High resolution inductively coupled plasma mass spectrometry (HR-ICPMS) determination and multivariate evaluation of 10 trace elements in mussels from 7 sites in Limfjorden, Denmark

The contents of V, Cr, Co, Ni, Cu, Ga, Rb, Cd, Ba, and Pb in the soft tissue of blue mussel (Mytilus edulis) were determined by a high resolution inductively coupled plasma mass spectrometry (HR-ICPMS) method. Sample digestions were performed in closed microwave vessels using nitric acid and hydrogen peroxide. Using HR-ICPMS it is possible to resolve the analytical peaks from otherwise interfering polyatomic ions with a mass resolution setting of 4,000 (Cr, Ni, Cu). The proposed method was validated using a mussel tissue reference material (NIST SRM 2974). The proposed method was applied to real samples of blue mussel from seven sites in the inlet "Limfjorden", Denmark, and the levels of trace elements found were compared with the levels found in an earlier study. For the mussel samples large inter-regional differences in trace element concentrations in the tissues were recorded. The mussels from the different sites could be separated using principal component analysis (PCA). Comparison with the levels of trace elements in mussels found in 1982 showed that the trace elemental contamination has increased during the last 15 years. From the data obtained, mussel tissue appears to be good bio-indicator for identification of coastal areas exposed to metallic contaminants.     

Trace metals in mussel shells and corresponding soft tissue samples: a validation experiment for the use of <Emphasis Type="Italic">Perna perna</Emphasis> shells in pollution monitoring

The uptake of Cr, Mn, Ni, Cu, Zn, Cd and Pb in soft tissue of Perna perna mussels and their shells has been studied in aquarium experiments in which mussels were exposed for 30 or 60 days to seawater spiked with different concentrations of these contaminants (125 and 500 μg L⁻¹). Tissue samples were analyzed after acid digestion by conventional solution nebulization ICP–MS. Laser ablation ICP–MS was used for the quantitative determination of trace elements in different areas of the corresponding shells. With the exception of Mn and Zn, all other elements studied showed a significant concentration enhancements in soft tissue, with the magnitude of this enhancement following the order: Cr > Ni > Cd > Cu > Pb. A corresponding increase in most contaminants, although less pronounced, was also observed in the newly formed growth rings of mussel shells, contributing to the validation of Perna perna mussel shell as a bioindicator of toxic elements.     

Metal distribution patterns in the mussel Mytilus edulis cytosols using size-exclusion chromatography and double focusing ICP-MS detection

In order to estimate metal distribution patterns in biomolecules of different sizes and their possible relationship with environmental heavy metal contamination, multi-elemental distributions in different fractions of the cytosols of mussels were studied. To do so, samples were collected from natural populations of two coastal regions in Spain: a wild (uncontaminated) coast and an industrialised (contaminated) area in Asturias. Moreover, some commercial mussels from the Galicia coast were also investigated for comparison. Aliquots of the mussel cytosol extracts from each sample were applied to a calibrated Sephadex G-75 column (100 x 1 cm) and forty 3 ml fractions were obtained. After suitable dilution, 18 trace metals were determined by double focusing inductively coupled plasma mass spectrometry (DF-ICP-MS). The use of DF-ICP-MS detection allowed the resolution of several spectral interferences that cannot be resolved by quadrupole ICP-MS. Accurate results for ultratrace elements at basal levels are possible even after sample dilution to prevent matrix effects. After biomolecule-metal association pattern has been established, quantitative analysis of mussel cytosols from the three coastal areas was carried out, using external aqueous calibration plus standard additions to correct for possible matrix effects. Results showed that total metal contents increased following the expected order: wild coast < Galicia coast < industrial area coast. Speciation of Cu, Zn, Ca, U, Ni, Mo, Mn, Cr, V, Cd, Al and Sb showed a similar distribution pattern among cytosolic ligands for all the studied samples. Conversely, Fe, Pb, Sn, Co, Hg and Ag were found to exhibit different speciation patterns when samples from industrialised (contaminated) and non-industrialised areas were compared.     

Determination of trace concentrations of elements in high purity tellurium by radio frequency glow discharge optical emission spectrometer (RF-GDOES)

A method was established for the determination of trace impurities in high purity tellurium (Te) 99.9999 (6N) by radio frequency glow discharge optical emission spectrometry (RF-GDOES). The optimized parameters are power, argon pressure, pre-integration time, analysis time and selection of wavelength. Nine elements Se, Ca, Mg, Si, Fe, Cr, Cu, Ni and Pb were analysed in 6N Te, out of which only three elemental peaks (Se, Ca, and Mg) were detected and the remaining six elements ( Si, Fe, Cr, Cu, Ni and Pb) were below detection levels. Finally, the method was evaluated by the analysis of the above traces using inductively coupled plasma mass spectrometry (ICP-MS) and was found to be satisfactory. The detection limits for most of the elements were below 10 ng/g and R.S.D. was around 10%, which indicated that this method could fully satisfy the requirements for the trace analysis in high purity Te metal.     

Principal component analysis: a chemometric aid for classification of polluted and unpolluted mussels

Ten trace elements (Al, Cr, Mn, Fe, Co, Ni, Cu, Zn, Cd and Pb) were determined in the dissolved ash of the edible part of wild mussels (28 samples) from a polluted site by electrothermal atomic absorption spectrometry. The distribution of the concentration of each element in the mussels was first investigated by means of a test of normality. The correlation matrix around the mean was used as a starting matrix for principal component analysis (PCA). Ten variables were reduced to two principal components, accounting for 77% of the total variance; Al, Cr, Mn, Fe, Zn, Cd and Pb are all positively associated with the first principal component and form a cluster of variables, indicating a common terrigenous origin. Comparison with 43 samples of unpolluted mussels from a nearby hatchery, on the basis of eight common variables (concentration of Mn, Fe, Co, Ni, Cu, Zn, Cd and Pb; 71 samples) by using a two-dimensional plot of PC scores, allows the mussels from the two sites to be differentiated.     

Some trace elements in the waters,marine organisms and sediments of the Adriatic by neutron activation analysis

A number of investigations of trace elements in the waters, organisms and sediments of the Adriatic, using neutron activation analysis with radiochemical, separations are reported. These include studies of Hg in mussels from the Northern Adriatic, of Hg and Se in edible animals from the Rijeka region, and of seven elements (As, Cd, Cu, Hg, Mn, Se and Zn) in marine invertebrates from the Slovene coast. Additionally, plankton, sediment cores and water samples were taken from a grid of stations covering the whole Adriatic and analyzed for 6 to 11 of the trace elements As, Cd, Co, Cr, Cu, Fe, Hg, Mn, Sb and Zn (Hg only in water). Generally, levels found were not indicative of pollution as compared with oceanic samples, but some evidence of locally increased levels was found, especially for Hg. The levels of eleven trace elements in three marine Intercomparison samples prepared by the IAEA Monaco Laboratory are also presented.     

Element fingerprinting of marine organisms by dynamic reaction cell inductively coupled plasma mass spectrometry

A method for the determination of sixteen elements (Al, As, Cd, Co, Cr, Cu, Fe, Hg, Mn, Mo, Ni, Pb, Se, Sn, V, Zn) in seafood by dynamic reaction cell inductively coupled plasma mass spectrometry (ICP–DRC–MS) is presented. A preliminary study of polyatomic interferences was carried out in relation to the chemical composition of marine organisms belonging to different taxa. Acid effects and other matrix effects in marine organisms submitted to closed-vessel microwave digestion were investigated as well. Ammonia was the reactive gas used in the DRC to remove polyatomic ions interfering with ²⁷Al, ⁵²Cr, ⁵⁶Fe and ⁵¹V. Optimal conditions for the simultaneous determination of analytes were identified in order to develop a fast multielement method. A suite of real samples (mussels and various fish species) were used during method development along with three certified reference materials: BCR CRM 278R (mussel tissue), BCR CRM 422 (cod muscle) and DORM-2 (dogfish muscle). The proposed analytical approach can be used in conjunction with suitable chemometric procedures to address quality and safety issues in aquaculture and fisheries. As an example, a case study is described in which mussels from three farming sites in the Venice Lagoon were distinguished by multivariate analysis of element fingerprints.      

Concentration Levels of Trace Elements in Carrots,Onions, and Potatoes Cultivated in Asopos Region,Central Greece

The objective of the work was to investigate the correlation between the environmental pollution of Asopos river area in Viotia, Greece and the concentration of Ni, Cr, Cd, Pb, Cu, and As in specific crops (carrots, onions, and potatoes) produced in this region. Samples of these crops from Asopos and other Greek areas (control) were collected. For method accuracy, the Certified Reference Material, CRM 281 (trace elements in rye grass) was measured. Simultaneous multi-element graphite furnace atomic absorption spectrometry was used after a microwave acid digestion. The levels of Ni in Asopos food were found up to 9 times higher than control (e.g., Asopos potatoes had an average Ni content of 800 µg/kg compared to 78 µg/kg in control, whereas Asopos carrots had an average Ni content of 474 µg/kg compared to 93 µg/kg in control). Likewise, the levels of Cr were found to be about 2 times higher than control (e.g., Asopos carrots were found to have an average Cr content of 43 µg/kg compared to 20 µg/kg in control). The levels of Cd and Pb had a high variance in the Asopos sourced food. Arsenic was not detected in any sample. Our results indicate that the mean intake of trace elements (Ni, Cr, Pb, Cd, and Cu) by adults through consumption of crops from Asopos, for an average consumption pattern, generally is well below the Allowable Daily Intakes (ADIs). Comparison was also made with data from literature from Greece.     

Direct inductively coupled plasma-atomic emission spectrometry analysis of trace elements in muscle tissues of hairtail using electrothermal vaporization with slurry sampling

A procedure for direct determination of trace elements in muscle tissue of hairtail was developed using inductively coupled plasma-atomic emission spectrometry and electrothermal vaporization with slurry sampling. Due to use of polytetrafluoroethylene as the chemical modifier, the vaporization behaviors of analytes from the slurry and the aqueous standard solutions were very similar. In this case, the aqueous standards could be used for the calibration of slurry samples. The main factors influencing this method were studied systematically. The detection limits for Cr, Ni, Zn, Cd, and Pb were 3.1, 10.5, 176, 6.9, and 83 ng/mL, respectively, and the relative standard deviations were less than 10%. The proposed method was applied to the determination of trace Cr, Ni, Zn, Cd, and Pb in hairtail samples with satisfactory accuracy and precision. A certified reference material of mussel (GBW 08571) was analyzed, and good agreement was obtained between the results from the proposed method and certificate values.     

ICP-MS混合模式测定植物性农产品中的9种痕量元素

建立了ICP- MS混合模式测定蔬菜、水果、大米等植物性农产品中痕量元素的检测方法.样品经HNO3 + H2O2消解,以74Ge,115In、209Bi作为内标溶液消除基体干扰,动能歧视型碰撞/反应池技术消除质谱干扰的方式测定植物性农产品中As,Hg,Pb,Cd,Cr,Se,Cu,Ni,Zn 9种痕量元素.结果表明:该...     

Trace elements in mussels (Mytilus Edulis) from coastal areas of the North Sea and the Baltic. Multielement analyses using instrumental neutron activation analysis

Samples of the mussel Mytilus edulis were collected from different sites of estuarine and coastal areas of the North Sea and the Baltic. The following elements were determined by INAA: Ca, Sc, Cr, Fe, Co, Ni, Zn, As, Se, Br, Rb, Sr, Zr, Ag, Cd, Sn, Cs, Ba, Ta, Eu, Tb, Yb, Hf, Au, Hg, Th. Multielement correlation analysis was used for the evaluation of the data. Differences in trace element patterns are found and described calculating trace element ratios. Regional differences in trace element concentrations are superimposed by typical seasonal variations, with highest concentration levels found in late winter and spring, and lowest in summer and autumn. With support of Deutsche Forschungsgemeinschaft     

Determination and confirmation of the amnesic shellfish poisoning toxin, domoic acid, in shellfish from Scotland by liquid chromatography and mass spectrometry

During 1998 and early 1999, shellfish samples from sites in Scotland were found to contain the amnesic shellfish poisoning toxin, domoic acid (DA). Two different techniques, liquid chromatography (LC) with UV diode-array detection and LC with mass spectrometric (MS) detection, were used to detect and confirm DA in shellfish extracts. The LC/UV method was validated for routine monitoring by recovery experiments on spiked mussel and scallop tissues with a certified mussel tissue used as reference material. Crude extracts of selected samples as well as extracts cleaned with strong anion exchange (SAX) were analyzed by both LC/UV and LC/MS. Good correlation (linear regression r2 = 0.996, slope = 0.93) between the 2 methods was found for cleaned extracts. Analyses of crude extracts by LC/UV produced false-positive results in 2 crab samples, whereas LC/MS analyses gave accurate results. It was concluded that LC/UV is a valid approach for routine monitoring of DA in shellfish when cleanup is performed with a SAX cartridge to prevent false positives. A variety of shellfish species were surveyed for DA content, including Pecten maximus (king scallops), Chlamys opercularis (queen scallop), Mytilus edulis (blue mussels), Cancer pugaris (crab), and Ensis ensis (razor fish). The highest concentration of DA was 105 microg/g in Pecten maximus.     

Optimization of a centrifugation and ultrasound-assisted procedure for the determination of trace and major elements in marine invertebrates by ICP OES

A three factor Doehlert design was applied to optimize the extraction of elements in marine invertebrate samples (oyster, mussel and clam) using centrifugation with diluted acids. The factors were: concentration of acid mixture (HCl + HNO₃ + H₃CCOOH; 1–3 mol L^{− 1}), centrifugation time (10–40 min), and rotation velocity (6000–10,000 rpm). In order to evaluate the ultrasound effect on the extraction of trace metals, a portion of the certified oyster tissue sample (NIST 1556b; 0.250 g) was sonicated for 15 min and then the solution was centrifuged at the optimized conditions. The optimized procedure was then applied to nine marine invertebrate samples (oysters, clams and mussels) collected at Todos os Santos Bay, Bahia, Brazil. The optimized condition of the developed method was: 20 min of centrifugation at 9000 rpm using the acid mixture 1.0 mol L^{− 1}. The effect of sonication prior centrifugation was very variable, but it promoted a significant increase in the extraction (12 to 44%) of some trace elements. Moreover, the combination of the centrifugation with sonication offered other advantages, such as improvement of the precision and accuracy, both demonstrated using the oyster tissue reference sample. The results of major and trace elements in marine invertebrate samples showed that elements such us Cd and Cu in oyster samples and Zn in mussel and clam samples were above recommendations, suggesting that its consumption may impose health risks.     

火焰原子吸收法测定夏枯草果穗的微量元素

使用灰化法处理样品,火焰原子吸收光谱法测定夏枯草果穗中的铬、银、锌、镍、镉、铁、铜的含量。结果表明,除Ag元素未检出外,夏枯草果穗的微量元素含量Cr、Zn、Ni、Cd、Fe、Cu分别为1．024、1．096、36．152、0．580、0．656、6．872μg/g,各元素含量由高到低顺序为：Ni,Cu,Zn,Cr,Fe,Cd,加标回收率为98．6％～115．2％,该法测定快速、简单,原子吸收光谱法测定夏枯草果穗中微量元素具有可行性。     

Nanometer-size titanium dioxide microcolumn on-line preconcentration of trace metals and their determination by inductively coupled plasma atomic emission spectrometry in water

A new method using a microcolumn packed with nanometer TiO₂ as solid-phase extractant has been developed for the simultaneous preconcentration of trace amounts of Cu, Mn, Cr and Ni prior to their measurements by inductively coupled plasma atomic emission spectrometry (ICP-AES). Effects of pH, sample flow rate and volume, elution solution and interfering ions on the recovery of the analytes have been investigated. The adsorption capacity of nanometer TiO₂ was found as 0.108, 0.149, 0.039 and 0.034 mmol g⁻¹ for Cu, Cr, Mn and Ni, respectively. The separation of analytes can be achieved from water samples with a concentration factor of 50 times. The method has been applied for the determination of trace elements in biological sample and lake water with satisfactory results.     

Determination of trace elements in the water cycle by total-reflection x-ray fluorescence spectrometry

The determination of trace elements in the various stages of the water cycle is very important. Economic procedures for multi-element determinations of trace elements in various matrices are needed. The applications of total-reflection x-ray fluorescence spectrometry in this general area are reviewed briefly, with examples relating to rain, river and sea waters, sediments, particulate matter and manganese nodules and crusts, as well as mussel tissue. Up to 25 elements can be determined; these are S, K, Ca, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, As, Pb, Se, Rb, Sr, Y, Zr, Mo, Ag, Cd, Sb and Ba. Preliminary treatments of the various matrices are described. Accuracy checks by analysis of reference standards and by application of independent techniques are reported.     

Determination of impurities in high-purity niobium(V) oxide by high-resolution continuum source graphite furnace atomic absorption spectrometry after sorption preconcentration

Method of sorption–atomic-absorption determination of Co, Cr, Cu, Fe, Mn, and Ni in samples of high-purity Nb₂O₅ with heterochain S,N-containing sorbents was developed. The method is based on the sorption preconcentration of trace impurities followed by their determination by high-resolution continuum source graphite furnace atomic absorption spectrometry (HR CS GFAAS). Selectivity of three original inhouse synthesized S,N-containing heterochain sorbents was studied. The recoveries of Co, Cr, Cu, Fe, Mn, and Ni using heterochain sorbents OKS, MTH, and GLSH were 100, 80, and 76%, correspondingly. Sorbent “OKS”, which provided the quantitative recovery of trace impurities, was chosen for further research. The sorption conditions for chloride solutions of different acidities (0.1–3 M HCl) were studied and optimized. Using the conditions established for the sorption and HR CS GFAAS analysis, trace Co, Cr, Cu, Fe, Mn, and Ni were determined in high purity Nb₂O₅ with a relative error less than 5%. The trueness control of the obtained results is confirmed by the “added–found” method. The developed method allows us to determine concentrations of analytes: 0.02–0.20 ppm Co, 2.0–3.3 ppm Cr, 0.2–1.5 ppm Cu, 6.0–21.0 ppm Fe, 0.6–0.8 ppm Mn, and 2.8–3.5 ppm Ni. The proposed methodology can be successfully extended to the determination of various trace elements in other high-purity inorganic materials.     

Application of total reflection X-ray fluorescence spectrometry for multi-elements characterization in human hair

Biomonitoring of Cr, Fe, Ni, Cu, Zn and Pb in scalp hair of the rural population in Punjab state of India was carried out using TXRF. The objective of the study was to understand their exposure to the trace elements from the local environment. The volunteers having age group 30–45 years were selected from rural region of Punjab. Validity of method was checked by analyzing Certified Reference Materials IAEA-436 and INCT-MPH-2. The results of trace elements analysis in hair samples shows no environmental gradient in the concentration of the elements like Cr, Fe, Ni, Cu, Zn however Pb was observed higher in few volunteers as compared to published value of concentrations in volunteers from Delhi.     

Simultaneous Determination of Trace Elements in Hepatocellular Carcinoma Tissue by Sector Field Inductively Coupled Plasma Mass Spectrometry

An analytical method using sector field inductively coupled plasma mass spectrometry (SF-ICP-MS) for rapid simultaneous determination of Na, Mg, K, Ca, Cr, Mn, Fe, Co, Ni, Cu, Zn, Se, Sr, Mo, and Cd elements in hepatocellular carcinoma (HCC) tissue is reported. The sample was dissolved in HNO₃ and H₂O₂ by microwave digestion and then the aforementioned 15 elements in the solution were analyzed directly by SF-ICP-MS. Most of the spectral interferences were avoided by measuring in medium resolution mode (MRM, M/?M = 4400) and high resolution mode (HRM, M/ΔM = 8000). Correction for matrix effects was made using Sc and Rh as internal standards. The optimum conditions for the determination were tested and discussed. The results showed that SF-ICP-MS is a useful tool for simultaneous determination of multi-elements in HCC tissue and could be widely used in other biological samples analysis.     

Three new mussel tissue standard reference materials (SRMs) for the determination of organic contaminants

Three new mussel tissue standard reference materials (SRMs) have been developed by the National Institute of Standards and Technology (NIST) for the determination of the concentrations of organic contaminants. The most recently prepared material, SRM 1974b, is a fresh frozen tissue homogenate prepared from mussels (Mytilus edulis) collected in Boston Harbor, Massachusetts. The other two materials, SRMs 2977 and 2978, are freeze-dried tissue homogenates prepared from mussels collected in Guanabara Bay, Brazil and Raritan Bay, New Jersey, respectively. All three new mussel tissue SRMs complement the current suite of marine natural-matrix SRMs available from NIST that are characterized for a wide range of contaminants (organic and inorganic). SRM 1974b has been developed to replace its predecessor SRM 1974a, Organics in Mussel Tissue, for which the supply is depleted. Similarly, SRMs 2977 and 2978 were developed to replace a previously available (supply depleted) freeze-dried version of SRM 1974a, SRM 2974, Organics in Freeze-Dried Mussel Tissue. SRM 1974b is the third in a series of fresh frozen mussel tissue homogenate SRMs prepared from mussels collected in Boston Harbor starting in 1988. SRM 1974b has certified concentration values for 22 polycyclic aromatic hydrocarbons (PAHs), 31 polychlorinated biphenyl congeners (PCBs), and 7 chlorinated pesticides. Reference values are provided for additional constituents: 16 PAHs, 8 PCBs plus total PCBs, 6 pesticides, total extractable organics, methylmercury, and 11 trace elements. PAH concentrations range from about 2 ng g^–1 dry mass (cyclopenta[cd]pyrene) to 180 ng g^–1 dry mass (pyrene). PCB concentrations range from about 2 ng g^–1 dry mass (PCB 157) to 120 ng g^–1 dry mass (PCB 153). The reference value for total PCBs in SRM 1974b is (2020 ± 420) ng g^–1 dry mass. Pesticide concentrations range from about 4 ng g^–1 dry mass (4,4-DDT) to 40 ng g^–1 dry mass (4,4-DDE). SRM 2977 has certified values for 14 PAHs, 25 PCB congeners, 7 pesticides, 6 trace elements, and methylmercury. Reference values for 16 additional PAHs and 9 inorganic constituents are provided, and information values are given for 23 additional trace elements. SRM 2978 has certified and reference concentrations for 41 and 22 organic compounds, respectively, and contains contaminant levels similar to those of SRM 1974b. Organic contaminant levels in SRM 2977 (mussels from Guanabara Bay, Brazil) are typically a factor of 2 to 4 lower than those in SRM 1974b and SRM 2978. The organic contaminant concentrations in each new mussel tissue SRM are presented and compared in this paper. In addition, a chronological review of contaminant concentrations associated with mussels collected in Boston Harbor is discussed as well as a stability assessment of SRM 1974a.Electronic Supplementary Material Supplementary material is available in the online version of this article at . A link in the frame on the left on that page takes you directly to the supplementary material.