Strategy for water analysis using ICP-MS

The developed strategy permits determination in three steps of sixty-seven elements using inductively coupled plasma mass spectrometry (ICP-MS). Sodium, Mg, Si, S, Cl, K, and Ca are determined in a first step; B, Al, P, Cr, Fe, Mn, Ni, Cu, Zn, As, Se, Ag, Cd, Sb, Ba, Hg, and Pb are determined in a second step; and Li, Be, Ti, V, Co, Ga, Ge, Br, Rb, Sr, Y, Zr, Nb, Mo, Sn, Te, I, Cs, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Hf, Ta, W, Pt, Au, Tl, Bi, Th, and U are analyzed in a third step. The figures of merit obtained are adequate to carry out water quality monitoring and other hydrochemical studies, such those based in the application of hydrochemical fingerprinting to water management.     

Determination of trace elements in ambient aerosol samples

A microwave-assisted digestion procedure using HNO₃, HF, and H₂O₂ has been developed for analysis of elements in ambient particulate matter (PM). The samples are collected on cellulose filters and analyzed by inductively coupled plasma mass spectrometry (ICP-MS). The ICP-MS is calibrated with external standards, and recovery of analytes is tested with NIST SRM 1648 Urban Dust. This method has been used to quantify the airborne concentrations of a large number of elements, including Ag, As, Ba, Be, Ca, Cd, Ce, Co, Cr, Cs, Cu, Fe, Ga, K, Li, Mg, Mn, Mo, Ni, Pb, Rb, Se, Sb, Sr, Ti, Tl, V, and Zn. For the majority of these elements, recovery of the NIST SRM is within 15% of the certified values.     

Neutron activation analysis of an iranian cigarette and its smoke

Non-destructive neutron activation analysis, employing a high-resolution Ge(Li) detector, was applied to determine the concentration of 24 trace elements in the tobacco of the Zarrin cigarette which is commercially made in Iran. These elements are: Na, K, Sc, Cr, Mn, Fe, Co, Zn, Se, Br, Rb, Ag, Sb, Cs, Ba, La, Ce, Sm, Eu, Tb, Hf, Au, Hg and Th. The smokes from the combustion of this tobacco and of the cigarette paper were also analysed for these elements and the percentage transference values were calculated.     

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     

封闭压力酸溶-ICP-MS法分析地质样品中47个元素的评价

对封闭压力酸溶－ICP－MS法同时测定地质样品中47个元素的效果和适用范围进行了实测评价。并对溶样条件进行了优化。实验结果表明，HF－HNO3高温高压酸溶是一种有效的样品分解方法，在所测定的47个元素中，大部分元素如Li,Be,Ti,V,Mn,Co,Ni,Cu,Zn,As,Zr,Nb,Mo,Cd,In,Sn,Sb,Hf,Ta,W,Tl,Pb,Bi等在大多数标样中在三种取样量下都可以得到满意的回收率。而Sc,Cr,Ga,Y,REE,Rb,Cs,Sr,Ba,Th,U等元素在大部分样品中则随取样量减少，回收率上升，在一些样品中，当取样量降至25mg时，可以获得满意的回收率。用王水代替HNO3复溶残渣，利用氯离子的络合作用促进复溶，使许多元素的回收率有了明显的提高。     

Diagrammes d'equilibre des systemes d'halogenures CuY-MYn

Phase diagrams for the series of CuY-M^IY and CuY-M^IIY systems (whereM ^I=Li, Na, K, Rb, Cs, Tl,M ^II=Zn, Cd, Hg, Sn, Pb andY=Cl, Br, I) were compared. Changes and trends accompanying the increase of charge of the second cation were discussed.

     

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.     

Preparation of the Bovine Kidney and Bovine Muscle reference materials and the certification of element contents from interlaboratory comparisons

Results obtained in interlaboratory comparisons on candidate reference materials Bovine Kidney and Bovine Muscle, in which more than 32 laboratories participated employing atomic spectrometry, electrochemical, and nuclear analytical techniques, have been evaluated using combined statistical and analytical considerations. Certified and/or information values for the elements Br, Ca, Cd, Co, Cr, Cu, Fe, Hg, K, Mg, Mn, Mo, Na, P, Pb, Rb, Se, and Zn have been established. Information on contents of the elements Al, As, Au, Cs, Li, Ni, Sb, Sn, Sr, and V is also presented.     

Distribution of some major and trace elements in Danube Delta lacustrine sediments and soil

Sediment cores collected from lakes Mesteru and Furtuna (eastern part), Sontea channel and soil samples collected from Caraorman bar, all located in the Danube Delta, were analyzed for 42 elements (Ag, Al, As, Be, Na, Mg, P, S, K, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, As, Se, Br, Rb, Sr, Y, Mo, Ag, Cd, In, Sn, Sb, Cs, Ce, Hf, Hg, Tl. Pb, Bi, Th. U) by instrumental neutron activation analysis (INAA), thick target proton induced X-ray emission (TT-PIXE) and inductively coupled plasma-mass spectrometry (ICP-MS). The INAA and TTPIXE yielded total concentrations whereas the ICP-MS data reflected the fractions soluble in 14M HNO₃. The ICP-MS data exhibited surface enrichment relative to the lower part of the sediment core of Cu, Zn, As, Ag, Cd, In, Sn, Sb, Hg, Tl, Pb, and Bi, most prominently by Cd and Hg. Their vertical distribution in the investigated cores generally reflected the pollution history of recent sediments in Danube delta, showing a steady increase until the end of the 1980s followed by a slow decrease after 1990. The vertical profiles of most remaining elements were characterized by a relatively uniform distribution along the cores. In some cases, the concentrations of As, Cd, Cu, Cr, Mn, Ni and Pb exceeded minimum thresholds of safety, as defined by the Romanian regulations. The elemental composition of the sediment below 20 cm depth (total concentrations) was similar to that of the upper continental crust (UCC) for most elements. Values distinctly higher than UCC were observed for As, Sb (factor ~5) and Cr, Ni, Cu (factor 2 to 3). The nitric acid soluble element concentrations in the soil samples in some cases showed increased values at the surface as compared to 30 cm depth, either due to air pollution or to the action of plants. In no case a large contribution to the topsoil from atmospheric deposition was evident, indicating that the surface contamination of the sediments was mainly by riverine transport. This revised version was published online in July 2006 with corrections to the Cover Date.     

Characterization of Indian cigarette tobacco and its smoke aerosol by nuclear and allied techniques

Forty brands of tobacco used in Indian cigarettes, 20 brands of bidis (tobacco rolled in wrapper leaves), 15 brands of chewing tobacco and 15 brands of snuff tobacco were analyzed by nuclear and allied techniques. The elements measured into tobacco can be grouped into seven categories from less than 1 ppm to 5% by weight. Concentration level varied from 0.5-5% for (Ca, K, Cl), 400-1500 ppm (Fe), 200-600 ppm (Na), 100-300 ppm (Ti, Mn, Br and Sr), 10-100 ppm (Cu, Zn and Rb), 1-10 ppm (Cr, Ni, Pb and La) and less than 1 ppm (As, Co, Cd, Sb, Hg and Eu). Among the above elements Cr, Ni, As, Cd, Pb, Hg and Sb are considered toxic. The percentage transfer of the elements from cigarette tobacco to smoke particles during smoking was also estimated using a smoking machine and collecting the smoke particles on a filter paper. The results show that Br, Cr, Sb and Zn have high percentage transfer from tobacco to its smoke of the order of 2-15%. Out of these Sb has the highest 15%. Cobalt, Fe and Sc have lowest percentage of transfer of the order of less than 1%. The percent transfer of these elements from tobacco to tobacco smoke is higher in case of bidis (1.5-3.0 times) as compared to cigarettes. In cigarettes also non-filter cigarettes have higher transfer (2-3 times) as compared to filter tip cigarettes.     

Preparation of the bovine liver 12-02-01 reference material and the certification of element contents from an interlaboratory comparison

Summary The preparation of the bovine liver 12-02-01 reference material, its stabilization and homogeneity testing is presented. Evaluation of an interlaboratory comparison in which 31 laboratories took part using several analytical methods is described. From the results of the intercomparison, the contents of the elements Cd, Cu, Hg, Mn, Pb, Se, and Zn were certified, while for the elements Br, Co, Fe, K, Mo, Na, and Rb, information values were derived. Non-recommended values for the elements Ag, As, Ca, Cl, Cr, Cs, La, Mg, S, Sb, Sn, Sr, and V were also evaluated.Denoted as CZIM-liver in the report [23]     

Egyptian and foreign cigarettes

Neutron activation analysis has been employed to determine the concentration of 27 elements in an Egyptian cigarette filter before and after smoking. The filter of three foreign cigarette brands are also analyzed and compared to the Egyptian brand. The elements determined are Al, As, Ba, Br, Ce, Cl, Co, Cr, Cs, Eu, Fe, Hf, K, La, Mg, Mn, Na, Ni, Rb, Sb, Sc, Se, Sr, Th, Ti, V and Zn. It is observed that the concentration of the measured elements in the Egyptian brand are within the concentration range of foreign brands, and that the concentration of As, Br, Cl, K, Na and Se in the filters are increased after smoking regardless the brand examined.     

Study of hair element content from an urban Bulgarian population using NAA assessment of environmental status

In this preliminary study, scalp hair samples from 36 individuals resident in Sofia, Bulgaria, were analysed and Ag, Al, As, Au, Ba, Br, Ca, Cd, Ce, Cl, Co, Cr, Cs, Cu, F, Fe, Hg, I, K, La, Mg, Mn, Mo, Na, Ni, Rb, S, Sb, Sc, Se, Sn, Sr, Ti, V, W, and Zn were determined. Instrumental neutron activation analysis (INAA) methods were used. Three washing procedures.: distilled-deionised water; acidacetone-water; and Triton X-100 detergent-water, showed a variable elemental change strongly dependent on the procedure used. More than 18 elements (Al, As, Ba, Ca, Ce, Cl, Co, Cs, F, Fe, I, K, La, Mo, Na, Ni, Sb, Sc, Sr and V) were easily removed by water-washing. Triton X-100 detergent was more effective in removing Ag, As, Au, Cl, Cs, K, Na and Rb; but not Hg. Only S and Zn were strongly incorporated in the hair structure (less than 10% being removable by any washing technique). There is no significant age correlation with any element between the various hair treatment groups. Elevated cadmium levels were found in the hair of smokers (0.711–4.913 g/g Cd) compared with nonsmokers (0.568–2.681 g/g Cd). Comparison of the elemental data for distilled water-washed hair and studies from Oxford, England and Hastings, and Hastings, New Zealand (using the same INAA method) revealed interesting variations dependent on local industrial and nutritional factors.     

Neutron activation analysis of an Egyptian cigarette and its ash

The concentration of 28 elements in tobacco and cigarette paper in an Egyptian Cigarette were determined using instrumental neutron activation analysis. These elements are: Al, As, Ba, Br, Ca, Ce, Cl, Co, Cr, Cs, Eu, Fe, Hf, K, La, Mg, Mn, Na, Ni, Rb, Sb, Sc, Se, Sr, Th, Ti, V and Zn. The cigarette filter (before and after normal smoking) and the produced ash were analyzed to determine the adsorption of the elements on the filter and their remains in ash. The material balance for the determined elements were calculated.     

Single-step microwave digestion with HNO(3) alone for determination of trace elements in coal by ICP spectrometry

A microwave digestion method with HNO₃ alone was conducted at a temperature as high as 250 °C for determination of 19 trace elements (Li, Be, V, Cr, Mn, Co, Ni, Cu, Zn, Ga, As, Se, Rb, Sr, Cd, Cs, Ba, Hg, and Pb) in coal jointly by inductively coupled plasma optical emission spectrometry (ICP-OES), inductively coupled plasma mass spectrometry (ICP-MS), and flow injection ICP-MS (FI-ICP-MS). The validity of determination was assessed by using three standard coals, SRM 1632c, BCR 180, and SARM 19. It was found that the high-temperature digestion led to an extensive decomposition of the organic matrix and clay in coal, and no dissolved and solid carbon remained in the final solution after evaporation. Good recoveries were observed for all trace elements in three coals, with the exception of V, Rb, and Cs in high-ash SARM 19. Additionally, FI-ICP-MS combined with the present digestion without evaporation pretreatment was proved to be a rapid and efficient approach for determination of ultra-trace elements such as Se, Cd, and Hg in coal.     

Elemental content in wheat products of Al-Qusim region, Saudi Arabia using the INAA technique

Wheat is one of the most grown crops in Saudi Arabia. It is grown in various regions of the country. Accurate knowledge of the elemental concentrations in wheat and its products (bran and flour) is of great importance from a nutritional point of view. Wheat samples were obtained from the Al-Qusim region, 300 km northwest of Riyadh, and analyzed. Up to 50 elements (Al, Sb, As, Ba, Br, Cd, Ca, Cs, Cl, Cr, Co, Cu, Ga, Au, Hf, In, I, Ir, Fe, Mg, Mn, Hg, Mo, Ni, K, Rb, Sc, Se, Ag, Na, Sr, Ta, Te, Th, Sn, Ti, W, U, V, Zn, Zr, Ce, Dy, Eu, La, Lu, Nd, Sm, Tb and Yb) were determined in the wheat products. It was observed that the elemental content of bran was much higher than that of white flour.     

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.     

Egyptian and foreign cigarettes

The concentration of 27 elements has been measured using neutron activation analysis in a cigarette brand commercially manufactured in Egypt and in three foreign brands available on the Egyptian market. The cigarette components examined were cigarette tobacco, cigarette wrapping paper and cigarette ash. All results are expressed in absolute values per cigarette. The concentration of Al, As, Ba, Br, Cl, Cs, Eu, Fe, Mn, Na, Ni, Rb, Sb, Sc, Sr, Th, Ti and V in the Egyptian cigarette were above the range determined for the foreign brands examined; however, Ce, Co, Cr, Hf, K, La, Mg, Se and Zn were within that range. Except for K, Mn, Ni and Ti, the above conclusions was the same for elements determined in the ash. The wrapping paper used for the Egyptian cigarette contains the lowest quantity of Cl and Mn.     

Determination of trace elements of some Egyptian crops by instrumental neutron activation,inductively coupled plasma-atomic emission spectrometric and flameless atomic absorption spectrophotometric analysis

Instrumental neutron activation analysis was used for the determination of Al, Br, Ca, Ce, Cl, Co, Cr, Cs, Eu, Fe, K, La, Mg, Mn, Na, Rb, Sb, Sc, Se, Ti, Th, V and Zn, ICP-AES for the determination Al, Ag, Ba, Be, Ca, Co, Cr, Cu, Fe, Ga, K, Li, Mg, Mn, Na, Ni, P, Sc, Sr, Ti, V and Zn and flameless AAS for the determination of Cd, Hg and Pb in egg plant, potatoes, green pepper (Leguminosae), vegetable marrow (Cucurbitaceae), pears, apple (Rosaceae), castor oil plant (Euphorbiaceae), lettuce (compositae), dill, parsley, coriander (Umbelliferae), and in some soil samples collected from Aswan province.     

Determination of trace elements in Iranian cigarette tobacco by neutron activation analysis

The concentration of 24 trace elements in the tobacco of two different brands of Iranian cigarettes, “Zarrin” and “Oshnoo”, has been measured by neutron activation analysis employing a high-resolution Ge(Li) detector. These elements are: Na, K, Sc, Cr, Mn, Fe, Co, Zn, Se, Br, Rb, Ag, Sb, Cs, Ba, La, Ce, Sm, Eu, Tb, Hf, Au, Hg and Th.