High Resolution Inductively Coupled Plasma Mass Spectrometer Research Articles

Automated determination of gallium in seawater using seaFAST pre-concentration and high-resolution inductively-coupled plasma mass spectrometry

There has been increased interest in dissolved gallium (Ga) in natural waters due to its long residence time and its usefulness in tracking water masses; however, current analytical approaches are time consuming and labor intensive (e.g., magnesium hydroxide co-precipitation method, (Mg(OH)2)) or have concerns such as carryover and sample recovery (automated resin column extraction). Ocean observing programs, such as GEOTRACES, recover hundreds of samples per expedition. There are both logistical (sample volume) and analytical (person-hour) demands to economically collect and analyze Ga. We present an automated isotope dilution method (using 99.8% enriched 71Ga) to determine Ga in seawater utilizing commercially available equipment while addressing the challenges of a) sample volume and sample pre-concentration factor, b) instrumental interferences, c) sample-sample carryover, d) sample recovery variability, and e) improving sample detection limits, accuracy and precision. A seaFAST SC-4DXS pico (Elemental Scientific, Inc.; ESI) was used to pre-concentrate 20 mL of sample on a Nobias PA1 resin column 67-fold before analysis in medium resolution on a ThermoFisher high-resolution inductively-coupled plasma mass spectrometer (HR-ICP-MS) equipped with an APEX Q FAST enabled spray chamber (ESI) to increase signal intensity and decrease instrument interferences. The new automated seaFAST method reproduced Ga concentrations determined by the Mg(OH)2 method, but with greater precision (RSD <4%) and a lower detection limit (0.10 pmol L−1). This method is ideal for high throughput applications and can be easily implemented using commercially available equipment.

Lanthanoid analysis in seawater by seaFAST-SP3™ system in off-line mode and magnetic sector high-resolution inductively coupled plasma source mass spectrometer

Analysis of lanthanoids in seawater is challenging due to the complex matrix (∼35 g L−1 TDS) and low dissolved concentrations (in ng L−1). A 4-step strict analytical protocol and state-of-the-art technology were implemented and validated in this study. The 4-steps method involves the 1) sample filtration and acidification (pH<2); 2) pre-concentration by the matrix separation system, 3) off-line injection of the eluted sample; and 4) determination of lanthanoids by high-resolution inductively coupled plasma mass spectrometer (HR-ICP-MS). Since there are no certified values for lanthanoids in seawater are available, the method validation was done by analyzing SLEW-3 (estuarine water reference samples) and comparing with other reports and artificial seawater (100 ng L−1 lanthanoid multi-element standard solutions). SLEW-3 recovery varied from 78.6% to 106% and in artificial samples it ranged from 87 to 110%. Low recovery can be explained by complex organic in seawater, because the UV oxidation was not performed in the acidified samples. The variation was ≤10%, except for Gd, Tb, and Yb (11–13.75%). Blanks varied between 0.01 and 0.07 ng L−1, except for La and Ce (0.13–0.21 ng L−1). Blanks represent <5% SLEW-3 values and <1% synthetic seawater. The procedural detection limit varied from 0.01 to 0.03 ng L−1.•Lanthanoids as geochemical tracers in seawaters•A 4-step strict analytical protocol and state-of-the-art technology for lanthanoids analyses in seawaters•Sample pre-concentration system for matrix separation for the detection of ultra-low lanthanoids levels

Geochemistry and mineralogy of coal mine overburden (waste): A study towards their environmental implications

Open-cast mining of coal generates waste material, including rock and soil with different minerals, and traditionally dumped as waste over the valuable lands worldwide. Overburden (OB) is devoid of actual soil characteristics, low micro and macronutrient content, and a sufficient amount of rare earth elements, silicate, sulphate, and clay minerals. This study aimed to determine the geochemistry and mineralogy of OB samples collected from Makum coalfield, Margherita of Northeast (NE) India. The geochemical and mineralogical analyses of overburden (OB) were carried out by using X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), High resolution-inductively coupled plasma mass spectrometer (HR-ICP-MS), Field-emission scanning electron microscopy (FE-SEM) techniques. This study shows potentially hazardous elements (PHEs), including Pb, Co Cu, Cr, Ni, and Zn, and their association with minerals observed in OB samples. The major oxides (SiO2, Al2O3, Fe2O3, MgO, CaO, K2O, and Na2O) are present in all the overburden samples analyzed by the X-ray fluorescence (XRF) technique. Various minerals such as quartz, kaolinite, gypsum, melanterite, rozenite, hematite, and pyrite were identified. The overburden samples contain considerable amounts of rare earth elements and yttrium (REY; as received basis) with an average of 26.3 (ppm). The presence of abundant minerals and REY opens up a new avenue for the gainful and sustainable utilization of such waste materials.

Hydrogeochemistry as a Tool for Platinum Group Element (PGE) Exploration — A Case Study from Sittampundi Anorthosite Complex, Southern India

The use of surface and ground water for exploration of platinum group elements (PGE) has been studied in the Sittampundi anorthosite complex, Tamil Nadu, south India, where PGE mineralization is known to occur in basic and ultrabasic rocks. Groundwater interacting with mineralized rocks creates a geochemical signature which can be linked to the occurrence and distribution of PGE, especially Pd because of its leachability and relatively high mobility in aqueous environment. Forty surface and ground water samples collected from the area were analyzed for PGE and several other major, minor and trace elements using high resolution inductively coupled plasma mass spectrometer (HR-ICP-MS) to investigate the distribution patterns of individual PGE and other elements for the purpose of evaluating the utility of hydrogeochemistry as a tool for PGE exploration studies. Ground and surface water chemistry reflected the chemical composition of host lithology, particularly the basic-ultrabasic rocks of the region, with the dispersion of PGE and high anomalous concentrations of Pd, Ru and Rh along with several other metals such as Zn, V, Cr and Ni indicating PGE mineralization. The results of this study suggest that groundwater chemistry has significant potential as a PGE exploration tool with advantages such as rapid and low-cost sampling, high contrast anomalies and a uniform sampling medium.

Trace element concentrations in feathers and blood of Northern goshawk (Accipiter gentilis) nestlings from Norway and Spain

Information on trace element pollution in the terrestrial environment and its biota is limited compared to the marine environment. In the present study, we collected body feathers and blood of 37 Northern goshawk (Accipiter gentilis) nestlings from Tromsø (northern Norway), Trondheim (central Norway), and Murcia (southeastern Spain) to study regional exposure, hypothesizing the potential health risks of metals and other trace elements. Blood and body feathers were analyzed by a high resolution inductively coupled plasma mass spectrometer (HR-ICP-MS) for aluminum (Al), nickel (Ni), copper (Cu), zinc (Zn), arsenic (As), selenium (Se), cadmium (Cd), mercury (Hg) and lead (Pb). The influence of regional differences, urbanization and agricultural land usage in proximity to the nesting Northern goshawks was investigated using particular spatial analysis techniques. Most trace elements were detected below literature blood toxicity thresholds, except for elevated concentrations (mean ± SD µgml−1 ww) found for Zn (5.4 ± 1.5), Cd (0.00023 ± 0.0002), and Hg (0.021 ± 0.01). Corresponding mean concentrations in feathers (mean ± SD µgg−1 dw) were 82.0 ± 12.4, 0.0018 ± 0.002, and 0.26 ± 0.2 for Zn, Cd and Hg respectively. Multiple linear regressions indicated region was a significant factor influencing Al, Zn, Se and Hg feather concentrations. Blood Cd and Hg concentrations were significantly influenced by agricultural land cover. Urbanization did not have a significant impact on trace element concentrations in either blood or feathers. Overall metal and trace element levels do not indicate a high risk for toxic effects in the nestlings. Levels of Cd in Tromsø and Hg in Trondheim were however above sub-lethal toxic threshold levels. For holistic risk assessment purposes it is important that the concentrations found in the nestlings of this study indicate that terrestrial raptors are exposed to various trace elements.

Evaluation of Uranium, Thorium and Some Metal Elements in Rocks by HR-ICP-MS and LIBS

The aim of the work was to assess the mineral radioactive materials and the some metal elements using High Resolution Inductively Coupled Plasma Mass spectrometer (HR-ICP-MS) and laser induced breakdown spectroscopy. The LIBS was used to prove the ability to provide on-line analyses for raw ores in field conditions for uranium and elemental analysis for thorium, calcium, iron and zinc detections. A comprehensive study was conducted to determine the concentration of the elements in rock samples to explain the conditions for exploration radioactive mineralization in different selected areas in Gattar Mountain in Egypt with comparison to rock monazite sample. The HR-ICP-MS at Nuclear Research Centre (NRC), Inshas, Egypt was used to measure the isotopic uranium concentration that to be (0.43 ± 0.11-0.63 ± 0.13) % and thorium (0.02 ± 0.001- 0.05 ± 0.001) % in the rocks. Consequently, the emission spectra of LIBS on rock samples in the range 402.46 – 460.57nm was obtained. The high accuracy measurement of HR-ICP-MS for elements concentration and the high resolution of wavelength selections of LIBS analytical technique for uranium that is improved a significant reduction of mineral processing and energy costs of uranium, thorium and metals mining. Accordingly, the assessment of the uranium and thorium concentration in the Gattar rock is greatly recommended for economic exploration and extraction processing of nuclear materials recovery.

Effect of Namomaterials on Heavy Metal Transport in Alkaline Soil

A high level of heavy metals in soil would negatively impact human health if these metals are consumed by humans through the food chain. The effect of nanomaterials, including SiO2-Al2O3-Fe2O3, on heavy metals in alkaline soil was studied through simulating leaching in the soil column. Nanomaterials that weighed 4%, 6%, and 10% of the soil mass were added to a soil column in which garlic was planted. Leaching tests were conducted. Heavy metals in the soil leachate of different soil depths and different parts of the plant planted in the soil column were determined using a high-resolution inductively coupled plasma mass spectrometer (HR-ICP-MS). The results indicated that the migration of heavy metals through alkaline soil was inhibited. In the test with nanomaterials of 4% soil mass, 63% Cu, 79% Cd, 68% Pb, 89% Zn, and 76% Ni were decreased compared to the control. When the addition of nanomaterials was up to 6% of soil mass, 82% Cu, 92% Cd, 76% Pb, 91% Zn, and 88% Ni were reduced, respectively. No additional apparent results were observed with more nanomaterials added to the soil column. The nanomaterials effectively prevented heavy metal migration, especially inhibiting heavy metal migration downward. Nanomaterials will be promising in subsequent studies.

Precise age determination of a single plutonium particle using inductively coupled plasma mass spectrometer

Abstract Age-dating of single plutonium oxide particles ∼ 1 µm in diameter was demonstrated using eight particles. For this demonstration, the particles were prepared from a standard reference material SRM-947 that had been stored for 3.9 years since the last Pu purification. The Pu particles were separately dissolved, and Am and Pu were chemically separated from the solution via anion-exchange chromatography. The isotope ratios of Am and Pu in the eluted fractions were measured using a high-resolution inductively coupled plasma mass spectrometer (HR-ICP-MS). The precision and accuracy of the Pu age were improved through the addition of an 243Am spike to the sample solutions and by the trace chemical separation of Pu and Am. The determined age in this work was in good agreement with the expected age with high accuracy (deviation: 7.1–105 days) and precision (uncertainty: 0.16–0.5 years (k = 1)). These results indicate that a combination of ICP-MS and chemical separation after spiking with 243Am provides an effective tool for the analysis of environmental samples collected during nuclear safeguard inspections.

Asymmetric flow field-flow fractionation as a new approach to analyse iron-(hydr)oxide nanoparticles in soil extracts

Iron-(hydr)oxide nanoparticles are important for the sequestration of organic carbon because of their small size and consequently large specific surface area. Therefore, there is an increasing interest in analytical techniques such as asymmetric flow field-flow fractionation (AF4) that allow for a direct measurement of the size distribution of nanoparticles (1–150nm). We used AF4 coupled to high-resolution inductively coupled plasma mass spectrometer (HR-ICP-MS) to analyse the size distribution and elemental composition of nanoparticles dispersed from three horizons of a podzol. We tested three extractants for the amount of dispersed Fe-(hydr)oxide nanoparticles. No Fe-(hydr)oxide nanoparticles were dispersed in 5mM NaCl. In a 1mM NaOH extraction (pH9.0), the amount of Fe dispersed in the form of Fe-(hydr)oxide nanoparticles amounted to 0.2–0.8gkg−1, which corresponded to 2–13% of the Fe content as extracted with ammonium oxalate (Fe-ox). Pyrophosphate was found to be the most effective extractant for Fe-(hydr)oxide nanoparticles and extracted 1.0–4.7gkg−1 Fe as Fe-(hydr)oxide nanoparticles, corresponding to 16–47% of the Fe-ox content. These Fe-(hydr)oxide nanoparticles were 2–20nm in size and maximum concentrations were found at a particle diameter of 5nm. The dispersion of Fe-(hydr)oxide nanoparticles in pyrophosphate coincided with the extraction of a large fraction of the soil organic carbon content (55–69%) which shows that dispersion of organo-mineral aggregates results in the release of Fe-(hydr)oxide nanoparticles from the soil. The amount of Fe-(hydr)oxide nanoparticles extracted from the soil did not increase after ultrasonic treatment of the pyrophosphate suspension. Since not all Fe-(hydr)oxides can be dispersed from the soil as primary particles, AF4 cannot be used as a tool to analyse the specific surface area of the Fe-(hydr)oxides in the soil. Instead, AF4 should be considered as a complementary technique providing a direct measurement for the size of the Fe-(hydr)oxide nanoparticles in soil extracts.

Blood and urine metal ion levels in young and active patients after Birmingham hip resurfacing arthroplasty

This is a longitudinal study of the daily urinary output and the concentrations in whole blood of cobalt and chromium in patients with metal-on-metal resurfacings over a period of four years. Twelve-hour urine collections and whole blood specimens were collected before and periodically after a Birmingham hip resurfacing in 26 patients. All ion analyses were carried out using a high-resolution inductively-coupled plasma mass spectrometer. Clinical and radiological assessment, hip function scoring and activity level assessment revealed excellent hip function. There was a significant early increase in urinary metal output, reaching a peak at six months for cobalt and one year for chromium post-operatively. There was thereafter a steady decrease in the median urinary output of cobalt over the following three years, although the differences are not statistically significant. The mean whole blood levels of cobalt and chromium also showed a significant increase between the pre-operative and one-year post-operative periods. The blood levels then decreased to a lower level at four years, compared with the one-year levels. This late reduction was statistically significant for chromium but not for cobalt. The effects of systemic metal ion exposure in patients with metal-on-metal resurfacing arthroplasties continue to be a matter of concern. The levels in this study provide a baseline against which the in vivo wear performance of newer bearings can be compared.

Substrate Effect on Plasma Clean Efficiency in Plasma Enhanced Chemical Vapor Deposition System

The plasma clean in a plasma-enhanced chemical vapor deposition (PECVD) system plays an important role to ensure the same chamber condition after numerous film depositions. The periodic and applicable plasma clean in deposition chamber also increases wafer yield due to less defect produced during the deposition process. In this study, the plasma clean rate (PCR) of silicon oxide is investigated after the silicon nitride deposited on Cu and silicon oxide substrates by remote plasma system (RPS), respectively. The experimental results show that the PCR drastically decreases with Cu substrate compared to that with silicon oxide substrate after numerous silicon nitride depositions. To understand the substrate effect on PCR, the surface element analysis and bonding configuration are executed by X-ray photoelectron spectroscopy (XPS). The high resolution inductively coupled plasma mass spectrometer (HR-ICP-MS) is used to analyze microelement of metal ions on the surface of shower head in the PECVD chamber. According to Cu substrate, the results show that micro Cu ion and theCuOxbonding can be detected on the surface of shower head. The Cu ion contamination might grab the fluorine radicals produced byNF3ddissociation in the RPS and that induces the drastic decrease on PCR.

Complete Trace Elemental Characterisation of Granitoid (USGS G‐2, GSP‐2) Reference Materials by High Resolution Inductively Coupled Plasma‐Mass Spectrometry

The United States Geological Survey granitic and granodioritic reference materials G‐2 and GSP‐2 were decomposed in high‐pressure bombs using both HF‐HNO3 and HF‐HNO3‐HClO4 in order to evaluate the feasibility of characterising the entire suite of geologically relevant trace elements through direct analysis with a high‐resolution inductively coupled plasma‐mass spectrometer (HR‐ICP‐MS). The digested samples were diluted to the appropriate levels and analysed at low, medium and high resolution depending on the required sensitivity and potential interferences for each element. Memory effects during analysis of the high field strength elements (HFSE) were negligible when analysed using an all‐Teflon, uncooled sample introduction system and combined with adequate wash times with 4% v/v aqua regia + 0.5% v/v HF between samples. The concentration of the remaining lithophile elements was determined with a conventional, cooled, Scott‐type spray chamber using a wash solution of 1% v/v HNO3. Total procedural blanks contributed between 0.01 to 0.5% to final sample concentrations and blank subtractions were typically unnecessary. Abundances for Li, Hf, Ba, Zr, Ga, Rb, Sr, La, Ce, Th and U were systematically higher, while those for the heavy rare earth elements (HREEs), Cu and Y were systematically lower in this study compared to USGS values for G‐2 and GSP‐2. This is likely to be related to, respectively, higher recoveries from more efficient digestion of refractory phases (i.e., zircon, tourmaline), and better resolution of interferences when using a HR‐ICP‐MS. Sample digestion experiments also showed that perchloric acid digestion in high pressure bombs resulted in superior recoveries and better precision for the bulk of the trace elements analysed. The concentration of the remaining elements overlapped within uncertainty with recommended reference values and with values determined in other studies using isotope‐dilution TIMS, ICP‐MS and XRF. Concentrations for the elements Cd, Sn, Sb, Ta, Bi, Tb, Ni and Mo are also reported for G‐2 and GSP‐2 reference materials. Our study shows therefore that it is feasible to determine thirty‐nine geologically relevant trace elements accurately and directly in granitoid sample digests when using a HR‐ICP‐MS, thereby negating the need for ion exchange or isotopic spiking.

Multi-elemental concentrations in tissues of Japanese common squid (Todarodes pacificus).

Forty-five elements were determined in mantle muscle and liver of juvenile Japanese common squid, Todarodes pacificus, collected from three locations in and near Japanese coasts, using a high-resolution inductively coupled plasma mass spectrometer (HR-ICP-MS) and an inductively coupled plasma atomic emission spectroscope (ICP-AES). Multivariate statistical techniques were applied to discriminate populations of squids from these three locations by treating absolute and relative concentrations of trace elements. Significant differences were found in the concentrations of elements, particularly for some alkaline and alkaline earth elements in the muscle and liver and for some 3d transition elements in the liver of three groups of squids. Squids from the Pacific Ocean could be distinguished from those of the Sea of Japan by discriminant function analysis of elemental concentrations. Based on the analysis, the squids collected from the Nemuro Strait in Japan were predicted to belong to those from the Sea of Japan. Elemental concentrations and discriminant function analysis can be used to identify subpopulations and migratory routes of squids.

Rapid Separation of Plutonium in Environmental Samples Using an Anion Exchange Resin Disk

A rapid analytical method of Pu in environmental samples by alpha-ray spectrometry and high-resolution inductively coupled plasma mass spectrometer (HR-ICP-MS) using a 3M Empore™ anion exchange resin disk for solid phase extraction has been developed. A trace amount of Pu was quantitatively adsorbed with an Empore™ anion exchange resin disk (47 mm diam.) at a flow rate of 150–200 ml/min from 8M HNO3 sample solution. The disk was washed with 10 ml of 8M HNO3 and 12 ml of 9M HCl and then the Pu was quantitatively eluted with 15 ml of 1M HNO3/0.03M ascorbic acid solution. The time needed to separate Pu from the sample solution with the present method was about 20 minutes. The separated Pu was determined with alpha-ray spectrometry and HR-ICP-MS. The present method was applied to the determination of Pu in the certified reference material (IAEA-135) and the environmental soil sample. The analytical results were almost in good agreement with the literature values.

Some investigations on stability and precision of an HR-ICP-MS

Over a period of 4 months long- and short time stability (precision) of a high resolution inductively coupled plasma mass spectrometer (HR-ICP-MS) was investigated using an ELEMENT (Finnigan MAT, Germany) instrument. By using a special torch design, significant improvements could be achieved. Without changing any electrical parameters of the mass spectrometer, the long time stability over a time period of 4 months was measured as about ± 15% for 115In for all three steps of resolution (300, 3000, 7500). The short time stability over a period of 2–8 h was measured as about ± 10% (at maximum), also nearly independent of the resolution. The main result was the near independence of the stability from the mass-spectrometer itself, but a strong dependence on the sample introduction system, the ICP-torch and the cones.