Microwave digestion-ICP-MS for elemental analysis in ambient airborne fine particulate matter: rare earth elements and validation using a filter borne fine particle certified reference material

NIST standard reference material SRM 2783 was employed to validate a high temperature, high pressure, two-stage microwave assisted acid digestion procedure using HNO₃, HF and H₃BO₃ developed for the analysis of trace elements (including rare earths) in atmospheric fine particulate matter (PM_2.5) prior to inductively coupled plasma mass spectrometry (ICP-MS). This method quantitatively solubilized Na, Mg, Al, K, Ti, V, Mn, Fe, Co, Ni, Cu, Zn, As, Se, Rb, Sb, Cd, Cs, Ba, Pb, Th, U and several rare earth elements (REEs) (La, Ce, Pr, Nd, Gd, Dy, Er, Sm and Eu) from SRM 1648 and SRM 2783. A small amount of HF in the first stage was required to dissolve silicates necessitating the corresponding addition of H₃BO₃ in second stage to dissolve fluoride precipitates of Mg, La, Ce and Th. The optimized microwave dissolution—ICP-MS method detected Na, Mg, Al, K, Ti, V, Mn, Fe, Co, Ni, Cu, Zn, As, Se, Rb, Sr, Cd, Mo, Sb, Cs, Ba, La, Ce, Pr, Nd, Sm, Gd, Pb, Th and U at trace to ultra-trace levels in ambient airborne fine particles from three sites in North Carolina. La to light lanthanide signature ratios suggested that soil and motor vehicles are the dominant REE sources in SRM 2783 and PM_2.5 samples collected during this study.     

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.     

Trace elements in Variegated Bolete (Suillus variegatus) fungi

Metallic elements such as Ag, Al, Ba, Ca, Cd, Co, Cr, Cu, Fe, K, Mg, Mn, Na, Ni, Pb, Rb, Sr, and Zn were determined using ICP-OES in a representative set of fifteen fruiting bodies of the edible fungus Suillus variegatus. Fruiting bodies were collected from unpolluted areas near the village of Lubichowo of the Bory Tucholskie forest complex in northern Poland in 2007?C2008. The caps were richer in Ag, Al, Cd, Cr, Cu, Fe, K,Mg, Ni, Rb, and Zn, and the stipes in Ba, Ca, Mn, Na, Pb, and Sr. Cobalt concentration in the caps and stipes was similar. In the caps, the content of the elements decreased in the order (mg per kg of dry weight): K 29000 ± 3700, Fe 1600 ± 80, Mg 990 ± 110, Rb 320 ± 86, Zn 90 ± 19, Ca 75 ± 34, Al 68 ± 32, Na 40 ± 18, Cu 19 ± 7, Mn 13 ± 7, Cd 1.0 ± 0.5, Ni 0.64 ± 0.32, Ag 0.40 ± 0.20, Cr 0.33 ± 0.06, Pb 0.20 ± 0.17, Ba 0.19 ± 0.11, Sr 0.15 ± 0.09, and Co 0.070 ± 0.050. Apparently, S. variegatus collected from background areas are relatively low in Pb and Cd and so are suitable for human consumption.     

电感耦合等离子体原子发射光谱法同时测定植物样品中多种元素

本文为环境样品分析建立了准确、灵敏、快速的分析方法,探讨了酸类及酸度对谱线强度的影响,同时对基体元素的谱线干扰进行了校正和背景扣除,测定了环境背景值样品树干和树叶中15种元素,经标样测定结果满意。     

Geographical Discrimination of Honeysuckle (Lonicera japonica Thunb.) from China by Characterization of the Stable Isotope Ratio and Multielemental Analysis

A total of 117 honeysuckle (Lonicera japonica Thunb.) samples from four major regions of production in China, including Fengqiu in Henan, Pingyi in Shandong, Julu in Hebei, and Xiushan in Chongqing, were analyzed to determine their geographical origin. δ¹³C, δ¹⁵N, and δ¹⁸O values were determined by isotope ratio mass spectrometry (IRMS), and the contents of 18 elements (Fe, Mn, Cu, Zn, K, Ca, Mg, Pb, Cd, Cr, As, Hg, Se, Sr, Ni, Co, B, and Mo) were measured by inductively coupled plasma optical emission spectrometry (ICP-OES) and inductively coupled plasma mass spectrometry (ICP-MS). Multivariate statistical analysis by analysis of variance (ANOVA), principal component analysis (PCA), and linear discriminant analysis (LDA) were performed. The results showed that there were very significant differences in the stable isotope ratios and elemental concentrations in honeysuckle based on geographical origin, with plants from each region having a unique fingerprint. Discriminant functions were established to distinguish the origin of honeysuckle using suitable indicators including Cd, Cr, As, Hg, Se, Co, Ni, Sr, Fe, δ¹³C, δ¹⁵N, and δ¹⁸O. Cross-validated cases of 95.7% were correctly classified.     

Comparison of nondestructive proton and neutron activation: The case of biological samples

The capabilities of reactor neutron and 12 MeV proton activation were evaluted on samples of orchard leaves, beef liver and bovine liver. Based on γ-ray spectrometry, As, Ca, Cu, Fe, Mo, Pb, Sr, Ti, Zn and Zr at levels ranging from 2 to 20 900 ppm were detected following proton activation of 1 hour. Al, Br, Ca, Cl, Cu, Mg, Mn, Rb and V (ranging from 0.4 to 20 900 ppm) were measured by neutron activation (1 min irradiation). As, Ba, Br, Cr, Co, Fe, Hg, La, Na, Rb, Sb and Zn (ranging from 0.2 to 2400 ppm) were determined following a 14 h neutron irradiation. Although covering different elements, the two techniques are comparable in their scope, i. e. detection limits that can be achieved and number of elements that can be detected simultaneously.     

Application of nondestructive X-ray fluorescence analysis to determine the element composition of medicinal plants

A nondestructive X-ray fluorescence technique has been developed to determine Na, Mg, Al, Si, P, S, Cl, K, Ca, Ti, Cr, Mn, Fe, Ni, Cu, Zn, Br, Rb, Sr, Ba, and Pb in plants. The line element intensities were measured by an S4 Pioneer X-ray sequence spectrometer (Bruker AXS, Germany). The inversely proportional relationship was obtained between the analyte line intensity and mass of the plant, pressed on boric acid backing, for elements with an atomic number 11 < Z < 20. It was found that reduction of plant mass from 6 to 1 g leads to an increase in element determination sensitivity. The detection limits for 1 g of pressed plant were evaluated as μg/g: 5–20 (Na, Mg, Al); 1–4 (Si, P, S, Cl, K, Ca, Ti, Ba, Pb); 0.4-0.8 (Cr, Mn, Fe, Ni, Br, Cu, Zn, Rb and Sr). This technique was applied to determine the element composition of violets of Violaceae family, which are used in medicine.     

57Fe Mössbauer spectroscopy of banded iron formations from eastern India

Samples of the mosses Hylocomium splendens and Pleurozium schreberi, collected in the summer of 1998, were used to study the atmospheric deposition of heavy metals and other toxic elements in the Chelyabinsk Region situated in the South Urals, one of the most heavily polluted industrial areas of the Russian Federation. Samples of natural soils were collected simultaneously with moss at the same 30 sites in order to investigate surface accumulation of heavy metals and to examine the correlation of elements in moss and soil samples in order to separate contributions from atmospheric deposition and from soil minerals. A total of 38 elements (Na, Mg, Al, K, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Zn, As, Se, Rb, Sr, Zr, Mo, Sb, Cs, Ba, La, Ce, Nd, Sm, Eu, Gd, Tb, Dy, Yb, Hf, Ta, W, Au, Th, U) in soil and 33 elements Na, Mg, Al, Cl, K, Ca, Sc, V, Cr, Mn, Fe, Co, Ni, Zn, As, Se, Br, Rb, Ag, Sb, Cs, Ba, La, Ce, Sm, Tb, Yb, Hf, Ta, W, Au, Th, U) were determined by epithermal neutron activation analysis. The elements Cu, Cd and Pb (in moss samples only) were obtained by atomic absorption spectrometry. VARIMAX rotated principal component analysis was used to identify and characterize different pollution sources and to point out the most polluted areas.     

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 21 elements by INAA for certification of SRM 1570a,Spinach

Analyses for certification have been made by instrumental neutron activation analysis (INAA) for the determination of 21 elements in the National Institute of Standards and Technology (NIST) Spinach renewal reference material, SRM 1570a. Elements determined included ones with short halflife products (Al, V, Ca, Mg), intermediate halflife products (Mn, Na, K, La), and long halflife products (Ba, Co, Cr, Cs, Eu, Fe, Rb, Sb, Sc, Se, Sr, Th, and Zn). For the first time a new robotic sample changer was used in the counting of long halflife indicator isotopes for certification of an SRM. Uncertainties obtained averaged±1.80% for the four major and minor constituents (Ca, K, Mg, Na); ±3.14% for elements with concentrations from 1 to 400 mg/kg (Al, Ba, Cr, Fe, Mn, Rb, Sr, and Zn); and±8.31% for the ultra trace elements (<1 mg/kg) (Co, Cs, Eu, La, Sb, Sc, Se, Th, and V).     

Room temperature acid sonication ICP-MS multielemental analysis of milk

Room temperature acid sonication of milk samples is proposed as a fast alternative methodology for the determination of the total content of 45 elements (Li, Al, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, As, Se, Rb, Sr, Y, Mo, Ag, Cd, In, Sn, U, Sb, Te, Cs, Ba, Hg, Pb, Bi, Th, La, Ce, Pr, Nd, Sm, Eu, Gd, Dy, Ho, Er, Tm, Yb, Lu, Hf and Ta) in milk by inductively coupled plasma mass spectrometry (ICP-MS). The aforementioned procedure involves a 10 min sample pre-treatment. Measurements were made in quantitative and semiquantitative (Totalquant^®) modes of analysis using Rh as internal standard and Be, Ge, Tb and Re for internal calibration of the equipment in the semiquantitative mode. The selected isotopes were in general the most abundant ones of each element, except in cases where polyatomic or isobaric interferences were detected. Results of total concentrations in 10 liquid and 11 powdered commercially available milk samples were presented. Method validation was performed by measuring a SRM NIST-1549 non-fat milk powder and through the use of recovery experiments. Additionally, the proposed methodology was compared with a method based on a previous microwave-assisted digestion of samples and a direct analysis of 1:4 diluted samples.     

Multielement analysis of green coffee and its possible use for the determination of origin

Using instrumental neutron activation analysis (INAA), graphite furnace atomic absorption spectrometry (GFAAS), flame atomic absorption spectrometry (FAAS) and combustion elemental analysis, green coffees of the Arabica species produced in crop year 1987/88 in Colombia, Costa Rica, Cuba, El Salvador, Mexico, Nicaragua, Panamá and Papua New Guinea were analysed for the elements Ba, Br, C, Ca, Co, Cr, Cu, Cs, Fe, H, K, La, Mg, Mn, N, Na, Rb, Sc, Sr and Zn. In accordance with the concentrations determined, the elements could be ranked into five groups: Sc (sub-ppb level); Br, Co, Cr, Cs and La (ppb level); Ba, Cu, Fe, Mn, Na, Rb, Sr and Zn (ppm level); Ca and Mg (%o level); and C, H, K and N (% level). On the basis of the results obtained, an attempt was made to establish the origin of the green coffee via its elemental composition. Among the investigated elements, manganese was found to be best suited as an indicator for this purpose. However, the elements C, Co, Cs, Na and Rb proved to be of interest too.     

Determination of 32 elements in rocks by neutron activation analysis and high resolution gamma-ray spectroscopy

Neutron activation analysis and Ge(Li) spectroscopy was used to determine 32 elements in seven U.S.G.S. standard rocks of a wide range of composition. Short half-life nuclides (10 sec-10 min) were used to measure Sc, Hf, Dy, Mg, Al, Ca, Ti, V (and Na) in an automated rabbit Ge(Li) detector system. The elements K, Cu, Zn, Ga, Sr, Ba, La, Eu, Sm (and Mn) were determined by dissolution of the irradiated sample followed by removal of²⁴Na on hydrated antimony pentoxide (HAP). Long-lived nuclides were used to measure Sc, Cr, Fe, Co, Zr, Rb, Sb, Cs, Ba, Ce, Eu, Yb, Tb, Lu, Hf, Ta and Th after decay of²⁴Na. The method involves little radiochemistry and the separation is selective for²⁴Na under the experimental conditions used. Elemental concentrations determined agree well with previously published data.     

Trace Elements in Pleurotus Ostreatus,P. Eryngii,and P. Nebrodensis Mushrooms Cultivated on Various Agricultural By-Products

Abstract

Mushrooms are efficient accumulators of essential and toxic elements. Although oyster (Pleurotus spp.) mushrooms are widely commercialized and consumed, few data exist regarding trace elements content and bioaccumulation in cultivated P. ostreatus and P. eryngii, while no data are available for P. nebrodensis. The contents of Al, As, Ba, Cd, Co, Cr, Cs, Cu, Fe, K, Mn, Na, Ni, Pb, Rb, Sr, V, and Zn were monitored using inductively coupled plasma-mass spectrometry (ICP-MS) and atomic emission spectrometry (AES) in P. ostreatus, P. eryngii, and P. nebrodensis mushrooms and their cultivation substrates that include wheat straw (WHS), grape marc (GMC), olive leaves (OLV), and two-phase olive mill wastes (OMW), separately or in mixtures. Bioaccumulation factors (BAFs) less than 0.3 were obtained for Al, Ba, Co, Cr, Fe, Mn, Ni, Pb, Sr, and V; BAFs exceeding 1 for K?>?Zn?>?Cd?>?Cr?>?Rb?>?As, while the BAFs for Na were less 0.7. Mushrooms grown on OLV and OMW presented lower BAFs than those grown on WHS and GMC for all elements except for K, Cd, and Cu. P. ostreatus was an effective accumulator for Cr, Fe, and Zn; P. eryngii for Al, Cs, Ni, and V; and P. nebrodensis for As and Cd. The estimated daily intakes (μg kg^?1 body weight) from mushroom consumption were less than 0.010 for As, Cd, Co, Cs, Pb, and V, 0.010–0.10 for Ba, Cr, Ni, and Sr, 0.10–5.0 for Al, Cu, Fe, Mn, Rb, and Zn, 65–83 for Na, and 858–1030 for K. Overall, the mushrooms studied provide significant amounts of K, adequate amounts of Mn and Zn and low amounts of Na and toxic elements.     

Trace element content of some Polish hard and brown coals

Instrumental neutron activation analysis /INAA/ method was applied to measure major, minor and trace elements in 34 samples of hard and brown coal originating from eight Polish coal mines. The elemental concentrations of 38 elements /Na, Mg, Al, Cl, K, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, As, Se, Br, Rb, Sr, Mo, Ag, Cd, In, Sb, I, Cs, Ba, La, Ce, Sm, Eu, Lu, W, Au and Th/ are presented and compared with published data for coals from various origin. Enrichment factors, calculated relative to iron and the average crustal rock composition, indicated that several elements are highly enriched in Polish coals.     

High-precision direct determination of the Sr/Sr isotope ratio of bottled Sr-rich natural mineral drinking water using multiple collector inductively coupled plasma mass spectrometry

We describe a precise and accurate method for the direct determination of the ⁸⁷Sr/⁸⁶Sr isotope ratio of bottled Sr-rich natural mineral drinking water using multiple collector inductively coupled plasma mass spectrometry (MC-ICP-MS). The method is validated by the comparative analysis of the same water with and without cation-exchange resin purification. The work indicates that isobarically interfering elements can be corrected for when ⁸⁷Rb/⁸⁶Sr < 0.05 (Rb/Sr < 0.015), and that the matrix elements (Ca, Mg, K and Na) have no significant effect on the accuracy of the Sr isotope data. The method is simple, rapid, eliminates sample preparation time, and avoids potential contamination during complicated sample-preparation procedures. Therefore, the high sample throughput inherent to the MC-ICP-MS can be fully exploited.     

Excretion of biotrace elements using the multitracer technique in mice

A radioactive multitracer solution obtained from the nuclear reaction of selenium with 25 MeV/nucleon⁴⁰Ar ions was applied to the investigation of the trace elements behavior in feces and urine of mouse. The excretion rates of 23 elements, Na, K, Rb, Mg, Ca, Sr, Ga, As, Sc, V, Cr, Mn, Co, Fe, Zn, Y, Zr, Mo, Nb, Tc, Ru, Ag and In were simultaneously detected under strictly identical experimental conditions, in order to clarify the excretion behavior of the elements in mice. Fecal and urinary excretion rates of the elements in mice reached the highest value separately at 48 and 24 hours. The total excretion of Mo, Tc and Co within 96 hours were all larger, more than 60%. Accumulative excretion rates of Ca, Nb, Mg, Sr, V, Sc, Na, Cr, Fe, Ag, Mn and Zr were 60-30%. The total rates of Ru, K, As, Zn, Rb, Y, Ga and In were less than 30%, and low excretion. The main excretion pathway of Mo, Co, Mg, Fe and Ag was through urine, and Na, K, As and Rb were eliminated from the body also in urine. But fecal excretion of Tc, Nb, Sr, Y, Ru, and In were larger than urinary excretion, and Ca, Sc, Mn, Zr, Zn were eliminated from the body in feces.     

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.     

Assessment of atmospheric deposition of metals in Ha Noi using the moss bio-monitoring technique and proton induced X-ray emission

Journal of Radioanalytical and Nuclear Chemistry - The concentration of 22 metal elements including Mg, Al, Si, P, S, Cl, K, Ca, Ti, Cr, Mn, Fe, Ni, Cu, Zn, As, Br, Rb, Sr, Zr, Ba and Pb in Barbula...     

Comparison of digestion methods for ICP-MS determination of trace elements in fish tissues

A comparison is presented of six methods involving nitric acid in conjunction with other reagents to digest three certified marine biological samples (DOLT-3, DORM-3, IAEA-407) and a fish bone homogenate (prepared from Merluccius australis). An inductively coupled plasma-mass spectrometer with an octopole collision cell was used to determine up to 40 elements (Li, B, Na, Mg, Al, K, Ca, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, As, Se, Rb, Sr, Y, Ag, Cd, Cs, Ba, La, Ce, Pr, Nd, Sm, Eu, Gd, Dy, Ho, Er, Tm, Yb, Lu, Pb, Th, U) in the digests. These results were assessed in terms of their accuracy and precision, and a flow chart was developed to aid the selection of the optimal digestion method. Although none of the methods was found to give accurate determinations for all elements in the different reference materials, a relatively simple method involving nitric acid and hydrogen peroxide heated in a domestic microwave oven gave the most acceptable results.