Quantification of trace amounts of impurities in high purity cobalt by high resolution inductively coupled plasma mass spectrometry

A An analytical method using high resolution inductively coupled plasma mass spectrometry （HR-ICP-MS） for rapid simultaneous determination of 24 elements （Be, Mg, A1, Ti, V, Cr, Mn, Fe, Ni, Cu, Zn, Ga, Ge, As, Se, Mo, Ag, Cd, Sn Sb, Ba, Pt, Au, and Pb） in high purity cobalt was described. Sample digestions were performed in closed microwave vessels using HNO3 and HCI. The matrix effects because of the presence of excess HCI and Co were evaluated. The usefulness of high mass resolution for overcoming some spectral interference was demonstrated. The optimum conditions for the determination were tested and discussed. The standard addition method was employed for quantitative analysis. The detection limits were 0.016-1.50 ].tg·g^-1, the recovery ratios were 92.2%-111.2%, and the RSD was less than 3.6%. The method was accurate, quick, and convenient. It was applied to the determination of trace impurities in high purity cobalt with satisfactory results.

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

An analytical method using high resolution inductively coupled plasma mass spectrometry （HR-ICP-MS） for rapid simultaneous determination of Be, Mg, Al, Ti, V, Cr, Mn, Fe, Ni, Cu, Zn, Ga, Ge, As, Se, Mo, Ag, Cd, Sn, Sb, Ba, Pt, Au and Pb in high purity cobalt was described. Sample digestions were performed in closed microwave vessels using HNO3 and HCl. The matrix effects due to the presence of excess HCl and Co were evaluated. The usefulness of high mass resolution for overcoming some spectral interference was demonstrated. The optimum conditions for the determination was tested and discussed. Correction for matrix effects, Sc, Rh and Bi were used as internal standards. The detection limits is 0.003-0.57 μg/g, the recovery ratio is 92.2%-111.2%, and the RSD is less than 3.6%. The method is accurate, quick and convenient. It has been applied to the determination of trace impurities in high purity cobalt with satisfactory results.

The determination of 52 elements in marine geological samples by an inductively coupled plasma optical emission spectrometry and an inductively coupled plasma mass spectrometry with a high-pressure closed digestion method

An improved analytical method to determine the content of 52 major, minor and trace elements in marine geological samples, using a HF-HCl-HNO_3 acid system with a high-pressure closed digestion method（HPCD）, is studied by an inductively coupled plasma optical emission spectrometry（ICP-OES） and an inductively coupled plasma mass spectrometry（ICP-MS）. The operating parameters of the instruments are optimized, and the optimal analytical parameters are determined. The influences of optical spectrum and mass spectrum interferences, digestion methods and acid systems on the analytical results are investigated. The optimal spectral lines and isotopes are chosen, and internal standard element of rhodium is selected to compensate for matrix effects and analytical signals drifting. Compared with the methods of an electric heating plate digestion and a microwave digestion, a high-pressure closed digestion method is optimized with less acid, complete digestion,less damage for digestion process. The marine geological samples are dissolved completely by a HF-HCl-HNO_3 system, the relative error（RE） for the analytical results are all less than 6.0%. The method detection limits are 2–40μg/g by the ICP-OES, and 6–80 ng/g by ICP-MS. The methods are used to determine the marine sediment reference materials（GBW07309, GBW07311, GBW07313）, rock reference materials（GBW07103, GBW07104,GBW07105）, and cobalt-rich crust reference materials（GBW07337, GBW07338, GBW07339）, the obtained analytical results are in agreement with the certified values, and both of the relative standard deviation（RSD） and the relative error（RE） are less than 6.0%. The analytical method meets the requirements for determining 52 elements contents of bulk marine geological samples.

Determination of micro yttrium in an ytterbium matrix by inductively coupled plasma atomic emission spectrometry and wavelet transform

In the determination of trace yttrium (Y) in an ytterbium (Yb) matrix byinductively coupled plasma atomic emission spectrometry (ICP-AES), the most prominent line ofyttrium, Y 371.030 nm line, suffers from strong interference due to an emission line of ytterbium.In mis work, a method based on wavelet transform was proposed for the spectral interferencecorrection. Haar wavelet was selected as the mother wavelet. The discrete detail after the thirddecomposition, D3, was chosen for quantitative analysis based on the consideration of bothseparation degree and peak height. The linear correlation coefficient between the height of the leftpositive peak in D3 and the concentration of Y was calculated to be 0.9926. Six synthetic sampleswere analyzed, and the recovery for yttrium varied from 96.3 percent to 110.0 percent. The amountsof yttrium in three ytterbium metal samples were determined by the proposed approach with an averagerelative standard deviation (RSD) of 2.5 percent, and the detection limit for yttrium was 0.016percent. This novel correction technique is fast and convenient, since neither complicated modelassumption nor time-consuming iteration is required. Furthermore, it is not affected by thewavelength drift inherent in monochromators that will severely reduce the accuracy of resultsobtained by some chemometric methods.

Direct Determination of Trace Impurities in High Purity Zinc Oxide by High Resolution Inductively Coupled Plasma Mass Spectrometry

The determination of trace impurities in high purity zinc oxide by high resolution inductively coupled plasma mass spectrometry （ HR-ICP-MS ） was investigated. To overcome some poteutially problematic spectral iuterference, measurements were acquired in both middle and high resolution modes. The matrix effects due to the presence of excess HCl and zinc were evaluated. The optimum conditions for the determination were tested and discussed. The standard addition method was employed for quantitative analysis. The detection limits ranged from 0.02μg/ g to 6 μg/ g depending on the elements. The experimental resalts for the determination of Na, Mg, Ca, Cr, Mn, Fe, Co, Ni, Cu, Mo, Cd, Sb and Pb in several high purity zinc oxide powders were presented.

Analysis of Cu,Co,V and Zn in Coastal Waters of the East China Sea by Inductively Coupled Plasma Mass Spectrometry(ICP-MS)

In this study, a simple method for the simultaneous determination of trace metals(Cu, V, Co, Zn) in coastal seawater using the Mg(OH)2 coprecipitation inductively coupled plasma mass spectrometry(ICP-MS) was developed. This multi-element method enables the simultaneous extraction of four metals, particularly Co and V. The recoveries of Cu, Co, V and Zn after Mg(OH)2 coprecipitation were 73%, 96%, 94% and 92%, which means that our procedure was well-suited to the determination of these four trace metals. The detection limits were 3.81, 0.18, 6.09 and 1.91 nmol L-1, respectively. Then, applying this method to the simultaneous determination of these four metals in coastal water samples from the East China Sea revealed that the concentrations of Cu, Zn, Co and V were higher in bottom waters compared to water at other depths, and higher concentrations were generally observed at the Yangtze River estuary. Additionally, example vertical profiles of dissolved trace metal concentrations for the East China Sea in spring and autumn are compared. These findings indicate that Zn had the greatest seasonal variation followed by Cu, V and Co. For Zn and Co, the concentrations were higher during spring than during autumn. For Cu and V, the seasonal variation in the concentrations was opposite.

Determination of Trace Elements in High Purity Gold by High Resolution Inductively Coupled Plasma Mass Spectrometry

Trace elements were determined in high purity gold by high resolution inductively coupled plasma mass spectrometry （HR-ICP-MS）. Sample were decomposed by aqua regia. To overcome some potentially problematic spectra/ interference, measurements were acquired in both medium and high resolution modes. The matrix effects due to the presence of excessive HCl and Au were evaluated. The optimum conditions for the determination was tested and discussed. The standard addition method was employed for quantitative analysis. The detection limits range from 0.01ug/g to 0.28ug/g depending on the elements. The method is accurate, quick and convenient. It has been applied to the determination of trace elements in high purity gold with satisfactory results.

Uncertainty Evaluation of Simultaneous Determination of Lead, Cadmium and Arsenic in Cosmetics by Inductively Coupled Plasma Mass Spectrometry

This study aimed to evaluate the uncertainty of simultaneous determination of lead(Pb),cadmium(Cd)and arsenic(As)in cosmetics by microwave digestion-inductively coupled plasma mass spectrometry(ICP-MS)with ^72Ge,^115In and ^209Bi as internal standards.According to the method of Safety and Technical Standards for Cosmetics(2015),a mathematical model was established to evaluate the sources and components of uncertainty for the determination of lead,cadmium and arsenic in cosmetics.The results showed that the uncertainties in the determination of lead,cadmium,and arsenic elements in cosmetics were(10.1±0.6)mg/kg,k=2,(4.84±0.28)mg/kg,k=2,(2.04±0.18)mg/kg,k=2,respectively.The main factors that affect the uncertainty of determination results were standard substance,calibration curve,recovery and measurement repeatability.

In vivo and in vitro inductively coupled plasma mass spectrometry quantification of minerals and heavy metals in Qishiwei Zhenzhu pill and their effect on intestinal flora

OBJECTIVE Cerebral ischemia or ischemic stroke is due to insufficient blood supply to the brain,which causes hypoxia or ischemia in some areas.This work aimed to quantify the minerals and heavy metals in Qishiwei Zhenzhu pill in vivo and in vitro,analyze its effect on the types and abundance of intestinal flora,and study its mechanism on inflammation and apoptosis pathways as a treatment for cerebral ischemia.METHODS Microwave digestion and inductively coupled plasma mass spectrometry(ICP-MS)were used to determine the minerals and heavy metals in 10 batches of Qishiwei Zhenzhu pill in vitro.With the use of the middle cerebral artery obstruction(MCAO)model,ICP-MS was applied to determine the content of minerals and heavy metals in hepatic portal vein blood,abdominal aortic blood,brain,liver,kidney,hair,urine and feces at different time periods.On this model,the ileum,cecum,and colon tissues were tested for intestinal pathology,and 16S rRNA was used for sequencing.Species taxonomy,αdiversity,and species microbial composition and structure analysis were also performed.Polymerase chain reaction and Western blotting were employed to determine the mRNA and protein expression of p38 MAPK,caspase-3,IL^(-1)βand TNF-αin the ischemic brain tissues of rats.RESULTS The average content of heavy metals in the 10 batches of Qishiwei Zhenzhu pill samples is in the descending order Hg>Cu>Pb.Significant differences in the metal elements are found among Qishiwei Zhenzhu pill from different manufacturers but not among the different batches of the same manufacturer.An extremely low content of heavy metals are absorbed into the blood or accumulated in the brain,liver,kidney,and other tissues.Stool is the main excretion route of minerals and heavy metals from Qishiwei Zhenzhu pill.This medicine helps repair the intestinal mucosa in MCAO rats.At the phylum level,it can regulate the abundance of Firmicutes and Proteobacteria in the intestinal flora of rats with cerebral ischemia.At the genus level,it can adjust the abundance of Escherichia Shigella.At the species level,it can adjust the abundance of Lactobacillus yoelii and Lactobacillus reuteri.Cluster classification results show that Qishiwei Zhenzhu pill can improve the intestinal flora of rats with cerebral ischemia,reduce the mRNA and protein expression of caspase-3 and IL^(-1)βin rat brain tissues,and have a tendency to decrease the mRNA expression of p38 MAPK and TNF-α.CONCLUSION Quantifying the minerals and heavy metals in Qishiwei Zhenzhu pill in vivo and in vitro will help improve their quality standards.Minerals and heavy metals are mainly excreted in feces,accumulate in extremely low levels in various tissues,and do not damage the intestinal mucosa.The effective material basis of Qishiwei Zhenzhu pill in treating cerebral ischemia may be related to their Li,Cr,and Cd elements.These pills can improve the environment of intestinal flora,and their mechanism of treatment for cerebral ischemia may be related to the down-regulation of IL^(-1)βinflammatory factor and inhibition of cell apoptosis.

Inductively coupled plasma mass spectrometry (ICP-MS) and its application in life sciences

Inductively-coupled plasma mass spectrometry (ICP-MS) has made much progress since its birth in the late 1990s. This paper will give a rather systematic overview on the use of this technique in new devices and technologies related to plasma source, sample-introducing device and detecting spectrometer etc. In this overview, an emphasis will be put on the evaluation of the ICP- MS technique in combination with a series of physical, chemical and biological techniques, such as laser ablation (LA), capillary electrophoresis (CE) and high performance liquid chromatograph (HPLC), along with their representative high accuracy and high sensitivity. Finally, comprehensive and fruitful applications of the ICP-MS and its combinative techniques in the detection of trace metallic elements and isotopes in complex biological and environmental samples will be revealed.

EVALUATON OF MICROWAVE PLASMA TORCH FOR ATOMIC FLUORESCENCE SPECTROMETRY WITH AN ULTRASONIC NEBULIZATION SAMPLE INTRODUCTION SYSTEM

In this paper, a new MPT(microwave plasma torch) device has been used as a atomizer for atomic fluorescence spectrometry. Spme elements, such as Zn, Cd, Hg, Pb, As, Co, Mg, Cu, Ag, Mn, Fe have been investigated in detail.

Diagnostic of capacitively coupled radio frequency plasma from electrical discharge characteristics：comparison with optical emission spectroscopy and fluid model simulation

The capacitively coupled radio frequency（CCRF）plasma has been widely used in various fields.In some cases,it requires us to estimate the range of key plasma parameters simpler and quicker in order to understand the behavior in plasma.In this paper,a glass vacuum chamber and a pair of plate electrodes were designed and fabricated,using 13.56 MHz radio frequency（RF）discharge technology to ionize the working gas of Ar.This discharge was mathematically described with equivalent circuit model.The discharge voltage and current of the plasma were measured atdifferent pressures and different powers.Based on the capacitively coupled homogeneous discharge model,the equivalent circuit and the analytical formula were established.The plasma density and temperature were calculated by using the equivalent impedance principle and energy balance equation.The experimental results show that when RF discharge power is 50–300 W and pressure is 25–250 Pa,the average electron temperature is about 1.7–2.1 e V and the average electron density is about 0.5？×10^17–3.6？×10^17m^-3.Agreement was found when the results were compared to those given by optical emission spectroscopy and COMSOL simulation.

An improved LC–MS/MS method for the quantification of alverine and para hydroxy alverine in human plasma for a bioequivalence study

A highly sensitive and selective high performance liquid chromatography–tandem mass spectrometry method was developed and validated for the quantification of alverine（ALV） and its active metabolite, para hydroxy alverine（PHA）, in human plasma. For sample preparation, solid phase extraction of analytes was performed on Phenomenex Strata-X cartridges using alverine-d5 as the internal standard. The analytes were separated on Symmetry Shield RP18（150 mm×3.9 mm, 5 μm） column with a mobile phase consisting of acetonitrile and10 mM ammonium formate（65：35, v/v）. Detection and quantitation was done by electrospray ionization mass spectrometry in the positive mode using multiple reaction monitoring. The assay method was fully validated over the concentration range of 15.0–15,000 pg/mL for ALV and 30.0–15,000 pg/mL for PHA. The intra-day and inter-day accuracy and precision（% CV） ranged from 94.00% to 96.00% and 0.48% to 4.15% for both the analytes. The mean recovery obtained for ALV and PHA was 80.59% and 81.26%, respectively. Matrix effect,expressed as IS-normalized matrix factor ranged from 0.982 to 1.009 for both the analytes. The application of the method was demonstrated for the specific analysis of ALV and PHA for a bioequivalence study in 52 healthy subjects using 120 mg ALV capsules. The assay reproducibility was also verified by reanalysis of 175 incurred subject samples.

Mg/Ca,Ba/Ca,and S/Ca ratios as environmental and growth proxies for bivalve shells from the Haima cold seep,South China Sea

Bivalve shell fossils,cemented by authigenic carbonates,are widely spread in the Haima cold seep,Qiongdongnan Basin of the South China Sea(SCS).In this study,we examined an element profile of Gigantidas platifrons in the Haima cold seeps at a water depth of 1381 m.Based on the scanning electron microscope(SEM)analyses,the prismatic layer and nacreous layer were identified,which are characterized by prismatic structure and stratified structure,respectively.In addition,the profile can be subdivided into two parts:altered and unaltered zones.Laser inductively coupled plasma mass spectrometry(LA-ICP-MS)mapping shows that the element concentrations of the altered zones were influenced by the authigenic carbonate rocks,whereas the element concentrations of unaltered zones remain stable.In-situ X-ray diffraction(XRD)analyses show that the mineral constituent of the prismatic layer is mainly composed of aragonite.Along with the growth profile,Mg/Ca ratios of unaltered zones have minor variations,ranging 0.72-0.97 mmol/mol(mean=0.87 mmol/mol),with estimated temperatures of 3.8-4.1℃,indicating that the temperature of the surrounding seawater remains constant and agree with the measured data of 3.9℃which was conducted by a conductivity-temperature-depth system(CTD).The minor variations of Ba/Ca ratios(0.01-0.06 mmol/mol;mean=0.04 mmol/mol)indicate a relatively stabilized salinity of the surrounding seawater.S/Ca ratios show large variations of 0.04-4.15 mmol/mol(mean=1.37 mmol/mol).S/Ca ratios have regular variations which generally correspond to the variations of the Mg/Ca ratios,highlighting that the S/Ca ratios of bivalve shells show the potential to reflect the growth rate of the Gigantides.However,further studies should be carried out on the understanding of the links between the S/Ca ratios and seepage intensity of cold-seep fluids.

Determination of Trace Amount of Vanadium in High Purity Y_2O_3 by Electrothermal Vaporization－ICP－AES With Bi（PDC）_3 Coprecipitation

A new method for the determination of vanadium in high purity Y2O3 by fluorination assisted electrothermal vaporization-ICP-AES is presented in this paper. After the sample dissolved,the vanadium in the sample solution was coprecipitated with Bi(PDC)_3 at pH 3. 7. The precipitates were made into a slurry with the fluorinating agent PTFE and directly introduced into the graphite furnace for determination. The analytical results were obtained by aqueous calibration curve method. The detection limit of the method is 1. 1 ng/mL, the RSD is 2. 8% (n=10,1 5 ng/mL vanadium solution), and the recovery of vanadium added to real sample is more than 96%.

电感耦合等离子体质谱测定大气铅污染物

Inductively coupled plasma mass spectrometry(ICP-MS) was used to determine the concentration of Pb in atmospheric particulate samples,and the enrichment factor was calculated.The causes of the results were also discussed.

Determination of wholesome elements and heavy metals in safflower(Carthamus tinctorius L.)from Xinjiang and Henan by ICP-MS/ICP-AES

An inductively coupled plasma mass spectrometry （ICP-MS） or inductively coupled plasma atomic emission spectrometry （ICP-AES） was developed to determine 19 elements in safflower, a traditional Chinese medicinal herb from Xinjiang Autonomous Region and Henan Province of China. Totally 19 elements in safflower included heavy metals, i.e. As, Cd, Cu, Hg and Pb, and wholesome elements, i.e. Al, Ca, Co, Cr, Fe, Mg, Mn, Mo, Ni, P, Se, Sr, V and Zn. The results showed that the concentrations of heavy metals in safflower samples were both low, all of which met the national hygiene standards except for Pb in Xinjiang sample. Meanwhile, the distribution tendency of elements in the two samples was similar, which indicated that the plant might absorb given elements in a proportional way. The method can be used for the quality control of elements in safflower, and it provides a way for the determination of the contents of safflower from Xinjiang and Henan.

Lipopolysaccharide inhibits or accelerates biomedical titanium corrosion depending on environmental acidity

Titanium and its alloys are routinely used as biomedical implants and are usually considered to be corrosion resistant under physiological conditions. However, during inflammation, chemical modifications of the peri-implant environment including acidification occur. In addition certain biomolecules including lipopolysaccharide（LPS）, a component of Gram-negative bacterial cell walls and driver of inflammation have been shown to interact strongly with Ti and modify its corrosion resistance. Gram-negative microbes are abundant in biofilms which form on dental implants. The objective was to investigate the influence of LPS on the corrosion properties of relevant biomedical Ti substrates as a function of environmental acidity. Inductively coupled plasma mass spectrometry was used to quantify Ti dissolution following immersion testing in physiological saline for three common biomedical grades of Ti（ASTM Grade 2, Grade 4 and Grade 5）. Complementary electrochemical tests including anodic and cathodic polarisation experiments and potentiostatic measurements were also conducted. All three Ti alloys were observed to behave similarly and ion release was sensitive to p H of the immersion solution. However, LPS significantly inhibited Ti release under the most acidic conditions（p H 2）, which may develop in localized corrosion sites, but promoted dissolution at p H 4–7, which would be more commonly encountered physiologically.The observed pattern of sensitivity to environmental acidity of the effect of LPS on Ti corrosion has not previously been reported. LPS is found extensively on the surfaces of skin and mucosal penetrating Ti implants and the findings are therefore relevant when considering the chemical stability of Ti implant surfaces in vivo.

A Study of the Rhenium-Osmium Geochronometry of Molybdenites

This study deals with the first application of the isotope dilution - inductively coupled plasma mass spectrometry in the rhenium-osmium geochronometry in China. The chemical separation procedure included decomposition of samples by means of alkali fusion, extraction of rhenium by acetone and extraction of osmium by distillation. The recovery of both elements in the entire process was more than 90% . The blanks of analyses were 0.07 ng for rhenium and 0.01 ng for 187Os. The mineralization ages of molybdenites from four molybdenum deposits in China were determined by using this method, with a precision (2σ)of about ±3% . These results agree satisfactorily with their geological backgrounds. The Re-Os method can directly determine ages of metal deposits and reflect the true ages more reliably than other dating methods that only determine the ages of country rocks from which mineralization ages are inferred. As many hydrothermal sulphide deposits usually contain molybdenites, this method has bright prospects of wide application.

Elemental Quantitative Distribution and Statistical Analysis on Cross Section of Stainless Steel Sheet by Laser Ablation Inductively Coupled Plasma Mass Spectrometry

An innovative application of laser ablation inductively coupled plasma mass spectrometry （LA-ICP-MS） technique in illustrating elemental distributions on stainless steel sheets was presented. The technique proved to be a systematic and accurate ap- proach in producing visual images or maps of elemental distributions at cross-sectional surface of a stainless steel sheet. Two stain- less steel sheets served as research objects： 3 mm×l 300 mm hot-rolled stainless steel plate and 1 mm×l 260 mm cold-rolled plate. The cross-sectional surfaces of the two samples at 1/4 position along the width direction were scanned （raster area -44 mm2 and 11 mm2） with a focused laser beam （wavelength 213 nm, diameter of laser crater 100 μm, and laser power 1.6 mJ） in a laser abla- tion chamber. The laser ablation system was coupled to a quadrupole ICP-MS, which made the detection of ion intensities of 27A1＋, 44Ca＋, 47Ti-, 55Mn＋ and 56Fe＋ within an area of interest possible. One-dimensional （ID） content line distribution maps and two- dimensional （2D） contour maps for specific positions or areas were plotted to indicate the element distribution of a target area with high accuracy. Statistic method was used to analyze the acquired data by calculating median contents, maximum segregation, sta- tistic segregation and content-frequency distribution.