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The heavy metal toxicity of marketed Ayurvedic herbal formulations has been sporadically reported in the literature. Drakshadi (DK) and Gandharvahastadi (GK) decoctions are widely prescribed classical Ayurvedic herbal formulations. The potential adverse heavy metal toxicity due to consequent intake of DK and GK have been published in scientific papers or reported through pharmacovigilance. The objective of our investigation was to determine the presence of heavy metals in marketed DK and GK, with reference to the Ayurveda Pharmacopeia of India (API) standards. In this study, the concentration of four heavy metals, Arsenic (As), Cadmium (Cd), Lead (Pb), and Mercury (Hg) were investigated using Inductively Coupled Plasma-Mass Spectrometer (ICP-MS). These metals are not known to have any role in the pharmacological activity of these formulations. However, their presence beyond acceptable limits can have harmful consequences. Eighteen random samples each of DK and GK decoctions were collected from different pharmacy outlets, Kerala province, India. We tested 36 market samples of the above formulations for heavy metals, which were found to be within the limits prescribed by the Ayurvedic Pharmacopoeia of India. Our study suggests that heavy metal contamination of Ayurvedic formulations may not be widespread as suspected. However, continuous dynamic monitoring of Ayurvedic herbal formulations for heavy metal contamination is warranted considering the possibility of inadvertent contamination of raw drugs from environmental exposure. [ABSTRACT FROM AUTHOR]

The LEGEND collaboration has been developing a 76Ge-based double-beta decay experimental program where precise radiopurity measurements of ultraclean materials are crucial. Ultralow concentrations of thorium and uranium, the main contributors to the detector background via their decay products, can be determined by inductively coupled plasma mass spectrometry (ICPMS) and accelerator mass spectrometry (AMS). Here we shall present recent developments in thorium and uranium mass spectrometry methods, together with basics of separation chemistry applied to process different samples. The new possibilities to measure 232Th and 238U by ICPMS and AMS at the Comenius University in Bratislava are discussed as well. [ABSTRACT FROM AUTHOR]

This study aimed to conduct a systematic review to analyze heavy metals seasonal concentrations in Uttarakhand tourist hotspot cities (Almora, Nainital, Ranikhet, Mussoorie, and Dhanaulti). A total of 45 samples of liverwort Dumotiera hirsuta were collected from five different cities during winter (Dry deposition) and monsoon (Wet deposition) in the year 2021. The concentrations of Zn, As, Cd, and Pb due to anthropogenic pollution load in the selected locations were analyzed by active biomonitoring using Inductive Coupled Plasma Mass Spectrometry (ICP-MS). Concentration loading of zinc, arsenic, cadmium, and lead was observed to be 79%, 71%, 48%, and 33%, respectively, higher during the dry (winter) season when compared with the monsoon dataset. Multivariant data were analyzed using Principal Component Analysis (PCA) with three components explaining maximum variation in data by factor loading through varimax rotation. The rapid growth and development have connected tourists to the mountain of the western Himalayas. Thus, a monitoring program is needed in these areas for further assessment. So that necessary action can be taken to conserve the eco-sensitive zones of Uttarakhand. [ABSTRACT FROM AUTHOR]

Abstract Background These days, the presence of simple impurities in pharmaceuticals is a major cause for worry. This is because some contaminants are dangerous on their own, and even small impurities can make a drug less stable and shorten its shelf life. The goal of this study was to see if creams with ximenynic acid could be tested with inductively coupled plasma-mass spectrometry to find out how much arsenic, mercury, lead, cadmium, vanadium, cobalt, and nickel were in them. The best way to do things would be one that was quick, accurate, sensitive, and very productive (ICP-MS). The method included both inductively coupled plasma mass spectrometry (ICP-MS) and microwave digestion. Results Seven of the seven linearity correlation coefficient (‘R’) value were more than 0.99. LOD values were calculated using 33% of the 0.25 J threshold. Six LOQ responses (0.25 J level) were taken after considerable discussion. Calculated and reported %RSD for six LOQ copies. All elemental impurities Vanadium (V), Cobalt (Co), Nickel (Ni), Arsenic (As), Cadmium (Cd), Mercury (Hg), and Lead (Pb) were recovered between 83.33% and 115.97%, within acceptability limits. RSD% for procedure precision and intermediate precision data never exceeded 5%. The available evidence shows that the ICP-MS technique is a good way to measure these components. Conclusion The statistical analysis showed that the developed ICP-MS method for measuring elements in Topical Cream with Ximenynic Acid is selective and accurate. Since this ICPMS method is good at estimating several elements simultaneously, it could be used to check for elemental contaminants in the formulation.

Spiny-like spherical copper metal–organic frameworks (SSC-MOFs) were prepared and characterized via SEM, TEM, EDS, XRD, FTIR and the BET surface area. The fabricated SSC-MOFs were applied to develop a procedure for the microextraction of trace arsenic(III) for preconcentration. The results show that a copper- and imidazole-derived metal–organic framework was formed in a sphere with a spiny surface and a surface area of 120.7 m2/g. The TEM confirmed the perforated network structures of the SSC-MOFs, which were prepared at room temperature. The surface functional groups were found to contain NH and C=N groups. The XRD analysis confirmed the crystalline structure of the prepared SSC-MOFs. The application for the process of microextracting the arsenic(III) for preconcentration was achieved with superior efficiency. The optimum conditions for the recovery of the arsenic(III) were a pH of 7 and the use of a sample volume up to 40 mL. The developed SSC-MOF-derived microextraction process has an LOD of 0.554 µg·L−1 and an LOQ of 1.66 µg·L−10. The developed SSC-MOF-derived microextraction process was applied for the accurate preconcentration of arsenic(III) from real samples, including food and water, with the promised performance efficiency. [ABSTRACT FROM AUTHOR]

Simple Summary: Modern ecotoxicology analyses the biological material collected from animals to study the impact of the long-term exposure to contaminants on the environment. Among all contaminants, metals are particularly challenging to monitor, as they are typically present at trace levels. At the same time, toxicological concern is raised by their persistence in the organism and their possibility to be transferred through the food chain. Feathers could represent a non-invasive and valuable tool to study trace metal contamination, in view of their capability to accumulate trace elements over a long period of time. In the present study, feathers from the Muscovy duck were used to compare the levels of trace metals in two areas of Palermo (Sicily), one being in a central urban location and the other farther from the city centre. The comparison between feathers and blood samples also allowed to validate feathers as a suitable tool to monitor the long-term exposure to metals. Eventually, washing feathers with nitric acid could provide an insight on the actual concentration of metals accumulated within the feathers as a result of an intake as compared to the amount of metals deposited on them through air. Biomonitoring is the qualitative observation and the measurement of biosphere parameters aimed at modelling the environment, evaluating its quality, and studying the effects of alterations on different ecological levels. In this work, trace metal concentrations were assessed using non-destructive biomonitoring tools as blood and feathers of the allochthonous aquatic bird Cairina moschata, collected within two areas of the Palermo metropolitan area, Sicily, differently exposed to air pollution: Parco D'Orleans, in a central urban location, and Monreale, southwest of the city centre. Higher concentrations in both blood and feathers collected in Parco D' Orleans were found for lead, tin and selenium, but the same was not observed for other metals. The concentrations were not above physiological tolerance in any case. The comparison between blood and feathers allowed to realize that the latter are more useful for biomonitoring analyses, as they are indicative of both external contamination and bioaccumulation. Treatment with nitric acid highlighted that the feathers collected in Parco D' Orleans had higher metal bioaccumulation than the ones collected in Monreale; however, the treatment needs standardization. The present study confirms that feathers and blood from C. moschata are a convenient and non-destructive sampling tool for metal contamination analysis. [ABSTRACT FROM AUTHOR]

The bioaccumulation of trace metals in 10 selected edible seaweeds was studied using inductively coupled plasma mass spectroscopy (ICP-MS). Bioaccumulation of higher levels of manganese (4.94 ± 0.15 μg/g) and aluminium (4.21 ± 0.18 μg/g) and lower levels of arsenic (0.18 ± 0.02 μg/g) and vanadium (0.09 ± 0.02 μg/g) were observed in Chlorophyta. In Rhodophyta, bioaccumulation of iron (8.51 ± 0.19 μg/g) was high, while lower levels of magnesium (0.13 ± 0.02 μg/g) and strontium (0.21 ± 0.01 μg/g) were observed among the seaweeds studied. Health assessment studies were also conducted on seaweeds to understand their effects on human consumption. The findings imply that consuming macroalgae has no health risk due to these elements in the general population. Furthermore, the confirmative toxicity of specific metals, such as Cd, Pb, and Zn metals in macroalgae, should be monitored constantly. [ABSTRACT FROM AUTHOR]

Recent developments in multiplex bioassay around the theme of precision diagnostics have gained great focus. Inductively coupled plasma mass spectrometry (ICPMS) is emerging as a powerful platform for multiplex bioassay due to its high sensitivity, wide dynamic range, particularly its reliable multiplex sensing ability. This review discusses the progress being made in the multiplex bioassay applicating ICPMS, mainly emphasizes on varieties of biomarkers and methodological innovations. Also, we summarized limitations and proposed prospects to shed new light on the emergence of more powerful and application-oriented analytical methods. [ABSTRACT FROM AUTHOR]

Environmental context: With mushroom consumption increasing worldwide, it is important to know about the concentration of different arsenic species in the most commonly eaten mushroom species, especially since the toxicity depends on the chemical structure. No dangerous amounts of the highly toxic inorganic arsenic were detected in the studied mushrooms. It is therefore safe to consume mushroom fruit-bodies of the investigated species, at least with regard to the arsenic content. Rationale: A large variety of different mushroom species is considered edible. They are often considerably distinct from each other in a wide range of properties, among others the elemental profile and the speciation of various elements, e.g. arsenic. Methodology: In this first comprehensive study of arsenic and its species in the most popular cultivated and wild-grown edible mushrooms in central Europe, the arsenic mass fraction and the arsenic speciation of a total of 93 mushroom samples were investigated with inductively coupled plasma mass spectrometry (ICPMS) and high performance liquid chromatography coupled to ICPMS. Results: The arsenic mass fractions ranged from <0.004 to 1.02 mg kg−1 dry mass. For some mushroom species (e.g. Cantharellus cibarius), only low amounts of the total arsenic could be extracted with water, and other mushrooms revealed unusual arsenic speciation profiles and the presence of compounds that are rarely found in the terrestrial environment, for example dimethylarsinoylacetic acid, accounting for around 12% of the total arsenic in Boletus edulis. Over all, the results highlight the diversity of arsenic species in mushrooms, but also reveal a high consistency within the individual mushroom species. Discussion: With mushroom production increasing each year, it is important to know the content of possibly dangerous compounds. The toxic inorganic arsenic was generally below 0.2 mg kg−1 dry mass. Considering the maximum limit that can be eaten of inorganic arsenic without increased health risk, at least 2 kg of the studied mushrooms could be consumed by an average person per day on a regular basis. Environmental context. With mushroom consumption increasing worldwide, it is important to know about the concentration of different arsenic species in the most commonly eaten mushroom species, especially since the toxicity depends on the chemical structure. No dangerous amounts of the highly toxic inorganic arsenic were detected in the studied mushrooms. It is therefore safe to consume mushroom fruit-bodies of the investigated species, at least with regard to the arsenic content. [ABSTRACT FROM AUTHOR]

Environmental context: The arsenic content and its speciation in harvested rice are dependent on the genetics of the rice variety, the agricultural practise as well as the speciation of arsenic in the soil. The geochemical conditions and therefore the microbiological regime in the paddy fields can influence the biomethylation of the arsenic in the porewater and therefore can influence the extent of arsenic uptake and its speciation in rice plants. Rationale: Rice is routinely monitored throughout the world for compliance with regulatory limits of inorganic arsenic. Rice grains are well known for their relatively high arsenic concentration in the form of dimethylarsinic acid, methylarsonic acid and inorganic arsenic with other arsenic containing compounds rarely occurring. During a routine survey by the US FDA, an unexpected arsenic compound was noted. Methodology: The compound was eventually identified using a combination of liquid chromatography with elemental (HPLC–ICPMS) and molecular mass spectrometry (HPLC–ESMS) as well as chemical derivatisation. Results: Here we report the identification of the previously unknown arsenical in rice grain, dimethylarsonyldimethylarsinic acid; its origin is unknown. Environmental context. The arsenic content and its speciation in harvested rice are dependent on the genetics of the rice variety, the agricultural practise as well as the speciation of arsenic in the soil. The geochemical conditions and therefore the microbiological regime in the paddy fields can influence the biomethylation of the arsenic in the porewater and therefore can influence the extent of arsenic uptake and its speciation in rice plants. [ABSTRACT FROM AUTHOR]

Spiny-like spherical copper metal–organic frameworks (SSC-MOFs) were prepared and characterized via SEM, TEM, EDS, XRD, FTIR and the BET surface area. The fabricated SSC-MOFs were applied to develop a procedure for the microextraction of trace arsenic(III) for preconcentration. The results show that a copper- and imidazole-derived metal–organic framework was formed in a sphere with a spiny surface and a surface area of 120.7 m2/g. The TEM confirmed the perforated network structures of the SSC-MOFs, which were prepared at room temperature. The surface functional groups were found to contain NH and C=N groups. The XRD analysis confirmed the crystalline structure of the prepared SSC-MOFs. The application for the process of microextracting the arsenic(III) for preconcentration was achieved with superior efficiency. The optimum conditions for the recovery of the arsenic(III) were a pH of 7 and the use of a sample volume up to 40 mL. The developed SSC-MOF-derived microextraction process has an LOD of 0.554 µg·L−1 and an LOQ of 1.66 µg·L−10. The developed SSC-MOF-derived microextraction process was applied for the accurate preconcentration of arsenic(III) from real samples, including food and water, with the promised performance efficiency.

The analytical method development and validation of Medroxyprogesterone tablets 10mg summarizes the outcome of the results for content of Cadmium, Lead, Arsenic, Mercury, and Lithium in by ICP-MS1. The test sample was prepared with microwave assisted acid digestion and introduced into optimized instrumental parameters for use of a quadruple based Agilent 7700 inductively coupled plasma mass spectrometry instrument. This method development and validation by ICP-MS to prove that it is Specific, Precise, Accurate, Linear, Robust, Reproducible and Capable of producing reliable results. [ABSTRACT FROM AUTHOR]

Exchange plays a number of roles within societies, including the provisioning of necessary and prestige resources. The elucidation of these different roles requires documenting how different kinds of material were used and how these resources became distributed. These studies are particularly prominent in Polynesia, especially the Sāmoan archipelago. However, the nature and scale of artifact transfer within and outside the archipelago are debated given deficiencies in the empirical record. Here, we remedy this situation by examining trends in Sāmoan intra-archipelago exchange using geochemical and limited technological analyses of a lithic assemblage from the Manu‘a group of the Sāmoan archipelago. Our results indicate that material from multiple basalt sources is present, including several sources outside the Manu‘a group. It is apparent that this nonlocal material was used differently than local material as 95% of analyzed adzes were manufactured of the former. However, there is no evidence to suggest that this nonlocal material was differentially distributed or controlled at the scale of the group or site. We argue that this is evidence of decentralized exchange and that imported materials became common pool resources to support community resiliency and sustainability. [ABSTRACT FROM AUTHOR]

[Display omitted] • Development of a sensitive CRISPR/Cas12a-based amplification-free nanoparticle counting method for detection of AFB1. • The first report of the ICPMS single particle counting-based CRISPR/Cas12a biosensing study. • This method has been successfully applied to determination of AFB1 in food matrices (peanut oil, beer, and wheat meal). CRISPR (clustered regularly interspaced short palindromic repeats) and CRISPR-associated protein (Cas) have gained extensive applications in bioassays. However, CRISPR-based detection platforms are often hampered by limited analytical sensitivity, while nucleic acid-based amplification strategies are usually indispensable for additional signal enhancement with potential risks of amplification leakages. To address these challenges, an amplification-free CRISPR-based bioassay of aflatoxin B1 (AFB1) was proposed by applying single nanoparticle counting. Single-particle mode inductively coupled plasma mass spectrometry (Sp-ICPMS) has been regarded as a sensitive tool for nanoparticle counting since one nanoparticle can generate considerable signals above backgrounds. With AFB1, activator strands were introduced to initiate the trans -cleavage of CRISPR/Cas12a for cutting the nanoparticles-tagged-magnetic beads, which were transduced to nanoparticle count signals after separation. Finally, a pico-mole level limit-of-detections (LODs) with moderate selectivity was achieved. Certified reference materials (CRMs) analysis and recovery tests were conducted with promising results. To our best knowledge, this is the first report of the single particle counting-based CRISPR/Cas12a biosensing study. [ABSTRACT FROM AUTHOR]

Gradually rising atmospheric temperature is the vital component of the environment, which is anticipated as the riskiest abiotic stress for crop growth. Nanotechnology revolutionizing the agricultural sectors, notably, zinc oxide nanoparticles (nano-ZnO) has captured intensive research interests due to their distinctive properties and numerous applications against abiotic stresses. Mungbean (Vigna radiata L.), being a summer crop, is grown all over the world at an optimum temperature of 28–30°C. A rise in temperature above this range, particularly during the flowering stage, can jeopardize the potential performance of the plant. Hence, an outdoor study was performed to evaluate the effect of multiple suspensions of nano-ZnO (0, 15, 30, 45, and 60 mg l–1) on physicochemical attributes and yield of mungbean crop under heat stress. Heat stress was induced by fine-tuning of sowing time as: S1 is the optimal sowing time having day/night temperatures <40/25°C and S2 and S3 are late sown that were above >40/25°C during the flowering stage. In vitro studies on Zn release from nano-ZnO by inductively coupled plasma mass spectroscopy (ICPMS) disclosed that the Zn release and particles uptake from nano-ZnO were concentration-dependent. Exogenous foliar application of nano-ZnO significantly upstreamed the production of antioxidants and osmolytes to attenuate the shocks of heat stress in S2 and S3. Likewise, nano-ZnO substantially rebated the production of reactive oxygen species in both S2 and S3 that was associated with curtailment in lipid peroxidation. Adding to that, foliar-applied nano-ZnO inflates not only the chlorophyll contents and gas exchange attributes, but also the seeds per pod (SPP) and pods per plant (PPP), which results in the better grain yield under heat stress. Thus, among all the sowing dates, S1 statistically performed better than S2 and S3, although foliar exposure of nano-ZnO boosted up mungbean performance under both the no heat and heat-induced environments. Hence, foliar application of nano-ZnO can be suggested as an efficient way to protect the crop from heat stress-mediated damages with the most negligible chances of nanoparticles delivery to environmental compartments that could be possible in case of soil application. [ABSTRACT FROM AUTHOR]

Mapping of regolith is significant to identify and discriminate geomorphic expression, regolith evolution, weathering histories and assistance in clarification of relationships between parent and surface materials. In this research work, the hydrothermally altered regolith of Western Jahajpur Belt, Bhilwara, India is studied using ASTER and AVIRIS imageries by PCA, decorrelation stretching supervised classification image processing methods. Results of decorrelation stretching of ASTER spectral bands 6, 7 and 9 showed the regolith in blue, green and red colour with the associated geological formations. Analyses of VNIR-SWIR spectral bands of ASTER by PCA showed the bed rocks associated to the regolith green, yellow, white and red colours, respectively. The minerals of the regolith and parent geological formations are identified using AVIRIS data by supervised classification and endmember spectral analyses. The study also identified six regolith-landforms which include the regolith (vegetation cover), crop land (vegetation cover), water, crop land with vegetation, alluvium and regolith (ferruginous and calcareous mineral zone). The discrimination of regoliths and geological formations are verified in the field and confirmed by XRF and ICP-MS geochemical analysis of samples. [ABSTRACT FROM AUTHOR]

Gradually rising atmospheric temperature is the vital component of the environment, which is anticipated as the riskiest abiotic stress for crop growth. Nanotechnology revolutionizing the agricultural sectors, notably, zinc oxide nanoparticles (nano-ZnO) has captured intensive research interests due to their distinctive properties and numerous applications against abiotic stresses. Mungbean (Vigna radiata L.), being a summer crop, is grown all over the world at an optimum temperature of 28–30°C. A rise in temperature above this range, particularly during the flowering stage, can jeopardize the potential performance of the plant. Hence, an outdoor study was performed to evaluate the effect of multiple suspensions of nano-ZnO (0, 15, 30, 45, and 60 mg l–1) on physicochemical attributes and yield of mungbean crop under heat stress. Heat stress was induced by fine-tuning of sowing time as: S1 is the optimal sowing time having day/night temperatures 40/25°C during the flowering stage. In vitro studies on Zn release from nano-ZnO by inductively coupled plasma mass spectroscopy (ICPMS) disclosed that the Zn release and particles uptake from nano-ZnO were concentration-dependent. Exogenous foliar application of nano-ZnO significantly upstreamed the production of antioxidants and osmolytes to attenuate the shocks of heat stress in S2 and S3. Likewise, nano-ZnO substantially rebated the production of reactive oxygen species in both S2 and S3 that was associated with curtailment in lipid peroxidation. Adding to that, foliar-applied nano-ZnO inflates not only the chlorophyll contents and gas exchange attributes, but also the seeds per pod (SPP) and pods per plant (PPP), which results in the better grain yield under heat stress. Thus, among all the sowing dates, S1 statistically performed better than S2 and S3, although foliar exposure of nano-ZnO boosted up mungbean performance under both the no heat and heat-induced environments. Hence, foliar application of nano-ZnO can be suggested as an efficient way to protect the crop from heat stress-mediated damages with the most negligible chances of nanoparticles delivery to environmental compartments that could be possible in case of soil application.

The release of certain metallic constituents within some dental implants could contribute to peri-implantitis and mucositis. While the release rate into surrounding bones and tissues may be dependent on the biocompatibility of dental materials and their designs, the patient's oral hygiene and even the prevalence of certain resident oral bacteria may also affect the service lives of these dental implants by altering their gross corrosion rates. In this study, the levels of Fe, Cr, and Ni released during microbiologically induced intergranular corrosion of medical grade 316L stainless-steel dental material are measured across defined culture durations. Porphyromonas gingivalis , a prominent component of the oral microbiome known to associate with periodontitis and peri-implantitis, is the test bacterium in this study. From the evidence obtained from electrochemical and surface investigations in artificial salivary culture media, dental substates corroded significantly upon maturation of bacterial growth. Corrosion was accompanied by higher levels of metal ion release at extended culture duration. About 1.5 and 9.5 μg/cm2 of Ni and Cr were leached from the metal alloy after a 30-day exposure to the bacterial culture relative to the control; Fe was released 30 times more in the former. This study highlights how oral metal contact influences the corrosion of metallic dental implants (e.g., stainless-steel crowns) in patients infected by certain resident oral bacterium. • Higher amounts of metallic leachants released from dental substrates in salivary culture. • Higher levels of Fe were observed in the culture compared to Ni and Cr. • The above trend continued with and without bacterial inoculation. • Bacterial growth accelerated MIC accompanied by increased j corr and lowered R p. • Intergranular corrosion intensified with evolving volatile sulfur compounds. [ABSTRACT FROM AUTHOR]

New method was developed to analyze Pu and Am sequentially for soil and sediment by inductively coupled plasma mass spectrometry (ICPMS). The developed method uses conc. HNO3 to leach Pu and Am, Fe(OH)3 coprecipitation to remove alkali and alkaline metals, extraction chromatographic separation using UTEVA, DGA and TEVA resins to remove interfering elements (IEs) and separate Pu and Am from each other, and sector field-ICPMS to measure Pu and Am. The analysis of four standard reference materials showed that both Pu isotopes and 241Am were accurately determined by this method, as a result of its excellent decontamination ability of IEs. Especially the high decontamination factor of Pu [DF(Pu), 4.2 × 102] in Am fraction and high DF(Am) (7.0 × 103) in Pu fraction sufficiently eliminated the cross interference between 241Pu and 241Am in ICPMS measurement. In addition, stable and high chemical recoveries were achieved for Pu (71–91%) and Am (70–88%). The low LODs of Pu isotopes, short analytical time (14 h) and high DFs of IEs allows this method to sequentially analyze Pu and Am, for both global fallout and nuclear accident sourced samples. [ABSTRACT FROM AUTHOR]

It is common knowledge that untreated abandoned mining sites are one of the leading causes of elevated heavy metal levels in soil and as well as vegetables growing in these areas. Ingestion of heavy metal contaminated vegetables is one of the primary ways in which these elements get access to human body. Thus, it is a necessity to analyse heavy metal levels in crops and agricultural soils. The aim of this study was to investigate the levels of heavy metals in vegetables and agricultural soil samples and to calculate bioconcentration factors of samples from the abandoned mining district, Gemikonagi and to compare these results with a control area, Dipkarpaz. The most common vegetables used in the local human diet were collected from Gemikonagi (n=7) and Dipkarpaz (n=7) with 7 agricultural topsoil samples from each region and they were analysed using inductively coupled plasma mass spectrometer. According to the results obtained, it was seen that malva samples had the highest mean concentration of heavy metals in both Gemikonagi and Dipkarpaz (718.53 mg/kg and 240.47 mg/kg, respectively). In both regions, the highest mean heavy metal concentration in soil was Fe (Gemikonagi; 25073.74 mg/kg and Dipkarpaz; 15061.58 mg/kg). In accordance with the obtained data, it was found that Cr accumulation in lettuce grown in Dipkarpaz is the only Bioconcentration Factor value that is above the limit. The soil in both regions is concentrated with high levels of heavy metals. Therefore, a large-scale monitoring of the soil is mandatory, and remediation of the heavy metal contaminated soil is necessary. [ABSTRACT FROM AUTHOR]

This study aims to synthesize and characterize an economical and ecological adsorbent with high adsorption capacity. For this purpose, the peanut shells (Pistacia vera L.) were modified chemically. After the synthesis of activated carbon (AC), the optimum conditions for enrichment steps were performed using parameters: pH and contact time for uranium in the model solutions. The measurements were carried out by inductively coupled plasma-mass spectrometry (ICP-MS). From the shapes of the BET isotherms, the AC obtained exhibits type I. The study indicated that the surface area and total pore volume of the AC were found to be 679.9 m2 g−1 and 0.31 cc g−1, respectively. The adsorption capacity was found to be 260 mg g−1. The optimum pH was found to be 6.0 for enrichment using the AC obtained by sulfuric acid as a chemical-modifier. The optimized method was applied to enrichment of U at ppb levels in the model solutions. [ABSTRACT FROM AUTHOR]

The inorganic and total arsenic concentration in rice samples with different origins was determined by continuous hydride generation-atomic absorption spectrometry (HG-AAS) and inductivity coupled plasma mass spectrometry (ICP/MS). Only one sample preparation method was used for total arsenic and inorganic arsenic determination in rice samples. LOD and LOQ for HGAAS and ICPMS were 0.3, 1, and 0.003, 0.01 μg kg−1, respectively. The relative standard deviation (RSD %) of the method was in the range of 5-15 %, and 7-25 % as the relative standard deviation of 3 replicates. The validation of the method was done using CRM NIST 1568b and IGI 1385 rice flour, successfully. This method was applied for the determination of inorganic arsenic and total in 72 rice samples from five different countries of origin. The average concentration of total arsenic was 370, 269, 214, 110, and 97 μg kg−1; and inorganic arsenic was 64, 80, 92, 99, and 82 μg kg−1 in the rice samples for Argentina (AR), Uruguay (UR), United States of America (USA), Iran (IR), and India (IN), respectively. [ABSTRACT FROM AUTHOR]

The aim of the study was to develop an analytical procedure for determining 13 elements in 40 herbs and mixtures of herbs of Chinese origin by the ICPMS method after acidic digestion of samples. The correctness of the analytical procedure was verified by estimating the validation parameters. The traceability of a measurement result was established by the certified reference materials: Mixed Polish Herbs (INCT-MPH-2) Apple Leaves (1515 NIST) and Spinach Leaves (1570a NIST). Appropriate optimization has determined the sensitivity of determinations, precision, detection limits. The limits of detection were in the range 0.015-15 mg kg-1 for Co and Mg respectively, the precision was in the range 1% - 48% for Ba and Se, respectively, and the recoveries were in the range 69% - 101% for Ni and Mn, respectively. The determined content (mg kg-1) of elements in all samples was in the ranges: Mg (288-5755), V (<0.031-2.4), Mn (8.1-2095), Co (0.020-1.36), Ni (<1.1-6.9), Cu (<0.55-24), Zn (3.2-232), As (<0.096-1.4), Se (<0.15-0.85), Sr (1.1-277), Cd (<0.048-1.5), Ba (2.1-117) and Pb (<0.15-2.94). The content of As was higher than 0.25 mg kg-1 in 30% of the samples, the content of Cd was above the 0.2 mg kg-1 in 42.5% of the samples, and the content of Pb was above the value 0.3 mg kg-1 in 72.5% of the herbs. This means that the toxic elements were present in significant amounts able to cause toxic effects in the human body. Principal component analysis allowed us to distinguish 3 groups in which elements are well correlated: (i) V, As and Mg, (ii) Mn, Zn and Pb and (iii) Ni, Co and Cu. [ABSTRACT FROM AUTHOR]

Various studies in rodents have shown that nanoparticles are transferred to the breast milk. Under the present study, lactating Wistar rats were repetitively gavaged 5, 25, and 50 mg/kg bw of zinc oxide nanoparticles (ZnO-NPs) and 50 mg kg−1 bw of bulk zinc oxide (bZnO) for 19 days after parturition. The results showed that ZnO-NPs were absorbed in the small intestine of dams and distributed to the liver. Furthermore, ZnO-NPs were distributed to the intestine and liver of rat pups through dam's milk. No significant change in body weight was observed in the dams treated with ZnO-NPs or bZnO and their offsprings as compared to the control group. The spleen weight significantly increased in the rat dams treated with 50 mg kg−1 of ZnO-NPs. ZnO-NPs were mostly excreted through feces. The levels of liver cytochrome P450 reductase and serum total antioxidant capacity significantly decreased in the rat dams treated with ZnO-NPs (50 mg kg−1) and their offsprings. The levels of serum cytokines (tumor necrosis factor-alpha and interleukin-1 beta) and liver injury marker enzymes (alanine aminotransferase and aspartate aminotransferase) significantly increased in the rat dams treated with ZnO-NPs (25 and 50 mg kg−1) and their offsprings. The level of immunoglobulin A secretion in the intestinal fluid of rat dams and their offsprings is significantly increased by increasing the dose of ZnO-NPs. Histopathology of intestine and liver of offsprings whose rat dams were treated with ZnO-NPs (50 mg kg−1) showed gross pathological changes. These results provide information for the safety evaluation of ZnO-NPs use during lactation. In conclusion, a dose-dependent postnatal transfer of ZnO-NPs is hazardous to the breastfed offsprings. [ABSTRACT FROM AUTHOR]

Minerals are important components of thousands of enzymes and other compounds in the body. Although the content of minerals in the human body is small, their importance is immense. Edible insects can provide many of these minerals in abundance, and are therefore thought to be a good source of micronutrients. This study dealt with the effect of a rearing temperature and feed on the mineral content and on the content of selected heavy metals in mealworm (Tenebrio molitor). Mealworm larvae were kept at temperatures of 15, 20 and 25°C, and fed with wheat bran, lentil flour and a mixture of both. The types of feed for the experimental groups were chosen purposefully, considering the availability on site, price and especially the impact on the nutrition composition suitable for human. The concentrations of the most significant elements in terms of human nutrition concerns, that is zinc and copper, were determined with inductively coupled plasma mass spectrometry. The results showed that the normality condition was not achieved for Ca, Fe, P and Pb (p<0.05). Therefore, these data were compared using the Kruskal-Wallis method, while ANOVA test was performed for the other elements. There was a statistically significant dependence of the Cd concentration on feed at a constant rearing temperature of 15°C and 25°C over the entire feed change range. The results included a change in Mg over the whole range of monitored values with a change of the rearing temperature and constant feed of lentils-bran,and with a change of feed and constant rearing temperature of 15°C. In contrast, concentrations of Na, P, Ca and Cu over the whole observed range of feed or rearing temperature changes were independent from the variables. With an appropriately chosen rearing temperature and feed, it is possible to obtain mealworm with specific nutritional properties for a target group of consumers. [ABSTRACT FROM AUTHOR]

In the present study, the larvicidal efficacy of mycogenic zinc oxide nanoparticles (ZONPs) were tested against white grubs, a potent pest of sugarcane in western Uttar Pradesh (India). The ZONPs were synthesized using Aspergillus niger biomass and characterized using UV–Vis spectroscopy, field emission scanning electron microscopy (FESEM), energy dispersive X-ray (EDX), dynamic light scattering (DLS) and Fourier transform infrared (FTIR). the parts per million (ppm) concentration of synthesized ZONPs was established by the inductively coupled plasma mass spectrometry (ICPMS) technique and several ppm dilutions were prepared to determine 50% lethal dose (LD50). The UV–Vis spectroscopy showed peaks at 240, 290, 340, and 380 nm, corresponding to ZONPs. The FESEM results also confirmed the synthesis of nano-sized particles. EDX analysis result showed the optical absorption peaks specific to ZONPs. The DLS result confirmed the synthesis of ZONPs with sizes ranging from 76.2 to 183.8 nm. The FTIR spectrum analysis confirmed the presence of various functional group interactions in the nanoparticle sample. The ZONPs were tested against the first instar larvae of white grubs. The LD50 was calculated to be 12.63 ppm which still needs to be validated for significance. In the near future, we are planning to establish the minimal lethal dosage of ZONPs to prepare effective larvicidal formulations against white grub infection with minimal toxicity to the environment. [ABSTRACT FROM AUTHOR]

The palm-pruning leaves considered as valuable source for low cost adsorbent materials. Such application, enhance the environmental conditions by reducing the bad effects from un-managed palm-pruning leaves such as spreading insects. Herein, the palm-pruning leaves were treated with by water and acid washing to produce cleaned palm leaves (CPL) and then impregnation with iron(III) chloride and thermally treated to produce palm leaves/iron oxide- nanocomposite (PL/IO-NC). The prepared materials were applied for adsorption of some toxic metal ions from solutions. The original palm-pruning leaves as well as the treated adsorbent were characterized by SEM, EDS, FTIR, XRD. Results showed the formation of spots iron oxide nanoparticles onto the palm-pruning leaves. The efficiency of the treated adsorbent for uptake of Mn(II), Co(II) and Pb(II) was studied in term of kinetic, isotherm and thermodynamic to optimize and evaluate the effectiveness of the palm-pruning leaves treatment. The adsorption data was found to be more comfortable with Second order kinetic-model while the isotherm of Langmuir wasn't suitable and the adsorption data was in agreement with Freundlich assumption. The values of ΔG° in the range (−5.8 to −3.5 kJ/mol) for Mn(II), (−4.2 to −2.1 kJ/mol) for Co(II), (−3.4 to −2.3 kJ/mol) for Pb(II), confirm the confirm the spontaneous and physical nature of the adsorption process. [ABSTRACT FROM AUTHOR]

Analytical techniques employing energetic beams are widely used for material characterization. In the present study, energy dispersive X-ray fluorescence spectroscopy and inductively coupled plasma mass spectrometry were used to prepare the trace elemental profile of the Ayurvedic formulation—Triphala Churna. The samples were prepared as per the procedure referred to in Ayurvedic Pharmacopoeia of India. Profiles for major, minor and trace elements were prepared for the formulation as well as the constituent herbs qualitatively and quantitatively. The profile will act as a fingerprint reference data for the quality assurance of the formulation and as a novel and sensitive method for the standardization of herbal compound medicines. [ABSTRACT FROM AUTHOR]

In the present study pesticidal efficacy of mycogenic silver nanoparticles (AgNPs) was tested against white grubs (Holotrichia sp), a potent pest of sugarcane in western Uttar Pradesh (India). The AgNPs were synthesized by using Aspergillus niger biomass and characterized by color based method, UV (ultra voilet) - Visible Spectroscopy, Field Emission Scanning Electron Microscopy (FESEM), Energy Dispersive X-Ray (EDX), Dynamic Light Scattering (DLS), Fourier-transform infrared spectroscopy (FTIR) and Inductively coupled plasma mass spectroscopy (ICPMS). The development of paint-like mustard colored solution by color-based identification method confirmed the synthesis of AgNPs. The UV-Vis spectroscopy showed peak at 425nm, corresponding to AgNPs. The FESEM results also confirmed the synthesis of nano sized particles. EDX analysis result showed the optical absorption peak at 3 keV which is specific to AgNPs. The DLS result confirmed the synthesis of AgNPs with average size of 76.6 nm. FTIR analysis depicted information about all the interaction of AgNPs with other chemicals present in environment. The AgNPs were applied against first instar white grub larvae in vitro and lethal dosage (LD50) was formulated by Probit analysis, which was further validated and found to be significant at 0.05 levels by chi-square test and analysis of variance (ANOVA) including least significant difference (LSD). [ABSTRACT FROM AUTHOR]

Natural thorium and uranium found in construction components of underground experiments can significantly contribute to detector background. Here we present the determination of 232Th and 238U in selected selenium, aluminum and copper materials, exploiting a highly effective chromatography method based on the TRU Resin and inductively coupled plasma mass spectrometry. While selenium samples as isotope sources were analyzed for the purpose of the SuperNEMO experiment, the results of aluminum and copper samples have been used for development of accelerator mass spectrometry for ultra-sensitive radiopurity analyses of construction materials. Semi-quantitative analysis was also conducted for some selenium and aluminum materials. [ABSTRACT FROM AUTHOR]

The aim of this work was to determine the concentration of trace elements (Zn, As, Cd and Pb) in mangrove sediments using the European community bureau of reference (BCR) sequential extraction method. The sampling was conducted in August 2016 at 8 stations of Songkhla Lake in southern Thailand. Trace element concentrations were determined using the inductively coupled plasma mass spectrophotometer (ICPMS). Zn (37.20-64.42%) and Cd (63.44-77.50%) were found dominant in the acid-soluble fraction (F1). Pb (62.01-89.48%) was detected dominantly in reducible fraction (F2). As (49.92-73.45%) was found dominant in F2 (at stations 2, 4, 6, and 8) and in oxidizable fraction (F3) with the concentrations of 48.71-68.02% (at stations 1, 3, 5, and 7). All trace elements (Zn, As, Cd, and Pb) were bound to the bioavailable fractions (first three fractions) and were low in residual fraction (F4). Calculation of ecological risk assessment of Cd revealed that the individual concentration factor (ICF) >6, the global concentration factor (GCF) >24 and the risk assessment code (RAC) >50% in all stations were classified as high concentration and very high risk for aquatic organisms. [ABSTRACT FROM AUTHOR]

DNA walking machines opened new avenues for the biosensing and demonstrated great success in the past few years. Since DNA machines are mainly nonequilibrium systems driven by dynamic interactions, the matrix effects on DNA machines is a bottleneck and more intricate than common DNA‐mediated assays, especially for complicated physiological samples. Herein, to realize an accurate and reliable quantitative machine, a ratiometric DNA walking machine was developed in human serums and cell lysates based on the elemental isotope ratio measurement. The target DNA‐triggered walking machine converted and amplified biological signals into mass spectrometric signal ratios (197Au/115In) via a burnt‐bridge mechanism. Under the optimized conditions, the limit of detection (LOD, 3σ) was 8 fM for target DNA, with a dynamic linear range of 0.05–0.7 pM. The ratiometric DNA walking machine was directly applied in human serum samples with satisfactory recoveries of 94 to 105 %, demonstrating an excellent stability and a high accuracy. Combining the aptamer‐based specific recognition, the proposed DNA machine is expected to be a versatile platform for other targets, such as small biomolecules and proteins. [ABSTRACT FROM AUTHOR]

As novel metallodrugs continue to emerge, they are evaluated using models, including zebrafish, that offer unique sublethal endpoints. Testing metal‐based anticancer compounds with high‐throughput zebrafish toxicological assays requires analytical methods with the sensitivity to detect these sublethal tissue doses in very small sample masses (e.g., egg mass 100 μg). A robust bioanalytical model, zebrafish embryos coupled with inductively coupled plasma‐mass spectrometry (ICPMS) for measurement of delivered dose, creates a very effective means for screening metal‐based chemotherapeutic agents. In this study, we used ICPMS quantitation with the zebrafish embryo assays to detect metal equivalents at multiple response endpoints for two compounds, the chemotherapeutic agent cisplatin and ruthenium (Ru)‐based prospective metallodrug, PMC79. We hypothesized that cisplatin and PMC79 have different mechanisms for inducing apoptosis and result in similar lesions but different potencies following water‐borne exposure. An ICPMS method was developed to detect the metal in waterborne solution and tissue (detection limit: 5 parts per trillion for Ru or platinum [Pt]). The Ru‐based compound was more potent (LC50: 7.8 μm) than cisplatin (LC50: 158 μm) and induced disparate lesions. Lethality from cisplatin exposure exhibited a threshold (values >15 mg/L) while no threshold was observed for delayed hatching (lowest observed adverse effect level 3.75 mg/L cisplatin; 8.7 Pt (ng)/organism). The Ru organometallic did not have a threshold for lethality. Cisplatin‐induced delayed hatching was investigated further by larval‐Pt distribution and preferentially distributed to the chorion. We propose that zebrafish embryo‐larval assays coupled with ICPMS serve as a powerful platform to evaluate relative potency and toxic effects of metallodrug candidates. Anticancer metallodrug evaluation requires a high‐throughput model, testing potency and toxicity. This study evaluated inductively coupled plasma‐mass spectrometry metal equivalent detection coupled with a zebrafish embryo‐larval assay. We evaluated a popular chemotherapeutic, cisplatin, with a novel ruthenium‐based anticancer compound, PMC79. This method allowed comparison of the two compounds showing different uptake, distribution, potency and lesions. We believe this bioanalytical model will serve as a platform for metallodrug evaluation. [ABSTRACT FROM AUTHOR]

Ru(bpy)3@SiO2-COOH and Ru(bpy)3@SiO2@CD47-peptide nanoparticles (NPs) with fluorescent and mass spectrometric properties were designed and synthesized as the models of drug-nanocarriers. Their phagocytic internalization could be quantitatively measured using more sensitive inductively coupled plasma mass spectrometry (ICPMS) (102Ru) versus traditional laser confocal scanning microscope (λex/em = 458/600 nm) for the first time. Modification of a self-signal trigging CD47-peptide on the NPs' surface decreased internalization by 10 times, (2.79 ± 0.21) × 104 Ru(bpy)3@SiO2-COOH and (0.28 ± 0.04) × 104 Ru(bpy)3@SiO2@CD47-peptide NPs per RAW264.7 macrophage (n = 5). The alkynyl-linked CD47-peptide allowed us to quantify the number (2412 ± 250) of CD47-peptide modified on the NP and the total content (5.14 ± 0.25 amol) of signal regulatory protein α (SIRPα) on the macrophage by measuring the clickable tagged Eu using ICPMS. Furthermore, the interaction between CD47-peptide and SIRPα as well as the changes of the remaining free SIRPα during the internalization process of Ru(bpy)3@SiO2@CD47-peptide NPs were quantitatively evaluated, providing direct experimental evidence of the longspeculated crucial CD47-SIRPα interaction for drug-nanocarriers to escape internalization by phagocytic cells. Remarkable difference in the internalization ratio of 12.3 ± 4.8 of Ru(bpy)3@SiO2-COOH NPs and 4.3 ± 0.5 Ru(bpy)3@SiO2@CD47-peptide NPs with and without the protein corona indicated that CD47-peptide still worked when the protein corona formed. Not limited to the evaluation of the NPs studied here, such a fluorescent and mass spectrometric approach is very much expected to apply to the assessment of other drug-nanocarriers designed by chemists and before their medical applications. [ABSTRACT FROM AUTHOR]

New Year's Eve fireworks represent one of the most unusual atmospheric pollution events in the course of a year. A majority of particles aerosolized by burning of fireworks consist of metals and their compounds used in firework displays. In this study, ambient particulate matter was sampled using a 14 stage cascade impactor in two European cities during turn of the years 2016/17 and 2017/18. Concentrations of 33 elements were determined by inductively coupled plasma mass spectrometry. To assess the impact of New Year's Eve fireworks on ambient air quality, chemically resolved size distributions of particles with diameters between 15 nm and 10 μm collected during fireworks episodes were compared to ones collected in normal winter weeks. For some metals a distinct shift of their concentration maximum related to fireworks could be observed, which is in between the maxima for accumulation and coarse mode particles. Concentrations of these elements (Sr, Ba, Mg, Bi, Al, Cu and K) were also higher during weeks with fireworks episodes than during control weeks. Although New Year's Eve fireworks only take place once a year, these results show that air pollution caused by fireworks can be a potential health risk, especially for people with pre-existing diseases. Unlabelled Image • Fireworks can change the size resolved element distributions in urban aerosols. • Elements are enriched in between the maxima for accumulation and coarse mode. • Metals like Mg, Al, Cu, Sr and Ba become more respirable during fireworks episodes. • Higher health risk because of smaller particles [ABSTRACT FROM AUTHOR]

The present work aims to assess health risks associated with the exposure to uranium and heavy metals via potable groundwater in Uttarakhand state of India. For this purpose, potable groundwater samples were collected from the area and analyzed using LED fluorimetry and inductively coupled plasma mass spectrometry (ICPMS). The radiological (carcinogenic) and chemical (non-carcinogenic) risks associated with the exposure to uranium in majority of locations were observed below the safe limits suggested by WHO and USEPA. The levels of heavy metals present in potable groundwater were found well below the permissible limits recommended by WHO. An inter-comparison exercise between the results obtained with LED fluorimetry and ICPMS techniques was performed for the assurance of reliability and accuracy of results. The results were found in good agreement with each other. [ABSTRACT FROM AUTHOR]

Environmental context: Transformation of silver nanoparticles in the environment is an important issue because the form they take directly influences what effect they have. We show that the size of the primary particles of silver nanosuspensions is a major factor determining their evolution under sunlight irradiation (dissolution, formation of nanoseeds and nanoprisms, agglomeration). The persistence of nano-sized silver particles after exposure to sunlight irradiation implies that their ecotoxicological impact will likely last well beyond their introduction in the environment. The environmental fate of silver nanoparticles (Ag NPs) is a serious cause for concern with regard to their ecotoxicity. In this study, an aging scenario intended to evaluate the effect of sunlight on three Ag NP suspensions of various particle size was assessed. Suspensions of citrate-stabilised Ag NPs of 20, 60, and 100 nm diameter were aged for a week in a climatic chamber under controlled temperature (40 °C) and irradiation (1.44 W m−2 at 420 nm). The suspensions were analysed by asymmetric flow field flow fractionation – inductively coupled plasma mass spectrometry (AF4-ICP-MS), dynamic light scattering (DLS) and transmission electron microscopy (TEM). The AF4-ICP-MS monitoring showed that only a small fraction (10 % at most) of the primary 20 nm particles are converted into multi-faceted particles. Larger particles undergo shape modifications correlated with dissolution (60 nm Ag NPs) and aggregation (100 nm Ag NPs) processes. Silicate structures – supposedly originating from the glassware degradation – stabilise the primary particles. The occurrence of smaller Ag seeds, also associated with silicates, was revealed and quantified by AF4-ICP-MS and confirmed by TEM. The physical fractionation of the particles according to their size provided by AF4, together with the quantitative analysis provided by ICP-MS, helped to determine the role of size in the fate of silver nanoparticles under sunlight exposure. Environmental context. Transformation of silver nanoparticles in the environment is an important issue because the form they take directly influences what effect they have. We show that the size of the primary particles of silver nanosuspensions is a major factor determining their evolution under sunlight irradiation (dissolution, formation of nanoseeds and nanoprisms, agglomeration). The persistence of nano-sized silver particles after exposure to sunlight irradiation implies that their ecotoxicological impact will likely last well beyond their introduction in the environment. [ABSTRACT FROM AUTHOR]

Organic and inorganic colloids play important roles governing the speciation, transport, and bioaccessibility of trace elements in aquatic systems. These carriers are especially important in the boreal zone, where rivers that contain high concentrations of iron and organic matter are prevalent. The distribution of trace elements amongst different colloidal species (or “speciation profile”) can therefore be useful as a fingerprint to detect different trace element sources and for tracking colloid transformations, with implications for bioaccessibility. Asymmetrical flow field-flow fractionation coupled to an inductively coupled plasma mass spectrometer was applied to detect the source of trace elements based on their speciation profile along a 125-km stretch of a large river in the Canadian boreal forest. Both the concentration and proportion of bound trace elements were increased by tributary inputs: bound As, Co, Fe, Mn, Pb, U, and Zn increased monotonically from upstream to downstream, increasingly resembling the speciation profile of tributaries. Principal component (PC) analysis also revealed tributary contributions of bound Cu, Ni, Th, V, and Y reflecting their higher concentrations in tributaries, and PC scores also increased monotonically from upstream–downstream. Monotonically decreasing concentrations of mainly ionic and small (i.e.

The zirconium isotope 93Zr is a long-lived pure β-particle-emitting radionuclide produced from 235U fission and from neutron activation of the stable isotope 92Zr and thus occurring as one of the radionuclides found in nuclear reactors. Due to its long half-life, 93Zr is one of the radionuclides of interest for the performance of assessment studies of waste storage or disposal. This paper describes the determination of 93Zr in evaporator concentrate (EC) sample from nuclear power plant (PWR). A zirconium selective separation using liquid-liquid extraction and TRU column were used before the ICPMS measurement to remove isobaric interferences.20-21 93Nb detection limit of 0.045 μg L-1 was obtained for 93Zr determination by ICPMS technique.