Nano-SIMS analysis of Mg, Sr, Ba and U in natural calcium carbonate.

Concentrations of minor (Mg and Sr) and trace (Ba and U) elements in four natural calcium carbonate samples were first analyzed by inductively coupled plasma mass spectrometry (ICP-MS) after chemical dissolution and calibrated against a standard dolomite. Their homogeneities were checked by in situ laser ablation (LA) ICP-MS with 10-20 spots. The carbonate samples were measured by using a high lateral resolution secondary ion mass spectrometer (Nano-SIMS NS50). A approximately 4 nA O- primary beam was used to sputter a 5-6-microm diameter crater on the sample surface, and secondary positive ions were extracted for mass analysis using an accelerating voltage of 8 kV and a Mattauch-Herzog geometry. A multi-collector system was adjusted to detect 26Mg+, 43Ca+, 88Sr+, 138Ba+, 238U16O+ and 238U16O2+ ions at the same time. A resolving power of 2500-5000 at 10% peak height was attained by an entrance slit set at 40 microm, and each exit slit at 50 microm with adequate flat-topped peaks. The observed 26Mg/43Ca, 88Sr/43Ca, 138Ba/43Ca and 238U16O2/43Ca ratios agreed well with those measured by LA-ICP-MS. Foraminifera shells were analyzed at 5-6 microm scale by Nano-SIMS. There was a large variation of the Mg/Ca ratios, up to +/- 38%, even in a single fragment of the shell, suggesting that although the ratios provide a useful paleoceanographic proxy at bulk scale, they may reflect a more complex pattern at < 10 microm scale.     

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.     

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     

Chromatographische trennung von metallionen durch elution mit ammoniumsulfat: Bestimmung von magnesium,calcium und strontium in salzreichen wässern

The chromatographic separation of Mg, Ca, Sr, Ba, Fe(II, III) and Mn(II) by elution with ammonium sulphate solution from Dowex 50–X₁₀ was studied. The optimum conditions for the separation of the alkaline earths from each other were established. The method was applied for the separation of Mg, Ca and Sr in salt waters; Mg and Ca were determined by EDTA titration and Sr spectrographically, the coefficient of variation being 1.9% for Mg and 1.4% for Ca.     

Characterization of metal binding properties of rhamnogalacturonan II from plant cell walls by size-exclusion HPLC/ICP-MS.

The binding properties of metal ions to a pectic polysaccharide, rhamnogalacturonan II (RG-II), from plant cell walls were analyzed by size-exclusion HPLC/ICP-MS. The dimeric RG-II borate complex (dRG-II-B) from sugar beet and red wine contained 0.8 - 1.1 mol/mol of B, 0.8 - 1.1 mol/mol of Ca, 0.1 - 0.3 mol/mol of Sr, and 0.03 - 0.07 mol/mol of Ba. The treatment of dRG-II-B with Sr2+, Ba2+, Pb2+ or La3+ exchanged the originally present Ca, Sr and Ba. In contrast, monomeric RG-II (mRG-II), which contained approximately 0.1 mol/mol of Ca, formed complexes with La3+, Eu3+, and Lu3+ added to the solution, but did not do so with Ca2+, Sr2+, Ba2+ and Pb2+. The HPLC/ICP-MS and HPLC/RI (refractive index detector) analysis of the partially hydrolyzed mRG-II that was treated with La3+ indicated that the side chains and backbone of mRG-II together form a lanthanoid binding site.     

ICP-MS法测定不同采收期山楂叶中微量元素

建立了电感耦合等离子体质谱法(ICP-MS)测定不同采收期山楂叶中微量元素的半定量分析模式。结果表明,不同采收期山楂叶可测定的28种微量元素中,Mg、Si、K、Ca、Na、Al、Mn、Fe、Sr和Ba为主要元素。Zn、Rb、Sc、Li、Ge、In和Bi的含量随叶的生长逐渐下降,而Zr、Sn、Sb和Th与之相反,其它元素基本没有变化。该法简单、选择性强、灵敏度高、定量准确,适用于不同采收期山楂叶中微量元素测定,为全面控制山楂叶质量提供依据,也为合理开发和利用山楂叶提供借鉴。     

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.     

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.     

Elemental analysis of silicon based minerals by ultrasonic slurry sampling electrothermal vaporisation ICP-MS

Ultrasonic slurry sampling electrothermal vaporisation inductively coupled plasma mass spectrometry (USS-ETV-ICP-MS) was applied to the elemental analysis of silicate based minerals, such as talc or quartz, without any pre-treatment except the grinding of the sample. The electrothermal vaporisation device consists of a tungsten coil connected to a home-made power supply. The voltage program, carrier gas flow rate and sonication time were optimised in order to obtain the best sensitivity for elements determined. The relationship between the amount of sample in the slurry and the signal intensity was also evaluated. Unfortunately, in all cases, quantification had to be carried out by the standard additions method owing to the strong matrix interferences. The global precision of the proposed method was always better than 12%. The limits of detection, calculated as three times the standard deviation of the blank value divided by the slope of the calibration curve, were between 0.5 ng/g for As and 3.5 ng/g for Ba. The method was validated by comparing the concentrations found for Cu, Mn, Cr, V, Li, Pb, Sn, Mg, U, Ba, Sr, Zn, Sb, Rb and Ce using the proposed methodology with those obtained by conventional nebulisation ICP-MS after acid digestion of the samples in a microwave oven. The concentration range in the solid samples was between 0.2 μg/g for Cr and 60 μg/g for Ba. All results were statistically in agreement with those found by conventional nebulisation.     

Vibrational spectra of four alkaline earth cyclo-hexaphosphates

FT-IR and FT-Raman spectra of four alkaline earth (Mg, Ca, Sr and Ba) cyclo-hexaphosphates have been recorded and analysed. FT-Raman spectra of the deuterated analogues of these compounds are used to clear the ambiguity regarding the OH vibrations in the low frequency region. The spectra reveal that the P6O18(6) anion ring in all compounds have independent PO4 tetrahedra present in it. The P-O(P)and P-O(M')(M'-Mg, Ca, Sr and Ba) bonds become stronger as the cation size decreases. The P6O18(6-) anion ring is distorted in the Mg and Ca compounds. In the Sr and Ba compounds, free and hydrogen bonded water molecules of varying strength are present, whereas in Mg and Ca compounds no free water molecules exist. The POP bridge angle of the Mg, Ca and Sr compounds are estimated using the correlations between the POP bridge stretching frequencies and the bridge angle value.     

Rapid multi-element analysis of groundwater by high-resolution inductively coupled plasma mass spectrometry

A rapid and sensitive method was developed to determine, with a single dilution, the concentration of 33 major and trace elements (Na, Mg, Si, K, Ca, Li, Al, P, S, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, As, Se, Sr, Mo, Cd, In, Sn, Sb, Cs, Ba, Re, Hg, Pb, Bi, U) in groundwater. The method relies on high-resolution inductively coupled plasma mass spectrometry (HR ICP-MS) and works across nine orders of magnitude of concentrations. For most elements, detection limits for this method are considerably lower than methods based on quadrupole ICP-MS. Precision was within or close to ±3% (1) for all elements analyzed, with the exception of Se (±10%) and Al (±6%). The usefulness of the method is demonstrated with a set of 629 groundwater samples collected from tube wells in Bangladesh (Northeast Araiharzar). The results show that a majority of tube well samples in this area exceed the WHO guideline for As of 10 g L^–1, and that those As-safe wells frequently do not meet the guideline for Mn of 500 µg L^–1 and U of 2 µg L^–1.     

Ultratrace Elements in Terrestrial Water as Determined by High-Resolution ICP-MS

The double-focusing inductively coupled plasma-mass spectrometry (ICP-MS) was proved to be an extraordinarily sensitive analytical technique. When this ICP-MS was combined with an ultrasonic nebulizer to increase the sample introduction efficiency, the detection power of the system was enhanced even further. The detection limits of most elements attained by this technique were less than 0.1 ppt and reached as low as 1 ppq (1/1000 ppt) for several elements. Analytical results of the standard reference materials, SRM 1643c (trace elements in water) provided by the National Institute of Standards and Technology, and SLRS-2 (riverine water) supplied by the National Research Council of Canada showed that the concentration values obtained by this method were in good agreement with the certified values for all the elements examined. Although the concentration levels of elements in freshwater were in most cases lower than 1 ppm with the exception of several major elements (Na, K, Ca, Mg, Si, S, and CI), it was possible to determine around 40 ultratrace elements (Li, Be, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Rb, Sr, Y, Cd, Cs, Ba, La, Ce, Pr, Nd, Sm, Eu, Gd, Th, Dy, Ho, Er, Tm, Yb, Lu, TI, Pb, Bi, Th, and U) with acceptable speed (less than 30 s per element) and precision (around 5% RSD) by direct sample introduction. No sample pretreatment, such as chemical separation and/or preconcentration, was necessary. It was also possible to directly determine as many as about 40 ultratrace elements in rainwater on as routine basis, although a much longer integration time (about 5 min/element) was applied because the concentration levels of elements in rainwater are far lower than those observed in river and lake water,     

ICP-MS法同时测定烟草中17种微量元素

采用微波消解前处理样品、电感耦合等离子体质谱检测的方法,同时测定了烟叶中铍(Be)、钛(Ti)、钒(V)、铬(Cr)、镍(Ni)、铜(Cu)、砷(As)、锶(Sr)、钼(Mo)、银(Ag)、镉(Cd)、铯(Cs)、钡(Ba)、铊(Tl)、铅(Pb)、钍(Th)和铀(U)共17种元素,回收率90·27%~110·4%,检出限0·3521~345·3ng/L,相对标准偏差1·65%~9·86%。实验结果表明,该方法能满足痕量分析的要求。用此方法对来自5个地区的烟叶样品进行了考察,研究了以上元素随产地、部位不同的分布特性,发现同一品种不同地区、部位的烟叶中上述元素的含量存在一定的差别。     

古人类骨骼中微量元素的分析及其与古代食谱的关联

采用等离子体质谱(ICP-Ms)法对三峡地区及长江下游地区出土的古墓中的人体骨骼中的微量元素Zn、Sr、Ba、Ca进行了分析，并与原子吸收光谱(AAS)对照，结果表明：ICP-MS是骨化学微量元素分析很好的方法，它相对FAAS，具有灵敏度高，检出限低，可快速进行多元素检测等优点，对溶液中元素的检出限可达到ng/L数量级，对元素的高含量和低含量都能进行准确测量。本实验以Zn、Sr、Ba、Ca为指示剂，根据其测量结果，还对上述两地区的古人类食谱进行了初步探讨。     

微波辅助消解-电感耦合等离子体原子发射光谱法(ICP-AES)测定几种血藤中17种元素

建立电感耦合等离子体原子发射光谱法(ICP-AES)测定血藤类中药中K,Ca,Mg,P,Sr,Fe,Mn,Zn,Cu,Co,Cr,Al,Ba,Ni,As,Pb和Cd 17种常量和微量元素含量的分析方法。样品用微波辅助消解,ICP-AES法检测几种血藤中17种元素的含量,方法的检出限为0.000 03~0.009 81μg/mL,加标回收率88.37%~110.00%,相对标准偏差(RSD)均小于5.0%,方法可快速、灵敏、准确测定血藤类中药中多种常量、微量元素的含量。血藤样品中除含有人体必需的常量元素K,Ca,Mg外,还含有Fe,Zn,Mn,Cr,Co等必需的微量元素和其它元素P,Ni,Ba,Al,Sr,Pb,Cd,Ba等。     

Separation of strontium from associated elements with selective specific resin and extraction chromatography

In this paper,separation of Sr from associated elements（Na,K,Ca,Mg,and Ba） was carried out using an extraction chromatographic column packed with Sr selective specific resin consisting of an octanol solution of 4,4’（5’）-bis（t-butylcyclohexo）-18-crown-6 sorbed on an inert polymeric support.Using 8.0 mol/L HNO₃ as the eluent,Ba and associated elements were eluted immediately from the column, whereas Sr was strongly retained.The adsorbed Sr could then be stripped from the column as the eluent was changed to 0.05 mol/L HNO₃.Complete Sr/Ba separation was demonstrated to be feasible in that Ba could be washed from the column leaving pure Sr by adequate rinsing with 8.0 mol/L HNO₃. Furthermore,matrix effect could be effectively eliminated and the selectivity of the method was improved.The method was applied for the determination of Sr in the high purity barium carbonate （BaCO₃） product and seawater.The recoveries of Sr in 2 samples were determined to be 93.2%and 109%, respectively.     

Application of multivariate optimization in the development of an ultrasound-assisted extraction procedure for multielemental determination in bean seeds samples using ICP OES

In this paper, multivariate optimization was applied for the development of an ultrasound-assisted multielemental extraction procedure for analysis of bean samples by inductively coupled plasma optical emission spectrometry. For this procedure, powdered samples were treated with an acid mixture and submitted to ultrasound energy for extracting the target elements (Ba, Ca, Cu, Fe, K, Mg, Mn, Sr and Zn). Centroid simplex mixture design was used for optimize the acid proportions (nitric, acetic and chloride acid) and Box Behnken design was applied for optimize the process variables (particle size, final concentration of extracting solution and sonication time) after mixture optimization. Iron had not presented quantitative extractions and it was excluded from final samples analysis. The developed method presents the follow limits of quantification in μg g^{− 1}: Ba (0.90); Ca (5.2); Cu (4.0); K (0.90); Mg (1.4); Mn (0.22); Sr (0.25) and Zn (4.0). Accuracy was accessed by comparison of determined concentration with the values obtained by the microwave digestion procedure. The proposed method was applied toward the determination of elemental composition in bean samples collected in the country zone from Jequié city located on the Bahia State, Brazil. The trace elements content ranged from 0.21 to 3.04, 3.84 to 10.8, 0.60 to 5.23, 31.0 to 46.5 and 10.8 to 19.6 μg g^{− 1} Ba, Cu, Sr, Zn, Mn, respectively. The major elements content ranged from 0.0418 to 0.0877, 0.109 to 0.153 and 1.30 to 1.56% (w/w) Ca, Mg and K, respectively.     

Measurements of contaminant elements of wines by inductively coupled plasma-mass spectrometry: A comparison of two calibration approaches

The aim of the present work was to develop and validate an accurate method by ICP-MS focalized to the measurement of contaminant elements in wines, in special those with legal importance. In addition, we intended to evaluate the suitability of ICP-MS semi-quantitative methodology in order to reduce the time and cost of analysis. Twenty-six contaminant elements of wine (Li, Be, Al, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, As, Se, Rb, Sr, Ag, Cd, In, Cs, Ba, Hg, Tl, Pb, Bi and U) were measured using quantitative and semi-quantitative calibration approaches, in diluted white and red wines. In an early step potential interferences caused by Cl and Ca species were evaluated, in order to establish suitable mathematical corrections. For validation of ICP-MS procedures a few elements were determined by flame and electrothermal AAS. Reference wines from 1992 year, with provisional values, were analyzed and the results showed satisfactory agreement. The semi-quantitative calibration provided slightly higher limits of detection than those obtained by the quantitative calibration, and always lower than 0.1 μg l⁻¹, except for Fe and Zn. For most elements the recovery percentages (between 90 and 100%) and precision of the results (R.S.D. (%) < 4) were similar for both modes. Differences lower than 20% of concentration was obtained for most elements. Both methodologies offer valuable alternatives to wine characterization and comparison purposes. For legal requirements control purposes, with reference to the importance of accurate results, quantitative approach is the most suitable alternative.     

Semiquantitative Analysis of Biological Materials by Inductively Coupled Plasma–Mass Spectrometry

Semiquantitative analysis with accuracy of ±30 to 50% is a valuable tool for rapid screening of samples prior to quantitative determination of trace metals. In this study semiquantitative analysis software available with commercial inductively coupled plasma–mass spectrometry (ICP-MS) instrumentation is applied for rapid multielemental analysis, and the accuracy and precision of this semiquantitative analysis approach is evaluated with biological certified reference materials. Samples were prepared by high-pressure, high-temperature nitric acid vapor-phase digestion. For most elements the measured semiquantitative results are in the range of the certified values. With appropriate analyte solution dilution, the measured concentrations of the major elements (e.g., Ca) also agree with certified values. The accuracy is within ±10% for 28 element determinations that include 16 individual elements (Ag, As, Cd, Co, Cr, Cu, Fe, Mn, Mo, Ni, Pb, Rb, Sb, Sr, Tl, and Zn) and ±20% for 54 element determinations that include three more elements (Mg, V, and U) in eight certified reference materials including water. The method precision is 11 ± 11% (relative standard deviation,n= 65).     

Analytical investigations of tree rings by laser ablation ICP-MS

Laser sampling inductively coupled plasma mass spectrometry has been used for the quantitative determination of trace elements to characterize annual growth rings of trees. The elements studied are Mg, Al, Ca, Cr, Mn, Fe, Co, Ni, Cu, Zn, Sr, Cd, Ba, Tl, Pb, Bi and U. Cellulose mixed with multielement standard solution pressed into pellets were used for the calibration. Using internal standardization with ¹²C the precision is typically better than 10% relative standard deviation. The limits of detection were limited by the purity of the cellulose. Analytical figures of merit and the analytical results are discussed in terms of environmental analysis.