Determination of trace elements including platinum in tree bark by ICP mass spectrometry

The increasing emission of Pt-group metals from automobile catalytic converters requires the development of highly sensitive procedures for ultratrace analysis of environmental and biological systems. Tree bark, located close to motorway or industrial areas, was utilised as a substrate for collection of airborne particulate matter and samples after digestion (microwave assisted dissolution with HNO₃ and HCl) were analysed by ICP mass spectrometry. The study targeted Pt and other metallic contaminants and involved analysis of some 57 tree bark samples using both quadrupole and double-focusing sector field ICP mass spectrometers. Detection limits for platinum determination in tree bark were 0.03 ng/g (DF-ICP-MS) and 0.2 ng/g (ICP-QMS). The platinum content of the bark samples ranged from 0.07–5.4 ng/g.     

火试金预浓集结合中子活化和电感耦合等离子体质谱法测定铂族元素

建立了两种以火试金预浓集为基础的、可用于准确测定铂族元素的方法;中子活化法和电感耦合等离子体质谱法。讨论了它们的分析检出限、准确度及其适应性。并用这两种方法测定了5种候选地质参考物质中铂族元素的含量。     

Microwave-assisted headspace solid-phase microextraction to quantify polycyclic aromatic hydrocarbons in pine trees

A methodology for the extraction and quantification of 16 polycyclic aromatic hydrocarbons (PAHs) based on microwave-assisted extraction coupled with headspace solid-phase microextraction followed by gas chromatography/mass spectroscopy was validated for needles and bark of two pine species (Pinus pinaster Ait. and Pinus pinea L.). The limits of detection were below 0.92 ng g(-1) (dry weight) for needles and below 0.43 ng g(-1) (dw) for bark. Recovery assays were performed with two sample masses spiked at three levels and the overall mean values were between 70 and 110 % for P. pinaster and 75 and 129 % for P. pinea. In the first species, the increase in sample mass lowered the recoveries slightly for most PAHs, whereas for the second, the recoveries were higher for the needles. Naturally contaminated samples from 4 sites were analysed, with higher levels for urban sites (1,320 and 942 ng g(-1) (dw) vs. 272 and 111 ng g(-1) (dw) for needles and 696 and 488 ng g(-1) (dw) vs. 270 and 103 ng g(-1) (dw) for bark) than for rural ones and also for P. pinaster samples over P. pinea. It is also shown that gas-phase PAHs are predominant in the needles (over 65 % of the total PAHs) and that the incidence for particulate material in bark, reaching 40 % as opposed to a maximum below 20 % for the needles. The method has proved to be fit and improved some of the existing approaches, on the assessment of particulate PAHs and bark levels.     

Analysis of tree leaves,bark and wood by sequential inductively coupled argon plasma atomic emission spectrometry

The analysis of extracts from tree leaf, bark and wood samples for Ca, Mg, K, Na, P, Mn, Fe, Al, B, Cu and Zn by inductively coupled argon plasma sequential emission spectrometry is described. Recovery percentages for simulated tree extracts and for spiked tree samples are presented together with typical analysis values for a leaf and a wood sample. The choice of analytical line for each element is discussed and spectral interferences, not listed in the ICP tables of Boumans, of Cu on the 214.9 nm line of P and of Fe on the 249.7 nm line of B are noted.     

Determination of long-lived radionuclides in concrete matrix by laser ablation inductively coupled plasma mass spectrometry

A laser ablation system using a Nd:YAG laser was coupled both to a quadrupole inductively coupled plasma (ICP) mass spectrometer and to a double-focusing sector field ICP mass spectrometer. Laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) was applied for the determination of long-lived radionuclides in a concrete matrix. The investigated samples were two laboratory standards with a concrete matrix, which we doped with different long-lived radionuclides (e.g. ⁹⁹Tc, ²³²Th, ²³³U, ²³⁷Np) from the ng g⁻¹ to μ g⁻¹ concentration range and an undoped concrete material (blank). Detection limits for long-lived radionuclides in the 10 ng g⁻¹ range are reached for LA-ICP-MS using the quadrupole mass spectrometer. With double-focusing sector field ICP-MS, the limits of detection are in general one order of magnitude lower and reach the sub ng g⁻¹ range for ²³³U and ²³⁷Np. A comparison of mass spectrometric results with those of neutron activation analysis on undoped concrete sample indicates that a semiquantitative determination of the concentrations of the minor and trace elements in the concrete matrix is possible with LA-ICP-MS without using a standard reference material.     

The Use of Tree Bark as a Passive Sampler for Polychlorinated Dibenzo- p -Dioxins and Furans

The potential of using tree bark as a passive sampling medium for detection of Polychlorinated dibenzo- p -dioxins and furans (PCDD/F) in an urban environment has been investigated. Bark samples (～ 30 g) were extracted with toluene using accelerated solvent extraction. Extracts were then cleaned up via a multi-bed silica column and a Florisil column followed by GC-MS/MS analysis. It is shown that PCDD/F are present in tree bark collected from sites close to a municipal waste incinerator, a crematorium, a hospital and a chemical incinerator. Furthermore, characteristic patterns for dioxin congeners were observed for the suspected emission sources.     

电感耦合等离子体质谱法检测农作物土壤中的镉、锡、锰、锑、钒、钛、锶金属污染物残留

建立全自动石墨消解- 电感耦合等离子体质谱(ICP-MS)法检测农作物土壤中的镉、锡、锰、锑、钒、钛、锶金属污染物残留的分析方法.随机采集农作物土壤,取约200 g,置于烘箱中烘干,烘干后的样品用粉碎机粉碎,精密称取粉碎后的样品约0.25 g,置于聚四氟乙烯材质的消解罐内,按既定消解程序进行自动消解处理,得样品溶液,上...     

Isotope dilution inductively coupled plasma quadrupole mass spectrometry in connection with a chromatographic separation for ultra trace determinations of platinum group elements (Pt, Pd, Ru, Ir) in environmental samples

An isotope dilution inductively coupled plasma quadrupole mass spectrometric (ID-ICP-QMS) method was developed for the simultaneous determination of the platinum group elements Pt, Pd, Ru, and Ir in environmental samples. Spike solutions, enriched with the isotopes 194Pt, 108Pd, 99Ru, and 191Ir, were used for the isotope dilution step. Interfering elements were eliminated by chromatographic separation using an anion-exchange resin. Samples were dissolved with aqua regia in a high pressure asher. Additional dissolution of possible silicate portions by hydrofluoric acid was usually not necessary. Detection limits of 0.15 ng x g(-1), 0.075 ng x g(-1), and 0.015 ng x g(-1) were achieved for Pt, Pd, Ru, and Ir, respectively, using sample weights of only 0.2 g. The reliability of the ID-ICP-QMS method was demonstrated by analyzing a Canadian geological reference material and by participating in an interlaboratory study for the determination of platinum and palladium in a homogenized road dust sample. Surface soil, sampled at different distances from a highway, showed concentrations in the range of 0.1-87 ng x g(-1). An exponential decrease of the platinum and palladium concentration with increasing distance and a small anthropogenic contribution to the natural background concentration of ruthenium and iridium was found in these samples.     

Simultaneous Determination of Platinum and Rhodium with Hydroxylamine and Acetone Oxime by Catalytic Adsorptive Stripping Voltammetry (CAdSV)

This paper describes a very sensitive catalytic adsorptive stripping voltammetry (CAdSV) procedure for the simultaneous determination of traces of platinum and rhodium in new supporting electrolyte containing hydroxylamine or acetone oxime and formaldehyde in sulfuric acid medium. Platinum and rhodium were pre‐accumulated simultaneously and after 120 s of accumulation time at 0.0 V, the achieved detection limits were equal 0.1 ng L^?1 and 0.2 ng L^?1 for platinum and rhodium respectively in the presence of acetone oxime and 0.6 ng L^?1 and 0.2 ng L^?1 for platinum and rhodium respectively in the presence of hydroxylamine. Described reagents were successfully applied to the determination of platinum and rhodium in plant material. Inductively coupled plasma mass spectrometry (ICP MS) was used as a reference method to the CAdSV measurements.     

Determination of trace elements in quartz glass by use of LINA-Spark-ICP-MS as a new method for bulk analysis of solid samples

The determination of trace elements in pure quartz glass samples has been performed by coupling an ICP quadrupole mass spectrometer with the LINA-Spark-Atomizer, an IR laser ablation system dedicated to direct bulk and surface analysis of solid samples. Linear calibration curves were obtained for nine elements (Na, Al, Ca, Ti, Cr, Mn, Zr, Ba, and Pb) in the ng g(-1) range with detection limits of less than 10 ng g(-1) for Ca, Cr, Mn, Zr, Ba, and Pb and in the range of 120-220 ng g(-1) for Na, Al, and Ti. The distance between the laser focal point and the sample surface has a significant influence on signal intensity and precision, both of which can be improved by a factor of approximately two by focusing the laser 15 mm behind the sample surface. Aerosol moistening reduced the standard deviation of the signal intensity by a factor of 2-4. Signal instability, which resulted from different ablation rates or variations in the transmission of the mass spectrometer, were compensated by use of the simultaneously measured SiAr+ ion as an internal standard. Under these conditions precision was usually better than 5% RSD. The results were compared with those obtained by use of a commercial LA-ICP-MS system. With this instrumentation linear calibration curves were achieved for three elements only (Al, Ti, and Pb), showing that LA-ICP-MS is less appropriate for bulk analysis in the ng g(-1) range.     

Determination of siloxanes,silicon, and platinum in tissues of women with silicone gel-filled implants

Silicone [poly(dimethylsiloxane)] gel used in breast implants has been known to migrate through intact silicone elastomer shells, resulting in the clinically observable "gel bleed" on the implant surface. Although silicon concentrations in capsular tissues of women with silicone prostheses have been measured with element-specific silicon analyses, no silicone-specific investigation of these tissues has been performed as yet.A combination of element-specific inductively coupled plasma high-resolution isotope dilution mass spectrometry (ICP-HR-IDMS) and species-specific gas chromatography coupled mass spectrometry (GC-MS) was used to analyze silicon, platinum, and siloxanes in prosthesis capsule, muscle, and fat tissues of women (n=3) who had silicone gel-filled breast implants and in breast tissue of non-augmented women (n=3) as controls.In all tissues of augmented women, siloxanes, in particular octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecamethylcyclohexasiloxane (D6) were identified. Depending on the siloxane species and type of tissue analyzed, siloxane levels in the range of about 10-1,400 ng g(-1) were detected; total silicon was found in all tissue samples in the range of about 8,900-85,000 ng g(-1). Higher platinum levels ranging from 25-90 ng g(-1 )were detected in fibrin layer and fat tissue of two patients with prostheses. No siloxanes were detected in control breast tissue samples.This investigation of human tissues by a combination of element-specific and species-specific analytical techniques clearly demonstrates for the first time that platinum and siloxanes leak from prostheses and accumulate in their surrounding tissues.     

Estimation of platinum in environmental water samples with solid phase extraction technique using inductively coupled plasma mass spectrometry

A solid phase extraction technique for the determination of platinum(IV) at trace levels by inductively coupled plasma mass spectromA solid phase extraction technique for the determination of platinum(IV) at trace levels by inductively coupled plasma mass spectrometry (ICP-MS) was developed. The method was based on retention of platinum in a sample on silica gel modified with aminepropyl groups. The retention of platinum(IV) from the sample solution and the recovery of platinum with 1.0 mol L⁻¹ thiourea solution were quantitative. The relative standard deviation (RSD) was calculated as 5% (n = 7) at the 10 ng L⁻¹ level. The enrichment factor was found to be (50-fold) for 250 mL of water sample. Under optimum conditions, the method detection limit (MDL) was found to be 1 ng L⁻¹ for platinum in water matrices. Recoveries of Pt from spike addition to atmospheric water samples were quantitative (80–95%). The present method was used for the determination of platinum in precipitation, throughfall and runoff water samples.      

Performance of sampling plans to determine aflatoxin in farmers' stock peanut lots by measuring aflatoxin in high-risk-grade components

Five 2 kg test samples were taken from each of 120 farmers' stock peanut lots contaminated with aflatoxin. Kernels from each 2 kg sample were divided into the following U.S. Department of Agriculture grade components: sound mature kernels plus sound splits (SMKSS), other kernels (OK), loose shelled kernels (LSK), and damaged kernels (DAM). The kernel mass (g), aflatoxin mass (ng), and aflatoxin concentration (ng of aflatoxin/g of peanuts) were measured for each of the 2400 component samples. The variabilities associated with measuring aflatoxin mass (ng) in OK + LSK + DAM, or A(OLD)ng, and in LSK + DAM, or A(LD)ng, and aflatoxin concentration (ng/g) in OK + LSK + DAM, or A(OLD)ng/g, and in LSK + DAM, or A(LD)ng/g, were determined. The variance associated with measuring aflatoxin in each of the 4 combinations of components increased with aflatoxin, and functional relationships were developed from regression analysis. The variability associated with estimating the lot concentration from each of the 4 combinations of components was also determined. The coefficients of variation (CV) associated with estimating the aflatoxin for a lot with aflatoxin at 100 ng/g were 90, 86, 94 and 96% for aflatoxin masses A(OLD)ng and A(LD)ng and aflatoxin concentrations A(OLD)ng/g and A(LD)ng/g, respectively. The performance of aflatoxin sampling plans using the combination of aflatoxin masses in OK + LD + DAM and LD + DAM components was evaluated with a 2 kg test sample and a 50 ng/g accept/reject limit.     

Determination of Platinum Group Elements and Evaluation of Their Traffic-Related Distribution in Italian Urban Environments

Abstract

The platinum (Pt) distribution in urban matrices, soils and dusts was studied in five cities, from north (Padova), central (Rome and Viterbo), and south (Naples and Palermo) Italy, in order to obtain a large set of data concerning pollution from autocatalysts. Quantitative analyses, made by inductively coupled plasma mass-spectroscopy (ICP-MS), show a beginning of Pt enrichment in urban soils, with concentration ranges of 0.1–5.7 ng/g (Padova), 7–19.4 ng/g (Rome), 4.9–20 ng/g (Viterbo), 4.7–14.3 ng/g (Naples), and 0.2–3.9 ng/g (Palermo). These results can be related to vehicular traffic, because the concentrations decrease with the distance from the roads. The high concentrations found in road and tunnel dusts (up to 1177 ng/g) confirm these samples as the major reserve of the particulate matter that is released with the exhaust fumes (which is responsible for the Pt enrichment). Qualitative analyses by laser-ablation-ICP-MS (LA-ICP-MS) were used, in addition, to determine the real presence of the catalyst particles in the urban dusts. The association of the analytical signals of cerium, platinum, and rhodium was used as a fingerprint to distinguish the catalyst particles from the other components of the urban dusts. The scanning electron microscopy (Energy Dispersive Spectrometer-Scanning Electron Microscope; EDS-SEM) qualitative analysis was also used to characterize the morphology of the autocatalyst and its related elemental distribution.     

Ultra-trace analysis of platinum in human tissue samples

Background levels of platinum were determined in human autopsy tissues taken from five individuals. The investigated specimens were lung, liver and kidney. Sample preparation involved microwave digestion followed by an open vessel treatment. Inductively-coupled plasma sector field mass spectrometry (ICP-SFMS) was applied in combination with an ultrasonic nebulization/membrane desolvation system for sample introduction. Isotope dilution analysis was employed for accurate quantification of platinum. Excellent procedural detection limits (3 s validation) of 20, 20 and 34 pg g^–1 dry weight were obtained for lung, liver and kidney tissue, respectively. Due to the lack of appropriate biological reference material, road dust (BCR-723) was used for method validation. Platinum levels ranging between 0.03 and 1.42 ng g^–1 were determined in the investigated samples. The platinum concentrations observed in human lung tissue may reflect the increasing atmospheric background levels of platinum originating from car catalysts. The presence of platinum in kidney and liver tissue samples clearly indicates the bioavailability of the element.     

Microwave-assisted extraction and ultrasonic extraction to determine polycyclic aromatic hydrocarbons in needles and bark of Pinus pinaster Ait. and Pinus pinea L. by GC-MS

Two different extraction strategies (microwave-assisted extraction (MAE) and ultrasonic extraction (USE)) were tested in the extraction of the 16 US Environmental Protection Agency (EPA) polycyclic aromatic hydrocarbons (PAHs) from pine trees. Extraction of needles and bark from two pine species common in the Iberian Peninsula (Pinus pinaster Ait. and Pinus pinea L.) was optimized using two amounts of sample (1 g and 5 g) and two PAHs spiking levels (20 ng/g and 100 ng/g). In all cases, the clean-up procedure following extraction consisted in solid-phase extraction (SPE) with alumina cartridges. Quantification was done by gas chromatography (GC) with mass spectrometry (MS), using five deuterated PAH surrogate standards as internal standards. Limits of detection were globally below 0.2 ng/g. The method was robust for the matrices studied regardless of the extraction procedures. Recovery values between 70 and 130% were reached in most cases, except for high molecular weight PAHs (indeno[1,2,3-cd]pyrene, dibenzo[a,h]anthracene and benzo[ghi]perylene). A field study with naturally contaminated samples from eight sites (four in Portugal and four in Catalonia, Spain) showed that needles are more suitable biomonitors for PAHs, yielding concentrations from 2 to 17 times higher than those found in bark. The levels varied according to the sampling site, with the sum of the individual PAH concentrations between 213 and 1773 ng/g (dry weight). Phenanthrene was the most abundant PAH, followed by fluoranthene, naphthalene and pyrene.     

Determination of trace metals in hydrothermal calcites by ICP-methods

Lanthanum, cerium, and europium in calcites from carbonate-sulfide banded ores were determined by standard addition using inductively coupled plasma mass spectrometry (ICP-MS). The concentration ranges in solution were for La 700-36 ng/g, Ce 2000-149 ng/g, and for Eu 140-2.4 ng/g. Only Ce was determined by both ICP methods, and the results agree within 3 to 4%. In a second step, a scan over the mass range of the rare earth elements (REE) was performed. The solutions were analyzed directly without applying preconcentration or separation procedures. ICP atomic emission spectrometry (AES) was used to determine Ca, Mn, and Fe. The matrix Ca is present in a concentration range from 1600 to 1300 g/g and the major impurities Mn and Fe are 152-32 and 100-28 g/g, respectively. The detection limits of ICP-MS for REE are found to be better by two orders of magnitude than for ICP-AES. A commercially available SCIEX Elan ICP-MS with additional software was used to make mathematical corrections for isobaric interferences and molecular ions.Presented in part at the 1989 European Winter Conference on Plasma Spectrochemistry, Reutte, Austria     

Direct determination of lead in biological samples by electrothermal vaporization inductively coupled plasma mass spectrometry (ETV-ICP-MS) after furnace-fusion in the sample cuvette-tungsten boat furnace

The newly conceived electrothermal vaporization (ETV) system using a tungsten boat furnace (TBF) sample cuvette was designed for the direct analysis of solid samples with detection by inductively coupled plasma mass spectrometry (ICP-MS). Into this small sample cuvette, a solid mixture of the biological samples and diammonium hydrogenphosphate powder as a fusion flux was placed and situated on a TBF. Tetramethylammonium hydroxide solution was added to the mixture. After the on-furnace digestion had been completed, the analyte in the cuvette was vaporized and introduced into the ICP mass spectrometer. The solid samples were analyzed by using a calibration curve prepared from the aqueous standard solutions. The detection limit was estimated to be 5.1 pg of lead, which corresponds to 10.2 ng g(-1) of lead in solid samples when a prepared sample amount of 1.0 mg was applied. The relative standard deviation for 8 replicate measurements obtained with 100 pg of lead was calculated to be 6.5%. The analytical results for various biological samples are described.     

螯合树脂富集-激光气化等离子体发射光谱测定地质样品中铂族元素和金

采用含N、S功能团的螯合树脂YPA_4富集铂族元素和金。Au、Pt、Pd、Os的吸附率为98％以上,Ir为92％,Ru为90％,Rh为87％。把树脂灰化,用激光将其灰份气化输入等离子体激发,光谱测定。取样5g时,可测定0.2ng/g的Au,0.6ng/g的Os、Ir,0.06ng/g的Pt、Pd、Rh、Ru。标样分析结果与标准植吻合。     

Determination of physiological noble metals in human urine using liquid-liquid extraction and Zeeman electrothermal atomic absorption spectrometry

An extremely sensitive, reliable and simple procedure is described for the determination of physiological palladium, platinum and gold in human urine. The urine samples were adjusted to pH 4 (Pd, Au) or pH 5 (Pt), followed by conversion of the analytes to their pyrrolidinedithiocarbamate complexes. These complexes were separated from the matrix by liquid-liquid extraction into 4-methyl-2-pentanone resulting in a 25-fold enrichment. Determination was by electrothermal atomic absorption spectrometry (ET-AAS) using longitudinal inverse alternating current Zeeman-effect background correction. The limits of detection calculated from three standard deviations of the blank values were 20 ng l⁻¹ for Pd and Au and 70 ng l⁻¹ Pt. Within-day precision (n = 10, 5 μg l⁻¹) ranged 5.2%–7.7%. The procedure is successfully applied to determine urinary palladium, platinum and gold in nine unexposed persons. Palladium levels in urine ranged < 20–80 ng l⁻¹ (arithmetical MEAN=38.7 ng l⁻¹), while gold levels ranged < 20–130 ng l⁻¹ (36.0 ng l⁻¹). Physiological platinum levels in urine were all < 70 ng l⁻¹. The accuracy of the procedure was checked by analyzing a series of urine samples by a second independent method (magnetic sector field inductively-coupled plasma-mass spectrometry) in combination with UV photolysis.