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A highly efficient electrochemical aptamer sensor for the detection of tetracycline (TC) was prepared by using SnC@Au@Apta. Metal tin has good electrochemical activity and high conductivity. It is often used as an electrochemical sensing material. The nanofibers prepared by electrospinning machine make the metal distribution more uniform, not easy to agglomerate, and have a certain porosity, which can improve the sensitivity of sensor detection. Carbonization further enhances conductivity. The gold nanoparticles (AuNPs) on the surface of SnC nanomaterials improve the electrochemical detection performance, and also act as the binding site of the TC aptamer, which is stably combined with the thiol group at the end of the TC aptamer. The TC aptamer specifically binds to TC to detect TC in the sample. The electrochemical performance of SnC@Au@Apta was evaluated by cyclic voltammetry (CV) and differential pulse voltammetry (DPV). Under the optimal conditions, the detection range of SnC@Au@Apta is wide (0.001-100 μM), the detection limit is low (0.83 nM), and it has excellent selectivity, stability and reproducibility. In addition, SnC@Au@Apta can be used to detect TC in milk samples., Competing Interests: Declaration of competing interest We declare that we have no financial and personal relationships with other people or organizations that can inappropriately influence our work, there is no professional or other personal interest of any nature or kind in any product, service and/or company that could be construed as influencing the position presented in, or the review of, the manuscript entitled., (Copyright © 2024 Elsevier B.V. All rights reserved.)

Radon, a radioactive gas can increase the risk of lung cancer when breathe in. Indoor Rn-222 and Rn-220 concentrations were determined using passive radon monitor in some dwellings in a Sn mining area of Jos Plateau. Outdoor gamma radiation was also measured with a hand-held survey meter. The range of Rn-222 and Rn-220 concentrations was from 7-53 Bq m-3 to 41-267 Bq m-3 with averages of 27 ± 17 and 92 ± 65 Bq m-3, respectively. The mean total effective dose due to Rn-222 + Rn-220 was estimated as 2.84 ± 1.57 mSv y-1. Rn-220 contributed between 50 and 95% to the total annual effective dose. There was no correlation between indoor Rn-220 and Rn-222 concentrations in the dwellings. Outdoor gamma radiation measured was between 0.31 ± 0.06 and 0.62 ± 0.08 μSv h-1, and mean annual effective dose calculated was 1.14 ± 0.21 mSv y-1. It is concluded from this study that thoron should not be neglected in dose assessment., (© The Author(s) 2024. Published by Oxford University Press. All rights reserved. For Permissions, please email: journals.permissions@oup.com.)

Studying the status and source analysis of heavy metal pollution in farmland in typical mining and processing areas is an important prerequisite for promoting farmland soil ecological restoration and farmland protection in concentrated mining areas. In this study, the heavy metal content of farmland soil around a mining area in southwest China was detected, and the pollution status, distribution law, health risks, and sources of heavy metals were studied by using the land accumulation index method, comprehensive pollution index method, kriging interpolation method, health risk assessment method, and PMF receptor model on the sampling data. The results showed that the mean values of eight heavy metals in farmland soil except Ni exceeded the local soil background values, and the results of the ground accumulation index evaluation showed that Cd and Hg were extremely polluted； Pb and As showed medium pollution-heavy pollution； and Cr, Zn, Ni, and Cu were lightly polluted. In the health risk assessment, oral ingestion was the main exposure route posing a health risk to the human body； the main element that constituted non-carcinogenic health risks was As, and the carcinogenic risks were from As and Cd. PMF model analysis showed that the contribution rate of weathering natural sources of iron-bearing ore was 28.02%, and the main factors were Ca and Fe. The contribution rate of agricultural sources was 3.02%, and the main factors were Pb and As. The contribution rate of industrial and atmospheric deposition composite sources was 33.09%, and the main factor was Hg. The contribution rate of the parent material source was 17.27%, and the main factor was Ca. The contribution rate of mining activities such as mining and smelting was 18.60%, and the main factors were Zn and Cd.

Background: An interlaboratory study was conducted at the U.S. Food and Drug Administration's (FDA) Northeast Food and Feed Laboratory (NFFL) and the Center for Food Safety and Applied Nutrition (CFSAN) with the purpose to expand FDA Elemental Analysis Manual (EAM) method 4.7 (Inductively Coupled Plasma-Mass Spectrometric Determination of Arsenic, Cadmium, Chromium, Lead, Mercury, and Other Elements in Food Using Microwave Assisted Digestion) to include new analytes., Objective: The goal of the study was to demonstrate the performance of FDA EAM method 4.7 when analyzing new analytes cobalt (Co), strontium (Sr), thallium (Tl), tin (Sn), uranium (U), and vanadium (V). This analyte extension method validation of EAM 4.7 for six additional elements, Co, Sr, Tl, Sn, U, and V, followed all guidelines for a Level 2 or single-laboratory validation and met all acceptance criteria for analyte extensions as per the Guidelines for the Validation of Chemical Methods., Method: As per EAM 4.7, this study followed the procedures and used specified equipment operated under recommended conditions. The analyte extension method validation was performed in accordance with protocol and with no deviations., Results: All quality control (QC) requirements for this analyte extension method validation of EAM 4.7 passed as evidenced by the analytical data. The results presented demonstrate accuracy, linearity, and precision by successful analyses of method blanks, matrix spikes, unfortified test samples, and reference materials. The data analyzed met each of the validation requirements for each analyte in all representative matrixes., Conclusions: The study showed that the new analytes performed satisfactorily using EAM 4.7 for total acidic extractable elemental analysis of food according to FDA's guidelines., Highlights: The method met or exceeded the performance criteria., (Published by Oxford University Press on behalf of AOAC INTERNATIONAL 2024.)

Determining the origin and pathways of contaminants in the natural environment is key to informing any mitigation process. The mass magnetic susceptibility of soils allows a rapid method to measure the concentration of magnetic minerals, derived from anthropogenic activities such as mining or industrial processes, i.e., smelting metals (technogenic origin), or from the local bedrock (of geogenic origin). This is especially effective when combined with rapid geochemical analyses of soils. The use of multivariate analysis (MVA) elucidates complex multiple-component relationships between soil geochemistry and magnetic susceptibility. In the case of soil mining sites, X-ray fluorescence (XRF) spectroscopic data of soils contaminated by mine waste shows statistically significant relationships between magnetic susceptibility and some base metal species (e.g., Fe, Pb, Zn, etc.). Here, we show how qualitative and quantitative MVA methodologies can be used to assess soil contamination pathways using mass magnetic susceptibility and XRF spectra of soils near abandoned coal and W/Sn mines (NW Portugal). Principal component analysis (PCA) showed how the first two primary components (PC-1 + PC-2) explained 94% of the sample variability, grouped them according to their geochemistry and magnetic susceptibility in to geogenic and technogenic groups. Regression analyses showed a strong positive correlation (R 2  > 0.95) between soil geochemistry and magnetic properties at the local scale. These parameters provided an insight into the multi-element variables that control magnetic susceptibility and indicated the possibility of efficient assessment of potentially contaminated sites through mass-specific soil magnetism., (© 2024. The Author(s).)

Whole milk powder (WMP) manufactured in New Zealand in 1907 was sent to the Antarctic continent with the Shackleton-led British Antarctic Expedition from 1907 to 1909. This powder was stored at ambient conditions at Shackleton's Hut at Cape Royds, Antarctica, for over 100 yr before a sample was collected on behalf of Fonterra by the Antarctic Heritage Trust. Having spent most of its existence both dried and in frozen storage, any deleterious reactions within the WMP would have been markedly retarded. The composition and some properties of the roller-dried Shackleton's WMP are reported along with those of 2 modern spray-dried New Zealand WMP. The Shackleton powder was less white and more yellow than the modern WMP and was composed of flakes rather than agglomerated particles, consistent with that expected of a roller-dried powder. Headspace analysis showed lipolytic and oxidative volatile compounds were present in the Shackleton WMP, indicting some deterioration of the milk either before powder manufacture or on storage of the finished product. On a moisture-free basis, the Shackleton WMP had higher protein, higher fat (with a markedly higher free fat level), higher ash, and a lower lactose level than the modern WMP. The lysine level was lower in the Shackleton WMP compared with the spray-dried powders, whereas the fatty acid composition was relatively similar. The sodium level was markedly higher in the Shackleton WMP compared with the spray-dried powder, which is probably due to the addition of an alkaline sodium salt to adjust the pH of the milk before roller drying. Lead, iron, and tin levels were markedly higher in the Shackleton WMP compared with the spray-dried powders, possibly due to the equipment used in powder manufacture and the tin-plated cases used for storage. The proteins in the Shackleton WMP were more lactosylated than in the spray-dried powders. The Shackleton WMP had a higher ratio of κ-casein A to B variants and a higher ratio of β-lactoglobulin B to A variants than the spray-dried powders, whereas the α S1 -casein, β-casein, α S2 -casein, and α-lactalbumin protein variants were similar in all powders. The total phospholipid content was markedly lower in the Shackleton WMP than the spray-dried powders, primarily due to a lower phosphatidylethanolamine concentration. The molecular species distributions within the phospholipid classes were generally similar in the 3 powders. Claims are sometimes encountered that the milk of today is different from that consumed by previous generations. However, this comparative study has shown that the Shackleton WMP was generally similar to modern WMP. Although differences in some components and properties were observed, these were attributable to the manufacturing equipment and processes used in the pioneering years of WMP manufacture., (The Authors. Published by Elsevier Inc. and Fass Inc. on behalf of the American Dairy Science Association®. This is an open access article under the CC BY license (http://creativecommons.org/licenses/by/4.0/).)

Objective: To establish an analytical method for determining the migration of 24 elements in Yixing clay pottery in 4% acetic acid simulated solution by inductively coupled plasma mass spectrometry., Methods: Four types of Yixing clay pottery, including Yixing clay teapot, Yixing clay kettle, Yixing clay pot, and Yixing clay electric stew pot, were immersed in 4% acetic acid as a food simulant for testing. The migration amount of 24 elements in the migration solution was determined using inductively coupled plasma mass spectrometry., Results: Lithium, magnesium, aluminum, iron, and barium elements with a mass concentration of 1000 μg/L; Lead, cadmium, total arsenic, chromium, nickel, copper, vanadium, manganese, antimony, tin, zinc, cobalt, molybdenum, silver, beryllium, thallium, titanium, and strontium elements within 100 μg/L there was a linear relationship within, the r value was between 0.998 739 and 0.999 989. Total mercury at 5.0 μg/L, there was a linear relationship within, the r value of 0.995 056. The detection limit of the elements measured by this method was between 0.5 and 45.0 μg/L, the recovery rate was 80.6%-108.9%, and the relative standard deviation was 1.0%-4.8%(n=6). A total of 32 samples of four types of Yixing clay pottery sold on the market, including teapots, boiling kettles, casseroles, and electric stewing pots, were tested. It was found that the migration of 16 elements, including beryllium, titanium, chromium, nickel, cobalt, zinc, silver, cadmium, antimony, total mercury, thallium, tin, copper, total arsenic, molybdenum, and lead, were lower than the quantitative limit. The element with the highest migration volume teapot was aluminum, magnesium, and barium; The kettle was aluminum and magnesium; Casserole was aluminum, magnesium, and lithium; The electric stew pot was aluminum., Conclusion: This method is easy to operate and has high accuracy, providing an effective and feasible detection method for the determination and evaluation of element migration in Yixing clay pottery.

Massive amounts of waste copper converter slags have been produced from pyrometallurgical extraction of copper from copper concentrates, and the disposal of them in landfills creates serious environmental problems. However, this converter slag contains numerous valuable heavy metals, including copper, cobalt and tin etc. In this research, due to similar properties of iron and cobalt, pig iron with a low melting point was creatively used as capturing agent for cobalt recycling in a smelting reduction. The recovery of copper and tin was also studied. The phase transformation during reduction process was clarified by X-ray diffraction and Scanning electron microscope-energy dispersive spectrometer analyses. After the reduction performed at 1250 °C, the copper, cobalt and tin were recovered in a copper-cobalt-tin-iron alloy. The addition of pig iron improved cobalt yield, which was ascribed to the enrichment of cobalt in an iron-cobalt alloy phase. This decreased activity of the reduced cobalt and promoted reduction of cobalt oxide. As a result, the cobalt yield had a significant increase from 66.2% to 90.1% by adding 2% pig iron. Similarly, the copper also accelerated tin recovery through the formation of a copper-tin alloy. The copper and tin yields reached 94.4% and 95.0%, respectively. This work provided a high efficiency method to recover copper, cobalt and tin from waste copper converter slags., 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.)

Tin (Sn) element plays a vital role in the human body, and its detection is a mandatory inspection item for canned food. The application of covalent organic frameworks (COFs) in fluorescence detection has received extensive attentions. In this work, we designed a kind of novel COFs (COF-ETTA-DMTA) with high specific surface area (353.13 m 2 /g) by solvothermal synthesis using 2,5-dimethoxy-1,4-dialdehyde and tetra (4-aminophenyl) ethylene as precursors. It shows fast response time (about 50 s), low detection limit (228 nM) and good linearity (R 2  = 0.9968) for the detection of Sn 2+ . Via coordination behavior, the recognition mechanism of COFs toward Sn 2+ was simulated and verified by the small molecule with the same functional unit. More importantly, this COFs was successfully applied to identify Sn 2+ in solid canned food (luncheon pork, canned fish, canned red kidney beans) with satisfactory results. This work provides a new approach for determining metal ions with COFs taking the advantage of their natural rich reaction set and specific surface area, improving the detection sensitivity and capacity., 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 B.V. All rights reserved.)

This research studied the performance of tin titanate (SnTiO 3 , SnT) and cellulose-based composites for the removal of clonazepam (CZP) drug by physical adsorption. The cellulose was extracted from a plant named tithonia tubaeformis, which is considered as weed in the crop fields of Mexico. The analysis by microscopy revealed that the SnTiO 3 powders are formed by a mixture of coalesced grains and nanotubes with lengths in the range of 97-633 nm. Furthermore, the X-ray diffraction analysis indicated that the SnT powders present a mixture of cassiterite and rutile phases. Experiments for the CZP removal from drinking water were carried out, and several parameters such as initial drug concentration (1-10 mg/L), amount of SnT adsorbent per liter of contaminated solution (10-50 mg/L), and pH (3-10) were varied in order to study their influence on the CZP removal percentage. Essentially, we found that the SnT dosage of 50 mg/L produced the most efficient and fastest CZP removal, since 94.3% of CZP was removed after only 10 min of reaction. Moreover, a piece of cellulose (Cell) was decorated with 50 mg of SnT powder to form the Cell+SnT composite, and this was able to remove a maximum of 80.5% of CZP after 180 min of reaction. If the amount of SnT powder deposited on the Cell+SnT composite is raised up to 100 mg, the composite can remove 95.5% of CZP. The adsorption capacity was also calculated for the SnT powders and Cell+SnT composite and found that it was 6.3 times higher for the SnT powders. Furthermore, the Raman spectra recorded for the Cell+SnT composites demonstrated the presence of surface defects, which acted as adsorption centers for the CZP molecules. The results of this investigation demonstrate that eco-friendly and low-cost floatable composites can be used for the removal of pharmaceutical contaminants, which is an advantage over adsorbent powders., (© 2023. The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature.)

The relationship between trace elements and neurological development is an emerging research focus. We performed a case-control study to explore (1) the differences of 13 trace elements chromium (Cr), manganese (Mn), cobalt (Co), zinc (Zn), arsenic (As), selenium (Se), molybdenum (Mo), cadmium (Cd), stannum (Sn), stibium (Sb), mercury (Hg), titanium (TI), and plumbum (Pb) concentration in whole blood and urine between autism spectrum disorder (ASD) children and their typical development peers, and (2) the association between the 13 trace elements and core behaviors of ASD. Thirty ASD subjects (cases) and 30 age-sex-matched healthy subjects from Baise City, Guangxi Zhuang Autonomous Region, China, were recruited. Element analysis was carried out by inductively coupled plasma-optical emission spectrometry. Autistic behaviors were assessed using Autism Behavior Checklist (ABC), Childhood Autism Rating Scale (CARS), and Children Neuropsychological and Behavior Scale (CNBS). The whole blood concentrations of Mo (p = 0.004), Cd (0.007), Sn (p = 0.003), and Pb (p = 0.037) were significantly higher in the ASD cases than in the controls. Moreover, Se (0.393), Hg (0.408), and Mn (- 0.373) concentrations were significantly correlated between whole blood and urine levels in ASD case subjects. There were significant correlations between whole blood Sb (0.406), Tl (0.365), Mo (- 0.4237), Mn (- 0.389), Zn (0.476), and Se (0.375) levels and core behaviors of ASD. Although the mechanism of trace element imbalance in ASD is unclear, these data demonstrate that core behaviors of ASD may be affected by certain trace elements. Further studies are recommended for exploring the mechanism of element imbalance and providing corresponding clinical treatment measures., (© 2022. The Author(s).)

Metal/loid pollution from shipwrecking activities has drawn significant concern due to their persistent threat to the marine ecosystem and human health. We investigated the spatiotemporal distribution, pollution characteristics, risks, sources, and potential impact of metal/loids in the sediments and seafood in the Bay of Bengal at nearby open beaching shipwrecking yards in Bangladesh. We collected 78 sediments and 208 seafood samples from the exposed and control sites from 2018 to 2020 during the dry and wet seasons. The concentrations of 16 elements, including cadmium, arsenic, lead, chromium, manganese, copper, zinc, iron, tin, antimony, nickel, cobalt, molybdenum, vanadium, selenium, and thallium were measured using validated inductively coupled plasma-mass spectrometry (ICP-MS) methods. Based on the pollution indices (enrichment factor, geoaccumulation index, pollution index, and pollution load index), lead, arsenic, cadmium, selenium, copper, zinc, and tin from the dry season showed higher contaminations compared to the wet and their concentrations were increased from 2018 to 2020 with seasonal fluctuations. Sediment cadmium and arsenic posed relatively higher and moderate ecological risks. Health risk analysis indicated that lead, cadmium, and inorganic arsenic (estimated) in seafood species pose a possible health threat to the general population. Further, there were possible ecological and health risks for the metal/loids in combination based on the ecological risk index in sediment and the hazard index in seafood, respectively. Source apportionment suggested that anthropogenic activities through uncontrolled shipwrecking operations over the last four decades were the largest polluting dominator, contributing 55-77% of the metal/loid concentrations. Therefore, the data may inform mitigation strategies for emission control at the shipwrecking yards to protect marine ecosystems and their local population., 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.)

The groundwater resources of mining areas have been in a challenging condition in terms of metal pollution and human health. Therefore, this study investigated the concentration of cobalt (Co), molybdenum (Mo), selenium (Se), tin (Sn), and antimony (Sb) in groundwater samples (wells, qanats, and springs) in a heavily contaminated mining district, South Khorasan, Eastern Iran. Human health risk of the studied metals to target groups was assessed, and water quality of the studied groundwater was investigated in the study area. A total of 367 sampling sites (279 wells, 74 qanats, and 14 springs) in South Khorasan Province were selected to collect the groundwater samples from June to July 2020. Sampling was performed thrice for each sampling point, and hydrochemical parameters were evaluated using a portable multiparameter. Inductively coupled plasma mass spectrometry (ICP-MS) was used to detect the metal concentrations. Results showed an order of Se > Mo > Sn > Co > Sb, and hazard index (HI) demonstrated a warning condition for south of South Khorasan (drinking application), southwest of South Khorasan (Irrigation application), and east and center of South Khorasan (drinking-irrigation application). Hydrochemical parameters showed a classification of "Na + K type" and "Mixed Ca-Mg-Cl type" with an overall group of "Na-Cl-HCO 3 " for sampled waters. Ficklin-Caboi diagram depicted a classification of "near-neutral low metal," and Schoeller diagram classified studied groundwater as "good" for drinking and irrigation consumptions and "Na-Cl" type based on ion balance diagram. Based on the correlation analysis, positive relationships were recorded among EC, TDS, Cl - , Na + , sulfate, Ca 2+ , salt, total hardness, Mg 2+ , ammonia, and K + measured in the water samples. In essence, arid regions of the world greatly rely upon groundwater resources for drinking and irrigation consumptions, and mining districts with a heavy load of active mines can be a serious threat to the groundwater quality and human health., (© 2022. The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature.)

Children are highly vulnerable to chemical exposure. Thus, metal and metalloid in infant formulas are a concern, although studies in this regard are still relatively scarce. Thus, the presence of aluminum, arsenic, cadmium, tin, mercury, lead, and uranium was investigated in infant formulas marketed in Brazil by inductively coupled plasma mass spectrometry, and the Target Hazard Quotients (THQ) and Target Cancer Risk (TCR) were calculated in to assess the potential risk of toxicity for children who consume these products continuously. Aluminum ranging from 0.432 ± 0.049 to 1.241 ± 0.113 mg·kg -1 , arsenic from 0.012 ± 0.009 to 0.034 ± 0.006 mg·kg -1 , and tin from 0.007 ± 0.003 to 0.095 ± 0.024 mg·kg -1 were the major elements, while cadmium and uranium were present at the lowest concentrations. According to the THQ, arsenic contents in infant formulas showed a THQ > 1, indicating potential health risk concerns for newborns or children. Minimal carcinogenic risks were observed for the elements considered carcinogenic. Metabolic and nutritional interactions are also discussed. This study indicates the need to improve infant formula surveillance concerning contamination by potentially toxic and carcinogenic elements.

Background: Trace metals have side-effect on human health. The association between trace metals exposure and hearing loss remains unclear., Methods: A total of 8,128 participants were exacted for analysis of association between trace metals and hearing loss from the database of the National Health and Nutrition Examination Survey (NHANES) (2013-2018). Multivariable logistic regression and restricted cubic spline models were used to examine the association between trace metals and hearing loss., Results: Participants with hearing loss had a higher level of lead, cadmium, molybdenum, tin, thallium, and tungsten (all p < 0.05). After adjusting for confounders, compared with the reference of the lowest quartile, the ORs with 95%CIs for hearing loss across quartiles were 1.14 (0.86, 1.51), 1.49 (1.12, 1.98), 1.32 (0.97, 1.80) for cobalt, and 1.35 (0.98, 1.87), 1.58 (1.15, 2.16), 1.75 (1.28, 2.40) for tin. Individuals with the level of cobalt at third quartile had 49% higher risks of hearing loss than those at lowest quartile. And participants with highest quartile of tin had 1.75-folds risks of hearing loss than those with lowest quartile of tin. There were increasing trends in risks of hearing loss with a raised level of thallium ( p for trend <0.05). Restricted cubic spline regression analysis indicated that there was a nonlinear association between hearing loss and the levels of tin ( p for nonlinearity = 0.021). Subgroup analysis showed that individuals of female, without hypertension and diabetes, and with a higher level of low-density lipoprotein cholesterol had modified effects on the associations between hearing loss and exposure to tin., Conclusions: Our study indicated that exposure to cobalt and tin were significantly associated with hearing loss., 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 Zou, Li, Chen, Ji, Xue, Wang, Xu and Cheng.)

The past mining activities in Bokkos Local Government Area (LGA) were performed in an uncontrolled way and gave rise to many abandoned ponds now serving as domestic and irrigation water sources. Past research focused mainly on the environmental impact, and we show for the first time what the human health risk through consumption of contaminated food crops is in these communities. This study was designed to determine the level of Potentially Toxic Elements (PTEs) contamination in pond water, soil, and food crops and assess the health risk of inhabitants in the abandoned tin mining community in Bokkos LGA. Samples of the mining pond water, soil, and selected food crops from farms irrigated with the pond water: bitter leaf (Vernonia amygdalina), pepper (Piper nigrum), okra (Albelmoschus esculentus), maize (Zea mays), sweet potato (Ipomoea batatas), and Irish potato (Solanum tuberosum) were analyzed for each of the eight PTEs (viz. Cu, Cr, Fe, Mn, Ni, Zn, Cd, and Pb) using inductively coupled plasma optical emission spectrometry (ICP-OES). The results obtained showed that the levels of all the PTEs analyzed in the soil, pond water, and selected food crops except for Fe and Mn in soil and Cd in sweet potato were greater than their corresponding background area values (p < 0.05). Also, the mean concentrations of all the PTEs except for Cu in pond water were significantly (p < 0.05) higher than the WHO maximum permissible limit. With the exception of Fe, Ni, and Zn for pepper and okra, Cu and Fe for maize grains as well as Cu, Ni, and Zn for sweet and Irish potatoes and Fe and Cd for sweet potato, the mean concentrations of PTEs in the food crops were significantly higher than WHO maximum permissible limit. The EF values of Cd (0.39); Cu (3.59) and Ni (2.81); Cr (9.38) and Pb (17.84); and Mn (178.13) and Zn (83.22) classified the soil as minimally, moderately, significantly, and extremely highly enriched, respectively. The PI values of all the PTEs in the soil studied were all greater than 5, indicating that the soils were severely contaminated. There was evidence that food crops significantly bioaccumulated PTEs either as a result of contaminated soil and/or irrigation water. The bioaccumulation was not uniform and was dominated by transfer from the polluted irrigation water. The bitter leaf, okra, and to some extent maize had the highest transfer of PTEs, and Mn, Cu, and Zn had the highest bioaccumulation in the food crops investigated. The hazardous index (HI) for the eight PTEs through the consumption of food crops was 107 for children and 33 for adults which greatly exceeded the recommended limit of 1, thus indicating that possible health risks exist for both local children and adults. For every PTE, the values of HI for children are many-fold higher than those for adults, which is of particular concern due to the high HI values for Pb found for maize consumption, a typical staple food. The cancer risk values for Cr and Ni for all the food crops were within 10 -3 -10 -1 which is several fold higher than the permissible limits (10 -6  and < 10 -4 ) indicating the high carcinogenic risk. It can be concluded based on the results and risk assessment provided by this study that human exposure to mining pond water and soil in farms around the mining pond through the food chain suggests the high vulnerability of the local community to PTE toxicity. Long-term preventive measures to safeguard the health of the residents need to be put in place., (© 2022. The Author(s), under exclusive licence to Springer Science+Business Media, LLC, part of Springer Nature.)

Humans are environmentally exposed to many metals throughout their lives. Simultaneous exposure to several metals could result in synergistic or antagonistic toxicological effects among them; however, the information on exposure to mixtures of metals and breast cancer (BC) is scarce. The objective of this report was to compare metals considered human carcinogens, individually and as mixtures, in women with and without BC. This is a secondary analysis of a population-based case-control study that was carried out from 2007 to 2011 in Northern Mexico. A total of 499 histologically confirmed BC cases and 499 controls were included. Information about sociodemographic, lifestyle and reproductive characteristics was obtained by in-person interviews. Urinary concentrations of aluminum (Al), cadmium (Cd), chromium (Cr), nickel (Ni), lead (Pb), antimony (Sb), cobalt (Co), molybdenum (Mo), tin (Sn), and vanadium (V) were determined by inductively coupled plasma triple quadrupole. Metal mixtures were identified by principal component analysis with creatinine-corrected metals. Over 90% of subjects had metal measurements above the detection limit except tin (86%) and antimony (78.4%). After adjusting by selected covariables, we observed that the individual urinary concentrations of V, Co, and Mo were lower among cases compared to controls; in contrast to Sn that had higher concentrations. We identified two principal component mixtures with opposite relationships with BC: Cr, Ni, Sb, Al, Pb and Sn (OR = 1.15; CI95% 1.06,1.25) and Mo and Co (OR = 0.56; CI95% 0.49,0.64). This is the first study that identified urinary metal mixtures that differed between women with and without BC. Our results warrant confirmation in further prospective epidemiological studies. In addition, the elucidation of underlying mechanisms of metal interactions on BC risk deserves further research., (Copyright © 2022 Elsevier Inc. All rights reserved.)

Background: This study is to assess the correlation between blood concentration ranges of eight elements of tin smelting workers from Guangxi Liuzhou and their job type, working years, age, and sex., Methods: We collected blood samples of 218 tin smelting workers from a Chinese tin smelting factory and determined the levels of elements by inductively coupled plasma mass spectrometry., Results: Within the blood concentrations of eight metal elements of the objects, the blood concentration of copper and zinc is affected by the job type of comprehensive work; that of arsenic and mercury is affected by refining; and that of chromium, cadmium, and lead is affected by primary smelting., Conclusions: We present the remarkable influence of four job types on the blood concentration of seven trace elements., Competing Interests: The authors report no conflicts of interest., (Copyright © 2022 The Author(s). Published by Wolters Kluwer Health, Inc. on behalf of the American College of Occupational and Environmental Medicine.)

Determining the concentrations of different Sn ions in glass containing iron oxide by wet chemical analysis is a challenge because a redox reaction occurs between Sn 2+ and Fe 3+ . A chemical analysis method for determining the concentrations of Sn 2+ and Sn 4+ in soda lime glass containing iron oxide was proposed. A mixture of ascorbic acid, hydrochloric acid, and hydrofluoric acid was used to decompose the sample in a vessel with nitrogen flow. Ascorbic acid functioned as a reductant for Fe 3+ . Subsequently, the Sn 2+ were separated as a diethyldithiocarbamate complex. Furthermore, inductively coupled plasma atomic emission spectroscopy was used to determine the concentrations of Sn 4+ and total Sn, from which the concentration of Sn 2+ can be calculated. The results were validated by comparing ratios of Sn 2+ to total Sn to results obtained using Mössbauer spectroscopy. The results were in agreement, thereby validating the use of the proposed approach., (© 2022. The Author(s), under exclusive licence to The Japan Society for Analytical Chemistry.)

A simple rhodamine-based compound CK was designed and synthesized as a fluorescent chemosensor for Sn 2+ based on Sn 2+ -mediated cyclization. The optical investigation indicated that the probe could quantitatively detect Sn 2+ in a concentration range of 10-30 μM, with a detection limit of 118 nM. Moreover, probe CK, with low cytotoxicity, was successfully applied for imaging of Sn 2+ in HeLa cells and mice, exhibiting excellent biocompatibility and cell membrane permeability. For on-site monitoring, CK-hybridized polymethyl methacrylate (PMMA) nanofibers were prepared by electrospinning and successfully employed for the visual detection of Sn 2+ in actual samples. All the results demonstrated that the chemosensor could be a promising tool for the detection of Sn 2+ in vitro and in vivo., (© 2021. Springer-Verlag GmbH Germany, part of Springer Nature.)

We investigated the application of energy-dispersive X-ray fluorescent spectrometry (EDX) analysis to the detection of aluminum (Al), tin (Sn) and zinc (Zn) as the electric conductor in experimental electrical injury. Experimental electrical injury was caused by exposure to alternating current at 100 V for 10 s. The peaks of Al, Sn, and Zn were detected by EDX in formalin-fixed skin samples of each current exposure group. Histological examination revealed blister formation in all samples of each current exposure group. EDX analysis technique can be applied to detect Al, Sn, and Zn as the electric conductor, and is useful in the diagnosis of electrocution., (Copyright © 2020 Elsevier B.V. All rights reserved.)

This study presents a new approach for the investigation of tributyltin (TBT) behaviour and fate in the marine environment. The approach is based on a simultaneous analysis of butyltins (BuTs) and total Sn in sediments, thus enabling an assessment of long-term persistence and historical input of TBT. The study also presents first evaluation of the extent to which the TBT-antifouling paints contribute to the contamination of coastal environments with inorganic Sn; it was demonstrated that the inorganic Sn in the investigated areas primarily originates from TBT degradation. The study was conducted by analyzing BuTs and total Sn in sediments from 34 locations along the Croatian Adriatic coast. The results revealed that 85% of the locations were contaminated with both BuTs and inorganic Sn. The share of ƩBuTs/total Sn was low (<10%) even in sediments with low TBT degradation efficiency (TBT/ƩBuTs >40%), demonstrating that only small portion of TBT introduced into the water column reached the sediment before being degraded. This means that recent TBT input into the marine environment may be at least 10 times higher than the amount estimated if only BuTs levels in sediments are considered. It was also demonstrated that TBT concentration in sediments with TOC <1% is not a good indicator of the overall pollution level, even if TBT/TOC approach is used in pollution assessment. Finally, in situ investigation showed that resuspension of contaminated sediments leads to significant release of MBT and DBT into the water column, whereas TBT mainly remains in sediment., 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.)

Fe-Ni-MOFs with different amounts of Fe are synthesized through a two-step template etching method. Kinetic analysis indicates that Fe-Ni-MOF exhibits prominent intrinsic peroxidase-like activity, which could catalytically oxidize 3,3',5,5'-tetramethylbenzidine (TMB) to produce oxidized TMB (oxTMB) with a blue color. As a peroxidase-mimicking MOF, Fe-Ni-MOF with its efficient stable catalysis properties is demonstrated to allow a sensitive colorimetric assay for Sn2+ ions. The mechanism is explored, whereby Sn2+ ions could reduce the peroxidase-like activity of Fe-Ni-MOF based on a redox interaction, making the oxTMB color lighter and decreasing the absorbance intensity at 652 nm. The linear determination of the Sn2+ ion concentration using a UV-vis spectrometer ranges from 0.01 mM to 1.0 mM and from 1.0 mM to 4.0 mM. The presented Fe-Ni-MOF-based assay of Sn2+ ions was successfully applied to real water samples.

A large assemblage (n = 307) of architectural glasses (tesserae and windows) from the early 8th-century Umayyad residential site at Khirbat al-Minya was analysed by laser ablation inductively coupled plasma mass spectrometry. Trace element patterns are essential to establish the provenance of the base glass, while the comparative evaluation of the colouring and opacifying additives allow us to advance a production model for the manufacture of glass mosaic tesserae during the early Islamic period. The primary glass types are Levantine I and Egypt 1a, as well as a few older, reused tesserae, and Mesopotamian plant ash glass used for amber-coloured window fragments. Chemical data revealed fundamental differences in the colouring and opacification technologies between the Egyptian and Levantine tesserae. Co-variations of lead and bismuth, and copper, tin and zinc in the Egypt 1a tesserae provide first evidence for the production of different mosaic colours in a single workshop, specialising in the manufacture of tesserae of different colours. No such trend is apparent in the Levantine samples. Red, cobalt blue and gold leaf tesserae were found to be exclusively made from a Levantine base glass, indicating that the generation of some colours may have been a specialised process. The same may apply to the amber-coloured window glass fragments of Mesopotamian origin that exhibit very unusual characteristics, combining elevated copper (2% CuO) with an excess in iron oxide (5% Fe2O3). These findings have significant implications for the production model of strongly coloured glass and the exploitation of resources during the early Islamic period., Competing Interests: The authors have declared that no competing interests exist.

One hundred and twenty-two red wines were analysed for their total tin, total mercury and speciation concentrations. Total Sn and Hg concentrations were in average 4.4 ± 7.2 µg/L and 0.22 ± 0.12 µg/L, respectively. Two GC-ICP-MS methods were developed and validated for speciation purposes: one to measure organotin compounds (OTCs) with internal standard correction; the other, to evaluate methylmercury (MeHg + ) by isotopic dilution. Methyltins (mainly dimethyltin, but also monomethyltin) were the most abundant OTCs recovered. Methylation seems to occur biotically during the wine making process and not during the bottling time. Therefore, it also seems to be roughly dependent on the geographical origin of the wine. For higher OTCs, monobutyltin was the most regularly found, but dibutyltin and monooctyltin were also detected sometimes. MeHg + was not recovered in any of the samples investigated, probably due to the low level of Hg. These results suggest that, in terms of these parameters, normal consumption of wine is not a hazard for human health.

A unique and novel μ-thin-layer chromatography method based on Sn(II) ion-imprinted polymer (Sn-IIP) for speciation of tin ion species in water and plasma samples is introduced for the first time. For this purpose, N-allylthiourea (NATU) and ethylene glycol dimethacrylate (EGDMA) were copolymerized in the presence of Sn(II). The obtained polymer particles were identified using multiple techniques like BET, FT-IR, XRD, and FESEM. The effects of different variables such as pH of the solution, mobile phase composition, and IIP per CaSO 4 mass ratio on the separation efficiency were also evaluated. After completion of the separation process on the plate, its surface was scanned by laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS). Under the established optimal condition, the detection limit, relative standard deviation (RSD) of responses, and linear dynamic range (LDR) of the method were obtained as 0.3 μg L -1 , 3.5%, and 0.8-900 μg L -1 for Sn(II) and 0.4 μg L -1 , 4%, and 1-740 μg L -1 for Sn(IV) assay, respectively. The developed method was finally applied to the speciation of tin in various water and plasma samples. Graphical abstract Schematic representation of μ-thin-layer chromatography method based on tin(II) ion-imprinted polymer (Sn-IIP) for speciation of tin ion species in water and plasma samples and scanned separated casts by laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS).

In order to recognize organic contaminants responsible for ecological stresses from intensive shipping traffic and dockyard works, this study aimed at characterizing the sediment contamination of a large industrialized port located in Hainan Island, China. Surface sediment samples were collected from 17 stations including the main docks, the dockyards and the major industrial wastewater outlets. Organotin compounds, the pesticide DDT (bis(chlorophenyl)trichloroethane) and its metabolites and polycyclic aromatic compounds were identified as main pollutant groups by GC/MS applying a non-target screening approach. The pesticide DDT and its metabolites were found in the same samples as the organotin derivatives pointing to similar emission sources. The concurrent presence of these compounds in the dockyard samples suggests a combined usage of organotin compounds and DDT as active ingredients in antifouling paints in Yangpu. As highly specific molecular indicators for dockyard activities, butyltin and phenyltin compounds were identified. Noteworthy, also tributylmethyltin and triphenylmethyltin were detected, likely resulting from microbial assisted biomethylation of synthetic organotin compounds in the sediments. The concentrations of PAHs, DDX and TBT in sediments from dockyards exceeded global sediment quality guidelines and the toxicity thresholds, and potentially have adverse biological effects on marine organisms., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

Recently, monoalkyl oxo-hydroxo tin clusters have emerged as a new class of metal-oxide resist to support the semiconductor industry's transition to extreme ultraviolet (EUV) lithography. Under EUV exposure, these tin-based clusters exhibit higher performance and wider process windows than conventional polymer materials. A promising new monoalkyl precursor, [(BuSn) 12 O 14 (OH) 6 ][OH] 2 (BuSn), is still in its infancy in terms of film formation. However, understanding potential environmental effects could significantly affect future development as a commercial product. We synthesized and explored the toxicity of nano-BuSn in the alga Chlamydomonas reinhardtii and the crustacean Daphnia magna at exposure concentrations ranging from 0 to 250 mg/L. Nano-BuSn had no effect on C. reinhardtii growth rate irrespective of concentration, whereas high nanoparticle concentrations (≥100 mg/L) increased D. magna immobilization and mortality significantly. To simulate an end-of-life disposal and leachate contamination, BuSn-coated film wafers were incubated in water at various pH values and temperatures for 14 and 90 d to investigate leaching rates and subsequent toxicity of the leachates. Although small quantities of tin (1.1-3.4% of deposited mass) leached from the wafers, it was insufficient to elicit a toxic response regardless of pH, incubation time, or temperature. The low toxicity of the tin-based thin films suggests that they can be an environmentally friendly addition to the material sets useful for semiconductor manufacturing. Environ Toxicol Chem 2019;38:2651-2658. © 2019 SETAC., (© 2019 SETAC.)

Despite being widely used in industry, the literature on tin and its effects in humans is scarce, especially regarding reference values in biological indicators such as blood and urine. Similarly, environmental limits are also rare. This study sought to assess the spatial distribution of hotspots in the environmental exposure to tin in the vicinity of an alloy industry in the south region of the state of Rio de Janeiro, Brazil. The study population consisted of 74 adults. Graphite furnace atomic absorption spectrometry determined tin in all samples. Households and points around the industry were georeferenced with the use of GPS to identify the most intense tin sites. Results of the first and second campaigns ranged from 0.022 to 0.153 and 0.003 to 0.445µg m-3 for the atmospheric air, whereas such ranges were 0.64 to 1.61 and 1.97 to 8.54µg m-2 for household dust, respectively. The mean tin concentration found in the blood of the population was 3.85 ± 1.57µg L-1. In urine the value was 3.56 ± 1.88µg L-1. The kernel map showed the highest spatial concentrations of tin in household dust in the eastern region of the industry. In the first sampling, atmospheric air samples presented the most elevated concentrations in the southwest and southeast. Although the direction of the wind was northwest, potentially high risks were concentrated in the central area in the second collection. The largest hotspots were in the north, south and southeast regions; however, urine samples showed medium to high levels in the west and east regions. Regarding blood samples, the greatest difference was the absence of hotspot areas in the west. Environmental monitoring becomes necessary to better assess the exposure to tin.

In this study, the selective adsorption performance of different Fe-Mn binary oxides (FMBOs) towards Sb(V) in the textile wastewater under different concentrations of coexisting anions, surfactants and dyes were investigated. Results showed that the influences of different anions on the Sb(V) removal followed an order of phosphate > carbonate > sulfate > nitrate > chloride. The frequently-used organic acid of acetate was found to have insignificant effect. The coexisting surfactant with sulfonic groups could have adverse effect on the removal due to sulfonic groups could compete the adsorptive sites on Fe oxides with Sb(V). While the quaternary ammonium surfactant might have minor effect. The influences of the three widely used dyes on the Sb(V) adsorption decreased in the following order: reactive black-5 >acid orange-7> disperse blue-60, which confirmed that the dyes with sulfonic groups would have relatively higher effect. The selective adsorption capacities of Sb(V) by FMBOs followed an order of FMBO 3 > FMBO 5 >FMBO 10 > FMBO 20 >PFO. Fixed-bed column adsorption supplied useful parameters and evidently indicated that the cyclic utilization of FMBO 3 was cost-efficient for practical dynamic Sb(V) removal. The Sb(V) removal by FMBO 3 from real textile wastewater can simultaneously improve the removal efficiency, stabilize pH and prevent the increase of iron concentration as compared to the traditional coagulation, further demonstrating the high practical applicability of FMBO 3 ., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

Porous uranium oxide hollow sphere nanoparticles were synthesized in ionic liquids under hydrothermal conditions. Various precipitating agents and ionic liquids were investigated to determine their respective impact on the resultant uranium oxide morphologies. Using hydrazine hydrate as precipitating agent and N-butyl pyridinium bromide as templating agent, a porous-hollow structure was created with a surface area of 1958 m 2 .g -1 and an average pore diameter of 30 nm. The nanoparticles revealed high peroxidase-mimicking activity. This was evaluated by using the peroxidase substrate 3,3',5,5'-tetramethylbenzidine (TMB) that is catalytically oxidized by H 2 O 2 to give oxidized TMB (oxTMB) which is blue (with an absorption peak at 652 nm). The material was used as a nanozyme for colorimetric detection of Sn 2+ . Meanwhile, it is found that BSA strongly improves the catalytic activity of the nanozyme, while Sn(II) inhibits its activity. Thus, a colorimetric method for Sn 2+ detection was designed. The method works in the 0.5-100 μM Sn(II) concentration range and has a lower detection limit of 0.36 μM (at S/N = 3). Graphical abstract The catalytic activity of porous-hollow nano-UO 2 toward the oxidation of 3,3',5,5'-tetramethylbenzidine by H 2 O 2 is remarkably improved in the presence of bovine serum albumin, while tin(II) inhibits its activity. This finding has been applied to design a method for colorimetric quantification of tin(II) in water samples.

This article presents a new method for the simpler and faster determination of tin in beverages using EDXRF. Absorption coefficients for aqueous calibration samples were calculated and shown to be nearly identical to those of the beverage samples, thus permitting the use of aqueous standard solutions for external calibration. Beverage samples could then be measured directly using the external calibration. Determination of tin using this method takes 4 min. The LOD and LOQ were 4 mg L -1 and 15 mg L -1 respectively, and the precision was 3.89%. Different canned beverages (cold coffee, various fruit juices) were measured and the results compared to the concentrations obtained using ICP-OES after digestion. The two methods showed good compatibility, thus establishing the newly developed method as a rapid, simple, and accurate method for the determination of tin in beverages., (Copyright © 2019 Elsevier B.V. All rights reserved.)

Aluminum and tin are ubiquitous in the environment. In normal biological systems, however, they are present only in trace amounts and have no recognized biological functions in humans. High exposure to these metals can result in adverse health effects such as neurodegenerative diseases. In non-occupationally exposed subjects, diet is the primary source of exposure. In this study, we aimed at estimating dietary aluminum and tin intake in an Italian adult population. We measured aluminum and tin concentrations through inductively-coupled plasma mass spectrometry in 908 food samples. We also estimated dietary intake of these two metals, by using a validated semi-quantitative food-frequency questionnaire administered to 719 subjects (319 men and 400 women) recruited from the general population of the Emilia Romagna region, Northern Italy. We found the highest aluminum levels in legumes, sweets, and cereals, while the highest tin levels were in sweets, meat and seafood. The estimated median daily dietary intake of aluminum was 4.1 mg/day (Interquartile range - IQR: 3.3-5.2), with a major contribution from beverages (28.6%), cereals (16.9%), and leafy vegetables (15.2%). As for tin, we estimated a median intake of 66.8 μg/day (IQR: 46.7-93.7), with a major contribution from vegetables (mainly tomatoes) (24.9%), fruit (15.5%), aged cheese (12.2%), and processed meat (10.4%). This study provides an updated estimate of the dietary intake of aluminum and tin in a Northern-Italy adult population, based on data from a validated food-frequency questionnaire. The intake determined for this population does not exceed the established thresholds of tolerable intake., (Copyright © 2019 Elsevier GmbH. All rights reserved.)

For the determination of organo-tin residues in edible vegetable oil, a method was developed based on gas chromatography-mass spectrometric (GC-MS) with positive chemical ionization (PCI). The edible oil samples were first dissolved by cyclohexane-ethyl acetate (1:1, v/v), and then purified by gel permeation chromatography (GPC). After derivatization by sodium tetraethylborate, the samples were analyzed by GC-MS with PCI source in the single ion monitor (SIM) mode. The seven organo-tin compounds showed good linear relationships in the range of 20-2000 μg/L and the correlation coefficients exceeded 0.99. The limits of quantitation (LOQs) and the average recoveries of the seven organo-tin compounds were 0.3-1.2 μg/kg and 66.2%-103.2%, respectively, and the relative standard deviations were less than 11.5% at three spike levels (0.05, 0.10, and 0.20 mg/kg). The method showed good linearity and high sensitivity and can be used for the determination of organo-tin residues in edible vegetable oil.

The objective of the present study was to assess the level of aluminium and toxic metals in hair of workers occupationally exposed to aluminium. 124 employees of the aluminium plant working in the hydrometallurgical (n = 43) and sintering units (n = 41), as well as 40 occupationally nonexposed controls were examined. Hair aluminium (Al), arsenic (As), beryllium (Be), cadmium (Cd), mercury (Hg), nickel (Ni), lead (Pb), and tin (Sn) content was assessed using inductively-coupled plasma mass spectrometry. The obtained data demonstrate that aluminium plant workers had significantly higher levels of hair Al (28.8 (15.4-58.6) vs 7.8 (4.3-14.2) μg/g, p < 0.001), Cd (0.053 (0.032 - 0.095) vs 0.025 (0.014 - 0.043) μg/g, p < 0.001) and Pb (0.672 (0.299-1.310) vs 0.322 (0.170 - 0.609) μg/g, p = 0.012) than the controls, respectively. Further analysis demonstrated that persons involved in different technological processes were characterized by distinct hair metal profiles. Hair Al, Be, Cd, Ni, Pb, and Sn levels in men working in the sintering unit of the aluminium plant exceeded the respective control values. In turn, workers of the hydrometallurgical unit were characterized by more than 2-fold higher levels of Al and Cd in hair as compared to the controls. The results of the present study demonstrate that workers of the aluminium plant are characterized by increased risk of Al as well as As, Cd, Pb, and Sn exposure., (Copyright © 2018 Elsevier GmbH. All rights reserved.)

The aim of this work is the evaluation of quality indicators for the estimation of the shelf life of opened cans using the migration of specific metals as variables. For this reason the determination of targeted analytes such as: Cd, Pb, As, Cu, Cr, Ni, Fe, Mn and Sn in different canned samples (cardoon, tuna, green and red beans, corn, and fungi) by Electrothermal Atomic Absorption Spectrometry (Perkin Elmer, SIMAA 6000) was developed and validated. Statistical analysis was performed using SPSS version 22. Principal component analysis (PCA) and cluster analysis were performed in order to examine the correlation between the content of metals and metalloids and the storage time of opened cans. The results showed that there is a strong correlation between metal concentration and storage time, especially for Fe and Sn. The storage time ranged from hours to days and the vast number of collected data sets, led to reliable conclusions about the evaluation of a new shelf life indicator. Principal component analysis indicated the appropriate storage time for opened cans, where no significant migration was observed., (Copyright © 2017 Elsevier Ltd. All rights reserved.)

The purpose of this study was to investigate whether or not the concentration levels of certain kinds of trace elements in hair are associated with periodontitis. We studied a total of 109 participants, which are composed of 25 participants with periodontitis and 84 participants without periodontitis. Periodontal conditions were assessed by measuring the periodontal clinical attachment loss and pocket depth, which were determined at six sites of all teeth. Periodontitis was defined according to the criteria of periodontitis proposed by CDC-AAP. The hair samples were washed with acetone, water, and extran (1%v/v), and then aliquots of hair samples were wet-ashed. This sample solution was analyzed by Perkin-Elmer Mass Spectrometer. The odds ratios and 95% confidence intervals of the concentration levels of trace elements for periodontitis were calculated by multivariate logistic regression analysis. After adjusting all confounders, it was found that the higher concentration level of germanium in hair was significantly and positively associated with periodontitis (odds ratio [OR] 7.12; 95% confidential interval [CI] 2.03-25.00). The higher concentration level of tin in hair was significantly and negatively associated with periodontitis (OR 0.27; 95% CI 0.08-0.94). It was concluded that there was a significant relationship between periodontitis and the concentration level of germanium and tin in hair.

An arsenic-resistant fungal strain, designated WKC-1, was isolated from a waste roaster pile in a historical tin mine in Cornwall, UK and successfully identified to be Acidomyces acidophilus using matrix-assisted laser desorption/ionization time-of-flight/time-of-flight tandem mass spectrometry (MALDI-TOF/TOF MS) proteomic-based biotyping approach. WKC-1 showed considerable resistance to As 5+ and Sb 5+ where the minimal inhibitory concentration (MIC) were 22500 and 100 mg L -1 , respectively, on Czapex-Dox Agar (CDA) medium; it was substantially more resistant to As 5+ than the reference strains CBS 335.97 and CCF 4251. In a modified CDA medium containing 0.02 mg L -1 phosphate, WKC-1 was able to remove 70.30% of As 5+ (100 mg L -1 ). Sorption experiment showed that the maximum capacity of As 5+ uptake was 170.82 mg g -1 dry biomass as predicted by the Langmuir model. The presence of Sb 5+ reduced the As 5+ uptake by nearly 40%. Based on the Fourier-transform infrared spectroscopy (FT-IR) analysis, we propose that Sb is competing with As for these sorption sites: OH, NH, CH, SO 3 and PO 4 on the fungal cell surface. To our knowledge, this is the first report on the impact of other Group 15 elements on the biosorption of As 5+ in Acidomyces acidophilus.

Tin is a naturally occurring heavy metal that occurs in the environment in both inorganic and organic forms. Human exposure to tin is almost ubiquitous; however, surprisingly little is known about factors affecting environmental tin exposure in humans. This study analyzed demographic, socioeconomic and lifestyle factors associated with total urinary tin levels in adults (N = 3522) and children (N = 1641) participating in the National Health and Nutrition Examination Survey (NHANES) 2011-2014, a nationally representative health survey in the United States. Urinary tin levels, a commonly used biomarker of environmental tin exposure, were determined by inductively coupled plasma mass spectrometry (ICP-MS). Detection frequencies of tin were 87.05% in adults and 91.29% in children. Median and geometric mean levels of urinary tin in the adult population were 0.42 μg/L and 0.49 μg/L, respectively. For children, median and geometric mean levels of urinary tin were 0.60 μg/L and 0.66 μg/L, respectively. Age was identified as an important factor associated with urinary tin levels. Median tin levels in the ≥60 year age group were almost 2-fold higher than the 20-39 year age group. Tin levels in children were 2-fold higher than in adolescents. Race/ethnicity and household income were associated with tin levels in both adults and children. In addition, physical activity was inversely associated with urinary tin levels in adults. These results demonstrate that total tin exposures vary across different segments of the general U.S., Population: Because the present study does not distinguish between organic and inorganic forms of tin, further studies are needed to better characterize modifiable factors associated with exposures to specific tin compounds, with the goal of reducing the overall exposure of the U.S., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

The current EU legislation lays down Environmental Quality Standards (EQS) for 45 priority substances in surface waters; among them levels for (organo)metallic species of Hg, Sn and Pb are set between ng L -1 (for Hg and Sn) and μg L -1 (for Pb). To date, only a few analytical methods can reach these very restrictive limits and there is thus a need for comprehensive methods able to analyze these species down to these levels in natural waters. The aim of this work was to develop an online automated pre-concentration method using large volume injections with a Programmed Temperature Vaporization (PTV) injector fitted with a sorbent packed liner coupled to GC-ICP-MS to further improve the detection limits associated to this well-established method. The influence of several parameters such as the PTV transfer temperature and time, carrier gas flow rate and amount of packing material was investigated. Finally, the maximum volume injected through single or multiple injection modes was optimized to obtain the best compromise between chromatographic resolution and sensitivity. After optimization, very satisfactory results in terms of absolute and methodological detection limits were achieved, down to the pg L -1 level for all species studied. The potential of the method was exemplified by determining the concentrations of organometallic compounds in unpolluted river waters samples from the Adour river basin (SW France) and results were compared with conventional (splitless) GC-ICP-MS. The strength of this analytical method lies in the low detection limits reached for the simultaneous analysis of a wide group of organometallic compounds, and the potential to transfer this method to other gas chromatographic applications with inherent lower sensitivity., (Copyright © 2018 Elsevier B.V. All rights reserved.)

This paper proposes a simple, rapid and green ultrasound assisted and ionic liquid dispersive microextraction procedure using pyrocatechol violet (PV) as complexing reagent and 1-hexyl-3-methylimidazolium bis(trifluoromethylsulfonyl)-imide [C 6 MIM][Tf 2 N] as ionic liquid for the detection of tin employing electrothermal atomic absorption spectrometry (ETAAS). The optimization step was performed using a two-level full factorial design involving the following factors: pH of the working media, amount reagents, ionic liquid volume and extraction time and the chemometric response was tin recovery. The procedure allowed the determination of tin with limits of detection and quantification of 3.4 and 11.3 ng L -1 , respectively. The relative standard deviation was 4.5% for a tin solution of 0.50 µg L -1 . The validation method was confirmed by analysis of rice flour certified reference material. The method was applied for the quantification of tin in several food samples. The concentration range found varied from 0.10 to 1.50 µg g -1 ., (Copyright © 2017 Elsevier Ltd. All rights reserved.)

Clinoptilolite nano-particles (CNP) were modified by hexadecyltrimethyl ammonium bromide surfactant (HDTMA) and dithizone (DZ). The modified zeolite was then used for the modification of carbon paste electrode (CPE). The resulted CNP-HDTMA-DZ-CPE was finally used for the voltammetric determination of Sn(II) in aqueous solution. The raw and modified CNP was characterized by SEM-EDX, BET, TG-DTG and FTIR techniques. The best voltammetric response was obtained in 0.1molL -1 NaNO 3 +HCl at pH 2.2 as supporting electrolyte. The electrode showed a linear response in the concentration range of 1×10 -8 to 1×10 -2 molL -1 Sn(II) with LOD about 9×10 -9 molL -1 Sn(II). The electrode showed good selectivity and applicability for the determination of Sn(II) in real samples such as river water, an steel company wastewater, tomato paste and a canned tuna fish., (Copyright © 2017 Elsevier Inc. All rights reserved.)

A microwave-induced plasma optical emission spectrometer with N 2 -based plasma was combined with a multimode sample introduction system (MSIS) for hydride generation (HG) and multielemental determination of As, Bi, Ge, Sb, and Sn in samples of forage, bovine liver, powdered milk, agricultural gypsum, rice, and mineral fertilizer, using a single condition of prereduction and reduction. The accuracy of the developed analytical method was evaluated using certified reference materials of water and mineral fertilizer, and recoveries ranged from 95 to 106%. Addition and recovery experiments were carried out, and the recoveries varied from 85 to 117% for all samples evaluated. The limits of detection for As, Bi, Ge, Sb, and Sn were 0.46, 0.09, 0.19, 0.46, and 5.2 μg/L, respectively, for liquid samples, and 0.18, 0.04, 0.08, 0.19, and 2.1 mg/kg, respectively, for solid samples. The method proposed offers a simple, fast, multielemental, and robust alternative for successful determination of all five analytes in agricultural samples with low operational cost without compromising analytical performance.

Effects caused in ecotoxicity tests by physical factors due to precipitated particles cannot be used for classification in Europe under the Registration, Evaluation, Authorisation and Restriction of Chemicals (REACH). For tin (Sn), results from ecotoxicity tests have been observed to be difficult to interpret in regard to exposures of dissolved Sn. Experiments were undertaken with Sn(IV) chloride at 2-2000 µg L -1 in aquatic test media of differing pHs and hardness. A predictive Sn precipitation model was derived using these data and speciation modelling. Previous ecotoxicity tests assessed with the model indicated that organisms were exposed to Sn precipitates. It was therefore not possible to establish the dissolved Sn doses in the tests, invalidating the results for use in risk assessment. Developing an understanding of the speciation and precipitation behaviour of trace elements should be considered a priority before conducting ecotoxicity testing.

This study investigates the geochemical characteristics of recent shallow-water aragonite-rich sediments from the karstic marine lakes located in the pristine environment on the island of Mljet (Adriatic Sea). Different trace elements were used as authigenic mineral formation, palaeoredox and pollution indicators. The distribution and the historical record of trace elements deposition mostly depended on the sedimentological processes associated with the formation of aragonite, early diagenetic processes governed by the prevailing physico-chemical conditions and on the recent anthropogenic activity. This study demonstrated that Sr could be used as a proxy indicating authigenic formation of aragonite in a marine carbonate sedimentological environment. Distribution of the redox sensitive elements Mo, Tl, U and Cd was used to identify changes in redox conditions in the investigated lake system and to determine the geochemical cycle of these elements through environmental changes over the last 100 years. The significant enrichment of these elements and the presence of early formed nanostructured authigenic framboidal pyrite in laminated deeper parts of sediment in Malo Jezero, indicate sporadic events of oxygen-depleted euxinic conditions in the recent past. Concentrations of trace elements were in the range characteristic for non-contaminated marine carbonates. However, the increase in the concentrations of Zn, Cu, Pb, Sn, Bi in the upper-most sediment strata of Veliko Jezero indicates a low level of trace element pollution, resulting from anthropogenic inputs over the last 40 years. The presence of butyltin compounds (BuTs) in the surface sediment of Veliko Jezero additionally indicates the anthropogenic influence in the recent past., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

The objective of the study was to investigate hair trace elements content in children suffering from autism spectrum disorder (ASD). A total of 74 ASD children and 74 sex- and age-matched controls divided into two age groups (2-4 and 5-9 years) were investigated. Hair trace elements content was assessed using inductively coupled plasma mass spectrometry. A general cohort of ASD children was characterized by 29 %, 41 %, and 24 % lower hair levels of chromium (Cr), iodine (I), and vanadium (V), respectively, whereas the level of selenium (Se) exceeded the respective control values by 31 %. In ASD children aged 2-4 years hair Cr, I and V content was 68 %, 36 % and 41 % lower than in the controls. Older ASD children were characterized by 45 % increase in hair Se levels. In a general cohort of ASD children hair beryllium (Be) and tin (Sn) levels were 50 % and 34 % lower than the control values. In the first age group (2-4 years) of ASD children 34 %, 42 %, and 73 % lower levels of arsenic (As), boron (B), and Be were detected. In the second age group of ASD children only a nearly significant 25 % decrease in hair lead (Pb) was detected. Surprisingly, no significant group difference in hair mercury (Hg), zinc (Zn), and copper (Cu) content was detected. Generally, the results of the present study demonstrate that children with ASD are characterized by lower values in hair of not only essential but also toxic trace elements.

Despite their ban on small vessels in 1989 in the EU, organotin compounds (OTCs) are still being released into the environment due to their presence in historic paint layers on leisure boats. 23 paint samples scraped from recreational boats from three countries around the Baltic Sea were analyzed for total tin (Sn) and OTCs. Two antifouling paint products were also subjected to the same analyses. A new method for the detection of Sn in paint flake samples was developed and found to yield more accurate results compared to four different acid digestion methods. A new method was also developed for the extraction of OTCs from ground paint flakes. This endeavor revealed that existing methods for organotin analysis of sediment may not have full recoveries of OTCs if paint flakes are present in the sample. The hull paint samples had Sn concentrations ranging from 25 to 18,000 mg/kg paint and results showed that tributyltin (TBT) was detected in all samples with concentrations as high as 4.7 g (as Sn)/kg paint. TBT was however not always the major OTC. Triphenyltin (TPhT) was abundant in many samples, especially in those originating from Finland. Several other compounds such as monobutyltin (MBT), dibutyltin (DBT), tetrabutyltin (TeBT), monophenyltin (MPhT) and diphenyltin (DPhT) were also detected. These could be the result of degradation occurring on the hull or of impurities in the paint products as they were also identified in the two analyzed paint products. A linear correlation (r 2  = 0.934) was found between the total tin content and the sum of all detected OTCs. The detection of tin can therefore be used to indicate the presence of OTCs on leisure boats., (Copyright © 2016 The Authors. Published by Elsevier Ltd.. All rights reserved.)

A study was carried out to determine the level of rare earth elements (REEs) in water and sediment samples from ex-mining lakes and River in Kinta Valley, Perak, Malaysia. Surface water and sediments from an ex-mining lake and Kinta River water samples were analyzed for REEs by inductively coupled plasma mass spectrometry. The total concentration of REEs in the ex-mining lake water samples and sediments were found to be 3685 mg/l and 14159 mg/kg, respectively, while the total concentration of REEs in Kinta River water sample was found to be 1224 mg/l. REEs in mining lake water were found to be within 2.42 mg/l (Tb) to 46.50 mg/l (Ce), while for the Kinta River, it was 1.33 mg/l (Ho) to 29.95 mg/l (Ce). Sediment samples were also found with REEs from 9.81 mg/kg (Ho) to 765.84 mg/kg (Ce). Ce showed the highest average concentrations for mining lake (3.88 to 49.08 mg/l) and Kinta River (4.44 to 33.15 mg/l) water samples, while the concentration of La was the highest (11.59 to 771.61 mg/kg) in the mining lake sediment. Lu was shown to have the highest enrichment of REEs in ex-mining lake sediments (107.3). Multivariate statistical analyses such as factor analysis and principal component analysis indicated that REEs were associated and controlled by mixed origin, with similar contributions from anthropogenic and geogenic sources. The speciation study of REEs in ex-tin mining sediments using a modified five-stage sequential extraction procedure indicated that yttrium (Y), gadolinium (Gd), and lanthanum (La) were obtained at higher percentages from the adsorbed/exchanged/carbonate fraction. The average potential mobility of the REEs was arranged in a descending order: Yb > Gd > Y = Dy > Pr > Er > Tm > Eu > Nd > Tb > Sc > Lu > Ce > La, implying that under favorable conditions, these REEs could be released and subsequently pollute the environment.

Chitosan (CS) of low molecular weight is prepared using γ-irradiation method in presence of H 2 O 2 as oxidizing agent. The chemical treatment of folic acid (FA) with low molecular weight CS is carried out to prepare FACS complex based on the reaction between NH 2 group of CS and γ-COOH group of FA. The structure and properties of FACS complex was characterized by FT-IR, 1 H NMR, UV, SEM, TEM, DLS and XRD analyses. TEM and DLS results showed that FACS complex has nanostructure and the mean size of particles was unimodal with average diameters in the range of 165-252nm. Radiolabeling of FACS complex ( 99m Tc-FACS) was done with Technetium-99m ( 99m Tc). The optimum conditions of labeling were investigated. The labeling yield was 85% at pH=6 and 30min reaction time. The effect of time on the stability of 99m Tc-FACS complex was studied and the results revealed that it is stable up to 6h after labeling. Biodistribution studies of 99m Tc-FACS complex in Quail showed that it distributed to different organs mainly in blood, liver and kidney. The results revealed that the uptake of 99m Tc-FACS in the sexual organs (ovary and ovarian) of female Quail was higher than that in the sexual organs (testes) of male Quail, so 99m Tc-FACS could be used to differentiate between them. It also showed that FACS is consumed and more essential in female than that in male., (Copyright © 2016 Elsevier B.V. All rights reserved.)