Comparison of inductively coupled plasma mass spectrometry techniques in the determination of platinum in urine: quadrupole vs. sector field

In recent years the increasing use of platinum (Pt) both in medical and in industrial applications has caused its growing anthropogenic emission and spread in the environment. Pt is released into the atmosphere by exhaust catalytic converters, and Pt compounds are often used in antitumour therapies. As a consequence, significant amounts of Pt can be detected in hospital wastewaters. This can lead to an increase in the exposure levels to Pt, especially in urban areas. It is therefore necessary to determine Pt reference values in the general population, by using suitable procedures able to achieve adequate analytical performances. Several measurements of Pt in biological fluids have been reported, but the analytical methods used for the determination of Pt often lack information about the uncertainty of the results, especially for low concentrations of urinary Pt in non-occupationally exposed subjects. The present paper considers the measurement of urinary Pt levels in a general population group from central Italy, by both quadrupole (Q) and sector field (SF) inductively coupled plasma mass spectrometry (ICP-MS). The two procedures were validated and their expanded uncertainties were evaluated. The limits of detection (LODs), calculated taking into account dilution factors, were 0.18 and 0.05 ng L(-1) of Pt for the Q and SF procedures, respectively. The median value observed was 4.13 ng L(-1) of Pt in urine, while the relative combined uncertainty at 5 ng L(-1) was below 20% with both ICP-MS techniques. These data are in good agreement with those reported in the literature for similar studies.     

Instrumental Neutron Activation Analysis (INAA) and Inductively Coupled Plasma/Mass Spectrometry (ICP-MS) for Trace Element Biomonitoring using Mosses

Two analytical methods - instrumental neutron activation analysis (INAA) and inductively coupled plasma mass spectrometry (ICP-MS) - were used for the trace element analysis of naturally growing mosses for a heavy metal biomonitoring survey. The techniques were applied to reference mosses to evaluate the feasibility, analytical variability, detection limits and accuracy. These parameters were evaluated using 563 mosses sampled in the 1996 French survey. All the elements of interest in the European program "Atmospheric Heavy Metal Deposition in Europe - estimation based on moss analysis" (As, Cd, Cr, Cu, Fe, Hg, Pb, Ni, V, Zn) were able to be determined by ICP-MS. INAA appeared suitable for the determination of As, Cr, Fe, Hg, V and Zn. The Cd, Cu, Ni and Pb concentrations determined by ICP-MS were preferred to the INAA results, because of increased feasibility or accuracy. The results provided by both methods on the French mosses were statistically compared for 14 elements. Significant linear correlation appeared for: Ba, Ce, Cs, La, Rb, Sm, Th and V. Among these eight elements, Ba, Cs, La and Sm concentrations determined by both methods exhibited a strong statistical similarity. The correlations obtained for As, Eu, Fe and Sb were not as strong and no correlation at all was observed for Co and Cr. These differences were attributed to instrumental factors (e.g. spectral interference occurred for both methods) or due to the sample preparation prior to ICP-MS. The consequences of such results on the regional trend evaluation of atmospheric heavy metal deposition were discussed.     

Intercomparison of moss reference material by different multi-element techniques

An intercomparison of data obtained for a moss reference material (Hylocomium splendens) used as biomonitor of atmospheric deposition by different multi-element techniques is presented. In total 43 elements (Na, Mg, Al, Cl, K, Ca, Sc, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, As, Se, Br, Rb, Sr, Zr, Ag, Sn, Sb, I, Cs, Ba, La, Ce, Nd, Sm, Eu, Gd, Tb, Tm, Yb, Lu, Hf, Ta, W, Au, Th, U) were determined using inductively coupled plasma-mass spectrometry (ICP-MS), conventional instrumental neutron activation analysis (INAA), epithermal neutron activation analysis (ENAA) and as well as shorttime neutron activation analysis without and with a⁶LiD-converter. Advantages and drawbacks of each method are discussed. The introduction of moss reference materials for atmospheric multi-element deposition studies involving nuclear analytical techniques is strongly recommended.     

Multi-element determination in earthworms with instrumental neutron activation analysis and inductively coupled plasma mass spectrometry: A comparison

Earthworms were collected from agricultural fields in Admont, Graz, Piber and Gumpenstein, Austria. Six earthworm samples were investigated with INAA and with ICP-MS in parallel for the element concentrations of As, Ba, Cd, Co, Cr, Cu, Fe, Hg, Pb, Rb, Sb, Se and Zn. With both techniques 14 elements were analysed in a wide concentration range (ng/g to mg/g) GF-AAS and HG-AAS were used for verification of some element concentrations. A comparison of analytical results between INAA and ICP-MS was discussed. In general, good agreement between ICP-MS and INAA was obtained, the relative difference values of most of the elements are within ±20% range, however, a methodical error for the determination of Hg by ICP-MS was found.     

Heat-treated Saccharomyces cerevisiae for antimony speciation and antimony(III) preconcentration in water samples

An analytical method was developed for antimony speciation and antimony(III) preconcentration in water samples. The method is based on the selective retention of Sb(III) by modified Saccharomyces cerevisiae in the presence of Sb(V). Heat, caustic and solvent pretreatments of the biomass were investigated to improve the kinetics and thermodynamics of Sb(III) uptake process at room temperature. Heating for 30 min at 80 degrees C was defined as the optimal treatment. Antimony accumulation by the cells was independent of pH (5-10) and ionic strength (0.01-0.1 mol L(-1)). 140 mg of yeast and 2h of contact were necessary to ensure quantitative sequestration of Sb(III) up to 750 microg L(-1). In these conditions, Sb(V) was not retained. Sb(V) was quantified in sorption supernatant by inductively coupled plasma mass spectrometry (ICP-MS) or inductively coupled plasma optical emission spectrometry (ICP-OES). Sb(III) was determined after elution with 40 mmol L(-1) thioglycolic acid at pH 10. A preconcentration factor close to nine was achieved for Sb(III) when 100mL of sample was processed. After preconcentration, the detection limits for Sb(III) and Sb(V) were 2 and 5 ng L(-1), respectively, using ICP-MS, 7 and 0.9 microg L(-1) using ICP-OES. The proposed method was successfully applied to the determination of Sb(III) and Sb(V) in spiked river and mineral water samples. The relative standard deviations (n=3) were in the 2-5% range at the tenth microg L(-1) level and less than 10% at the lowest Sb(III) and Sb(V) tested concentration (0.1 microg L(-1)). Corrected recoveries were in all cases close to 100%.     

Characterization of sealed radioactive sources: uncertainty analysis to improve detection methods

A radioactive ¹³⁷Cs source has been analyzed for the radioactive parent ¹³⁷Cs and stable decay daughter ¹³⁷Ba. The ratio of the daughter to parent atoms is used to estimate the date when Cs was purified prior to source encapsulation (an “age” since purification). The isotopes were analyzed by inductively coupled plasma mass spectrometry (ICP-MS) after chemical separation. In addition, Ba was analyzed by isotope dilution ICP-MS (ID-ICP-MS). A detailed error analysis of the mass spectrometric work has been undertaken to identify areas of improvement, as well as quantifying the effect the errors have on the “age” determined. This paper reports an uncertainty analysis to identifying areas of improvement and alternative techniques that may reduce the uncertainties. In particular, work on isotope dilution using ICP-MS for the “age” determination of sealed sources is presented. The results will be compared to the original work done using external standards to calibrate the ICP-MS instrument.     

Instrumental neutron activation analysis of rock samples from Ugep area of Cross River State,Nigeria

The theory and analytical procedures in Instrumental Neutron Activation Analysis (INAA) are discussed. Application of the method to the determination of sixteen trace elements: Na, K, Mn, Sm, La, Fe, Th, Sc, Co, Ba, Rb, Br, Sb, Cs and Ta in some rock samples from Ugep in the Lower Benue Region of Nigeria, is described. The high radioactivity observed in some of the samples analyzed has been associated with the higher-than-normal concentrations of Th and K in the samples. Also, Ba and Fe concentrations in some of the samples were found to be anomalous when compared with average expected values in normal sedimentary rocks.     

Determination of trace elements in wines and classification according to their provenance

Provenance and authenticity of wines can be recognized on the basis of typical mineral and trace element patterns by means of chemometric methods. Therefore analytical methods were developed for the determination of As, Be, Co, Cs, Ga, Li, Nb, Ni, Rb, Te, Ti, W, Y, and Zr as well as Mo, Cd, Sb, Tl, U, and the rare earth elements in wines by inductively coupled plasma mass spectrometry (ICP-MS). For low risk of contamination or loss of analyte as well as depletion of sample amount and an easy sample pretreatment, direct measurement of diluted wines was studied. The accuracy of the analytical results was proven by recovery experiments by method comparison with standard addition methods and measurement of digested wines. In addition to applying statistical methods for characterizing the precision of the methods, the uncertainty of the measurements was estimated.Results for the elements mentioned above and additional 16 elements (Al, B, Ba, Ca, Cr, Cu, Fe, Mn, Mg, P, Pb, Si, Sn, Sr, V, and Zn) were evaluated by data analytical methods. Due to a specific choice of the analytes for multivariate statistical investigation a prediction rate by cross validation of 88.6% could be achieved.     

Development of a certified reference material (NMIJ CRM 7505-a) for the determination of trace elements in tea leaves

A certified reference material (CRM) for trace elements in tea leaves has been developed in National Metrology Institute of Japan (NMIJ). The CRM was provided as a dry powder (<90 μm) after frozen pulverization of washed and dried fresh tea leaves from a tea plant farm in Shizuoka Prefecture, Japan. Characterization of the property value for each element was carried out exclusively by NMIJ with at least two independent analytical methods, including inductively coupled plasma mass spectrometry (ICP-MS), high-resolution (HR-) ICP-MS, isotope-dilution (ID-) ICP-MS, inductively coupled plasma optical emission spectrometry (ICP-OES), graphite-furnace atomic-absorption spectrometry (GF-AAS) and flame atomic-absorption spectrometry (FAAS). Property values were provided for 19 elements (Ca, K, Mg, P, Al, B, Ba, Cd, Cu, Fe, Li, Mn, Na, Ni, Pb, Rb, Sr, Zn and Co) and informative values for 18 elements (Ti, V, Cr, Y, and all of the lanthanides, except for Pm whose isotopes are exclusively radioactive). The concentration ranges of property values and informative values were from 1.59% (mass) of K to 0.0139 mg kg(-1) of Cd and from 0.6 mg kg(-1) of Ti to 0.0014 mg kg(-1) of Lu, respectively. Combined relatively standard uncertainties of the property values were estimated by considering the uncertainties of the homogeneity, analytical methods, characterization, calibration standard, and dry-mass correction factor. The range of the relative combined standard uncertainties was from 1.5% of Mg and K to 4.1% of Cd.     

Determination of 30 elements in colorectal biopsies by sector field inductively coupled plasma mass spectrometry: method development and preliminary baseline levels

An analytical procedure applicable to restricted sample sizes was developed and applied to the analysis of 30 chemical elements in colorectal biopsies of healthy patients. Acidic microwave digestion processed 相似文献   

Heterometallic cuboidal clusters M(3)M'Q(4) (M = Mo, W; M'= Sn, Pb, As, Sb; Q = S, Se): from coordination compounds to supramolecular adducts

Reactions of the incomplete cuboidal clusters [M3Q4(acac)3(py)3]+ (M = Mo, W; Q = S, Se) with group 14 and 15 metal complexes with the s2p0 electronic configuration (AsPh3, SbPh3, SbCl3, SbI3, PbI3-, SnCl3-) led to heterometal incorporation with the formation of cuboidal clusters of the type [M3(EX3)Q4(acac)3(py)3]n+ (n = 0 for Sn, Pb; n = 1 for As, Sb), whose structures were determined by X-ray diffraction. The cuboidal clusters can be described as complexes of the cluster tridentate ligand [M3Q4(acac)3(py)3]+ (mu2-chalcogen atoms as donors) with the EX3, where the E atom attains a distorted octahedral coordination. Analysis based on the bond distances E-Q gives the following sequence of affinity: As < Sb; Pb < Sn approximately Sb; SbPh3 < SbI3 approximately SbCl3; W3S4 < W3Se4. Interaction energies at the gas phase between [W3Q4(acac)3(py)3]+ (Q = S, Se) and SbX3 (X = I, Ph) were computed at the DFT level (BP86/TZP). The magnitude of the interaction depends strongly on the substituents at Sb, and the replacement of iodine by the phenyl group decreases the interaction energy from -9.21 to -2.70 kcal/mol and from -12.73 to -3.85 kcal/mol for the W3SbS4 and W3SbSe4 cores, respectively.     

A group separation scheme for radiochemical neutron activation analysis for 24 trace elements in rocks and minerals

A group separation scheme has been developed for radiochemical neutron activation analysis for Ca, Cu, Zn, Ga, Rb, Sr, Zr, Sb, Cs, Ba, La, Nd, Sm, Eu, Gd, Tb, Ho, Tm, Yb, Lu, Hf, Ta, W and Th in a wide variety of silicate rocks and minerals, especially ultrabasic rocks and mafic minerals. The samples are decomposed in a hydrofluoric acid-nitric acid mixture in a PTFE-lined bomb. The soluble fluorides (Cu, Zn, Ga, Rb, Zr, Sb, Cs, Ht, Ta, W and Pa) are separated into three groups of elements by sequential elution from a cationexchange resin. The insoluble fluorides (Ca, Rb, Sr, Cs, Ba and REE) are dissolved and purified from interfering iron and scandium activities by extraction with tri-n-butyl phosphate. If necessary, the four main groups can be purified further from interfering activities such as ⁵⁹Fe, ⁵¹Cr and ⁶⁰Co. The accuracy and reproducibility of the procedure were tested by repeated analysis of U.S. Geological Survey standard granite G-2, andesite AGV-1 and dunite DTS-1.     

Evaluation of strontium isotope abundance ratios in combination with multi-elemental analysis as a possible tool to study the geographical origin of ciders

In order to evaluate alternative analytical methodologies to study the geographical origin of ciders, both multi-elemental analysis and Sr isotope abundance ratios in combination with multivariate statistical analysis were estimated in 67 samples from England, Switzerland, France and two Spanish regions (Asturias and the Basque Country). A methodology for the precise and accurate determination of the ⁸⁷Sr/⁸⁶Sr isotope abundance ratio in ciders by multicollector inductively coupled plasma mass spectrometry (MC-ICP-MS) was developed. Major elements (Na, K, Ca and Mg) were measured by ICP-AES and minor and trace elements (Li, Be, B, Al, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, As, Se, Rb, Sr, Y, Mo, Cd, Sn, Sb, Cs, Ba, La, Ce, W, Tl, Pb, Bi, Th and U) were measured by ICP-MS using a collision cell instrument operated in multitune mode. An analysis of variance (ANOVA test) indicated that group means for B, Cr, Fe, Ni, Cu, Se, Cd, Cs, Ce, W, Pb, Bi and U did not show any significant differences at the 95% confidence level, so these elements were rejected for further statistical analysis. Another group of elements (Li, Be, Sc, Co, Ga, Y, Sn, Sb, La, Tl, Th) was removed from the data set because concentrations were close to the limits of detection for many samples. Therefore, the remaining elements (Na, Mg, Al, K, Ca, Ti, V, Mn, Zn, As, Rb, Sr, Mo, Ba) together with ⁸⁷Sr/⁸⁶Sr isotope abundance ratio were considered for principal component analysis (PCA) and linear discriminant analysis (LDA). Finally, LDA was able to classify correctly 100% of cider samples coming from different Spanish regions, France, England and Switzerland when considering Na, Mg, Al, K, Ca, Ti, V, Mn, Zn, As, Rb, Sr, Mo, Ba and ⁸⁷Sr/⁸⁶Sr isotope abundance ratio as original variables.     

ICP-MS法测定高纯钛中痕量元素

建立了ICP-MS直接测定高纯钛中Be,V,Co,Ni,Ga,Mo,Nb,Cd,Sb,TI,Pb的分析方法,并对ICP-MS工作参数及条件进行了优化和选择.高纯钛用HF与HNO3溶解后加入Sc、Cs、Re内标,用ICP-MS直接检测.方法的检出限为0.03～0.1 ng/mL,测定下限为0.2～0.5 ng/mL,各元...     

Multi-element analysis of 18 food groups using semi-quantitative ICP-MS

Fifteen radionuclides and stable elements in 18 food groups, which have been obtained by a market basket method, were determined by semiquantitative ICP-MS. Strontium, Cs,²³²Th, and²³⁸U were also determined by quantitative analytical ICP-MS or ICP-AES. For Sr,²³²Th, and²³⁸U, results of the semi-quantitative ICP-MS and the quantitative approaches were found to be in a good agreement, within ±10%. The other eleven elements (Li, V, Cr, Mn, Co, Ni, Cu, Rb, Mo, Cd, and Ba were determined with in 30% errors at the sub-ppb (ng/ml) level. More elements could be measured by the semi-quantitative mode if concentrations were at least at the sub-ppb level.     

NAA and ICP analysis of obsidian from Central Europe and the Aegean: Source characterisation and provenance determination

INAA and ICPES are compared for their discriminative power in obsidian source characterisation. Geological samples from the Aegean and Carpathian sources were analysed for Na, Sc, Fe, Co, Rb, Sb, Cs, Ba, La, Ce, Sm, Eu, Tb, Yb, Lu, Hf, Ta, Th, U by INAA and for B, Na, Mg, Al, K, Ca, Sc, Ti, Mn, Fe, Zn, Y, Yr, Cs, Ba, La, Ce, Sm, Eu, Gd, Tb, Yb, Lu, Hf by two ICPES procedures. It is shown that all techniques work successfully, however, INAA is more efficient in the chemical discrimination of neighbouring sources.     

Optode for uranium(VI) determination in aqueous medium

A quantification procedure of trace elements during colloid size fractionation was developed and validated. This procedure is based on the hyphenation between Asymmetrical Flow Field-Flow Fractionation (As-Fl-FFF) and Inductively Coupled Plasma Mass Spectrometer (ICP-MS). The optimisation of the procedure was performed on a soil leachate spiked with six trace elements selected for their environmental and health impact (As, Cd, Sb, Se, Sn and Pb). The elements in the spiked sample were on-line monitored during the fractionation. The validation was carried out by comparison with a second off-line quantification procedure based on fraction collection and total element analysis by ICP-MS. This off-line one was previously validated using reference materials. Finally, the analytical performances of the two procedures were compared.     

Comparative instrumental multi-element analysis I: Comparison of ICP source mass spectrometry with ICP atomic emission spectrometry, ICP atomic fluorescence spectrometry and atomic absorption spectrometry for the analysis of natural waters from a granite region

Summary Multi-element analysis by ICP source mass spectrometry for practically matrix-free natural waters, coming from a granitic area and, therefore, rich in trace elements, has been compared with ICP-atomic emission, ICP atomic fluorescence and atomic absorption spectrometry. The following elements have been investigated and their concentrations are in the decreasing order: Ca, Si, Na, Mg, K, Al; Sr, Mn, Ba, Fe, Rb, Zn, B, U, Y, Li, La, Be, Cs, Co, Cr, V, Sb, Bi, Th, Cu, Cd, Ni, Se, Pb, As, Hg, Mo, Tl, Sn. The concentration ranges were between 10 ppm and <0.01 ppb.As a measure of agreement between the different methods under investigation, two criteria have been used (a) the relative variation coefficient VK (%) of the mean element concentration of an element, determined by different methods in all the 98 water samples and (b) the linear, logarithmic and Spearman rank correlation coefficients between ICP-MS and each of the other methods. Detection limits are given from literature for about 32 elements using different methods.The elements Ca, Na, Mg, K, Mn, Sr, Zn, Fe, Li, Cu have been determined with ICP-MS, ICP-AES and AAS; Al, Ba with ICP-MS and ICP-AES; Si only with ICP-AES, whereas B, Be, Bi, Co, Cr, Cs, Hg, La, Mo, Ni, Pb, Rb, Sb, Sn, Th, Tl, U, V, Y only with ICP-MS. In all 34 of the investigated 36 elements could be analysed by ICP-MS, 14 (from about 20 possible) by AAS, 13 by ICP-AES and 12 by ICP-AFS.The agreement between ICP-MS and ICP-AES as well as between ICP-MS and AAS in most cases is remarkably good according to (a). VK (%) for each element in 98 water samples is in the range from ±2.6 to 10% for Na, Mg, Ca, K, Fe, Sr, Ba, Cu, Li (increasing order). Cd and Zn have unexpectedly higher values (±17.3 and ±20.5%); Cd concentrations are, however, near the detection limit.Comparing the different methods on the basis of correlation coefficients according to (b), gives for the Spearman rank correlation coefficient over the whole range of concentrations, respectively for ICP-MS/ICP-AES, AAS, ICP-AFS in case of Ca: 0.998; 0.984; 0.899; Na: 0.993; 0.991; 0.978; Mg: 0.997; 0.993; 0.959; K: 0.986; 0.942; 0.677; Al: 0.987; -; -; Fe: 0.864; 0.974; 0.701; Mn: 0.989; 0.990; 0.198; Sr: 0.988; 0.992; -; Zn: 0.894; 0.819; 0.300; Cu: -; 0.977; 0.202; Li: -; 0.907; 0.586.It is evident from these trace element concentrations as well as the electrical conductivities, that only about three fourths of the investigated samples are typical granitic waters and the remaining ones are associated with different geological background. The samples have been mainly radon waters with more than 18 nCi/l of Rn-222.

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Vergleichende Instrumentelle Multielementanalyse I: Vergleich von ICP-Massenspektrometrie mit ICP-Atomemissionsspektrometrie, ICP-Atomfluorescenzspektrometrie und Atomabsorptionsspektrometrie zur Analyse natürlicher Wässer aus einem Granitgebiet

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6th Contribution to the principles of trace analysis of elements and radionuclides

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Dedicated to Professor Dr. H. Kelker, Frankfurt, on the occasion of his 65th birthday     

Atmospheric heavy metal pollution in Slovenia derived from results for epiphytic lichens

In 1992, a monitoring survey has been started on the national scale in Slovenia using the epiphytic lichen Hypogymnia physodes (L.) Nyl. The primary aim has been to analyse lichens using the k(0)-based INAA method to obtain information about the levels of elements in the atmosphere and to identify significant pollution sources. Monte Carlo-Assisted Factor Analysis was applied to a data set of the 28 elements As, Ag, Ba, Br, Ce, Cd, Co, Cr, Cs, Fe, Ga, Hf, Hg, K, La, Mo, Na, Rb, Sb, Sc, Se, Sr, Sm, Tb, Th, U, W and Zn, which have been selected from the elements determined as the most important ones for the identification of pollution sources. A Monte Carlo approach has been used to give more insight into the uncertainties and significance levels of the factor analysis results. It has been found that concentration patterns in lichens yielded 9 factors (source types) which are presented and discussed in detail. The geographical patterns of the contributions of all factors are also shown.     

Major-to-ultratrace elements in bone-marrow fluid as determined by ICP-AES and ICP-MS.

The major-to-ultratrace elements in human bone-marrow fluid were determined by ICP-AES (inductively coupled plasma atomic emission spectrometry), and ICP-MS (inductively coupled plasma mass spectrometry). The bone-marrow fluid sample was centrifuged prior to acid digestion to exclude the bone piece from bone marrow, and then digested with nitric acid. As a result, 20 elements could be determined over the concentration range from 1610 microg g(-1) for Na to 0.00043 microg g(-1) for W. It was found that Fe, Zn and Sb were enriched by ca. 264-, 7- and 15-fold, respectively, in bone-marrow fluid, compared to those in human blood serum. Alkali metals (K, Rb, Cs), except for Na, were also significantly enriched in bone-marrow fluid. Furthermore, the concentrations of various elements, such as Fe, P, Al, Zn, Cu, Se, Zr, Sn, Ag and W, were significantly higher than those in open seawater.