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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., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

Honey bees are social insects that show division of labor and sexual dimorphism. Female honey bees differentiate in two different castes, queens or worker bees, while males are called drones. Worker bees have different tasks in the hive including collection of food, its processing, caring for brood, protecting the hive, or producing wax. The drones' only role is to mate with a virgin queen. Many studies have dealt with differences in physiology, behavior, and morphology of workers and drones. This is the first study that demonstrates differences in element accumulation and composition between workers and drones honey bees. Using inductively coupled plasma mass spectrometry, we found that worker honey bees have higher concentrations of most elements analyzed. Drones had higher concentrations of elements essential to bees, Na, P, S, Zn, Cu, and especially Se (2.2 × higher), which is known to be important for sperm quality and fertility in many animals. Until now higher Se content was not observed in male insects. These differences can be attributed to different environmental exposure, reproductive role of drones, but mostly to the food workers and drones consume. Worker bees feed on bee bread, which is rich in minerals. Drones are fed food pre-processed by worker bees., (© 2024. The Author(s).)

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.

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., (© 2023. The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature.)

Silver-based biocides are applied in face masks because of their antimicrobial properties. The added value of biocidal silver treatment of face masks to control SARS-CoV-2 infection needs to be balanced against possible toxicity due to inhalation exposure. Direct measurement of silver (particle) release to estimate exposure is problematic. Therefore, this study optimized methodologies to characterize silver-based biocides directly in the face masks, by measuring their total silver content using ICP-MS and ICP-OES based methods, and by visualizing the type(s) and localization of silver-based biocides using electron microscopy based methods. Thirteen of 20 selected masks intended for general use contained detectable amounts of silver ranging from 3 μg to 235 mg. Four of these masks contained silver nanoparticles, of which one mask was silver coated. Comparison of the silver content with limit values derived from existing inhalation exposure limits for both silver ions and silver nanoparticles allowed to differentiate safe face masks from face masks that require a more extensive safety assessment. These findings urge for in depth characterization of the applications of silver-based biocides and for the implementation of regulatory standards, quality control and product development based on the safe-by-design principle for nanotechnology applications in face masks in general., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 The Authors. Published by Elsevier B.V. All rights reserved.)

The mass and volume concentration of nanoplastics is extremely low, but incredibly high in terms of surface area; this is expected to increase their toxicity through the ab/adsorption and transport of chemical co-pollutants such as trace metals. In this context, we studied the interactions between nanoplastics model materials functionalized with carboxylated groups, with either smooth or raspberry-like surface morphologies, and copper as representative of trace metals. For this purpose, a new methodology, using two complementary surface analysis techniques: Time-of-Flight Secondary Ion Mass Spectrometry (ToF-SIMS) and X-ray Photoelectron Spectroscopy (XPS) was developed. In addition, inductively coupled plasma mass spectrometry (ICP-MS) was used to quantify the total mass of sorbed metal on the nanoplastics. This innovative analytical approach from the top surface to the core of nanoplastics demonstrated not only the interactions with copper at the surface level, but also the ability of nanoplastics to absorb metal at their core. Indeed, after 24 h of exposition, the copper concentration at the nanoplastic surface remained constant due to saturation whereas the copper concentration inside the nanoplastic keeps increasing with the time. The sorption kinetic was evaluated to increase with the density of charge of the nanoplastic and the pH. This study confirmed the ability of nanoplastics to act as metal pollutant carriers by both adsorption and absorption phenomena., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier Ltd. All rights reserved.)

Natural organic matter (NOM) readily interacts with nanoparticles, leading to the formation of NOM corona structures on their surface. NOM corona formation is closely related to the surface coatings and bioavailability of nanoparticles. However, the mechanism underlying NOM corona formation on silver nanoparticles (AgNPs) remains largely unknown due to the lack of effective analytical methods for identifying the changes in the AgNP surface. Herein, the separation ability of biased cyclical electrical field-flow fractionation (BCyElFFF) for same-sized polyvinyl pyrrolidone-coated and poly(ethylene glycol)-coated silver nanoparticles (AgNPs) with different electrophoretic mobilities was evaluated under various electrical conditions. Then, the mechanism behind the NOM corona formation on these AgNP surfaces was elucidated based on the changes in the elution time and off-line characterization of the collected fractions during their elution time in a BCyElFFF run. Finally, the survival rates of E. coli exposed to polyvinyl pyrrolidone-coated and poly(ethylene glycol)-coated AgNPs with or without NOM collected during repeated BCyElFFF runs were observed to increase with increasing NOM concentration, clearly demonstrating the negative effect of NOM corona structures on the bioavailability of AgNPs. These findings highlight the powerful separation and isolation ability of BCyElFFF in studying the transformation and fate of nanoparticles in aqueous environments., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022 Elsevier Ltd. All rights reserved.)

Homogenized or pooled samples of honey bees are already used for monitoring of metal pollution in the environment for a couple of decades. This is the first study that analyzed the elemental composition of individual honey bees. One apiary with 21 hives was used to test in-hive and between-hive differences at the same location. Highest in-hive variability was observed for Al (14.1x), Li (10.3x), V (10.3x), As (8.9x) and Cd (7.9x). For the elements Cu, K, Mg, Na, P, S and Zn the smallest both in-hive (2.3x, 1.8x, 2.0x, 2.2x, 1.9x, 1.7x, 2.4x respectively) as well as between-hive variability (1.5x, 1.4x, 1.4x, 1.6x, 1.4x, 1.4x and 1.5x respectively) was observed. Nonetheless, between-hive variability was statistically significant for all the analyzed elements. We proved that these differences significantly influence comparison of element concentrations in bees from different locations. One hive from Mesić apiary had significantly lower concentrations of Al (hive 18: 18.6 mg kg -1 ) and U (hive 1: 0.0013 mg kg -1 ), while at the same time a different hive from the same apiary showed higher concentration of these elements (Al, hive 14: 125 mg kg -1 ; U, hive 13: 0.012 mg kg -1 ) compared to another location (thermal power plant, Al: 97 mg kg -1 , U: 0.0044 mg kg -1 ). Therefore, when using honey bees as biomonitors, we recommend a larger number of hives to be sampled at each location to provide an adequate dataset for reliable interpretation of results. Comparing individual bee elemental concentrations, for Na, Mg, P, S, K, Fe, Cu, and Zn negative correlations were found between dry mass of a bee and concentrations of these elements. These negative correlations could be a consequence of higher honey or nectar content in some of the sampled bees. However, this should also be considered when using honey bees as bioindicators., (Copyright © 2021 The Authors. Published by Elsevier Inc. All rights reserved.)

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., Competing Interests: The authors declare that the research was conducted in the absence of any commercial or financial relationships that could be construed as a potential conflict of interest., (Copyright © 2022 Kareem, Saleem, Saleem, Rather, Wani, Siddiqui, Alamri, Kumar, Gaikwad, Guo, Niu and Wang.)

The As concentrations, along with 34 other elements, and the As speciation were investigated in wild-grown samples of the parasitic mushroom Tolypocladium ophioglossoides with inductively coupled plasma mass spectrometry (ICPMS) and high performance liquid chromatography coupled to ICPMS. The As concentrations were 0.070-3.44 mg kg -1 dry mass. More remarkable was the As speciation, where up to 56% of the extracted As were found to be an unknown As species, which was marginally retained under anion- and also cation-exchange conditions. After testing several different chromatographic settings, the compound was finally isolated and identified as 2-(sulfoxyethyl) trimethylarsonium ion (in short: arsenocholine-O-sulfate) with high resolution mass spectrometry. The compound was synthesized and further quantified in all investigated samples via ion-pair chromatography coupled to ICPMS. In addition to the high abundance of arsenocholine-O-sulfate in T. ophioglossoides, small amounts of this As species were also detected in one sample of the host mushroom, Elaphomyces asperulus. In a sample of another parasitic mushroom, Ophiocordyceps sinensis, arsenocholine-O-sulfate could not be detected, but the main species was another unknown compound that was oxidized to inorganic As(V) with hydrogen peroxide. This is the first discovery of arsenocholine-O-sulfate in nature. It is possible that it is present in many other organisms, at least in low concentrations, and just has not been detected there yet because of its unusual chromatographic behavior. The existence of arsenocholine-O-sulfate brings up questions again about the biotransformation pathways of As in the environment and the specific behavior of fungi., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 The Authors. Published by Elsevier Ltd.. All rights reserved.)

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 m 2 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.

Exposure to methylmercury (MeHg) through fish is a global public health problem. Exposure monitoring is essential for health risk assessment, especially in pregnant women and children due to the documented neurotoxicity. Herein, we evaluate a time series of MeHg exposure via fish in primiparous Swedish women, covering a time period of 23 years (1996-2019). The 655 included mothers were part of the POPUP study (Persistent Organic Pollutants in Uppsala Primiparas) conducted by the Swedish Food Agency (SFA). MeHg exposure was assessed via measurements of total mercury (Hg) in hair using either cold vapor atomic fluorescence spectrophotometry or inductively coupled plasma mass spectrometry, showing very good linear agreement (R 2  = 0.97). Maternal characteristics and fish consumption were obtained via questionnaires. The median concentration of total Hg in hair was 0.38 mg/kg (range 0.17-1.5) in 1996 and 0.25 mg/kg (range 0.03-1.1) in 2019. On average the women consumed 11 ± 8.2 meals of fish per month, and fish consumption was positively correlated with total Hg in hair (Spearman correlation: 0.39; p < 0.001). In multiple regression analyses, the geometric mean annual decrease of total Hg in hair was -2.5% (95% CI: -3.2, -1.8%). Total fish consumption increased up to 2011 (B: 0.32 times/month per year; 95% CI 0.17, 0.46) after which it started to decline (B: -0.66 times/month per year; 95% CI -0.92, -0.40). Moreover, both total Hg in hair and fish consumption was positively associated with maternal age and education, and inversely associated with pre-pregnancy BMI. In conclusion, the exposure to MeHg via fish appears to be slowly declining among Swedish pregnant women., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 The Author(s). Published by Elsevier Ltd.. All rights reserved.)

Fluorinated carboxylic acids have been in use as ion-pairing reagents for over three decades. It has been observed that ion-pairing reagents not only increase the retention of oppositely charged analytes on reversed-phase HPLC columns but also decrease the retention of similarly charged analytes; these latter effects, however, have not been thoroughly investigated for the fluorinated carboxylic acids, and the application of these reagents has been rather restricted to their ion-pairing capacity to separate basic analytes. In the present study, we report a systematic investigation about the effects of three fluorinated carboxylic acids (trifluoroacetic acid (TFA), pentafluoropropionic acid (PFPA), and heptafluorobutyric acid (HFBA)) on the retention and selectivity of the separation of halogenated carboxylic acids and sulfonic acids by reversed-phase chromatography with an inductively coupled plasma mass spectrometry detector (ICPMS). Several eluents were tested and compared at different concentrations (0-100 mM) and pH values, including sulfate, nitrate, phosphate, oxalate, TFA, PFPA, and HFBA. The fluorinated carboxylic acids resulted in a consistent decrease in the retention factors (up to ca. 9-fold with HFBA) in a concentration dependent manner, which plateaued at around 50 mM. Significant improvement of the peak symmetry of the chromatographed acids was also observed. We highlight the advantages of incorporating the fluorinated carboxylic acids in modifying the selectivity and retention of organic acids in reversed phase chromatography in general, and particularly when employing chromatographic detectors with limited compatibility with organic mobile phases such as the ICPMS., Competing Interests: Declaration of Competing Interest The authors claim no conflict of interest., (Copyright © 2020. Published by Elsevier B.V.)

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.

The Violet Crown Cup, Sarcosphaera coronaria, is a rather inconspicuous mushroom, but with an interesting and unresolved mystery. In earlier days, the mushroom was considered edible, but several poisonings were reported in the early 20 th century. The reason for the seemingly sporadic toxicity of S. coronaria is still unknown. One possible explanation is arsenic, since Crown Cups can take up high amounts of this element. We investigated the arsenic concentration and arsenic speciation in S. coronaria with inductively coupled plasma mass spectrometry (ICPMS) and HPLC coupled to ICPMS and found up to incredible 0.9% As (dry mass). Most of it was present as methylarsonic acid (MA), a less toxic form of this element. However, low concentrations of the highly toxic methylarsonous acid [MA (III)] were also detected. The amounts were too low to pose an acute risk for consumers, but the concentration of MA (III) significantly increased during simulated gastric digestion. We could not unambiguously identify arsenic as the toxic constituent of S. coronaria, but we demonstrated that the extremely toxic MA (III) can be formed under certain circumstances, which should be carefully investigated in future., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 The Authors. Published by Elsevier B.V. All rights reserved.)

Determining coffee region-of-origin is most appropriately addressed through analyses of the product available to the consumer. We analyzed the concentrations of 44 trace elements in 53 samples of roasted Arabica coffee beans (Coffea arabica) from 21 different countries. Variations in absolute elemental concentrations of coffee beans arise through varying degrees of roasting (from green through dark roasts). Since trace elements are not volatilized at roasting temperatures, we conducted analyses of element ratios to evaluate concentration-related differences among beans of different origins. We used kernel density estimates to compare the distributions of 1892 element ratios for each of these countries with the combined distribution of coffee samples from the other countries. Using this quantitative approach, we demonstrated that many of the world's coffee-producing regions can be distinguished from other regions of the world on the basis of element ratios., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier Ltd. All rights reserved.)

Background: Metal ion blood concentrations evaluation can be useful in monitoring wear and corrosion of orthopedic implants. Elevated metal ion level may help detecting defective hip arthroplasty implants and serve as an indicator for revision surgery. Our objective was to evaluate the reproducibility of titanium metal ion level measurements by two different laboratories., Methods: Seventy-one whole blood samples were collected from 64 patients with unilateral ceramic-on-ceramic hip arthroplasty. For each patient, two whole blood samples were collected and analyzed in two different laboratories., Results: For each case, laboratory 1 had significantly higher values than laboratory 2. There was a clinically significant absolute difference between the two laboratories, above the predetermined threshold, for 90% of samples. A mean variation ratio of 410% between the two laboratories was found., Conclusion: Not all laboratories use the same techniques and calibrations to perform these measurements. Therefore, their results should be interpreted with caution and clinical decision should rely on metal ion trends provided by the same laboratory., (© 2020 The Authors.)

Recycling of scrap metal into artisanal cookware is widespread in poorly resourced countries. The aim of the study was to determine the risk of metal exposure from the use of artisanal cookware available in South Africa. Twenty cookware samples were purchased from local manufacturers and informal traders across South Africa. Aluminum and silicon concentrations were determined using XRF and the total content of 18 elements (Ag, As, Ba, Cd, Co, Cr, Cu, Fe, Hg, Mn, Mo, Ni, Pb, Sb, Se, Sn, V and Zn) were evaluated using ICPMS. Leaching of metals from cut pieces of cookware over a 2-h period of boiling in a 3% acetic acid solution was repeated 3 times and revealed multi-metal migration that was compared to EU maximum permissible levels. The mean Al migration of 509 mg L -1 was over 100 times the EU maximum permissible level allowed for cookware. Lead was detected in all samples with 11 (55%), 12 (60%) and 9 (45%) of samples being over the maximum EU permissible level (10 μg Pb L -1 ) for 1st, 2nd and 3rd migrations respectively. The mean As migration concentrations in the first leaching event ranged from 0.23 to 24.1 μg L -1 with four pots (20%) over the maximum EU permissible limit for As (2 μg L -1 ). Notably, all four pots were well below the maximum EU permissible As limit by the 3rd migration. Cadmium and mercury were detected in each pot across all three migrations however the levels were relatively low. Transmission electron microscopy revealed dramatic changes in surface structure after leaching of cookware., (Copyright © 2019. Published by Elsevier B.V.)

This article presents the application of an automated online separation-direct analysis method, RAPID (Rapid Analysis of Post-Irradiation Debris), for the simultaneous measurement of both radioactive and stable fission isotopes from an irradiated highly-enriched uranium target. Developed for the measurement of the concentration and isotopic composition of over 40 elements down to the femtogram level, the RAPID method possesses the sensitivity, stability, and precision required to achieve accurate, low-level analyses of elements of non-natural origin. The isotopic compositions and concentrations of key fission elements cesium, strontium, yttrium, lanthanum, cerium, praseodymium, neodymium, promethium, and samarium have been measured repeatedly over a six-week period. The validity of these measurements was confirmed using ORIGEN (Oak Ridge Isotope GENeration), an isotope depletion and decay modeling software, to within 1-3%., (Published by Elsevier B.V.)

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 ( 197 Au/ 115 In) 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., (© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

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 (LC 50 : 7.8 μm) than cisplatin (LC 50 : 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., (© 2019 John Wiley & Sons, Ltd.)

Ru(bpy) 3 @SiO 2 -COOH and Ru(bpy) 3 @SiO 2 @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) ( 102 Ru) versus traditional laser confocal scanning microscope (λ ex/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) × 10 4 Ru(bpy) 3 @SiO 2 -COOH and (0.28 ± 0.04) × 10 4 Ru(bpy) 3 @SiO 2 @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 @SiO 2 @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 @SiO 2 -COOH NPs and 4.3 ± 0.5 Ru(bpy) 3 @SiO 2 @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. Graphical abstract.

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., (Copyright © 2019 The Authors. Published by Elsevier Ltd.. All rights reserved.)

Trace elements contained in single-crystal gallium nitride (GaN), which is a refractory material, were determined by inductively coupled plasma mass spectrometry with laser ablation in liquid (LAL) sampling. Particle size analysis by dynamic light scattering confirmed that LAL atomized the single-crystal GaN, and scanning electron microscopy/energy-dispersive X-ray spectrometry revealed that LAL sampling converted the GaN to gallium oxide particles. The atomization and changes in the chemical composition allowed for easy digestion of the sampled particles with nitric acid and a hot plate instead of with hydrochloric or sulfuric acid, a microwave digestion system, and a high-pressure vessel. Trace element analysis revealed the presence of trace Mg, Ge, Y, and Cd in single-crystal GaN, and the detection limits for these elements were 0.1 - 2 mg kg -1 . The uncertainty derived from the small amount of sample used, which is a disadvantage of LAL sampling, was reduced by calculating the amount of sample ablated by measuring the concentration of the major element, Ga. We expect that the trace-element profiles of other refractory materials will be able to be determined by using this analytical approach.

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 arsenic speciation was determined in macrofungi of the Ramaria genus with HPLC coupled to inductively coupled plasma mass spectrometry. Besides arsenic species that are already known for macrofungi, like arsenobetaine or arsenocholine, two compounds that were only known from marine samples so far (trimethylarsoniopropanate and dimethylarsinoylacetate) were found for the first time in a terrestrial sample. An unknown arsenical was isolated and identified as homoarsenocholine. This could be a key intermediate for further elucidation of the biotransformation mechanisms of arsenic., (Copyright © 2018 The Authors. Published by Elsevier B.V. All rights reserved.)

This study assesses the impact of the farming system on the levels of copper, zinc, arsenic, cadmium, lead and mercury in pig tissues from three types of production (Organic (n = 28), Label Rouge (n = 12) and Conventional (n = 30)) randomly sampled in different slaughterhouses. All the concentrations were below regulatory limits. In muscles, Cu, Zn and As were measured at slightly higher levels in organic samples but no differences between organic and Label Rouge was observed. Livers from conventional and Label Rouge pig farms exhibited higher Zn and Cd contents than the organic ones, probably due to different practice in zinc or phytase supplementation of fattening diets. Principal component analysis indicated a correlation between Cu and As concentrations in liver and carcass weight, and between Zn and Cd liver levels and lean meat percentage. The linear discriminant analysis succeeded in predicting the farming process on the basis of the lean meat percentage and the liver Cd level., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

The Ar-N 2 mix gas effect can easily improve the sensitivity of ICPMS; however, this effect discriminates against Sr. In this study, it was found that Ar-N 2 mixed gases introduced into nebulizing gas enhanced the sensitivity of online solid-phase extraction (SPE) with inductively coupled plasma mass spectrometry (ICPMS) for radioactive strontium quantification. An ultrasonic nebulizer (USN) improved the Ar-N 2 mixture gases effect of Sr and the mix gases (with USN) enhanced 3.7-times the signal intensity of Sr in normal pure Ar gas (with USN) in an online SPE-ICPMS. By adapting the gas-loading means from a nebulizing gas unit via USN, no careful tuning was necessary for the plasma turning. With this signal enhancement, a 0.06 pg/L detection limit (0.3 Bq/L) was achieved for radioactive strontium ( 90 Sr) in online SPE-ICPMS within 30 min. In addition, environmental paddle water in the Fukushima Nuclear Power Plant was measured and the valued correspond to that obtained by radiometry.

The total arsenic concentration and the arsenic speciation in urine and feces samples of the two Giant Pandas living at Vienna zoo and of their feed, bamboo, were determined with ICPMS and HPLC-ICPMS. Urine was the main excretion route and accounted for around 90% of the ingested arsenic. The urinary arsenic concentrations were very high, namely up to 179 μg/L. Dimethylarsinic acid (DMA) was the dominating arsenic compound in the urine samples and ranged from 73 to 92% of the total arsenic, which is unusually high for a terrestrial mammal. The feces samples contained around 70% inorganic arsenic and 30% DMA. The arsenic concentrations in the bamboo samples were between 16 and 920 μg/kg dry mass. The main arsenic species in the bamboo extracts was inorganic arsenic. This indicates that the Giant Panda possesses a unique way of very efficiently methylating and excreting the provided inorganic arsenic. This could be essential for the survival of the animal in its natural habitat, because parts of this area are contaminated with arsenic., (Copyright © 2017 Elsevier Ltd. All rights reserved.)

Recent developments in high-energy accelerator mass spectrometry (AMS) and low-energy inductively coupled plasma mass spectrometry (ICPMS) made them the most sensitive techniques for ultra low-level analysis of 238 U and 232 Th. Detection limits below 1 nBq g -1 for analysis of these radionuclides in construction materials were obtained. The most important development in the radiometric sector was operation of HPGe detectors in underground laboratories where detection limits of about 1 µBq kg -1 were obtained. Specific features of radiometric, mass spectrometry and neutron activation techniques for ultra low-level radionuclide measurements are discussed, and obtained results for analysis of radiopure materials prepared for underground experiments are compared., (Copyright © 2017 Elsevier Ltd. All rights reserved.)

Pu isotopes in various foods were detected using a quadrupole ICPMS and Aridus II desolvation nebulizer. The method has ability to detect 239 Pu and 240 Pu at concentrations of ~52pg/kg (0.12Bq/kg) and ~9.5pg/kg (0.08Bq/kg) as well as 240 Pu/ 239 Pu ratio in <8h after receiving the samples. Foods were wet-ashed followed by DGA extraction for eliminating matrix, isobaric, and polyatomic interferences. A UH + formation rate <10 -5 and a 5-fold enhanced sensitivity for Pu was achieved after system optimization., (Published by Elsevier Ltd.)

Heavy metals pose a potential danger to human health when present in textile materials. In the present study, inductive coupled plasma mass spectrometry (ICPMS) was used to determine the concentrations and the identity of extractable inorganic elements from different brands of women undergarments. A total of 120 samples consisting of 63 cottons, 44 nylons and 13 polyesters manufactured in 14 different countries having different colors were analyzed for their extractable metals contents. Elements analyzed were Ag, Al, As, Ba, Be, Bi, Ca, Cd, Co, Cr, Cu, Fe, Hg, K, Li, Mg, Mn, Na, Ni, Pb, Sb, Se, Sr, Ti, V and Zn. Cotton undergarments were rich in Al, Fe and Zn, nylon undergarments had high levels of Cr, Cu and Al, while polyester fabrics contained higher levels of Ni and Fe compared to cotton or nylon. With respect to manufacturing countries, China, Egypt and India showed the highest concentrations of metals in all fabrics. With respect to the color, black garments were characteristic by high concentration of Fe, blue colors with Cu, brown garments with Fe and Cu, green garments with Cu and Fe, pink garments with Al, purple garments with Al and Cu and red garments with Cr, Zn and Al. The consumer should be made aware of the potential dangers of these metals in their clothing.

Aims: p-tertbutylcalix[4]arene loaded nanoemulsion has been designed, characterized and evaluated for skin decontamination of radionuclides of interest in nuclear and radiological emergencies. Further, nanoemulsion was evaluated for Ex-vivo complexation, skin permeation, interaction and cytodermal toxicity., Materials and Methods: Ex-vivo skin complexation studies were conducted using High-resolution sector field inductively coupled plasma mass spectroscopy (HR-SF-ICPMS). Skin studies at dermal and cyto-dermal level have been carried out using techniques such as florescence microscopy, Differential scanning calorimetry (DSC), Flow cytometry, Confocal microscopy, Prestoblue and Comet assay., Key Findings: HR-SF-ICPMS study confirmed >95% complexation of surrogate nuclides of thallium and Iodine applied on excised rat skin mounted over Franz diffusion cell. Temporal analysis of aliquots obtained from Franz diffusion cell using UV-Vis absorption spectroscopy indicated that only 3.37% of formulation permeates through the skin. Skin penetration study of rhodamine 123 nanoemulsion carried out using florescence microscopy confirmed that formulation remains localised in epidermis of rat skin. DSC data confirmed skin compatibility of nanoemulsion, as no lipid extraction was observed from skin. In-vitro cell viability and cellular uptake assays performed on human skin fibroblasts prove no cellular uptake and cytotoxic effects. Comet assay, cell cycle arrest, and apoptosis-inducing mechanistic studies prove that prepared nanoemulsion is safe at cellular level., Significance: Taken together, data indicate that p-tertbutylcalix[4]arene nanoemulsion is both effective and safe formulation to use on skin for radio-decontamination., (Copyright © 2016 Elsevier Inc. All rights reserved.)

An improved matrix separation method has been described to characterize ultrapure germanium of 8N (99.999999%) purity. In this method, temperature of the reaction vessel in which in-situ generated chlorine gas reacts with germanium solid material directly is optimized to quantitatively remove Ge matrix from all its impurities. Optimized reaction temperature has been found to be 230±5°C. Recovery studies on more than 60 elements have been carried out at the optimized temperature. Recoveries of all the analytes except As, Se, Sn, Hg, Tl are found to be quantitative. The method has been examined for various amounts of Ge material and found to be suitable even for 10g of Ge sample and provides low parts per billion and trillion levels of process blanks. Determination of concentrations of impurities has been done by inductively coupled plasma quadrupole mass spectrometer (ICP-QMS) and high resolution continuum source graphite furnace atomic absorption spectrometer (HR-CS-GFAAS). In the absence of certified reference materials for ultrapure germanium, accuracy of the proposed method is established by spike recovery tests. Precision of this method is found to vary from 7% to 50% for concentrations between 4 and 0.004ngg(-1). Limits of detection (LOD) for the target analytes are found to be between 6 and 0.011ngmL(-1) or 1.8-0.003ngg(-1) for the proposed procedure. The method has been successfully applied for that characterization of ultrapure germanium material of 8N purity., (Copyright © 2016 Elsevier B.V. All rights reserved.)

Aim: To evaluate in vitro topographical and composition changes by piezoelectric ultrasonic instrumentation with metallic and plastic tips on machined and moderately roughened titanium surfaces., Methods: Twenty machined and moderately roughened laser-marked titanium discs were ultrasonically instrumented with metallic and plastic tips. Surface instrumentation was carried out with controlled pressure for 20 and 30 seconds at two power settings. For each time and power setting, instrumentation was repeated four times with one instrumentation per disc quadrant. Surface topography analysis was performed using scanning electron microscopy (SEM) and confocal laser scanning microscopy (CLSM). Surface roughness measurements were compared between instrumented and non-instrumented surfaces. Surface element composition and rinsing solutions were evaluated using energy-dispersive spectroscopy (EDS) and trace elemental analysis using inductively coupled plasma mass spectrometry (ICPMS), respectively., Results: SEM photomicrographs and CLSM 3D surface plot images of instrumented machined and moderately roughened surfaces demonstrated severe surface topographical alterations with metallic tips and mild to moderate changes for plastic tip instrumented sites. ICPMS analysis of the rinsing solutions identified titanium and other metal traces with the use of metallic tips, and mainly titanium and carbon when plastic tips were used. Surface EDS analysis showed elemental traces of the ultrasonic tips., Conclusion: Ultrasonic instrumentation with metallic or plastic tips created surface topographical and compositional changes. Different changes in surface topography were noted between the surfaces, as the roughness of the machined surfaces increased while the extent of roughness of the moderately roughened surfaces decreased. The clinical relevance of these changes is yet to be determined., (© 2015 John Wiley & Sons A/S. Published by John Wiley & Sons Ltd.)

This study was undertaken to assess the levels of trace metals (As, Cd, Cu, Pb, and Zn) in two common species of cockles (Anadara granosa and Anadara inaequivalvis) from two coastal areas in Thailand (Pattani Bay) and Malaysia (the Setiu Wetlands). A total of 350 cockles were collected in February and September 2014. Trace metals were determined by Inductively Coupled Plasma Mass Spectrometry. We observed that cockles in both areas had a higher accumulation of metals in September. Notably, the biota-sediment accumulation (BSAF) of Cd was highest in both areas. A strong positive correlation of Cd with the length of the cockles at Pattani Bay (r(2) = 0.597) and the Setiu Wetlands (r(2) = 0.675) was noted. It was suggested that As could be a limiting element (BSAF < 1) of cockles obtained from Pattani Bay. In comparison with the permissible limits set by the Thailand Ministry of Public Health and the Malaysia Food Regulations, mean values of As, Cd, Cu, Pb, and Zn were within acceptable limits, but the maximum values of Cd and Pb exceeded the limits for both areas. Regular monitoring of trace metals in cockles from both areas is suggested for more definitive contamination determination.

We describe trends in fast, high resolution elemental imaging by laser ablation-inductively coupled plasma mass spectrometry (LA-ICPMS). Recently developed low dispersion LA cells deliver quantitative transport of ablated aerosols within 10 ms and also provide enhanced sensitivity compared to conventional LA cells because the analyte ion signal becomes less diluted during aerosol transport. When connected to simultaneous ICPMS instruments, these low dispersion LA cells offer a platform for high speed and high lateral resolution shot-resolved LA-ICPMS imaging. Here, we examine the current paradigms of LA-ICPMS imaging and discuss how newly developed LA cell technology combined with simultaneous ICPMS instrumentation is poised to overcome current instrumental limitations to deliver faster, higher resolution elemental imaging.

The present study reports arsenic analysis in Lentinula edodes, Agaricus bisporus and Pleurotus ostreatus before and after being cooked. Furthermore, arsenic in raw and cooked mushroom was determined in the gastric and gastrointestinal bioaccessible fractions obtained after simulating human digestion by means of an in vitro physiologically based extraction test (PBET). Several certified reference materials (SRM 1568a, SRM 1570a, CRM 7503-a, BC211 and IPE-120) were analysed to evaluate the proposed methods. Total arsenic content was 1393, 181 and 335μgAskg(-1) for L. edodes, A. bisporus and P. ostreatus, respectively, and decreased by between 53% and 71% in boiled mushroom and less than 11% in griddled mushroom. High bioaccessibility was observed in raw, boiled and griddled mushroom, ranging from 74% to 89% and from 80% to 100% for gastric and gastrointestinal extracts, respectively, suggesting the need to consider the potential health risk of consumption of the mushrooms analysed., (Copyright © 2015 Elsevier Ltd. All rights reserved.)

Modified matrix volatilization (MV) method has been described to characterize high purity germanium material of 7 N (99.99999%) purity. Transport of both, the chlorine gas generated in-situ in this method and the argon gas (carrier) is fine controlled by means of a mass flow controller. This enabled both uniform reaction of chlorine gas with the germanium matrix and smooth removal of germanium matrix as its chloride. This resulted in improvement in the reproducibility of the analytical results. The use of quartz reaction vessel has lead to the reduction in the process blank levels. The combined effect of these modifications in the MV setup has resulted in very consistent and low process blanks and hence improved detection limits of this method. Applicability of the method has been expanded to rare earth elements and other elements after examining their recoveries. The quantification is done by using inductively coupled plasma quadrupole mass spectrometer (ICP-QMS) and continuum source graphite furnace atomic absorption spectrometry (CS-GFAAS). In the absence of certified reference materials for high pure germanium, the accuracy of the method is established by spike recovery tests. The precision of the method has been found to vary from 1 to 30% for concentrations between 1 and 30 ng g(-1). The limits of detection (LOD) for the target analytes are found to be between 18 and 0.033 ng g(-1)., (Copyright © 2015 Elsevier B.V. All rights reserved.)

In this study a novel method to determine iodine concentrations in human breast milk was developed and validated. The iodine was analyzed by inductively coupled plasma mass spectrometry (ICPMS) following tetramethylammonium hydroxide (TMAH) extraction at 90°C in disposable polypropylene tubes. While similar approaches have been used previously, this method adopted a shorter extraction time (1h vs. 3h) and used antimony (Sb) as the internal standard, which exhibited greater stability in breast milk and milk powder matrices compared to tellurium (Te). Method validation included: defining iodine linearity up to 200μgL(-1); confirming recovery of iodine from NIST 1549 milk powder. A recovery of 94-98% was also achieved for the NIST 1549 milk powder and human breast milk samples spiked with sodium iodide and thyroxine (T4) solutions. The method quantitation limit (MQL) for human breast milk was 1.6μgL(-1). The intra-assay and inter-assay coefficient of variation for the breast milk samples and NIST powder were <1% and <3.5%, respectively. NIST 1549 milk powder, human breast milk samples and calibration standards spiked with the internal standard were all stable for at least 2.5 months after extraction. The results of the validation process confirmed that this newly developed method provides greater accuracy and precision in the assessment of iodine concentrations in human breast milk than previous methods and therefore offers a more reliable approach for assessing iodine concentrations in human breast milk., (Copyright © 2014 Elsevier GmbH. All rights reserved.)

Three analytical methods were evaluated for hexavalent and trivalent chromium analyses in the presence of natural organic matter (NOM) and alkalinity. Each method was tested using a simulated tap water with 1 μg L(-1) Cr(VI) and 0.8 μg L(-1) Cr(III) and several concentrations of NOM and/or alkalinity. An ion chromatograph with post column reaction cell conforming to USEPA Method 218.7 could accurately quantify Cr(VI) in the presence of up to 8 mg CL(-1) NOM and up to 170 mg L(-1) as CaCO3 alkalinity, and no oxidation of chromium was observed when 0.8 μg L(-1) Cr(III) was also present. A high-performance liquid chromatography coupled with inductively coupled plasma (HPLC-ICPMS) method and a field speciation method were also evaluated. Each of these methods was unaffected by the presence of alkalinity; however, the presence of NOM created issues. For the HPLC-ICPMS method, as the concentration of NOM increased the recovery of Cr(VI) decreased, resulting in a 'false negative' for Cr(VI). However, for the field speciation method, Cr(III) was complexed by NOM and carried through the ion exchange column, resulting in a 'false positive' for Cr(VI)., (Copyright © 2014 Elsevier B.V. All rights reserved.)

Hexavalent chromium (Cr(VI)) in ambient airborne particulate matter (PM) is a known pulmonary carcinogen and may have both soluble and insoluble forms. The sum of the two forms is defined as total Cr(VI). Currently, there were no methods suitable for large-scale monitoring of total Cr(VI) in ambient PM. This study developed a method to measure total Cr(VI) in ambient PM. This method includes PM collection using a Teflon filter, microwave extraction with 3% Na 2 CO 3 -2% NaOH at 95°C for 60 minutes, and Cr(VI) analysis by 1,5-diphenylcarbazide colorimetry at 540 nm. The recoveries of total Cr(VI) were 119.5 ± 10.4% and 106.3 ± 16.7% for the Cr(VI)-certified reference materials, SQC 012 and SRM 2700, respectively. Total Cr(VI) in the reference urban PM (NIST 1648a) was 26.0 ± 3.1 mg/kg (%CV = 11.9%) determined by this method. The method detection limit was 0.33 ng/m 3 . This method and the one previously developed to measure ambient Cr(VI), which is soluble in pH ~9.0 aqueous solution, were applied to measure Cr(VI) in ambient PM 10 collected from three urban areas and one suburban area in New Jersey. The total Cr(VI) concentrations were 1.05-1.41 ng/m 3 in the winter and 0.99-1.56 ng/m 3 in the summer. The soluble Cr(VI) concentrations were 0.03-0.19 ng/m 3 in the winter and 0.12-0.37 ng/m 3 in the summer. The summer mean ratios of soluble to total Cr(VI) were 14.3-43.7%, significantly higher than 4.2-14.4% in the winter. The winter concentrations of soluble and total Cr(VI) in the suburban area were significantly lower than in the three urban areas. The results suggested that formation of Cr(VI) via atmospheric chemistry may contribute to the higher soluble Cr(VI) concentrations in the summer.

Monitoring of PGEs content in the natural samples is a crucial point in the environment science since catalytic car converters have been introduced. In the presented paper application of a very sensitive voltammetric method for determination of traces of Pt and Rh in the environmental samples contaminated by automobile exhausts is discussed. Voltammetric measurements were carried out in the supporting electrolyte containing formaldehyde and semicarbazide. PGEs were separated from the digested solutions of soils or quartz samples, collected from monitoring plots-by applying an ion-exchange resin Cellex-T. Pt was very effectively separated from the matrix approaching nearly 100% recovery after its elution by hydrochloric acid. Moreover the conditions of soil and quartz samples digestion were discussed. To validate the obtained result an independent analytical method-ICP MS was applied and analysis of certified reference material road dust 723-was completed., (Copyright © 2014 Elsevier B.V. All rights reserved.)

The concentrations of eight trace elements: lead (Pb), cadmium (Cd), chromium (Cr), manganese (Mn), cobalt (Co), arsenic (As), bismuth (Bi) and molybdenum (Mo), in chocolate, cocoa beans and products were studied by ICPMS. The study examined chocolate samples from different brands and countries with different concentrations of cocoa solids from each brand. The samples were digested and filtered to remove lipids and indium was used as an internal standard to correct matrix effects. A linear correlation was found between the level of several trace elements in chocolate and the cocoa solids content. Significant levels of Bi and As were found in the cocoa bean shells but not in the cocoa bean and chocolate. This may be attributed to environmental contamination. The presence of other elements was attributed to the manufacturing processes of cocoa and chocolate products. Children, who are big consumers of chocolates, may be at risk of exceeding the daily limit of lead; whereas one 10 g cube of dark chocolate may contain as much as 20% of the daily lead oral limit. Moreover chocolate may not be the only source of lead in their nutrition. For adults there is almost no risk of exceeding daily limits for trace metals ingestion because their digestive absorption of metals is very poor., (© 2013 Published by Elsevier B.V.)

Arsenic Crystallization Technology (ACT) is a potentially eco-friendly, effective technology for stabilization of arsenic-bearing solid residuals (ABSRs). The strategy is to convert ABSRs generated by water treatment facilities into minerals with a high arsenic capacity and long-term stability in mature, municipal solid waste landfills. Candidate minerals considered in this study include scorodite, arsenate hydroxyapatites, ferrous arsenates (symplesite-type minerals), tooeleite, and arsenated-schwertmannite. These minerals were evaluated as to ease of synthesis, applicability to use of iron-based ABSRs as a starting material, and arsenic leachability. The Toxicity Characteristic Leaching Procedure (TCLP) was used for preliminary assessment of candidate mineral leaching. Minerals that passed the TCLP and whose synthesis route was promising were subjected to a more aggressive leaching test using a simulated landfill leachate (SLL) solution. Scorodite and arsenate hydroxyapatites were not considered further because their synthesis conditions were not found to be favorable for general application. Tooeleite and silica-amended tooeleite showed high TCLP arsenic leaching and were also not investigated further. The synthesis process and leaching of ferrous arsenate and arsenated-schwertmannite were promising and of these, arsenated-schwertmannite was most stable during SLL testing. The latter two candidate minerals warrant synthesis optimization and more extensive testing., (Copyright © 2013 Elsevier B.V. All rights reserved.)

The results of this paper are an initiation to capture the drinking water and/or groundwater elemental situation in the youngest European country, Kosovo. We aim to present a clear picture of the natural uranium concentration in drinking water and/or groundwater as it is distributed to the population of Kosovo. Nine hundred and fifty-one (951) drinking water samples were analyzed by inductively coupled plasma mass spectrometry (ICPMS). The results are the first countrywide interpretation of the uranium concentration in drinking water and/or groundwater, directly following the Kosovo war of 1999. More than 98% of the samples had uranium concentrations above 0.01 μg L(-1), which was also our limit of quantification. Concentrations up to 166 μg L(-1) were found with a mean of 5 μg L(-1) and median 1.6 μg L(-1) were found. Two point six percent (2.6%) of the analyzed samples exceeded the World Health Organization maximum acceptable concentration of 30 μg L(-1), and 44.2% of the samples exceeded the 2 μg L(-1) German maximum acceptable concentrations recommended for infant food preparations., (Copyright © 2013 Elsevier Ltd. All rights reserved.)

Oral cancer is a major cause of cancer morbidity and mortality worldwide and is prevalent in most areas where tobacco related practices are observed. Essential elements play a role in many biochemical reactions as a micro-source and there is growing evidence that their concentrations are altered on the onset and progress of malignant disease. In this study the levels of copper (Cu), zinc (Zn), selenium (Se) and molybdenum (Mo) in serum of patients with oral sub mucous fibrosis (OSMF) (n = 30) and oral squamous cell carcinoma (OSCC) (n = 30); were determined and the alterations of these critical parameters were analyzed in comparison with controls (n = 30) to identify predictors amongst these parameters for disease occurrence and progression. The serum Cu and Zn were established using Flame Atomic Absorption Spectrometry. Serum estimation of Se and Mo was done by graphite furnace atomic absorption spectrometry (GFAAS). Data analysis revealed a marked, progressive and significant increase in Cu levels in precancer (OSMF) and cancer (OSCC) groups as compared to the normal group. The level of Zn in serum was slightly elevated in OSMF and OSCC though not statistically significant. Cu/Zn ratio was slightly but not significantly elevated. Serum levels of Se and Mo were significantly decreased in the precancer and cancer groups as compared to the normals., (Copyright © 2013 Elsevier GmbH. All rights reserved.)

Illicit drugs manufactured from clandestine laboratories are often impure due to poor laboratory conditions, variations in synthesis and impure starting materials extracted either from common household products or pharmaceutical grade chemicals. Inductively coupled plasma mass spectrometry (ICPMS) can be utilised as a multi-element analytical tool to elicit the inorganic impurities which may be present in such samples, however the interpretation of the resultant data can be problematic and complex. This is particularly true when dealing with seized samples of unknown provenance. In this work, we have presented and interpreted inorganic profiles as a means to explore within and between batch variations in known provenance samples produced via two different popular synthetic routes. Samples were prepared from essential chemicals recovered from household materials and pharmaceutical medication available in the UK and extracted using different solvents. The presence or absence of elements in the final synthesised products could be linked to the synthesis route, salting out method and potentially the solvent used in the precursor extraction process., (Copyright © 2012 Forensic Science Society. Published by Elsevier Ireland Ltd. All rights reserved.)

In this study, the corrosion behavior of Mg-Zn-Se and Mg-Zn-Cu alloys was investigated to evaluate their corrosion behavior related to use as implantable biomaterials. The corrosion behavior of these alloys and a commercially available Mg-Zn alloy were examined using static solution electrochemical testing, dynamic solution gravimetric testing, ion leaching testing, and microscopic evaluation. Fluctuations in the pH of the Dulbecco's Modified Eagles Medium (DMEM) used for the gravimetric and ion leaching immersion testing were also recorded over the 30-day duration to assess whether the media conditions induced by the alloy degradation would permit for cellular survival. Weight loss experimentation and electrochemical tests revealed the Mg-Zn-Cu alloy to have the greatest corrosion rate.

The levels of 20 essential or toxic trace elements in 159 fish, other seafood and seafood products on the French coastal market collected between January and April 2005 were measured by ICP-MS. The concentration ranges (mg/kg of fresh mass) for the elements determined were compared with previous studies. The contents of Co, Cu, Fe, Li, Mn, Se, Zn and Pb found in fish are close to or often lower than previous studies. For other seafood, comparison is difficult due to the lack of data on a more global scale. However, it should be noted that the contents of Ag were found considerably higher in this study., (Copyright © 2011 Elsevier Ltd. All rights reserved.)