively coupled plasma mass spectrometry after previous digestion of sapmles using microwaves. Concentrations of elements in leaves and grapes from organic and integrated farming did not differ significantly only in the case of copper concentrations were measured higher concentrations in samples from organic farming. This difference is probably caused by different doses of authorized protective equipment based on copper in the organic and integrated farming.

Laser Ablation Inductively coupled plasma mass spectrometry (LA-ICP-MS) and Raman spectroscopy are both powerful imaging techniques. Their applications are numerous and extremely potential in the field of biology. In order to improve upon LA-ICP-MS an in-house built cold cell was developed and its effectiveness studied by imaging Brassica napus seeds. To further apply LA-ICP-MS and Raman imaging to the field of entomology a prong gilled mayfly (Ephemeroptera: Leptophlebiidae) from the Róbalo River, located on Navarino Island in Chile, was studied. Analysis of both samples showcased LA-ICP-MS and Raman spectroscopy as effective instruments for imaging trace elements and larger molecules in biological samples respectively.

周囲プラズマベースの周囲脱離/イオン化ソースにより、従来の大気圧イオン化では不可能な周囲条件下でのサンプルの直接分析が可能になります。これにより、面倒な準備と、多くの有害で複雑なサンプルの分析用質量分析計への導入が解消されます。既存のプラズマベースのアンビエント脱離/イオン化ソースは、通常、2つの電極間にキロヘルツから数メガヘルツの範囲の周波数で直流（DC）または交流（AC）電圧を印加することによって形成されます。この研究では、新しいプラズマベースの周囲脱離/イオン化は、13.56 MHz RFソースから供給される非常に低い電力密度で動作する誘導結合によって生成されたワイヤ安定化大気圧プラズマで構成されています。ワイヤ安定化大気圧プラズマの点火特性、安定性およびプラズマ特性を研究した。 / Ambient plasma-based ambient desorption/ionization source enables direct analysis of samples under ambient conditions that traditional atmospheric pressure ionization is incapable. It overcomes the tedious preprocessing and often detrimental and complicated sample introduction to the mass spectrometer for analysis. Existing plasma-based ambient desorption/ionization sources feature an electrical discharge typically formed between two electrodes by applying either a direct-current (DC) voltage or an alternating-current (AC) voltage with frequencies ranging from kilohertz to several megahertz. In this study, a novel plasma-based ambient desorption/ionization consists of a wire stabilized atmospheric pressure plasma produced by inductive coupling operated at very low power density supplied by a 13.56 MHz RF source. The ignition characteristics, stability and plasma properties of the wire stabilized atmospheric pressure plasma were studied. / 博士(工学) / Doctor of Philosophy in Engineering / 同志社大学 / Doshisha University

The inductively coupled plasma mass spectrometer (ICP-MS) has been used in laboratories for many years. The majority of the improvements to the instrument have been done empirically through trial and error. A few fluid models have been made, which have given a general description of the flow through the mass spectrometer interface. However, due to long mean free path effects and other factors, it is very difficult to simulate the flow details well enough to predict how changing the interface design will change the formation of the ion beam. Towards this end, Spencer et al. developed FENIX, a direct simulation Monte Carlo algorithm capable of modeling this transitional flow through the mass spectrometer interface, the transitional flow from disorganized plasma to focused ion beam. Their previous work describes how FENIX simulates the neutral ion flow. While understanding the argon flow is essential to understanding the ICP-MS, the true goal is to improve its analyte detection capabilities. In this work, we develop a model for adding analyte to FENIX and compare it to previously collected experimental data. We also calculate how much ambipolar fields, plasma sheaths, and electron-ion recombination affect the ion beam formation. We find that behind the sampling interface there is no evidence of turbulent mixing. The behavior of the analyte seems to be described simply by convection and diffusion. Also, ambipolar field effects are small and do not significantly affect ion beam formation between the sampler and skimmer cones. We also find that the plasma sheath that forms around the sampling cone does not significantly affect the analyte flow downstream from the skimmer. However, it does thermally insulate the electrons from the sampling cone, which reduces ion-electron recombination. We also develop a model for electron-ion recombination. By comparing it to experimental data, we find that significant amounts of electron-ion recombination occurs just downstream from the sampling interface.

A Direct Simulation Monte Carlo fluid dynamics code named FENIX has been employed to study gas flow-through properties of the inductively coupled plasma mass spectrometer (ICP-MS). Simulation data have been tested against the Navier-Stokes and heat equations in order to see if FENIX functions properly. The Navier-Stokes and heat equations have been constructed from simulation data and are compared term by term. This comparison shows that FENIX is able to correctly reproduce fluid dynamics throughout the ICP-MS simulation, with an exception immediately behind the ICP-MS sampler cone, where the continuum criterion for the Navier-Stokes equation is not met. Testing the data produced by Fenix also shows that this DSMC method correctly produces momentum and thermal boundary layer phenomenon as well. FENIX output data produce statistical fluctuations of about 2%. Limitations occur from fitting data near surfaces, incurring a relative error of about 5%, and fitting data to take second derivatives where fluid velocity gradients are steep, introducing a relative error of about 10%.

As permanent tattoos are becoming more popular and common, an increased number of allergic reactions to tattoos is reported. The purpose of this project was to analyze tattoo inks for hazardous substances, and whether they comply to current Swedish and European legislative requirements. The tattoo inks were qualitatively analyzed for pigments, and quantitatively analyzed for metals. A total of 73 tattoo inks were collected from various sources such as a tattoo ink supplier, online retailers, and provided directly from tattoo artists. The labels of each tattoo ink bottle were inspected to investigate their compliance with the Council of Europe and the Swedish Medical Products Agency. Matrix assisted laser desorption/ionization time of flight mass spectrometry (MALDI-ToF-MS) was used to qualitatively analyze 20 selected tattoo inks for different pigments. Inductively coupled plasma mass spectrometry (ICP-MS) was used to quantitatively analyze trace metals in 70 of the samples. A large majority (90%) of the tested samples violated the requirements and criteria in the European resolution ResAP 2008(1), such as information on name and address of the manufacturer, minimum date of durability, sterility, batch number, and storage. Patch and allergy testing were incorrectly recommended for many samples in a way that is not accepted by dermatologists. In a worst-case scenario, this testing could be a sensitizing step. Also, it can not prevent future allergic reactions from occurring or provide any juridical insurance. Only one brand, World Famous, fulfilled the requirements for labeling for six of the seven samples (one sample failed due to a faulty declared pigment). The brands Tang Dragon and Dynamic did not fulfill any of the requirements listed in ResAP 2008(1). The list of ingredients was incorrect for all samples from Tang Dragon (bought prior to 2019 online). Also, six of the other 50 samples from different brands (World Famous, Intenze, Fusion Tattoo Ink, Eternal Ink, Solid Ink) declared at least one pigment incorrectly in their ingredients list. 25% of the declared and theoretically detectable pigments were detected by means of MALDI-ToF-MS, whereas the other pigments were either absent or below the limit of detection. Future analyses should include an MS/MS analysis. Polyethylene glycol (PEG) was identified qualatively in 15 of the 20 samples analyzed with MALDI-ToF-MS but was not listed in any of the ingredients lists. ICP-QQQ-MS is a very sensitive technique and could both detect and verify the presence of all metal-containing pigments, as well as the level of impurities. Copper was clearly more present in green and blue colors, regardless of the brand. The metal content was evidently dependent on the brand for arsenic, aluminum, bismuth, chromium, nickel, zinc, and strontium. Elevated levels of barium and strontium (partially very high levels: up to 727 mg/kg barium and up to 8.06 g/kg strontium) were found in several samples. High amounts of aluminum (4 to 11,0 g/kg) and titanium (as judged from white precipitates and ingredients lists) were present in most samples. Nickel (0.1 to 41 mg/kg) and chromium (0.1 to 139 mg/kg) were also present in the samples. Some other impurities were also present (arsenic – 3.8 mg/kg, mercury – 1.6 mg/kg, and lead – 5.4 mg/kg for one sample, respectively). Known sensitizing pigments were declared and partially confirmed by MALDI-ToF-MS in 17 of 53 samples of the brands Radiant Colour, Eternal Ink, Fusion Tattoo Ink, and Kuro Sumi. Four samples (from Intenze, Eternal Ink, and Kuro Sumi) also declared pigments listed as non-suitable substance according to the European Commission regulation on cosmetic products from 2009.

This study is concerned with the compositional analysis of Roman and early post-Roman glass from both domestic assemblages and the remains derived from glass working and producing sites in Britain, using Inductively Coupled Plasma Spectrometry (ICPS). Samples analysed were from glassworking waste from Mancetter (midsecond century), Leicester (third century) and Worcester (first to third centuries), glass production debris, probably manufactured from the raw materials, in conjuncton with a domestic assemblage, from Coppergate (first to fourth centuries, or possibly later), and a domestic assemblage from Fishergate (spanning both the Roman and immediate post- Roman periods). All the glass analysed was shown to be of a typical and uniform soda-limesilica composition, except for a small number of vessel fragments from York which were higher in calcium. Any compositional differences between blue-green glasses typologically dated either to the Roman or Saxon periods, were found not to be consistent. Analysis of the colourless glass showed that the majority appeared to be actively decolorized using antimony, in conjunction with apparent differences In the compositions of the raw materials, when compared to glass of the same date in other 0 colours. Compositional differences between melted waste from Mancetter, Leicester and Worcester, were apparent, but not to an extent which allowed characterization to be successful. Analysis of glassmelting pots from Coppergate showed some high temperature glassworking (and possibly glassmaking) could have occurred. Other debris, thought to be indicative of glassmaking was also analysed and compared to the composition of the Roman domestic assemblage.

This study assessed the effect of cow milk (CM) and sheep milk (SM) consumption on the micro-structure, mechanical function, and mineral composition of rat femora in a male weanling rat model. Male weanling rats were fed a basal diet with a 50% reduction in calcium and phosphorus content (low Ca/P-diet) supplemented with either SM or CM. Rats were fed for 28 days, after which the femora were harvested and stored. The femora were analyzed by μ-CT, three-point bending, and inductively coupled plasma–mass spectrometry (ICP-MS). The addition of either milk to the low Ca/P-diet significantly increased (p < 0.05) trabecular bone volume, trabecular bone surface density, trabecular number, cortical bone volume, and maximum force, when compared to rats that consumed only the low Ca/P-diet. The consumption of either milk resulted in a significant decrease (p < 0.05) in trabecular pattern factor, and cortical bone surface to volume ratio when compared to rats that consumed only the low Ca/P-diet. The results were achieved with a lower consumption of SM compared to that of CM (p < 0.05). This work indicates that SM and CM can help overcome the effects on bone of a restriction in calcium and phosphorus intake.

No description available.

No description available.