Studies of Brisbane municipal water quality using Inductively Coupled Plasma - Mass Spectrometry and Chemometrics

This research established innovative methods and a predictive model to evaluate water quality using the trace element and heavy metal concentrations of drinking water from the greater Brisbane area. Significantly, the combined use of Inductively Coupled Plasma - Mass Spectrometry and Chemometrics can be used worldwide to provide comprehensive, rapid and affordable analyses of elements in drinking water that can have a considerable impact on human health.

Determination of refractive and volatile elements in sediment using laser ablation inductively coupled plasma mass spectrometry

Wet-milling protocol was employed to produce pressed powder tablets with excellent cohesion and homogeneity suitable for laser ablation (LA) analysis of volatile and refractive elements in sediment. The influence of sample preparation on analytical performance was also investigated, including sample homogeneity, accuracy and limit of detection. Milling in volatile solvent for 40 min ensured sample is well mixed and could reasonably recover both volatile (Hg) and refractive (Zr) elements. With the exception of Cr (−52%) and Nb (+26%) major, minor and trace elements in STSD-1 and MESS-3 could be analysed within ±20% of the certified values. Comparison of the method with total digestion method using HF was tested by analysing 10 different sediment samples. The laser method recovers significantly higher amounts of analytes such as Ag, Cd, Sn and Sn than the total digestion method making it a more robust method for elements across the periodic table. LA-ICP-MS also eliminates the interferences from chemical reagents as well as the health and safety risks associated with digestion processes. Therefore, it can be considered as an enhanced method for the analysis of heterogeneous matrices such as river sediments.

Fingerprinting of complex mixtures with the use of high performance liquid chromatography, inductively coupled plasma atomic emission spectroscopy and chemometrics

The molecular and metal profile fingerprints were obtained from a complex substance, Atractylis chinensis DC—a traditional Chinese medicine (TCM), with the use of the high performance liquid chromatography (HPLC) and inductively coupled plasma atomic emission spectroscopy (ICP-AES) techniques. This substance was used in this work as an example of a complex biological material, which has found application as a TCM. Such TCM samples are traditionally processed by the Bran, Cut, Fried and Swill methods, and were collected from five provinces in China. The data matrices obtained from the two types of analysis produced two principal component biplots, which showed that the HPLC fingerprint data were discriminated on the basis of the methods for processing the raw TCM, while the metal analysis grouped according to the geographical origin. When the two data matrices were combined into a one two-way matrix, the resulting biplot showed a clear separation on the basis of the HPLC fingerprints. Importantly, within each different grouping the objects separated according to their geographical origin, and they ranked approximately in the same order in each group. This result suggested that by using such an approach, it is possible to derive improved characterisation of the complex TCM materials on the basis of the two kinds of analytical data. In addition, two supervised pattern recognition methods, K-nearest neighbors (KNNs) method, and linear discriminant analysis (LDA), were successfully applied to the individual data matrices—thus, supporting the PCA approach.

Inductively coupled plasma-assisted RF magnetron sputtering deposition of boron-doped microcrystalline Si films

An innovative custom-designed inductively coupled plasma-assisted RF magnetron sputtering deposition system has been developed to synthesize B-doped microcrystalline silicon thin films using a pure boron sputtering target in a reactive silane and argon gas mixture. Films were deposited using different boron target powers ranging from 0 to 350 W at a substrate temperature of 250 °C. The effect of the boron target power on the structural and electrical properties of the synthesized films was extensively investigated using X-ray diffraction, Raman spectroscopy, scanning electron microscopy, and Hall-effect system. It is shown that, with an initial increase of the boron target power from 0 to 300 W, the structural and electrical properties of the B-doped microcrystalline films are improved. However, when the target power is increased too much (e.g. to 350 W), these properties become slightly worse. The variation of the structural and electrical properties of the synthesized B-doped microcrystalline thin films is related to the incorporation of boron atoms during the crystallization and doping of silicon in the inductively coupled plasma-based process. This work is particularly relevant to the microcrystalline silicon-based p-i-n junction solar cells.

Inductively coupled plasma-assisted RF magnetron sputtering deposition of highly uniform SiC nanoislanded films

A new deposition technique-inductively coupled plasma-assisted RF magnetron sputtering has been developed to fabricate SiC nanoislanded films. In this system, the plasma production and magnetron sputtering can be controlled independently during the discharge. The deposited SiC nanoislanded films are highly uniform, have excellent stoichiometry, have a typical size of 10-45 nm, and contain small (∼ 6 nm) cubic SiC nanocrystallites embedded in an amorphous SiC matrix.

Influence of hydrogen dilution on the growth of nanocrystalline silicon carbide films by low-frequency inductively coupled plasma chemical vapor deposition

Nanocrystalline silicon carbide (nc-SiC) films are prepared by low-frequency inductively coupled plasma chemical vapor deposition from feedstock gases silane and methane diluted with hydrogen at a substrate temperature of 500 °C. The effect of different hydrogen dilution ratios X [hydrogen flow (sccm) / silane + methane flow (sccm)] on the growth of nc-SiC films is investigated by X-ray diffraction, scanning electron microscopy, Fourier transform infrared (FTIR) spectroscopy, and X-ray photoelectron spectroscopy (XPS). At a low hydrogen dilution ratio X, cubic silicon carbide is the main crystal phase; whereas at a high hydrogen dilution ratio X, hexagonal silicon carbide is the main crystal phase. The SiC crystal phase transformation may be explained by the different surface mobility of reactive Si-based and C-based radicals deposited at different hydrogen dilution ratios X. The FTIR and XPS analyses show that the Si-C bonds are the main bonds in the films and elemental composition of SiC is nearly stoichiometric with almost equal share of silicon and carbon atoms.

Low-frequency, high-density, inductively coupled plasma sources : operation and applications

Operation regimes, plasma parameters, and applications of the low-frequency (∼500 kHz) inductively coupled plasma (ICP) sources with a planar external coil are investigated. It is shown that highly uniform, high-density (ne∼9×1012 cm-3) plasmas can be produced in low-pressure argon discharges with moderate rf powers. The low-frequency ICP sources operate in either electrostatic (E) or electromagnetic (H) regimes in a wide pressure range without any Faraday shield or an external multipolar magnetic confinement, and exhibit high power transfer efficiency, and low circuit loss. In the H mode, the ICP features high level of uniformity over large processing areas and volumes, low electron temperatures, and plasma potentials. The low-density, highly uniform over the cross-section, plasmas with high electron temperatures and plasma and sheath potentials are characteristic to the electrostatic regime. Both operation regimes offer great potential for various plasma processing applications. As examples, the efficiency of the low-frequency ICP for steel nitriding and plasma-enhanced chemical vapor deposition of hydrogenated diamond-like carbon (DLC) films, is demonstrated. It appears possible to achieve very high nitriding rates and dramatically increase micro-hardness and wear resistance of the AISI 304 stainless steel. It is also shown that the deposition rates and mechanical properties of the DLC films can be efficiently controlled by selecting the discharge operating regime.

E and H regimes of plasma enhanced chemical vapor deposition of diamond-like carbon film in low frequency inductively coupled plasma reactor

This paper reports on the efficient deposition of hydrogenated diamond-like carbon (DLC) film in a plasma reactor that features both the capacitively and inductively coupled operation regimes. The hydrogenated DLC films have been prepared on silicon wafers using a low-frequency (500 kHz) inductively coupled plasma (ICP) chemical vapor deposition (CVD) system. At low RF powers, the system operates as an asymmetric capacitively coupled plasma source, and the film deposition process is undertaken in the electrostatic (E) discharge regime. Above the mode transition threshold, the high-density inductively coupled plasma is produced in the electromagnetic (H) discharge regime. It has been shown that the deposition rate and hardness of the DLC film are much higher in the H-mode deposition regime. For a 2.66-Pa H-mode CH4 + Ar gas mixture discharge, the deposited DLC film exhibits a mechanical hardness of 18 GPa, Young's modulus of 170 GPa, and compressive stress of 1.3 GPa.

Hysteresis and mode transitions in a low-frequency inductively coupled plasma

The performance of the 500 KHz planar-coil inductively coupled plasma source was studied. The global electrical characteristics of the discharge, distributions of the induced electromagnetic fields, plasma density, potential, and electron temperature were investigated. Achieved high plasma density and low electron temperature implied that the studied plasma source was promising for industrial applications.

New insights into Crustal Contributions to Large-volume Rhyolite Generation in the Mid-Tertiary Sierra Madre Occidental Province, Mexico, revealed by U Pb Geochronology

Voluminous (≥3·9 × 105 km3), prolonged (∼18 Myr) explosive silicic volcanism makes the mid-Tertiary Sierra Madre Occidental province of Mexico one of the largest intact silicic volcanic provinces known. Previous models have proposed an assimilation–fractional crystallization origin for the rhyolites involving closed-system fractional crystallization from crustally contaminated andesitic parental magmas, with <20% crustal contributions. The lack of isotopic variation among the lower crustal xenoliths inferred to represent the crustal contaminants and coeval Sierra Madre Occidental rhyolite and basaltic andesite to andesite volcanic rocks has constrained interpretations for larger crustal contributions. Here, we use zircon age populations as probes to assess crustal involvement in Sierra Madre Occidental silicic magmatism. Laser ablation-inductively coupled plasma-mass spectrometry analyses of zircons from rhyolitic ignimbrites from the northeastern and southwestern sectors of the province yield U–Pb ages that show significant age discrepancies of 1–4 Myr compared with previously determined K/Ar and 40Ar/39Ar ages from the same ignimbrites; the age differences are greater than the errors attributable to analytical uncertainty. Zircon xenocrysts with new overgrowths in the Late Eocene to earliest Oligocene rhyolite ignimbrites from the northeastern sector provide direct evidence for some involvement of Proterozoic crustal materials, and, potentially more importantly, the derivation of zircon from Mesozoic and Eocene age, isotopically primitive, subduction-related igneous basement. The youngest rhyolitic ignimbrites from the southwestern sector show even stronger evidence for inheritance in the age spectra, but lack old inherited zircon (i.e. Eocene or older). Instead, these Early Miocene ignimbrites are dominated by antecrystic zircons, representing >33 to ∼100% of the dated population; most antecrysts range in age between ∼20 and 32 Ma. A sub-population of the antecrystic zircons is chemically distinct in terms of their high U (>1000 ppm to 1·3 wt %) and heavy REE contents; these are not present in the Oligocene ignimbrites in the northeastern sector of the Sierra Madre Occidental. The combination of antecryst zircon U–Pb ages and chemistry suggests that much of the zircon in the youngest rhyolites was derived by remelting of partially molten to solidified igneous rocks formed during preceding phases of Sierra Madre Occidental volcanism. Strong Zr undersaturation, and estimations for very rapid dissolution rates of entrained zircons, preclude coeval mafic magmas being parental to the rhyolite magmas by a process of lower crustal assimilation followed by closed-system crystal fractionation as interpreted in previous studies of the Sierra Madre Occidental rhyolites. Mafic magmas were more probably important in providing a long-lived heat and material flux into the crust, resulting in the remelting and recycling of older crust and newly formed igneous materials related to Sierra Madre Occidental magmatism.

Discriminating stromatolite formation modes using rare earth element geochemistry: Trapping and binding versus in situ precipitation of stromatolites from the Neoproterozoic Bitter Springs Formation, Northern Territory, Australia

Stromatolites consist primarily of trapped and bound ambient sediment and/or authigenic mineral precipitates, but discrimination of the two constituents is difficult where stromatolites have a fine texture. We used laser ablation-inductively coupled plasma-mass spectrometry to measure trace element (rare earth element – REE, Y and Th) concentrations in both stromatolites (domical and branched) and closely associated particulate carbonate sediment in interspaces (spaces between columns or branches) from bioherms within the Neoproterozoic Bitter Springs Formation, central Australia. Our high resolution sampling allows discrimination of shale-normalised REE patterns between carbonate in stromatolites and immediately adjacent, fine-grained ambient particulate carbonate sediment from interspaces. Whereas all samples show similar negative La and Ce anomalies, positive Gd anomalies and chondritic Y/Ho ratios, the stromatolites and non-stromatolite sediment are distinguishable on the basis of consistently elevated light REEs (LREEs) in the stromatolitic laminae and relatively depleted LREEs in the particulate sediment samples. Additionally, concentrations of the lithophile element Th are higher in ambient sediment samples than in stromatolites, consistent with accumulation of some fine siliciclastic detrital material in the ambient sediment but a near absence in the stromatolites. These findings are consistent with the stromatolites consisting dominantly of in situ carbonate precipitates rather than trapped and bound ambient sediment. Hence, high resolution trace element (REE + Y, Th) geochemistry can discriminate fine-grained carbonates in these stromatolites from coeval non-stromatolitic carbonate sediment and demonstrates that the sampled stromatolites formed primarily from in situ precipitation, presumably within microbial mats/biofilms, rather than by trapping and binding of ambient sediment. Identification of the source of fine carbonate in stromatolites is significant, because if it is not too heavily contaminated by trapped ambient sediment, it may contain geochemical biosignatures and/or direct evidence of the local water chemistry in which the precipitates formed.

Trace-element modeling of the magmatic evolution of rare-earth-rich carbonatite from the Miaoya deposit, Central China

Carbonatites are known to contain the highest concentrations of rare-earth elements (REE) among all igneous rocks. The REE distribution of carbonatites is commonly believed to be controlled by that of the rock forming Ca minerals (i.e., calcite, dolomite, and ankerite) and apatite because of their high modal content and tolerance for the substitution of Ca by light REE (LREE). Contrary to this conjecture, calcite from the Miaoya carbonatite (China), analyzed in situ by laser-ablation inductively-coupled-plasma mass-spectrometry, is characterized by low REE contents (100–260 ppm) and relatively !at chondrite-normalized REE distribution patterns [average (La/Yb)CN=1.6]. The carbonatite contains abundant REE-rich minerals, including monazite and !uorapatite, both precipitated earlier than the REE-poor calcite, and REE-fluorocarbonates that postdated the calcite. Hydrothermal REE-bearing !uorite and barite veins are not observed at Miaoya. The textural and analytical evidence indicates that the initially high concentrations of REE and P in the carbonatitic magma facilitated early precipitation of REE-rich phosphates. Subsequent crystallization of REE-poor calcite led to enrichment of the residual liquid in REE, particularly LREE. This implies that REE are generally incompatible with respect to calcite and the calcite/melt partition coefficients for heavy REE (HREE) are significantly greater than those for LREE. Precipitation of REE-fluorocarbonates late in the evolutionary history resulted in depletion of the residual liquid in LREE, as manifested by the development of HREE-enriched late-stage calcite [(La/Yb)CN=0.7] in syenites associated with the carbonatite. The observed variations of REE distribution between calcite and whole rocks are interpreted to arise from multistage fractional crystallization (phosphates!calcite!REE-!uorocarbonates) from an initially REE-rich carbonatitic liquid.

Combining HPLC-DAD and ICP-MS data for improved analysis of complex samples: Classification of the root samples from Cortex moutan

A combined data matrix consisting of high performance liquid chromatography–diode array detector (HPLC–DAD) and inductively coupled plasma-mass spectrometry (ICP-MS) measurements of samples from the plant roots of the Cortex moutan (CM), produced much better classification and prediction results in comparison with those obtained from either of the individual data sets. The HPLC peaks (organic components) of the CM samples, and the ICP-MS measurements (trace metal elements) were investigated with the use of principal component analysis (PCA) and the linear discriminant analysis (LDA) methods of data analysis; essentially, qualitative results suggested that discrimination of the CM samples from three different provinces was possible with the combined matrix producing best results. Another three methods, K-nearest neighbor (KNN), back-propagation artificial neural network (BP-ANN) and least squares support vector machines (LS-SVM) were applied for the classification and prediction of the samples. Again, the combined data matrix analyzed by the KNN method produced best results (100% correct; prediction set data). Additionally, multiple linear regression (MLR) was utilized to explore any relationship between the organic constituents and the metal elements of the CM samples; the extracted linear regression equations showed that the essential metals as well as some metallic pollutants were related to the organic compounds on the basis of their concentrations