Polarographic determination of cadmium, lead, nickel, thallium and uranium(VI) in isoquinoline formate

Summary The polarographic behaviour of Cd, Pb, Ni, Tl and U(VI) has been described in 0.1 M isoquinoline formate as base electrolyte. In all cases well defined reversible waves were obtained and determinations are possible in the presence of Mo, Co, Zn, Mn, Te, In, Se, Fe, Cr, V, Th, Zr, As, Sb, Ag, Hg and Cu.

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Polarographische Bestimmung von Cadmium, Blei, Nickel, Thallium und Uran(VI) in Isochinolinformiat

Zusammenfassung Das polarographische Verhalten von Cd, Pb, Ni, Th. und U(VI) in 0,1 M Isochinolinformiatlösung wird beschrieben, Bestimmungsmöglichkeiten werden aufgezeigt. In allen Fällen werden gut definierte reversible Stufen erhalten. Folgende Elemente stören nicht: Mo, Co, Zn, Mn, Te, In, Se, Fe, Cr, V, Th, Zr, As, Sb, Ag, Hg, Cu.

     

Radioactive and stable elements’ concentration in medicinal plants from Brazil

Since the early days of mankind, plants have been used as food and for medicinal purposes. Still, little information exists in literature about the activity concentration of ²³⁸U and ²³²Th decay products, as well as stable element concentrations in Brazilian plants. Activity concentrations of ²²⁶Ra, ²²⁸Ra and ²¹⁰Pb, and chemical concentrations of As, Ba, Br, Cs, Co, Cr, Cu, Eu, Fe, Hf, La, Lu, Rb, Sb, Sc, Sm, Ta, Tb, Yb, Zn and Zr were determined in ten samples commonly used in Brazilian medicinal plants.     

Chemical characterization and 210Pb dating in wetland sediments from the Nhecolândia Pantanal Pond, Brazil

Summary Pantanal, located in the central region of South America, is recognized as one of the world's largest freshwater wetlands. In order to verify possible changes in this environment, a study was undertaken in Nhecolandia Pantanal, Mato Grosso do Sul State, Brazil. Two sediment cores from the Salina do Meio pond (SM1 and SM2) and one core from a small flood land named Baía (B5) were collected in 2001. The elements As, Ba, Br, Ce, Co, Cr, Cs, Eu, Fe, Hf, La, Lu, Na, Nd, Rb, Sb, Sc, Sm, Ta, Tb, Th, U, Yb, Zn and Zr were determined by instrumental neutron activation analysis (INAA). Cluster and factorial analysis were applied to the chemical data. The sedimentation rate in the SM2 core was determined by ²¹⁰Pb method and the mean value found was 0.61 cm ^. y^-1. The results obtained in the present study showed that recent geochemical processes such as desorption, precipitation and dissolution can contribute for the high water alkalinity and salinity in the saline ponds.     

The certification of the contents of Cd, Co, Cu, Fe, Hg, Ni, Pb, Zn, Sb, Se, Tl and Cr in a city waste incineration ash

Summary The analysis of ashes being of increasing importance, a reference material was prepared from fly ash of a city waste incinerator. The procedures of preparation, homogeneity and stability testing are described as well as the way of certification of elements of major importance: Cd, Co, Cr, Cu, Fe, Hg, Ni, Pb, Zn, Sb, Se and Tl.

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Zertifizierung der Gehalte an Cd, Co, Cu, Fe, Hg, Ni, Pb, Zn, Sb, Se, Tl und Cr in einer Stadtmüll-Verbrennungsasche

Zusammenfassung Da die Analyse von Aschen zunehmend an Bedeutung gewinnt, wurde von der Flugasche einer Stadtmüll-Verbrennungsanlage ein Referenzmaterial hergestellt. Die Methoden der Herstellung sowie der Homogenitätsund Stabilitätsprüfung werden beschrieben und die Art der Zertifizierung der Elemente von hauptsächlicher Bedeutung aufgezeigt (Cd, Co, Cr, Cu, Fe, Hg, Ni, Pb, Zn, Sb, Se, Tl).

     

Multielemental determination by instrumental neutron activation analysis and recent sedimentation rates using 210 Pb dating method at Laguna del Plata, Cordoba, Argentina

Laguna del Plata (Cordoba, Argentina) is a small saline lake connectedto Laguna Mar Chiquita. Its level fluctuations have changed notably throughthe centuries with both high level (HLP) and low level (LLP) periods. Theradionuclides 226 Ra and 210 Pb were analyzed in a core to determine datesand sedimentation rates. The elements As, Ba, Br, Co, Cr, Cs, Fe, Hf, Na,Rb, Sb, Sc, Se, Ta, Th, U, Zn, Zr and rare earth Ce, Eu, La, Lu, Nd, Sm, Tband Yb were determined by instrumental neutron activation analysis. Statisticalanalysis of elemental concentrations (cluster analysis) reflects the associationof the samples along the core according to the provenance of the sedimentsand if they had been deposited during HLP or LLP.     

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.     

Simultaneous quantification of 17 trace elements in blood by dynamic reaction cell inductively coupled plasma mass spectrometry (DRC-ICP-MS) equipped with a high-efficiency sample introduction system

A quadrupole inductively coupled plasma mass spectrometer (Q-ICP-MS) equipped with a dynamic reaction cell (DRC) and coupled with a desolvating nebulization system (APEX-IR) was employed to determine 17 elements (Al, As, Ba, Cd, Co, Cr, Li, Mn, Mo, Ni, Pb, Sb, Se, Sn, Sr, V, and Zr) in blood samples. Ammonia (for Al, Cr, Mn, and V) and O₂ (for As and Se) were used as reacting gases. Selection of the best flow rate of the gases and optimization of the quadrupole dynamic bandpass tuning parameter (RPq) were carried out, using digested blood diluted 1 + 9 with deionized water and spiked with 1 μg L⁻¹ of Al, Cr, Mn, V and 5 μg L⁻¹ of As and Se. Detection limits were determined in digested blood using the 3σ criterion. The desolvating system allowed a sufficient sensitivity to be achieved to determine elements at levels of ng L⁻¹ without detriment of signal stability. The accuracy of the method was tested with the whole blood certified reference material (CRM), certified for Al, As, Cd, Co, Cr, Mn, Mo, Ni, Pb, Sb, Se, and V, and with indicative values for Ba, Li, Sn, Sr, and Zr. The addition calibration approach was chosen for analysis. In order to confirm the DRC data, samples were also analyzed by means of sector field inductively coupled plasma mass spectrometry (SF-ICP-MS), operating in medium (m/Δm = 4000) and high (m/Δm = 10,000) resolution mode and achieving a good agreement between the two techniques.     

Thermal stabilization of inorganic and organo-selenium compounds for direct electrothermal atomic absorption spectrometry

A ⁷⁵Se tracer technique is used to show that Sb, Cd, Mn, Mo, Ni, KI, KIO3, Ag, Th, Tl, Zn and Zr quantitatively stabilize inorganic selenium. Only Mo, Ni and Ag were effective for organoselenium compounds in urine, and only molybdenum was partially successful for blood samples.     

Determination of As, Ge, Hg, Pb, Sb, Se and Sn in coal slurries by CVG-ETV-ICP-MS using external or isotopic dilution calibration

A method for the multi-elemental determination of As, Ge, Hg, Pb, Sb, Se and Sn in coal reference materials by slurry sampling chemical vapor generation (CVG) using external calibration and isotopic dilution (ID) calibration and detection by electrothermal vaporization inductively coupled plasma mass spectrometry (ETV-ICP-MS) is proposed. As, Ge, Sb, Se and Sn were determined using the external calibration, while, Hg, Pb, Se and Sn were determined by isotopic dilution. About 50–250 mg of sample was mixed with an acid solution, containing aqua regia and HCl, in an ultrasonic bath. For the isotopic dilution calibration, the enriched isotopes ²⁰¹Hg, ²⁰⁶Pb, ⁷⁷Se and ¹¹⁹Sn were added to the slurry in an adequate amount in order to produce an altered isotopic ratio close to 1. The vapor produced by the reaction of the sample slurry with the reducing agent was transported to the vaporizer and trapped in a Ir-treated graphite tube at 200 °C, before vaporization at 2100 °C and transportation of the vapor to the plasma. The accuracy of the method was assured by the analysis of four certified reference coal samples, using external calibration with aqueous solutions, prepared in the same medium and subjected to the same CVG and trapping procedure as the slurries and also by isotopic dilution calibration. The obtained concentrations were in agreement with the certified values, using the t-Student test for a confidence level of 95%. The detection limits (3 s; n = 5) of isotopic dilution, in ng g^− 1, were: 0.4 for Hg, 900 for Pb, 0.3 for Se and 0.2 for Sn. For external calibration, the detection limits, in ng g^− 1, were: 1.6 for As, 0.1 for Ge, 0.3 for Sb, 0.9 for Se and 7.5 for Sn. The relative standard deviations generally were lower than 14%, adequate for slurry analysis.     

Inorganic speciation of As(III, V), Se(IV, VI) and Sb(III, V) in natural water with GF-AAS using solid phase extraction technology

The paper presents a procedure for the multi-element inorganic speciation of As(III, V), Se(IV, VI) and Sb(III, V) in natural water with GF-AAS using solid phase extraction technology. Total As(III, V), Se(IV, VI) and Sb(III, V) were determined according to the following procedure: titanium dioxide (TiO₂) was used to adsorb inorganic species of As, Se and Sb in sample solution; after filtration, the solid phase was prepared to be slurry for determination. For As(III), Se(IV) and Sb(III), their inorganic species were coprecipitated with Pb-PDC, dissolved in dilute nitric acid, and then determined. The concentrations of As(V), Se(VI) and Sb(V) can be calculated by the difference of the concentrations obtained by the above determinations. For the determination of As(III), Se(IV) and Sb(III), palladium was chosen as a modifier and pyrolysis temperature was 800 °C. Optimum conditions for the coprecipitation were listed for 100 ml of sample solution: pH 3.0, 15 min of stirring time, 40.0 μg l⁻¹ Pb(NO₃)₂ and 150.0 μg l⁻¹ APDC. The proposed method was applied to the determination of trace amounts of As(III, V), Se(IV, VI) and Sb(III, V) in river water and seawater.     

Determination of trace elements in marine plankton by inductively coupled plasma mass spectrometry (ICP-MS)

A method has been developed for the determination of 23 elements in marine plankton in which inductively coupled plasma (ICP) source mass spectrometry (MS) was used to quantify the elements in the solution after digestion in a mixture of hydrofluoric and nitric acids in sealed PTFE vessels in a microwave field. The procedure was validated by the analysis of a standard reference soil (SRM 2709 San Joaquin Soil) and a standard reference fresh water plankton (CRM 414). The method was applied to the analysis of several marine plankton samples grown under controlled conditions including several whose growth media had been enriched with selenium. Matrix induced signal suppressions and instrumental drift were corrected by internal standardization. The suitabilities of germanium, indium, rhodium, scandium and yttrium as internal standard elements were evaluated. Neither scandium nor yttrium could be used due to the presence of these elements in the samples, germanium was used for the determination of As, Co, Cu, Fe, Ni, Se, Si and Zn, indium was used for Al, Ba, Ca, Eu, Sr, and Tl, and rhodium was used for Cd, Cr, Hg, Mg, Pb, Sb, Sn, and V. For Al, Ca, Cr, Cu, Fe, Mg, Mn, Ni, Si, Sr, V, and Zn internal standardization did not completely compensate for the suppressive effect of the heavier elements and the solutions were diluted. However, for As, Ba, Cd, Co, Eu, Hg, Pb, Sb, Se, Sn and Tl, it was possible to obtain accurate results despite the 35–¶40% suppression in the signals. Isobaric overlap was only a problem in the cases of ⁴²Ca and ⁷⁸Se; ⁴⁴Ca and ⁷⁷Se, respectively, were used. Memory effects were only observed with Hg for which a nitric acid-sodium chloride solution was the most effective wash-out solution. The marine plankton samples were able to tolerate a higher concentration of Hg as the selenium concentration increased.     

TLC separation of some inorganic ions on diethylenetriamine impregnated layers

Summary A suitable TLC method for the separation of Co, Zn, Ni, As, Pb, Cd, Hg, Ag, Th, Se, Sn(IV), Fe(II), U, V, Cu, Ti, Zr and Sb on silica gel impregnated with diethylenetriamine and using ethanol-acetone-acetic acid (70∶50∶20) or (40∶50∶20) as solvent systems and employing 1% K₄Fe(CN)₆ or 0.5% dithizone as visualisation reagents has been developed.     

Sediment records of Sb and Pb stable isotopic ratios in Lake Qinghai

A sediment core in Lake Qinghai in northwest China was collected in 2006. ¹³⁷Cs and ²¹⁰Pb activities were analyzed to investigate the chronology of the sediment core. Sb and Pb concentrations, and Pb stable isotopic ratios were analyzed to study the historical atmospheric deposition records and sources of Sb over the past 15 centuries. The Sb concentration was 4.21 ± 1.52 μg/g in the sediments, its vertical distribution of Sb shows three large peaks in the recent two centuries, 1799, 1896 and 1944, coincided with Sb contamination from large wars, respectively. The peak in 1920 responded the large earthquake that happened in northern China, which was not far away from Lake Qinghai. The Sb/Pb ratio, ²⁰⁶Pb/²⁰⁷Pb and ²⁰⁸Pb/²⁰⁶Pb results suggest that Sb and Pb were probably from the ores in South China and coals in North China before 1965, but obviously from uses of leaded gasoline after 1965.     

Optimization of sample preparation and ICP-MS analysis for determination of 60 elements for characterization of the plant ionome

An ICP-MS method for determination of 60 elements in plant samples is proposed based on optimization of digestion, recommending use of HF besides HNO₃ and H₂O₂ and calibration procedures, using CRMs for construction of calibration curves. Adequate choice of analytical isotopes and various measurement conditions (cold plasma for the determination of Al, Ba, Ca, Fe, K, Mg, Mn, Na, Si and Sr and DRC mode for determination of Ag, As, Ni, Pd, Pt, Se and V) as well as introduction of appropriate corrections lead to determination of as large number of elements with quadropole ICP-MS as with the more expensive SF-ICP-MS. Two measurements are performed: cold plasma and standard/DRC mode. The analytical characteristics of the method are demonstrated by analysis of five CRMs and the agreement of the experimental results with the certified/information/literature values is very good. Detection limits are low enough to permit the determination of all elements but platinum metals at background level. The applicability of the method is demonstrated by analysis of Taraxacum officinale (dandelion) samples collected from regions with different anthropogenic influence. The results indicate high degree of pollution round the Pb-Zn smelter with As, Cd, Cu, Ni, Pb and Zn and increased concentrations of B, Be, Bi, Hg, In, Mn, Sb, Se, Sn, Ti, Tl, V and Zr. The dandelion sample, collected along a highway has increased concentrations of traffic released elements: Pt, Pd, Rh, Ce, La, Pb as well as Cu, Zn, Ba and Rb.     

Microwave assisted digestion of atmospheric aerosol samples followed by inductively coupled plasma mass spectrometry determination of trace elements

A microwave digestion method in a closed vessel was developed for the determination of trace metals in atmospheric aerosols using inductively coupled plasma mass spectrometry (ICP-MS). A recovery study for the elements V, Cr, Mn, Fe, Co, Ni, Cu, Zn, As, Se, Cd, Sb, and Pb was conducted using multi-elemental standard solutions, NIST 1633b Trace Elements in Coal Fly Ash, and NIST 1648 Urban Particulate Matter. A simple digestion method using only HNO₃/H₂O₂ gave good recoveries (90%–108%) for all elements except Cr in SRM 1648, but yielded low recoveries for SRM 1633b. A more robust method using HNO₃/H₂O₂/HF/H₃BO₃ yielded higher recoveries (82%–¶103%) for the lighter elements (V – Zn) in SRM 1633b, and improved the Cr recovery in SRM 1648, but decreased the Se recovery in both SRMs. A comparative analysis of aerosol samples obtained at a remote mountain location Nathiagali, Pakistan (2.5 km above mean sea level), and Mayville, New York, downwind from the highly industrialized Midwestern United States, was carried out using Instrumental Neutron Activation Analysis (INAA) for the elements Cr, Mn, Fe, Co, Zn, As, Se, and Sb. The simple digestion method yielded excellent agreement for Cr, Fe, Zn, As, Se, and Sb, with slopes of the ICP-MS vs. INAA regressions of 0.90–1.00 and R² values of 0.96–1.00. The regressions for Mn and Co had slopes of 0.82 and 0.84 with R² values of 0.83 and 0.82, respectively. Addition of HF/H₃BO₃ did not improve the correlation for any of the elements and degraded the precision somewhat. The technique provides sensitivity and accuracy for trace elements in relatively small aerosol samples used in atmospheric chemistry studies related to SO₂ oxidation in cloud droplets. The ability to determine concentrations of a very large number of elements from a single analysis will permit source apportionment of various trace pollutants and hence strategies to control the sources of air pollution. This is particularly important as the health effects of particulate matter are increasingly recognized.     

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.     

Trace multielement analysis using high-flux fast-neutron activation

The intense 14-MeV neutron facility at Lawrence Livermore National Laboratory was used for fast-neutron activation analysis (FNAA) of standard fly ash, orchard leaves, and bovine liver supplied by the U.S. National Bureau of Standards. The high flux of 14-MeV neutrons allowed concentration determinations of up to 20 elements from the set of Na, Mg, Al, Si, P, K, Sc, Ti, Fe, Co, Ni, Zn, As, Se, Rb, Sr, Y, Zr, Mo, Sb, Ba, Ce, Tl, and Pb. Interferences and steep flux-gradients were problems, but the elemental profile we obtained is the most complete analysis using FNAA to date.     

酸洗污泥与煤共燃烧过程中重金属的迁移分布研究

采用高温管式炉系统进行酸洗污泥与煤共燃烧实验。对共燃烧后As、Cr、Ni、Cd、Cu、Mn、Pb、Zn、Sb、Se重金属元素在烟气、飞灰及炉渣中的分配率进行分析。结果表明,Cd、Se、Zn是易挥发重金属,主要分布在烟气和飞灰中。Cd在烟气中的最大分配率为61%;Se在烟气中的分配率为38.58%~94.612%;Zn在低、高温段分别主要分布在烟气和飞灰中。As、Cu、Pb、Sb是半挥发重金属,Pb在炉渣中的分配率较稳定,分配率为42.67%~64.76%,在烟气和飞灰中的分配率波动较大,其分配率分别是14.176%~45.79%和9.78%~32.55%;Sb在烟气中的最大分配率为37.64%;温度升高反而会抑制As、Cu挥发,这与高温下As、Cu易与矿物质反应生成络合物有关。Ni、Cr、Mn属于难挥发重金属,绝大部分残留在炉渣中,且分配率对温度变化不敏感。赋存于炉渣中的Cr、Ni分别超过95%和97%;随着温度升高,Mn在炉渣中的分配率由71.46%增加到96.89%。     

Electrolytic hydride generation atomic absorption spectrometry for the determination of antimony, arsenic, selenium, and tin – mechanistic aspects and figures of merit

This article deals with the electrocatalytic and electrochemical mechanisms of hydride formation and their dependence on hydrogen overvoltage. A three-electrode-arrangement was used to determine the hydrogen overvoltage of different cathode materials (Pt, Au, Ag, glassy carbon, Cd, Pb, amalgamated Ag). The applicability of these cathode materials was tested for hydride formation using As(III), As(V), Sb(III), Sb(V), Se(IV), and Sn(IV). Glassy carbon is the most suitable cathode material for hydride generation with As(III), Sb(III), Se(IV), and Sn(IV). Hg–Ag is well suited for the production of stibine and arsine. As(III), As(V), Sb(III), and Sb(V) were all converted into their hydrides with efficiencies > 90%. A detection limit in the range of 0.11–0.13 μg L^–1 for As and Sb (sample volume 200 μL) was obtained for cathode materials with a high hydrogen overvoltage. The precision of replicate measurements was better than 5% calculated as variation coefficient. The accuracy of the presented method was verified by analysis of certified reference materials and tissues of cancer patients. The recovery rates for As and Se were calculated to be 93–108%.     

Preconcentration of trace elements on a support impregnated with sodium diethyldithiocarbamate prior to their determination by inductively coupled plasma-atomic emission spectrometry

A procedure is developed for determination of As, Co, Se, Cr, Pb, Zn, Cu, Mn, Cd, Sb, and Sn in water by ICP-AES analysis of alcohol eluates after pre-concentration of the samples. The pre-concentration is performed on a sodium diethyldithiocarbamate supported soft polyurethane foam. The sorbed elements are subsequently eluted with 1-propanol and the alcohol eluates are analysed by ICP-AES. A eight-fold concentration is achieved. An increased sensitivity in the analysis of propanol-water (30:70, v/v) solution is established as compared with aqueous solutions. The strongest effect is observed for As, Se, Pb, Cr, Sn, and Cd-increasing is more than twice. For other elements the matrix influence is by a factor of 1.45 (Cu), 1.36 (Sb), 2.08 (Zn). The method is applied to the analysis of natural water samples.