Space and time resolved rotational state populations and gas temperatures in an inductively coupled hydrogen RF discharge

Gas temperature is of major importance in plasma based surface treatment, since the surface processes are strongly temperature sensitive. The spatial distribution of reactive species responsible for surface modification is also influenced by the gas temperature. Industrial applications of RF plasma reactors require a high degree of homogeneity of the plasma in contact with the substrate. Reliable measurements of spatially resolved gas temperatures are, therefore, of great importance. The gas temperature can be obtained, e.g. by optical emission spectroscopy (OES). Common methods of OES to obtain gas temperatures from analysis of rotational distributions in excited states do not include the population dynamics influenced by cascading processes from higher electronic states. A model was developed to evaluate this effect on the apparent rotational temperature that is observed. Phase resolved OES confirmed the validity of this model. It was found that cascading leads to higher apparent temperatures, but the deviation (similar or equal to 25 K) is relatively small and can be ignored in most cases. This analysis is applied to investigate axially and radially resolved temperature profiles in an inductively coupled hydrogen RF discharge.

Comparison between fluid simulations and experiments in inductively coupled argon/chlorine plasmas

Comparisons of 2D fluid simulations with experimental measurements of Ar/Cl-2 plasmas in a low-pressure inductively coupled reactor are reported. Simulations show that the wall recombination coefficient of Cl atom (gamma) is a crucial parameter of the model and that neutral densities are very sensitive to its variations. The best agreement between model and experiment is obtained for gamma = 0.02, which is much lower than the value predicted for stainless steel walls (gamma = 0.6). This is consistent with reactor wall contaminations classically observed in such discharges. The electron density, negative ion fraction and Cl atom density have been investigated under various conditions of chlorine and argon concentrations, gas pressure and applied rf input power. The plasma electronegativity decreases with rf power and increases with chlorine concentration. At high pressure, the power absorption and distribution of charged particles become more localized below the quartz window. Although the experimental trends are well reproduced by the simulations, the calculated charged particle densities are systematically overestimated by a factor of 3-5. The reasons for this discrepancy are discussed in the paper.

Discharge kinetics of inductively coupled oxygen plasmas:Experiment and model

In this paper, neutral and charged particle dynamics in both the capacitive and inductive modes of an inductively coupled oxygen discharge are presented. Langmuir probes, laser-assisted photodetachment and two-photon laser-induced fluorescence are employed to measure plasma parameters in the 13.56MHz system for a range of plasma powers and gas pressures. It is found that the capacitive mode is more electronegative with lower molecular dissociation compared with the inductive mode. However, the negative ion density in each mode is comparable. A maximum is observed in the negative ion density and fraction with pressure for both modes. The experimental measurements are supplemented by a global model, which includes capacitive and inductive coupling effects. The model and experiments demonstrate that negative ion loss is dominated by ion-ion recombination and electron detachment at low pressures (

The role of the relative voltage and phase for frequency coupling in a dual-frequency capacitively coupled plasma

Frequency coupling in multifrequency discharges is a complex nonlinear interaction of the different frequency components. An alpha-mode low pressure rf capacitively coupled plasma operated simultaneously with two frequencies is investigated and the coupling of the two frequencies is observed to greatly influence the excitation and ionization within the discharge. Through this, plasma production and sustainment are dictated by the corresponding electron dynamics and can be manipulated through the dual-frequency sheath. These mechanisms are influenced by the relative voltage and also the relative phase of the two frequencies.

Nonlinear excitations in strongly-coupled plasma lattices: envelope solitons, kinks and intrinsic localized modes

Ensembles of charged particles (plasmas) are a highly complex form of matter, most often modeled as a many-body system characterized by weak inter-particle interactions (electrostatic coupling). However, strongly-coupled plasma configurations have recently been produced in laboratory, either by creating ultra-cold plasmas confined in a trap or by manipulating dusty plasmas in discharge experiments. In this paper, the nonlinear aspects involved in the motion of charged dust grains in a one-dimensional plasma monolayer (crystal) are discussed. Different types of collective excitations are reviewed, and characteristics and conditions for their occurrence in dusty plasma crystals are discussed, in a quasi-continuum approximation. Dust crystals are shown to support nonlinear kink-shaped supersonic solitary longitudinal excitations, as well as modulated envelope localized modes associated with longitudinal and transverse vibrations. Furthermore, the possibility for intrinsic localized modes (ILMs) — Discrete Breathers (DBs) — to occur is investigated, from first principles. The effect of mode-coupling is also briefly considered. The relation to previous results on atomic chains, and also to experimental results on strongly-coupled dust layers in gas discharge plasmas, is briefly discussed.

Green tea supplementation increases glutathione and plasma antioxidant capacity in adults with the metabolic syndrome

Green tea, a popular polyphenol-containing beverage, has been shown to alleviate clinical features of the metabolic syndrome. However, its effects in endogenous antioxidant biomarkers are not clearly understood. Thus, we tested the hypothesis that green tea supplementation will upregulate antioxidant parameters (enzymatic and nonenzymatic) in adults with the metabolic syndrome. Thirty-five obese participants with the metabolic syndrome were randomly assigned to receive one of the following for 8 weeks: green tea (4 cups per day), control (4 cups water per day), or green tea extract (2 capsules and 4 cups water per day). Blood samples and dietary information were collected at baseline (0 week) and 8 weeks of the study. Circulating carotenoids (a-carotene, ß-carotene, lycopene) and tocopherols (a-tocopherol, ?-tocopherol) and trace elements were measured using high-performance liquid chromatography and inductively coupled plasma mass spectroscopy, respectively. Serum antioxidant enzymes (glutathione peroxidase, glutathione, catalase) and plasma antioxidant capacity were measured spectrophotometrically. Green tea beverage and green tea extract significantly increased plasma antioxidant capacity (1.5 to 2.3 µmol/L and 1.2 to 2.5 µmol/L, respectively; P <.05) and whole blood glutathione (1783 to 2395 µg/g hemoglobin and 1905 to 2751 µg/g hemoglobin, respectively; P <.05) vs controls at 8 weeks. No effects were noted in serum levels of carotenoids and tocopherols and glutathione peroxidase and catalase activities. Green tea extract significantly reduced plasma iron vs baseline (128 to 92 µg/dL, P <.02), whereas copper, zinc, and selenium were not affected. These results support the hypothesis that green tea may provide antioxidant protection in the metabolic syndrome.

Neutrophil Elastase Increases Airway Epithelial Nonheme Iron Levels

Alpha-1-antitrypsin (A1AT) deficiency is characterized by increased neutrophil elastase (NE) activity and oxidative stress in the lung. We hypothesized that NE exposure generates reactive oxygen species by increasing lung nonheme iron. To test this hypothesis, we measured bronchoalveolar lavage (BAL) iron and ferritin levels, using inductively coupled plasma (ICP) optical emission spectroscopy and an ELISA, respectively, in A1AT-deficient patients and healthy subjects. To confirm the role of NE in regulating lung iron homeostasis, we administered intratracheally NE or control buffer to rats and measured BAL and lung iron and ferritin. Our results demonstrated that A1AT-deficient patients and rats postelastase exposure have elevated levels of iron and ferritin in the BAL. To investigate the mechanism of NE-induced increased iron levels, we exposed normal human airway epithelial cells to either NE or control vehicle in the presence or absence of ferritin, and quantified intracellular iron uptake using calcein fluorescence and ICP mass spectroscopy. We also tested whether NE degraded ferritin in vitro using ELISA and western analysis. We demonstrated in vitro that NE increased intracellular nonheme iron levels and degraded ferritin. Our results suggest that NE digests ferritin increasing the extracellular iron pool available for cellular uptake.

New Cu-Based Catalysts Supported on TiO2 Films for Ullmann SNAr-Type C-O Coupling Reactions

New routes for the preparation of highly active TiO2-supported Cu and CuZn catalysts have been developed for C-O coupling reactions. Slurries of a titania precursor were dip-coated onto glass beads to obtain either structured mesoporous or non-porous titania thin films. The Cu and CuZn nanoparticles, synthesized using a reduction by solvent method, were deposited onto calcined films to obtain a Cu loading of 2 wt%. The catalysts were characterized by inductively coupled plasma (ICP) spectroscopy, temperature-programmed oxidation/reduction (TPO/TPR) techniques, Cu-63 nuclear magnetic resonance (NMR) spectroscopy, X-ray diffraction (XRD), scanning and transmission electron microscopy (S/TEM-EDX) and X-ray photo-electron spectroscopy (XPS). The activity and stability of the catalysts obtained have been studied in the C-O Ullmann coupling of 4-chloropyridine and potassium phenolate. The titania-supported nanoparticles retained catalyst activity for up to 12 h. However, catalyst deactivation was observed for longer operation times due to oxidation of the Cu nanoparticles. The oxidation rate could be significantly reduced over the CuZn/TiO2 catalytic films due to the presence of Zn. The 4-phenoxypyridine yield was 64% on the Cu/nonporous TiO2 at 120 degrees C. The highest product yield of 84% was obtained on the Cu/mesoporous TiO2 at 140 degrees C, corresponding to an initial reaction rate of 104 mmol g(cat)(-1) s(-1). The activation energy on the Cu/mesoporous TiO2 catalyst was found to be (144 +/- 5) kJ mol(-1), which is close to the value obtained for the reaction over unsupported CuZn nanoparticles (123 +/- 3 kJ mol(-1)) and almost twice the value observed over the catalysts deposited onto the non-porous TiO2 support (75 +/- 2 kJ mol(-1)).

Uptake and translocation of inorganic and methylated arsenic species by plants

The uptake and translocation into shoots of arsenate, methylarsonate (MA), and dimethylarsinate (DMA) by 46 different plant species were studied. The plants (n = 3 per As species) were exposed for 24 h to 1 mg of As per litre under identical conditions. Total arsenic was measured in the roots and the shoots by acid digestion and inductively coupled plasma mass spectrometry from which, besides total As values, root absorption factors and shoot-to-root transfer factors were calculated. As uptake into the root for the different plant species ranged from 1.2 to 95 (mu g of As per g of dry weight) for As-V, from 0.9 to 44 for MA(V) and from 0.8 to 13 for DMA(V), whereas in shoots the As concentration ranged from 0.10 to 17 for As-V, 0.1 to 13 for MA(V), and 0.2 to 17 for DMA(V). The mean root absorption factor for As-V (1.2 to 95%) was five times higher than for DMA(V) (0.8 to 13%) and 2.5 times higher than for MA(V) (0.9 to 44%). Although the uptake of arsenic in the form of As-V was significantly higher than that of MA(V) and DMA(V), the translocation of the methylated species was more efficient in most plant species studied. Thus, an exposure of plants to DMA(V) or MA(V) can result in higher arsenic concentrations in the shoots than when exposed to As-V. Shoot-to-root transfer factors (TFs) for all plants varied with plant and arsenic species. While As-V had a median TF of 0.09, the TF of DMA(V) was nearly a factor of 10 higher (0.81). The median TF for MA(V) was in between (0.30). Although the TF for MA(V) correlates well with the TF for DMA(V), the plants can be separated into two groups according to their TF of DMA(V) in relation to their TF of As-V. One group can immobilise DMA(V) in the roots, while the other group translocates DMA(V) very efficiently into the shoot. The reason for this is as yet unknown.

Grain Accumulation of Selenium Species in Rice (Oryza sativa L.)

Efficient Se biofortification programs require a thorough understanding of the accumulation and distribution of Se species within the rice grain. Therefore, the translocation of Se species to the filling grain and their spatial unloading were investigated. Se species were supplied via cut flag leaves of intact plants and excised panicle stems subjected to a +/- stem-girdling treatment during grain fill. Total Se concentrations in the flag leaves and grain were quantified by inductively coupled plasma mass spectrometry. Spatial accumulation was investigated using synchrotron X-ray fluorescence microtomography. Selenomethionine (SeMet) and selenomethylcysteine (SeMeSeCys) were transported to the grain more efficiently than selenite and selenate. SeMet and SeMeSeCys were translocated exclusively via the phloem, while inorganic Se was transported via both the phloem and xylem. For SeMet- and SeMeSeCys-fed grain, Se dispersed throughout the external grain layers and into the endosperm and, for SeMeSeCys, into the embryo. Selenite was retained at the point of grain entry. These results demonstrate that the organic Se species SeMet and SeMeSeCys are rapidly loaded into the phloem and transported to the grain far more efficiently than inorganic species. Organic Se species are distributed more readily, and extensively, throughout the grain than selenite.

Risk assessment of potentially toxic elements in agricultural soils and maize tissues from selected districts in Tanzania

A field survey was conducted to investigate the contamination of potentially toxic elements (PTEs) arsenic (As), lead (Pb), chromium (Cr), and nickel (Ni) in Tanzanian agricultural soils and to evaluate their uptake and translocation in maize as proxy to the safety of maize used for human and animal consumption. Soils and maize tissues were sampled from 40 farms in Tanzania and analyzed using inductively coupled plasma-mass spectrometry in the United Kingdom. The results showed high levels of PTEs in both soils and maize tissues above the recommended limits. Nickel levels of up to 34.4 and 56.9mgkg(-1) respectively were found in some maize shoots and grains from several districts. Also, high Pb levels >0.2mgkg(-1) were found in some grains. The grains and shoots with high levels of Ni and Pb are unfit for human and animal consumption. Concentrations of individual elements in maize tissues and soils did not correlate and showed differences in uptake and translocation. However, Ni showed a more efficient transfer from soils to shoots than As, Pb and Cr. Transfer of Cr and Ni from shoots to grains was higher than other elements, implying that whatever amount is assimilated in maize shoots is efficiently mobilized and transferred to grains. Thus, the study recommended to the public to stop consuming and feeding their animals maize with high levels of PTEs for their safety.

Grain unloading of arsenic species in rice

Rice (Oryza sativa) is the staple food for over half the world's population yet may represent a significant dietary source of inorganic arsenic (As), a nonthreshold, class 1 human carcinogen. Rice grain As is dominated by the inorganic species, and the organic species dimethylarsinic acid (DMA). To investigate how As species are unloaded into grain rice, panicles were excised during grain filling and hydroponically pulsed with arsenite, arsenate, glutathione-complexed As, or DMA. Total As concentrations in flag leaf, grain, and husk, were quantified by inductively coupled plasma mass spectroscopy and As speciation in the fresh grain was determined by x-ray absorption near-edge spectroscopy. The roles of phloem and xylem transport were investigated by applying a +/- stem-girdling treatment to a second set of panicles, limiting phloem transport to the grain in panicles pulsed with arsenite or DMA. The results demonstrate that DMA is translocated to the rice grain with over an order magnitude greater efficiency than inorganic species and is more mobile than arsenite in both the phloem and the xylem. Phloem transport accounted for 90% of arsenite, and 55% of DMA, transport to the grain. Synchrotron x-ray fluorescence mapping and fluorescence microtomography revealed marked differences in the pattern of As unloading into the grain between DMA and arsenite-challenged grain. Arsenite was retained in the ovular vascular trace and DMA dispersed throughout the external grain parts and into the endosperm. This study also demonstrates that DMA speciation is altered in planta, potentially through complexation with thiols.

Speciation and distribution of arsenic and localization of nutrients in rice grains

Arsenic (As) contamination of rice grains and the generally low concentration of micronutrients in rice have been recognized as a major concern for human health. Here, we investigated the speciation and localization of As and the distribution of (micro)nutrients in rice grains because these are key factors controlling bioavailability of nutrients and contaminants. Bulk total and speciation analyses using high-pressure liquid chromatography (HPLC)-inductively coupled plasma mass spectrometry (ICP-MS) and X-ray absorption near-edge spectroscopy (XANES) was complemented by spatially resolved microspectroscopic techniques (micro-XANES, micro-X-ray fluorescence (micro-XRF) and particle induced X-ray emission (PIXE)) to investigate both speciation and distribution of As and localization of nutrients in situ. The distribution of As and micronutrients varied between the various parts of the grains (husk, bran and endosperm) and was characterized by element-specific distribution patterns. The speciation of As in bran and endosperm was dominated by As(III)-thiol complexes. The results indicate that the translocation from the maternal to filial tissues may be a bottleneck for As accumulation in the grain. Strong similarities between the distribution of iron (Fe), manganese (Mn) and phosphorus (P) and between zinc (Zn) and sulphur (S) may be indicative of complexation mechanisms in rice grains.