Plasma power measurement and hysteresis in the E-H transition of a rf inductively coupled plasma system

An experimental investigation of the argon plasma behavior near the E-H transition in an inductively coupled Gaseous Electronics Conference reference cell is reported. Electron density and temperature, ion density, argon metastable density, and optical emission measurements have been made as function of input power and gas pressure. When plotted versus plasma power, applied power corrected for coil and hardware losses, no hysteresis is observed in the measured plasma parameter dependence at the E-H mode transition. This suggests that hysteresis in the E-H mode transition is due to ignoring inherent power loss, primarily in the matching system.

Rotation of a nanoparticle cloud in an inductively coupled plasma induced by weak static magnetic fields

Hydrocarbon nanoparticles with diameters between 10 and 30 nanometres are created in a low pressure plasma combining capacitive and inductive power coupling. The particles are generated in the capacitive phase of the experiment and stay confined in the plasma in the inductive phase. The presence of these embedded particles induces a rotation of a particle-free region (void) around the symmetry axis of the reactor. The phenomenon is analysed using optical emission spectroscopy both line integrated and spatially resolved via an intensified charge coupled device camera. From these data, electron temperatures and densities are deduced. We find that the rotation of the void is driven by a tangential component of the ion drag force induced by an external static magnetic field. Two modes are observed: a fast rotation of the void in the direction opposite to that of the tangential component and a slow rotation in the same direction. The rotation speed decreases linearly with the size of the particles. In the fast mode the dependence on the applied magnetic field is weak and consequently the rotation speed can serve as a monitor to detect particle sizes in low temperature plasmas.

Transition phenomena in a radio-frequency inductively coupled plasma

Changes of the electron dynamics during the mode transition (E- to H-mode) in a hydrogen radio-frequency (rf) inductively coupled plasma are investigated using space and phase resolved optical emission spectroscopy. The E- mode is characterized through relatively weak optical emission which is strongly modulated on a nanosecond time scale during the rf-cycle, with one pronounced maximum per cycle. The modulation in H-mode, with twice the rf-frequency, is significantly weaker while the emission intensities are about two orders of magnitude higher. In particular the transition between these two modes is studied under variations of rf-power input and gas pressure. Characteristic spatio-temporal structures are observed and can be understood in the frame of a simple model combining both coupling mechanisms in the transition regime.

Argon metastable state densities in inductively coupled plasma in mixtures of Ar and O2

We have measured the densities of 1s5 and 1s3 argon metastables as a function of the abundance of molecular oxygen in an inductively coupled plasma (ICP) in mixtures of Ar and O2. Laser absorption spectroscopy was used to determine the densities of the metastables. It was found that even small abundances of oxygen lead to large increases in metastable density, mostly due to the reduction in the electron number density, since electron-induced quenching determines the metastable density. At abundances higher than 7% to 15% for powers between 50 and 150W, quenching by oxygen molecules begins to dominate and the metastable density drops again.

Electron dynamics and frequency coupling in a radio-frequency capacitively biased planar coil inductively coupled plasma system

The electron dynamics in a planar coil inductively coupled plasma (ICP) system with a capacitively biased electrode is investigated using space and phase resolved optical emission spectroscopy. The two power source frequencies are exact multiple of each other and phase-locked. In this configuration, the system is investigated when the coil is operated in both E-mode and H-mode. The results show that in a phase synchronized RF biased ICP, the electrode bias power couples with the capacitive contribution of the coil, in both E-mode and H-modes, similar to dual-frequency capacitively coupled plasmas (2f-CCPs). It is also demonstrated that in H-mode, the phase between the electrode bias frequency and the ICP coil frequency influences the electron heating, similar to the electrical asymmetry effect in 2f-CCPs.

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.

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.

Survey of arsenic and its speciation in rice products such as breakfast cereals, rice crackers and Japanese rice condiments

Rice has been demonstrated to be one of the major contributors to arsenic (As) in human diets in addition to drinking water, but little is known about rice products as an additional source of As exposure. Rice products were analyzed for total As and a subset of samples were measured for arsenic speciation using high performance liquid chromatography interfaced with inductively coupled plasma-mass spectrometry (HPLC-ICP-MS). A wide range of rice products had total and inorganic arsenic levels that typified those found in rice grain including, crisped rice, puffed rice, rice crackers, rice noodles and a range of Japanese rice condiments as well as rice products targeted at the macrobiotic, vegan, lactose intolerant and gluten intolerance food market. Most As in rice products are inorganic As (75.2-90.1%). This study provides a wider appreciation of how inorganic arsenic derived from rice products enters the human diet. (C) 2008 Elsevier Ltd. All rights reserved.

Uptake, translocation and transformation of arsenate and arsenite in sunflower (Helianthus annuus):formation of arsenic-phytochelatin complexes during exposure to high arsenic concentrations

The aim of the study was to determine the time-dependent formation of arsenic-phytochelatin (As-PC) complexes in the roots, stems and leaves of an arsenic-nontolerant plant (Helianthus annuus) during exposure to 66 mol l(-1) arsenite (As(III)) or arsenate (As(V)). We used our previously developed method of simultaneous element-specific (inductively coupled plasma mass spectrometry, ICP-MS) and molecular-specific (electrospray-ionization mass spectrometry, ES-MS) detection systems interfaced with a suitable chromatographic column and eluent conditions, which enabled us to identify and quantify As-PC complexes directly. Roots of As-exposed H. annuus contained up to 14 different arsenic species, including the complex of arsenite with two (gamma-Glu-Cys)(2)-Gly molecules [As((III))-(PC(2))(2)], the newly identified monomethylarsonic phytochelatin-2 or (gamma-Glu-Cys)(2)-Gly CH(3)As (MA((III))-PC(2)) and at least eight not yet identified species. The complex of arsenite with (gamma-Glu-Cys)(3)-Gly (As((III))-PC(3)) and the complex of arsenite with glutathione (GSH) and (gamma-Glu-Cys)(2)-Gly (GS-As((III))-PC(2)) were present in all samples (roots, stems and leaves) taken from plants exposed to As. The GS-As((III))-PC(2) complex was the dominant complex after 1 h of exposure. As((III))-PC(3) became the predominant As-PC complex after 3 h, binding up to 40% of the As present in the exposed plants. No As-PC complexes were found in sap (mainly xylem sap from the root system), in contrast to roots, stems and leaves, which is unequivocal evidence that As-PC complexes are not involved in the translocation of As from root to leaves of H. annuus.

The nature of arsenic-phytochelatin complexes in Holcus lanatus and Pteris cretica

We have developed a method to extract and separate phytochelatins (PCs)-metal(loid) complexes using parallel metal(loid)-specific (inductively coupled plasma-mass spectrometry) and organic-specific (electrospray ionization-mass spectrometry) detection systems-and use it here to ascertain the nature of arsenic (As)-PC complexes in plant extracts. This study is the first unequivocal report, to our knowledge, of PC complex coordination chemistry in plant extracts for any metal or metalloid ion. The As-tolerant grass Holcus lanatus and the As hyperaccumulator Pteris cretica were used as model plants. In an in vitro experiment using a mixture of reduced glutathione (GS), PC(2), and PC(3), As preferred the formation of the arsenite [As((III))]-PC(3) complex over GS-As((III))-PC(2), As((III))-(GS)(3), As((III))-PC(2), or As((III))-(PC(2))(2) (GS: glutathione bound to arsenic via sulphur of cysteine). In H. lanatus, the As((III))-PC(3) complex was the dominant complex, although reduced glutathione, PC(2), and PC(3) were found in the extract. P. cretica only synthesizes PC(2) and forms dominantly the GS-As((III))-PC(2) complex. This is the first evidence, to our knowledge, for the existence of mixed glutathione-PC-metal(loid) complexes in plant tissues or in vitro. In both plant species, As is dominantly in non-bound inorganic forms, with 13% being present in PC complexes for H. lanatus and 1% in P. cretica.

Arsenic speciation in the earthworms Lumbricus rubellus and Dendrodrilus rubidus

Two species of earthworm, Lumbricus rubellus Hoffmeister and Dendrodrilus rubidus (Savigny) collected from an arsenic-contaminated mine spoil site and an uncontaminated site were investigated for total tissue arsenic concentrations and for arsenic compounds by liquid chromatography-mass spectrometry (LC-MS) and liquid chromatography-inductively coupled plasma-mass spectrometry (HPLC-ICP-MS). For L. rubellus, whole-body total tissue arsenic concentrations were 7.0 to 17.0 mg arsenic/ kg dry weight in uncontaminated soil and 162 to 566 mg arsenic/kg dry weight in contaminated soil. For D. rubidus, whole-body tissue concentrations were 2.0 to 5.0 mg arsenic/kg dry weight and 97 to 321 mg arsenic/kg dry weight, respectively. Arsenobetaine was the only organic arsenic species detected in both species of earthworms, with the remainder of the extractable arsenic being arsenate and arsenite. There was an increase in the proportion of arsenic present as arsenobetaine in the total arsenic burden. Lumbricus rubellus and D. rubidus have similar life styles, both being surface living and litter feeding. Arsenic speciation was found to be similar in both species for both uncontaminated and contaminated sites, with dose-dependent formation of arsenobetaine. When L. rubellus and D. rabidus from contaminated sites were incubated in arsenic-free soils, the total tissue burden of arsenic diminished. Initially, L. rubellus from the tolerant populations (from the contaminated site) eliminated arsenic in the first 7 d of exposure before accumulating arsenic in tissues, whereas nontolerant populations (from the uncontaminated site) accumulated arsenic linearly. The tolerant and nontolerant L. rubellus eliminated tissue arsenic linearly over 21 d when incubated in uncontaminated soil.

Arsenate causes differential acute toxicity to two P-deprived genotypes of rice seedlings (Oryza sativa L.)

Significant genotypic difference in response to arsenate toxicity in rice (Oryza sativa) was investigated in root elongation, arsenate uptake kinetics, physiological and biochemical response and arsenic (As) speciation. Uptake kinetics data showed that P-deprived genotype 94D-54 had a little higher As uptake than P-deprived 94D-64, but the difference was not large enough to cause acute toxicity in P-deprived 94D-54. There was no difference in tissue P concentrations between the two genotypes under P deficient conditions. In addition, arsenic speciation in plant tissues (using high performance liquid chromatography-inductively coupled plasma mass spectrometry) was not different between P pretreatments and between genotypes. P-deprived genotype 94D-54 suffered much higher stress induced by arsenate toxicity than P-deprived genotype 94D-64, in terms of lipid peroxidation, tissue H2O2 concentrations and exosmosis of K, P and As. However, P-deprived 94D-54 also had higher overproduction of enzymatic antioxidants (with higher GPX, SOD, CAT) and NPT (non-protein thiols) than P-deprived 94D-64. It appeared that, the higher sensitivity of P-deprived 94D-54 to arsenate toxicity might cause the overproduction of NPT, thus leading to the depletion of GSH and to the accumulation of H2O2. The differential sensitivity of the two genotypes has major implications for breeding rice for As affected paddy soil.

Two-dimensional images of dissolved sulfide and metals in anoxic sediments by a novel diffusive gradients in thin film probe and optical scanning techniques

A novel diffusive gradients in thin film probe developed comprises diffusive gel layer of silver iodide (AgI) and a back-up Microchelex resin gel layer. 2D high-resolution images of sulfide and trace metals were determined respectively on the AgI gel by densitometric analysis and on the Microchelex resin layer with laser-ablation-inductively-coupled plasma mass spectrometry (LA-ICP-MS).We investigated the validity of the analytical procedures used for the determination of sulfide and trace metals. We found low relative standard deviations on replicate measurements, linear trace-metal calibration curves between the LA-ICP-MS signal and the true trace-metal concentration in the resin gel, and a good agreement of the sulfide results obtained with the AgI resin gel and with other analytical methods. The method was applied on anoxic sediment pore waters in an estuarine and marine system. Simultaneous remobilization of sulfide and trace metals was observed in the marine sediment.