Analysis of Niobium–Rare-Earth Ores by Inductively Coupled Plasma Mass Spectrometry

To determine the composition of niobium–rare-earth ores by atomic emission spectrometry and inductively coupled plasma mass spectrometry, two procedures are developed for sample preparation based on autoclave decomposition and flux fusion. Autoclave decomposition is carried out in a mixture of HF and HNO₃ at a temperature of up to 220°C and a pressure of up to 160 atm using a developed system with resistive heating. Subsequent evaporation to dry salts ensures the removal of F^– ions and silicon as SiF₄. The residue is dissolved in a mixture of HCl and H₂O₂ at 160°C under elevated pressure. The resulting solutions (10% with respect to HCl with the addition of H₂O₂) are diluted before measurements. The dissolution process is monitored for each sample using stable highly enriched isotopes of ⁹¹Zr, ¹⁰⁰Mo, ¹⁴⁹Sm, and ¹⁷⁸Hf. The second procedure is based on fusing samples with a mixture of Na₂CO₃ and Na₂B₄O₇ at 1050°C in a muffle furnace and dissolving the resulting melt in a mixture of HCl and H₂O₂. The procedures were tested using the national (NFS-23) and foreign standard samples of composition (OREAS-462, 463, 464, 465, Australia) and real samples of niobium–rare-earth ores.     

Inductively Coupled Plasma Zoom–Time-of-Flight Mass Spectrometry

A zoom–time-of-flight mass spectrometer has been coupled to an inductively coupled plasma (ICP) ionization source. Zoom–time-of-flight mass spectrometry (zoom-TOFMS) combines two complementary types of velocity-based mass separation. Specifically, zoom-TOFMS alternates between conventional, constant-energy acceleration (CEA) TOFMS and energy-focused, constant-momentum acceleration (CMA) (zoom) TOFMS. The CMA mode provides a mass-resolution enhancement of 1.5-1.7× over CEA-TOFMS in the current, 35-cm ICP-zoom-TOFMS instrument geometry. The maximum resolving power (full-width at half-maximum) for the ICP-zoom-TOFMS instrument is 1200 for CEA-TOFMS and 1900 for CMA-TOFMS. The CMA mode yields detection limits of between 0.02 and 0.8 ppt, depending upon the repetition rate and integration time—compared with single ppt detection limits for CEA-TOFMS. Isotope-ratio precision is shot-noise limited at approximately 0.2% relative-standard deviation (RSD) for both CEA- and CMA-TOFMS at a 10 kHz repetition rate and an integration time of 3–5 min. When the repetition rate is increased to 43.5 kHz for CMA, the shot-noise limited, zoom-mode isotope-ratio precision is improved to 0.09% RSD for the same integration time.

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Elemental Analysis of Phytotherapeutic Products by Inductively Coupled Plasma–Tandem Mass Spectrometry

A procedure for the determination of As, Cd, Cr, Ni, Pb, and V in phytotherapy medicines by inductively coupled plasma–tandem mass spectrometry is reported. The use of tandem mass spectrometry with oxygen into an octopole reaction system at various gas flow rates and the combination of on-mass and mass-shift modes was evaluated. Cadmium, Cr, Ni, and Pb were determined as free atomic ions while As and V were determined as the oxides AsO⁺ and VO⁺ in the same run. Samples were prepared by microwave-assisted digestion with dilute nitric acid and hydrogen peroxide. Two plant-certified reference materials (apple leaves and tomato leaves) were used to check the accuracy. For tandem mass spectrometry with 0.5?mL min^?1 O₂, recoveries in the 85–113% were typically obtained and no statistical differences were observed at the 95% confidence level (t-test) in comparison with the certified values. Using these conditions, the limits of detection for the method were 0.01, 0.0002, 0.008, 0.008, 0.003, and 0.002?µg g^?1 for As, Cd, Cr, Ni, Pb, and V, respectively. The procedure was used for the analysis of four phytotherapic drugs and the determined concentrations were up to 0.168?µg g^?1 As, 0.03?µg g^?1 Cd, 0.82?µg g^?1 Cr, 1.18?µg g^?1 Ni, 0.52?µg g^?1 Pb, and 2.4?µg g^?1 V with average precision values of 8% as the relative standard deviation. The found concentrations were compared with limits proposed in official guidelines and, in most cases, the values were below the maximum limits allowed.     

Multielemental Analysis of Human Serum by Dynamic Reaction Cell–Inductively Coupled Plasma Mass Spectrometry

The selection of the most suitable dilution methods for determination of trace elements in human serum using inductively coupled plasma mass spectrometry is reported. The trace elements were Al, V, Cr, Fe, Mn, Co, Cu, Zn, As, Cd, Sn, Tl, and Pb. The performance of various dilution methods was assessed by precision, linearity, detection limits, quantification limits, fortified recoveries, and the analysis of reference materials. The results demonstrate that diluted solution containing only nitric acid is most suitable for As, Cr, Mn, and Co in serum. Dilute solutions containing nitric acid and Triton X-100 were most appropriate for Cu, Zn, Cd, and Tl. The optimum conditions for Al, V, Mn, Fe, Cr, Co, Sn, and Pb used tetra-n-butylammonium hydroxide, Triton X-100, and ethylenediamine tetraacetic acid.     

Rapid Speciation of Lead in Water by High-Performance Liquid Chromatography–Inductively Coupled Plasma Mass Spectrometry

The rapid speciation of lead is reported by high performance liquid chromatography and inductively coupled plasma – mass spectrometry. The separation of inorganic lead, trimethyllead, triethyllead and triphenyllead was achieved within 3.5 minutes on a C₁₈ column using a gradient program of methanol and water containing 5 milligrams per liter sodium 1-pentanesulfonate at pH 5. The limits of detection for inorganic lead, trimethyllead, triethyllead, and triphenyllead were 0.01, 0.02, 0.02, and 0.02 micrograms per liter, respectively. The accuracy of the method was verified by the analysis of water (GSBZ 50009-88) and seawater (GBW (E) 080040) certified reference materials. The method was also employed for the analysis of water samples; inorganic lead was measured in river water.     

Trace Determination of Manganese in Urine by Graphite Furnace Atomic Absorption Spectrometry and Inductively Coupled Plasma–Mass Spectrometry

This paper describes a simple and sensitive method for the determination of manganese in human urine by graphite furnace atomic absorption spectroscopy (GFAAS), which includes sample preparation by microwave digestion. Matrix modifier combinations, the digestion power, pyrolysis, and atomization temperatures were optimized. A mixture of 5.0 µg Pd(NO₃)₂ and 3.2 µg Mg(NO₃)₂ modifier presented the best performance. The optimal temperatures for pyrolysis and atomization were 1500°C and 1950°C, respectively. The GFAAS method was compared to inductively coupled plasma–mass spectrometry (ICP–MS) for the determination of manganese in urine. Analytical figures of merit for GFAAS and ICP–MS were: accuracy (3.46%, 2.19%), precision (3.61%, 5.84%), LOD (0.109 µg · L^?1, 0.015 µg · L^?1), LOQ (0.327 µg · L^?1, 0.045 µg · L^?1), and recovery (80–100%, 74–89%). Both methods were employed for the determination of Mn in urine and the results were compared statistically.     

Determination of Essential and Toxic Elements in Tropical Fruit by Microwave-Assisted Digestion and Inductively Coupled Plasma–Mass Spectrometry

The concentrations of eight essential (Co, Cr, Cu, Mn, Ni, Se, V, and Zn) and five toxic elements (Al, As, Cd, Hg, and Pb) were determined in 457 samples of commonly consumed fresh tropical fruit including bananas (Musa acuminata), kiwi (Actinidia deliciosa), mangos (Mangifera indica), and pineapple (Ananas comosus) from supermarkets from Seoul, Busan, Gangneung, Daegu, Daejeon, and Gwangju, South Korea. The samples were digested by microwave-assisted combustion using HNO₃ and H₂O₂ and determined by inductively coupled plasma mass spectrometry. The Hg concentrations were evaluated by furnace-gold amalgamation direct mercury analysis. The techniques were validated by linearity, limits of detection and quantification, precision, recovery, and the analysis of a NIST-1570a spinach leaves certified reference material. The concentrations of essential elements varied considerably among the tropical fruit. Overall, the tropical fruit was higher in Mn (0.027–13.2?µg/g) and Zn (0.514–2.20?µg/g), while lower in Co (0.002–0.005?µg/g) and V (0.001–0.002?µg/g). The concentrations (µg/g) of toxic elements were 0.001 (kiwi) to 0.003 (mango) for As and Cd, 0.0004 (pineapple) to 0.002 (banana) for Hg, and 0.005 (kiwi) to 0.013 (mango) for Pb. The calculated values of estimated dietary intake, target hazard quotients and hazard indices were lower than one and the safety limits established by World Health Organization. The tropical fruits were therefore safe and did not pose any threat to consumers.     

Matrix Effects and Behaviors of Elements in Oxalic Acid Medium by Inductively Coupled Plasma Mass Spectrometry

Because of its high sensitivity, wide dynamic range and relative freedom from interferences, inductively coupled plasma mass spectrometry (ICP-MS) has been developed for the determination of trace and ultra-trace levels of elements in various fields1. Due…     

Study of the Chromium Distribution in New Materials Based on Tin Dioxide by Inductively Coupled Plasma–Mass Spectrometry

Moscow University Chemistry Bulletin - A new approach to determine additions of chromium and study its distribution in the bulk and on the surface of SnO2-based nanocrystalline semiconductor...     

Determination of Organotin Compounds in Wine by Microwave-Assisted Extraction and High Performance Liquid Chromatography–Inductively Coupled Plasma Mass Spectrometry

A new analytical procedure for the determination of five organotin compounds in several matrix wine samples is reported. The organotin compounds were extracted by microwave-assisted extraction with n-hexane. Extraction conditions, such as volume of n-hexane required, extraction temperature, and extraction time, were investigated and optimized by an orthogonal array experimental design. The determination of organotin compounds in the final extracts was carried out by liquid chromatography–inductively coupled plasma mass spectrometry. The procedure showed limits of detection between 0.029–0.049 µg · L^?1. The linearity was in the range of 0.5 to 100 µg · L^?1. The precision expressed as relative standard deviation (RSD) was below 9.43%. The developed method was successfully employed to analyze different matrix wine samples, and some analytes were detected at the level of 0.053 to 1.14 µg · L^?1.     

Speciation of Mercury in Terrestrial Plants Using Vapor Generation and Liquid Chromatography–Inductively Coupled Plasma Mass Spectrometry

A sensitive method for mercury speciation in biological samples is reported. A simple vapor generation apparatus was coupled to liquid chromatography and inductively coupled plasma–mass spectrometry (ICP–MS) to achieve a substantial increase in sensitivity. Mercury(II) and methylmercury were separated by reversed-phase chromatography as thiolate compounds with 2-mercaptoethanol. A short reverse phase column with an octylated stationary phase (75 × 4 millimeters) was used with a mobile phase containing 0.02 mole per liter ammonium acetate, 0.2 percent (v/v) 2-mercaptoethanol, and 1 percent methanol. The effluent was mixed with hydrochloric acid (0.06 mole per liter) containing platinum (40 micrograms per liter) as the internal standard and bismuth (30 micrograms per liter) as a modifying agent followed by sodium borohydride (0.016 mole per liter). The generated volatile species were introduced into the ICP–MS by conventional solution nebulization. In addition to the sensitivity enhancement induced by vapor generation, the addition of bismuth further increased the methylmercury signal with a reduced increase in the mercury(II) signal. As a result, comparable but unequal signals were achieved: the mercury(II) signal was approximately 1.6-fold higher than the methylmercury signal. Extraction with a hydrochloric acid-2-mercaptoethanol solution was used for sample preparation. The accuracy of determination was verified using two standard reference materials and an interlaboratory reference material based on barley grown hydroponically in mercury-contaminated solution. The method was employed for mercury speciation of plant samples from a polluted region.     

Quantification of Trace Amounts of Impurities in High Purity Cobalt by High Resolution Inductively Coupled Plasma Mass Spectrometry

Cobalt metal has been used in the production of magnetic alloys, cobalt and nickel based superalloys and sputtering targets in the field of advanced electronic devices1. The determination of trace impurities in high purity cobalt is extremely important be…     

Multielement Analysis of South Serbian Strawberry Cultivars by Inductively Coupled Plasma—Optical Emission Spectrometry

The contents of 17 elements in thirteen strawberry cultivars grown in the five districts of Southern Serbia were determined using inductively coupled plasma optical emission spectrometry (ICP-OES). The most abundant elements are K (875–1148 mg?·?kg^?1 fresh weight), P (307–664 mg?·?kg^?1 fresh weight), Ca (192–256 mg?·?kg^?1 fresh weight), and Mg (111–189 mg?·?kg^?1 fresh weight) in all samples. Strawberries were also found to be a good source of Sr (8.05–18.6 mg?·?kg^?1 fresh weight) and Fe (3.09–10.4 mg?·?kg^?1 fresh weight). The contents of As and Cd were below the detection limit (0.0828 mg?·?kg^?1 and 0.0205 mg?·?kg^?1, respectively) in all strawberry samples, while the contents of Ni, Cr, and Cu were below the recommended tolerable levels proposed by Joint Food and Agriculture Organization of the United Nations and World Health Organization Expert Committee on Food Additives, and did not a pose a health risk for the consumer. The application of Duncan’s test showed significant differences between contents of analyzed elements in all strawberry cultivars. The highest mean levels of analyzed elements were detected in strawberries grown in the Topli?ki, Jablani?ki, and P?injski districts. The spike recovery test was used to verify the accuracy of the method, and the spike recovery was in the range 93.8–107.8%. The contents of the metals in strawberry samples were also comparable with values previously reported in the literature.     

Speciation of Volatile Selenium Species in Plants Using Gas Chromatography/Inductively Coupled Plasma Mass Spectrometry

 Gas chromatography/inductively coupled plasma mass spectrometry (GC/ICP MS) coupled with solid phase micro extraction can provide a simple, extremely selective and sensitive technique for the analysis of volatile sulfur and selenium compounds in the hea     

Analytical Method Validation and Determination of Iron and Phosphorus in Vegetable Oil by Inductively Coupled Plasma–Mass Spectrometry with Microwave Assisted Digestion

Inductively coupled plasma–mass spectrometric determination of iron and phosphorus in three vegetable oils (soybean, coconut, and sunflower) was validated for the intermediate precision, trueness, linearity, and quantitation limit. The overall precision (n?=?5) for the analytes, which were above the method’s practical limit of quantification, were less than 2% relative standard deviation and the same as the laboratory control, NIST-SRM-1849a. Trueness was demonstrated with spike recoveries of the analytes in all vegetable oils at limit of quantification-level spiking. Although good linearity (regression coefficient greater than 0.9990) obtained, the recovery of phosphorus (156–189%) was high, possibly due to oil matrix enhancement, compared to the recovery of iron (91–106%). For soybean oil, sunflower oil, coconut oil, and medium chain triglycerides, the concentrations (mg/kg) of iron were in the range of 0.10–1.47, 0.09–1.51, 0.20–0.35, and 0.09–0.13, respectively. Similarly, phosphorus concentrations (mg/kg) were in the range of 0.77–124.56, 0.49–125.57, 0.52–9.72, and 0.85–11.90, respectively. The study achieved considerably low instrument-based practical limits of quantification for iron (0.005?mg/kg) and phosphorus (0.05?mg/kg), which are fivefold lower than the AOAC Official Method 2015.06. The high instrument sensitivity and selectivity of the method allow the determination of trace levels of iron and phosphorus in vegetable oils with good precision and trueness.     

Determination of Rhenium in Geological Samples by Isotope Dilution–Multicollector–Inductively Coupled Plasma-Mass Spectrometry with Novel Chromatographic Separation

A method was developed to determine rhenium contents in geological samples using multicollector–inductively coupled plasma-mass spectrometry (MC–ICP-MS) and extraction with an ion-exchange resin. Samples were digested in Carius tubes and osmium was converted into volatile OsO₄, which was purified by distillation and microdistillation. The purified Os contents and isotopic ratios were determined using negative thermal ionization mass spectrometry. After the distillation of Os, the samples were treated with HF, then 1.2?M HCl, and loaded on ion-exchange resin columns. Re was eluted using 0.75?M HNO₃ and directly determined by MC–ICP-MS. This method was validated using a series of reference materials and the analytical Re data are consistent with the literature values. This method precision (relative standard deviation) ranged from 0.8 to 6%. The procedural blank and detection limit (3σ) of Re were 1.1 pg and 0.5 pg/g (for a sample size of 2g), respectively. These results indicate that the proposed method can be applied to determine trace Re in geological samples. Using Carius tube digestion combined with HF desilicification and redissolution, the Re and Os contents found in the soluble and insoluble phases of several reference materials indicated that the distributions of Re and Os were homogeneous and heterogeneous, respectively.     

Determination of Phosphorus in Crude Oil and Middle Distillate Petroleum Products by Inductively Coupled Plasma–Optical Emission Spectrometry

A method for the precise and accurate determination of phosphorus in crude oil and middle distillate petroleum products was developed using inductively coupled plasma–optical emission spectrometry to rapidly determine phosphorus as a control method. The presence of phosphorus is undesirable in petrochemical products as it complexes with other metals generating residues that interrupt normal operation of refineries. The presence of phosphorus may be due to some anti-fouling additives or the crude oils processed. Consequently, it is necessary to control the phosphorus present at trace levels in the crude oil and in process streams that present various densities and viscosities. The instrumental power, nebulizer flow, pump rate, read time, and the sample preparation conditions were optimized. The desired level of quantification for the petrochemical industry was achieved allowing the simultaneous analysis of diverse liquid petroleum products.     

Determination of Rhenium in Seawater from the Jiulong River Estuary and Taiwan Strait,China by Automated Flow Injection Inductively Coupled Plasma–Mass Spectrometry

A novel and automated flow injection (FI) system using a commercially available anion-exchange resin was developed for the online determination of rhenium in seawater by inductively coupled plasma–mass spectrometry (ICP–MS). The flow rate, reagent concentration, and sample volume were optimized. The rhenium concentration was determined using the integrated peak area through interpolation of standard addition calibration curves. The relative standard deviation was less than 2.45% (n?=?5), the recoveries were from 94.59 to 104.11%, and the linear dynamic range of the method was up to 998?ng?kg^?1. There was a good agreement between the rhenium concentrations in a standard measured in this work with results from previous studies. The limit of detection was 0.11?ng?kg^?1 for a sample volume of 7.5?mL and one cycle required 8.33?min. The developed FI–ICP–MS method was used to determine rhenium in seawater from the Jiulong River Estuary and Taiwan Strait.     

Discrimination of Chili Powder Origin Using Inductively Coupled Plasma–Mass Spectrometry (ICP-MS), Inductively Coupled Plasma–Optical Emission Spectroscopy (ICP-OES), and Near Infrared (NIR) Spectroscopy

This study investigated the content of macronutrients (Ca, K, Mg, Na, P, and S), trace elements (Ba, Be, Co, Cr, Cu, Fe, Ga, Li, Mn, Ni, Rb, Se, Sr, V, and Zn), and trace toxic elements (As, Cd, In, Pb, and Tl) in chili powder from Korea, China, and Vietnam. For the analyses, inductively coupled plasma mass spectrometry (ICP-MS) and inductively coupled plasma-optical emission spectroscopy (ICP-OES) were used. In addition, near-infrared (NIR) spectroscopy was used to differentiate functional groups based on the chemical constituents. For the validation of the applied analytical methods, good linearity (coefficients of determination, 0.9443–0.99997), and relative standard deviations below 4% were obtained. The contents of the toxic elements were below the provisional tolerable weekly intake values. Linear discriminant analysis using elemental contents and NIR data was performed to establish and authenticate the geographical origin of chili powder, which confirmed the reliability of the obtained results.     

Determination of Rare Earth Elements in Garnet Minerals,Geological Materials by Inductively Coupled Plasma–Atomic Emission Spectral and Mass Spectral Analysis

Abstract

The performance of inductively coupled plasma–atomic emission spectrometry (ICP‐AES) for the determination of 14 lanthanides and Yttrium was evaluated by comparison with inductively coupled plasma–mass spectral (ICP‐MS) analysis. The geochemical reference samples (GRS), DNC‐1(diabase), AGV‐1(andesite), Sy‐2(syenite), MRG‐1(gabbro), AN‐G(anorthosite), AC‐E(granite), and MAG‐1(marine mud) were chosen as test materials and analyzed for checking the precision and reproducibility of the methods. The mineral garnet is separated from the black sands of the southwest coast of India, and the combined cation exchange–ICP method of AES analysis and MS analysis were carried out for the determination of rare earth elements. Both techniques are within the requirements needed for garnet minerals. The determination of rare‐earth elements in these minerals, which contain other elements as major contribution and trace distribution of rare‐earth elements, shows that ICP applied under the proper working condition lives up to the expectations. Major element analysis gives the formula of garnet of Manavalakurichi (MK) as (FeCaMg)_2.79Al_2.07Si_3.05O₁₂ approximated to Fe₃Al₂Si₃O₁₂, hence of almandine-type garnet. The enrichment of heavy lanthanides compared to the light lanthanides indicates that these lanthanides occupy the coordinaton site of Fe²⁺ by replacement. Both techniques are excellent in determining the very low concentration of lanthanides in geological materials, specifically garnet.