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Background: Titanium dioxide (TiO 2 ), a white powder, represents the opacifier used in many products, including drugs, foods, cosmetics, paints, and dyes., Method: The Uv-Vis spectrophotometry was a particularly suitable technique to quantify TiO 2 in the solutions obtained from cosmetics. In this work, we determined the TiO 2 content in a total of 88 samples of eye shadows and face powders of different brands and costs. Before to analyse the samples, we developed the mineralization and analysis method, in fact, fusion with potassium bisulphate would be very laborious because it must be carried out on one sample at a time and requires very long times, instead, the mineralization with the acid mixture and the aid of microwaves allowed us to solubilize six samples at the same time within 45 min., Results: From the results obtained, we can state that the highest concentrations of TiO 2 are found in the eyeshadows with a maximum value of 36% in a blue eyeshadow., (© 2024 The Author(s). Journal of Cosmetic Dermatology published by Wiley Periodicals LLC.)

Heavy mineral deposits occur in several coastal areas of the world, formed over a long period due to variations in mean sea level, wave action, and winds. These are the main sources of ilmenite (FeTiO3), which in turn is the source of more than 80% of the TiO2 produced and applied in various industries, most recently in nanotechnology. The present study mapped heavy mineral deposits on the coast of Rio Grande do Sul in southern Brazil using integrated proximal and orbital thermal infrared (TIR) remote sensing techniques. Mineral groups, such as oxides and silicates, have spectral features in the TIR wavelengths. Using laboratory spectroscopy at TIR using Nicolet 6700 Thermo Scientific Spectrometer, we measured the spectral signature of the local sample of heavy minerals (between 8 and 14 μm) and identified a diagnostic spectral feature at 10.75 μm. The signature was resampled to be compatible with the Advanced Spaceborne Thermal Emission Radiometer (ASTER) sensor bandwidth values and used as a reference endmember for the Spectral Angle Mapper (SAM) and Linear Spectral Unmixing (LSU) digital image classification algorithms. Thus, we identified the presence of the reference endmember (heavy minerals) in the pixels of the ASTER scene. In pixels classified by SAM as the presence of heavy minerals, LSU was applied to estimate the surface concentration within the pixel. The results showed a concentration of up to 20% of heavy minerals, with the highest concentration on the beach and dune fields. Opaque minerals such as ilmenite do not have spectral reflectance features in visible, near-infrared, and short-wave infrared, which makes their identification by remote sensing difficult. The present study showed that the integration of proximal and orbital as well as hyperspectral and multispectral thermal data can be considered as an alternative for detecting and mapping heavy minerals in coastal areas., Competing Interests: The authors declare no competing interests., (Copyright: © 2024 Prates Hallal et al. This is an open access article distributed under the terms of the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original author and source are credited.)

This study addressed primarily the characterisation and quantification of titanium dioxide (TiO 2 ) (nano)particles (NPs) in a large variety of commercial foodstuffs. The samples were purchased from local markets in Spain before the ban of TiO 2 food additive (E171) in the EU. The analyses were carried out by single particle inductively coupled plasma-tandem mass spectrometry (spICP-MS/MS) in mass shift mode (oxidation of 48 Ti to 48 Ti 16 O ( m/z  = 64)) and using a highly efficient sample introduction system (APEX™ Ω). This novel analytical approach allowed accurate characterisation of a large panel of TiO 2 NPs sizes ranging from ∼12 to ∼800 nm without isobaric interferences from 48 Ca isotope, which is highly abundant in most of the analysed foodstuffs. TiO 2 NPs were extracted from foodstuffs using sodium dodecyl sulphate (0.1%, w/v ) and diluted with ultra-pure water to reach ∼ 1000 particles signals per acquisition. All the analysed samples contained TiO 2 NPs with concentrations ranging from 10 10 to 10 14 particles kg -1 , but with significant low recoveries compared to the total Ti determination. A selection of samples was also analysed using a similar spICP-MS/MS approach with a conventional sample introduction system. The comparison of results highlighted the improvement of the limit of detection in size (12 nm) by the APEX™ Ω system, providing nanoparticulate fractions ranging from ∼4% (cheddar sauce) up to ∼87% (chewing gum), which is among the highest nanoparticulate fractions reported in literature using a spICP-MS approach. In addition, two commercially available E171 additives were analysed using the previous approaches and other techniques in different European laboratories with the aim of methods inter-comparison. This study provides occurrence data related to TiO 2 NPs in common commercial foodstuffs but it also demonstrates the potential of the novel analytical approach based on APEX™-ICP-MS/MS to characterise nano-size TiO 2 particles in complex matrices such as foodstuffs.

Background: Determining the concentration of nanoparticles (NPs) in marine organisms is important for evaluating their environmental impact and to assess potential food safety risks to human health., Objective: The current work aimed at developing an in-house method based on single-particle inductively coupled plasma-mass spectrometry (SP-ICP-MS) suitable for surveillance of NPs in mussels., Methods: A new low-cost and simple protease mixture was utilized for sample digestion, and novel open-source data processing was used, establishing detection limits on a statistical basis using false-positive and false-negative probabilities. The method was validated for 30 and 60 nm gold NPs spiked to mussels as a proxy for seafood., Results: Recoveries were 76-77% for particle mass concentration and 94-101% for particle number concentration. Intermediate precision was 8-9% for particle mass concentration and 7-8% for particle number concentration. The detection limit for size was 18 nm, for concentration 1.7 ng/g, and 4.2 × 105 particles/g mussel tissue., Conclusion: The performance characteristics of the method were satisfactory compared with numeric Codex criteria. Further, the method was applied to titanium-, chromium- and copper-based particles in mussels., Highlights: The method demonstrates a new practical and cost-effective sample treatment, and streamlined, transparent, and reproducible data treatment for the routine surveillance of NPs in mussels., (© The Author(s) 2024. Published by Oxford University Press on behalf of AOAC INTERNATIONAL.)

Engineered Nanomaterials (ENMs) or products containing ENMs, known as nano-enabled products are commercialized globally by a large number of companies. Concern about the potential risks and negative impacts of releasing ENMs into the environment is under investigation. For this reason, methodologies to estimate the probable mass concentrations of ENMs released in different regions of the world have been developed. As a first attempt to estimate the probable mass flows of nanosized titanium dioxide (nano-TiO 2 ) released in Mexico, we developed a Probabilistic Material Flow Analysis (PMFA) for 2015. The model describes probabilistic mass flows of released nano-TiO 2 during the life cycle of sunscreens, coatings, ceramic, and other nano-enabled products, including the flows through the solid waste and wastewater management systems, as well as the transfer of nano-TiO 2 to three environmental compartments (atmosphere, topsoil, and surface water). The PMFA incorporates the uncertainty related to the input data. We observed that the most significant nano-TiO 2 flows occur to the surface water, landfill, and soil compartments, targeted as the main "hot-spots", where living organisms could be more exposed to this material. Further improvements in the model are needed due to some data gaps at some life cycle stages, for instance, solid waste management and reused wastewater manipulation for irrigation purposes. Finally, the model developed in this study can be adjusted to assess other ENM releases and can be beneficial for further investigation in fate modeling and environmental risk assessment., Competing Interests: Declaration of competing interest The authors declare no competing interests., (Copyright © 2024 The Authors. Published by Elsevier B.V. All rights reserved.)

A multimodal approach combining inductively coupled plasma mass spectrometry (ICP-MS), single-particle ICP-MS (spICP-MS), scanning electron microscopy-energy-dispersive X-ray spectroscopy (SEM-EDS) and Raman spectroscopy enabled a deeper insight into the balance between total titanium (Ti), the soluble titanium fraction and titanium dioxide based particle fraction levels in periprosthetic tissues collected from patients undergoing revision surgery. Hydrofluoric acid usage in the sample digestion allowed for complete digestion of TiO 2 particles, thus enabling accurate estimation of total Ti levels. The TiO 2 fraction represents 38-94% of the titanium load in the six samples where particles were detected, and the fraction is present mainly in samples from patients with aseptically loosened total hip arthroplasty. Further attention was given to this fraction determining the elemental composition, particle count, particle size and modification of TiO 2 . The spICP-MS analysis confirmed the presence of the TiO 2 -derived (nano)particles (NPs) with a 39- to 187-nm median size and particle count up to 2.3 × 10 11 particles per gram of tissue. On top of that, the SEM-EDS confirmed the presence of the TiO 2 nanoparticles with 230-nm median size and an anatase crystal phase was determined by Raman spectroscopy. This study presents a novel multimodal approach for TiO 2 particle determination and characterization in tissue samples and is the first in vivo study of this character., (© 2024. The Author(s).)

Titanium dioxide (TiO 2 ) is an important industrial chemical, and studies suggest its major production route - the chloride process could lead to the generation of unintentional dl-POPs. However, no relevant studies assessed the occurrence of dl-POPs associated with TiO 2 production in the industrial zones, which is mostly due to the ultra-trace level distribution of these compounds in environmental compartments. The present study explored the novel possibility of utilising foraging animal-origin foods as sensitive indicators for addressing this challenge and generated a globally beneficial dataset by assessing the background levels of dl-POPs in the vicinity of a TiO 2 production house in Southern India. Systematic sampling of foraging cow's milk and free-ranging hen's eggs was carried out from the study site, and the dl-POPs assessments were conducted utilising an in-house developed cost-effective GC-MS/MS-based analytical methodology. The median dl-POPs levels in milk and egg samples were about 3 times higher than the control samples collected from farm-fed animals and retail markets. The contaminant loads in the foraging animal-origin food samples were further traced to their presence in environmental compartments of soil and sediment and admissible degree of correlations were observed in congener fingerprints. Elevated health risks were inferred for the population in the industrial zones with weekly intakes weighing about 0.15-17 times the European Food Safety Authority-assigned levels. The consumption of foraging cow's milk was observed to have a higher contribution towards the hazard indices and cancer risk estimates and were significantly higher (p < 0.05) for children. The study also presents a critical validation of the GC-MS/MS-based method for the purpose of regulatory monitoring of dl-POPs, which could be of practical significance in economies in transition., 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.)

TiO 2 is the most widely used white pigment in plastics and food packaging industry, thus the question of its migration towards food and hence the impact on consumers is raised. Since recent research indicate its potential toxicity, it is necessary to study TiO 2 contamination as a consequence of food storage. For this purpose, plastic containers from commercially-available dairy products and custom-made TiO 2 -spiked polypropylene materials were put in contact with 50% (v/v) ethanol and 3% (w/v) acetic acid, which were used here as food simulants. The migration assays were carried out under standard contact conditions of packaging use (as recommended by Commission Regulation (EU) N° 10/2011 for food contact migration testing), and under conditions of extreme mechanical degradation of the packaging. The TiO 2 (nano)particles released in the food simulants were analysed by single particle inductively coupled plasma-tandem mass spectrometry in mass-shift mode and using a high efficiency sample introduction system (APEX™ Ω) to avoid matrix effects from food simulants. For the dairy product containers and for the spiked polypropylene, results showed release of TiO 2 particles of rather large sizes (average size: 164 and 175 nm, respectively) under mechanical degradation conditions, i.e. when the polymeric structure is damaged. The highest amounts of TiO 2 were observed in 50% ethanol after 10 days of storage at 50 °C (0.62 ng cm -2 ) for the dairy product containers and after 1 day of storage at 50 °C (0.68 ng cm -2 ) for the spiked polypropylene. However, the level of Ti released in particle form was very small compared to the total Ti content in the packaging and far below the acceptable migration limits set by European legislation. Release under standard contact conditions of use of the container was not measurable, thus the migration of TiO 2 particles from this packaging to dairy products among storage is expected to be negligible., 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 B.V. All rights reserved.)

Chromium (Cr) toxicity can negatively affect plant growth and development, impacting agricultural productivity and posing risks to human health. Metallic nanoparticles (MNPs) such as titanium dioxide (TiO 2 ) and natural growth regulators such as melatonin (MT) become a promising technology to manage heavy metal-contaminated soils and promote safe food production. The present work was conducted to find the effect of foliar application of TiO 2 NPs (15 mg L -1 ) and MT (100 µM) on growth, biochemical attributes, and Cr accumulation in plant tissues of Melissa officinalis L. under Cr toxicity (50 and 100 mg Cr kg -1 soil). The results showed that Cr toxicity led to decreased plant performance, where 100 mg Cr kg -1 soil led to notable decreases in shoot weight (28%), root weight (27%), essential oil (EO) yield (34%), chlorophyll (Chl) a + b (33%), while increased malondialdehyde (MDA, 30%), superoxide dismutase (SOD) activity (51%), and catalase (CAT) activity (122%). The use of TiO 2 NPs and MT, particularly their co-application, remarkably reduced Cr toxicity by enhancing plant weight, Chl content, and lowered MDA and antioxidant activity. Total phenolic content (TPC), total flavonoid content (TFC), EO percentage, and rosmarinic acid in plants treated with Cr at 50 mg Cr kg -1 soil and co-application of TiO 2 NPs and MT were relatively higher than in other treatments. Under 100 mg Cr kg -1 soil, the synergic effect of TiO 2 NPs and MT-enhanced rosmarinic acid content (22%) but lowered Cr accumulation in roots (51%) and shoots (72%). Heat map analysis showed that CAT, SOD, MDA, and EO yield had the maximum variability under Cr, TiO 2 NPs, and MT. Exogenous TiO 2 NPs and MT can be recommended to modulate Cr toxicity in lemon balm under soil Cr toxicity., (© 2024. The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature.)

Trace metals are naturally occurring metals found in very small concentrations in the environment. In the context of fish flesh, metals such as copper, calcium, potassium, sodium, zinc, iron, and manganese are absorbed by fish and play vital roles in various physiological functions. However, if these metals exceed the recommended limits set by WHO/FAO, they are termed 'toxic metals' due to their harmful impacts on both the fish and its consumers. Therefore, the present study aims to analyze the levels of protein, lipids, and certain metals-Aluminum (Al), Sodium (Na), Zinc (Zn), Titanium (Ti), Iron (Fe), Copper (Cu), Potassium (K), and Calcium (Ca) in three commercially important marine fishes i.e. Rastrelliger kanagurta, Sardinella abella, and Otolithes ruber. The study also aims to assess their potential impact on human health. The macro-Kjeldhal method and Soxhlet apparatus were used to estimate protein and lipid contents, while atomic absorption spectroscopy (AAS) was used to estimate trace metals found in fishes. The study found that these fish species are valuable sources of protein, lipids, and certain essential minerals. The protein content (CP) in these three species ranged from 63.35 to 86.57%, while lipid content was from 21.05 to 23.86%. The overall results of the trace metal concentrations analyzed in the present study revealed that Aluminum (Al), Sodium (Na), Zinc (Zn), Titanium (Ti), Copper (Cu), Potassium (K), and Calcium (Ca) were found in low concentration or traces and also within suitable ranges as set by WHO/FAO. However, Iron (Fe) was absent in all three species. Moreover, both copper and potassium were found in all three species, while Zinc was present in Rastrelliger kanagurta and Sardinella abella, calcium in Sardinella abella, and sodium in Otolithes ruber only. Titanium was recorded for the first time in S. abella. However, the total health risk assessment associated with these fish food consumption was measured by THQ and TTHQ and found to be less than 1, which shows no potential risk related to trace metals found in these fishes on human health upon their consumption. In conclusion, these commercially important marine fish species were found valuable sources of protein, lipids, and essential trace minerals that are necessary for human health. Thus, the current study provides useful information for the local population to make informed decisions about their daily diets and highlights the importance of sustainable fishing practices to maintain these valuable marine resources by periodical monitoring of their ecosystem., (© 2024. The Author(s).)

Wearable, noninvasive sensors enable the continuous monitoring of metabolites in sweat and provide clinical information related to an individual ' s health and disease states. Uric acid (UA) is a key indicator highly associated with gout, hyperuricaemia, hypertension, kidney disease, and Lesch-Nyhan syndrome. However, the detection of UA levels typically relies on invasive blood tests. Therefore, developing a wearable device for noninvasive monitoring of UA concentrations in sweat could facilitate real-time personalized disease prevention. Here, we introduce 1,3,6,8-pyrene tetrasulfonic acid sodium salt (PyTS) as a bifunctional molecule functionalized with Ti 3 C 2 T x via π-π conjugation to design nonenzymatic wearable sensors for sensitive and selective detection of UA concentration in human sweat. PyTS@Ti 3 C 2 T x provides many oxidation-reduction active groups to enhance the electrocatalytic ability of the UA oxidation reaction. The PyTS@Ti 3 C 2 T x -based electrochemical sensor demonstrates highly sensitive detection of UA in the concentration range of 5 μM-100 μM, exhibiting a lower detection limit of 0.48 μM compared to the uricase-based sensor (0.84 μM). In volunteers, the PyTS@Ti 3 C 2 T x -based wearable sensor is integrated with flexible microfluidic sweat sampling and wireless electronics to enable real-time monitoring of UA levels during aerobic exercise. Simultaneously, it allows for comparison of blood UA levels via a commercial UA analyzer. Herein, this study provides a promising electrocatalyst strategy for nonenzymatic electrochemical UA sensor, enabling noninvasive real-time monitoring of UA levels in human sweat and personalized disease prevention.

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.

Exosomes, a growing focus for liquid biopsies, contain diverse molecular cargos. In particular, exosome metabolites with valuable information have exhibited great potential for improving the efficiency of liquid biopsies for addressing complex medical conditions. In this work, we design the directional growth of Ti-metal-organic frameworks on polar-functionalized magnetic particles. This design facilitates the rapid synergistic capture of exosomes with the assistance of an external magnetic field and additionally synergistically enhances the ionization of their metabolites during mass spectrometry detection. Benefiting from this dual synergistic effect, we identified three high-performance exosome metabolites through the differential comparison of a large number of serum samples from individuals with Alzheimer's disease (AD) and normal cognition. Notably, the accuracy of AD identification ranges from 93.18 to 100% using a single exosome metabolite and reaches a flawless 100% with three metabolites. These findings emphasize the transformative potential of this work to enhance the precision and reliability of AD diagnosis, ushering in a new era of improved diagnostic accuracy.

Micro and nanoplastics (MNPLs) are emergent environmental pollutants, resulting from the degradation of plastic waste, requiring urgent information on their potential risks to human health. To determine such risks, reliable true-to-life materials are essential. In this work, we have used titanium-doped PET NPLs [PET(Ti)NPLs], obtained by grinding opaque milk polyethylene terephthalate (PET) bottles, as a true-to-life MNPLs model. These opaque PET bottles, with an average size of 112 nm, contain about 3% Ti in the form of titanium dioxide rod nanoparticles. TEM investigation confirmed the mixed Ti/PET nature of the obtained true-to-life NPLs, and the rod shape of the embedded TiO 2 NPs. In the in vivo Drosophila model neither PET(Ti)NPLs nor TiO 2 NPs reduced the survival rates, although their internalization was confirmed in different compartments of the larval body by using confocal and transmission electron microscopies. The presence of Ti in the PET(Ti)NPLs permitted to quantify its presence both in larvae (2.1 ± 2.2 μg/g of Ti) and in the resulting adults (3.4 ± 3.2 μg/g of Ti) after treatment with 500 μg/g food of PET(Ti)NPL, suggesting its potential use to track their fate in more complex organisms such as mammals. PET(Ti)NPLs, as well as TiO 2 NPs, altered the expression of genes driving different response pathways, inducing significant oxidative stress levels (up to 10 folds), and genotoxicity. This last result on the genotoxic effects is remarkable in the frame of the hot topic discussion on the risk that titanium compounds, used as food additives, may pose to humans., 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 Ltd.. All rights reserved.)

Improving the kinetics rate and mass transfer is essential for expanding the potential of electrochemical technologies in wastewater treatment. The electrochemical flow-through configuration promises a high oxidation efficiency and low energy consumption. We aimed to provide a thorough understanding of the enhanced kinetics, mass transfer, and thermodynamic parameters during the degradation of amoxicillin (AMX) in a multi-stage flow-through (MSFT) system using porous Ti-ENTA/SnO 2 -Sb anodes. All operating conditions strongly influenced the kinetics of AMX degradation and followed pseudo-first-order rate kinetic model (R 2  > 0.85), with the highest k obs of 0.228 min -1  at high temperature (318 K). In comparison to the flow-by mode, the AMX removal rate in the three-stage flow-through mode was greatly enhanced by 70%, exhibiting the superior capacity of a porous anode. This system exhibited outstanding performance regarding the high kinetics rate and mass transfer rate (k m ), which increased by factors of 3.46 and 10.74, respectively, obtained in the flow-by mode. It also revealed that •OH generation was 5.64 times higher, and the EE/O was 19.89-fold lower than those in flow-by mode. Temperature plays a vital role in the reaction process, and thermodynamic features found the positive enthalpy (ΔH o ) of +27.06 kJ mol -1 , signifying the process was endothermic. A Hatta number (Ha) of >0.02 at all temperatures proved this finding, confirming an undeniable role in mass transfer. Finally, these findings reveal the system's performance and offer the possibility of establishing a multi-stage flow-through for wastewater treatment., Competing Interests: Declaration of competing interest The authors declare no competing financial interests or personal relationships that could have influenced the work reported in this study., (Copyright © 2023 Elsevier Ltd. All rights reserved.)

Titanium dioxide is a food additive commonly used as a white food coloring (E171). Its wide use by the food industry associated with the nanometric size distribution of the particles of this pigment has shown high genotoxicity associated with recurrent exposure by ingestion. Therefore, the use of E171 in food products has already been banned by some industries and in the European Union. Such banishment should soon be extended to other countries around the world, making it important to establish techniques for the efficient determination of TiO 2 in different food products. The association between hyperspectral images and chemometric tools can be useful in this sense, aiming to enable the use of a single method for sample preparation and analysis of different types of food. Thus, the present work aims to evaluate the use of Raman mapping associated with the resolution of multivariate curves with alternating least squares (MCR-ALS) for the determination of titanium dioxide in solid food samples with different compositions, without the need to introduce specific sample preparation. The proposed method allowed for the first-time quantification of TiO 2 in different food matrices without specific sample preparation, with a simple, rapid, accurate (93% of recovery), low detection limits (0.0111% m/m) and quantification (0.0370% m/m) and adequate linearity (r = 0.9990) and precise (standard deviation around 0.020-0.030% w/w) methodology. Such results highlight the potential use of Raman mapping associated with the MCR-ALS for quantification of the nano-TiO 2 in commercial samples., (© 2023. The Author(s), under exclusive licence to Springer-Verlag GmbH, DE part of Springer Nature.)

Titanium dioxide (TiO 2 ), an E171 manufacturer-made food additive, is extensively utilised as a colourant in drug and a food products. Some studies showed that most of confectionary and food items contain inexplicable particles. The aim of this article is to determine the size and structure of TiO 2 nanoparticles in different food products. Ten food samples, including coffee cream, white chocolate concentrate, frosting, gum, yoghurt candy, hard candies and chewy candies, were investigated for this purpose. The crystalline structure and particle size of TiO 2 were determined by Powder X-ray Diffraction (PXRD) and Transmission Electron Microscopy (TEM). TEM images revealed that a few of the extracted nanoparticles had a rod-like shape, but most were spherical. Also, the size of the TiO 2 particle had a wide distribution between 12 and 450 nm. Thus, to avoid human health risk, crucial factors such as size, and shape should be considered and regulated by food authorities.

Vanadium-titanium (V-Ti) magnetite tailings contain toxic metals that could potentially pollute the surrounding environment. However, the impact of beneficiation agents, an integral part of mining activities, on the dynamics of V and the microbial community composition in tailings remains unclear. To fill this knowledge gap, we compared the physicochemical properties and microbial community structure of V-Ti magnetite tailings under different environmental conditions, including illumination, temperature, and residual beneficiation agents (salicylhydroxamic acid, sodium isobutyl xanthate, and benzyl arsonic acid) during a 28-day reaction. The results revealed that beneficiation agents exacerbated the acidification of the tailings and the release of V, among which benzyl arsonic acid had the greatest impact. The concentration of soluble V in the leachate of tailings with benzyl arsonic acid was 6.4 times higher than that with deionized water. Moreover, illumination, high temperatures, and beneficiation agents contributed to the reduction of V in V-containing tailings. High-throughput sequencing revealed that Thiobacillus and Limnohabitans adapted to the tailings environment. Proteobacteria was the most diverse phylum, and the relative abundance was 85.0%-99.1%. Desulfovibrio, Thiobacillus, and Limnohabitans survived in the V-Ti magnetite tailings with residual beneficiation agents. These microorganisms could contribute to the development of bioremediation technologies. The main factors affecting the diversity and composition of bacteria in the tailings were Fe, Mn, V, SO 4 2- , total nitrogen, and pH of the tailings. Illumination inhibited microbial community abundance, while the high temperature (39.5 °C) stimulated microbial community abundance. Overall, this study strengthens the understanding of the geochemical cycling of V in tailings influenced by residual beneficiation agents and the application of inherent microbial techniques in the remediation of tailing-affected 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 © 2023 Elsevier Ltd. All rights reserved.)

Titanium dental implants are one of the modalities to replace missing teeth. The release of titanium particles from the implant's surface may modulate the immune cells, resulting in implant failure. However, little is known about the immune microenvironment that plays a role in peri-implant inflammation as a consequence of titanium particles. In this study, the peri-implant gingival tissues were collected from patients with failed implants, successful implants and no implants, and then a whole transcriptome analysis was performed. The gene set enrichment analysis confirmed that macrophage M1/M2 polarization and lymphocyte proliferation were differentially expressed between the study groups. The functional clustering and pathway analysis of the differentially expressed genes between the failed implants and successful implants versus no implants revealed that the immune response pathways were the most common in both comparisons, implying the critical role of infiltrating immune cells in the peri-implant tissues. The H&E and IHC staining confirmed the presence of titanium particles and immune cells in the tissue samples, with an increase in the infiltration of lymphocytes and macrophages in the failed implant samples. The in vitro validation showed a significant increase in the level of IL-1β, IL-8 and IL-18 expression by macrophages. Our findings showed evidence that titanium particles modulate lymphocyte and macrophage polarization in peri-implant gingival tissues, which can help in the understanding of the imbalance in osteoblast-osteoclast activity and failure of dental implant osseointegration.

Background: This work studies the presence of the Ti, Al and V metal ions and Ti nanoparticles released from the debris produced by the implantoplasty, a surgical procedure used in the clinic, in rat organs., Methods: The sample preparation for total Ti determination was carefully optimized using microsampling inserts to minimize the dilution during the acid attack of the lyophilized tissues by a microwave-assisted acid digestion method. An enzymatic digestion method was optimized and applied to the different tissue samples in order to extract the titanium nanoparticles for the single-particle ICP-MS analysis., Results: A statistically significant increase was found for Ti concentrations from control to experimental groups for several of the studied tissues, being and particularly significant in the case of brain and spleen. Al and V concentrations were detected in all tissues but they were not different when comparing control and experimental animals, except for V in brain. The possible presence of Ti-containing nanoparticles mobilized from the implantoplasty debris was tested using enzymatic digestions and SP-ICP-MS. The presence of Ti-containing nanoparticles was observed in all the analyzed tissues, however, differences on the Ti mass per particle were found between the blanks and the digested tissue and between control and experimental animals in some organs., Conclusion: The developed methodologies, both for ionic and nanoparticulated metal contents in rat organs, have shown the possible increase in the levels of Ti both as ions and nanoparticles in rats subjected to implantoplasty., 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 GmbH.. All rights reserved.)

Anthracene biodegradation potential has been studied in liquid culture and soil microcosm environment by employing green synthesized TiO 2 nanoparticles (NPs) and Alcaligenes faecalis HP8. The bacterium was isolated from crude oil contaminated soil, while TiO 2 nanoparticles were synthesized using Paenibacillus sp. HD1PAH and Cyperus brevifolius which have PAHs remediation abilities. The dual application of TiO 2 nanoparticles and Alcaligenes faecalis HP8 decreases anthracene concentration up to 21.3% in liquid at the end of 7 days and 37.9% in the soil treatments after completion of 30 days. Besides, the GC-MS analysis revealed production of five metabolites including 1,2-anthracenedihydrodiol; 6,7-benzocoumarin; 3-hydroxy-2-naphthoic acid; salicylic acid and 9,10-anthraquinone at different time interval of the treatments. Anthracene degradation pathway confirms the breakdown of three ring anthracene to one ring salicylic acid. Additionally, soil dehydrogenase, urease, alkaline phosphatase, catalase and amylase activities increased up to 4.09 folds, 8.6 folds, 4.4 folds, 3.6 folds and 2.1 folds respectively after the combined treatments of TiO 2 nanoparticles and Alcaligenes faecalis HP8. The bacterial biomass and residual anthracene concentration were found to be negatively correlated. Finally, the study brings into light a novel anthracene biodegradation pathway and provides a new dimension in nano assisted bacterial remediation., 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.)

Excessive phosphorus in water causes environmental security problems like eutrophication. Advanced two-dimensional material MXene has attracted raising attention in aquatic adsorption, while lack of selectivity and difficult recovery limit its application in phosphate removal. In this study, Ti 3 C 2 -MXene embedded zirconium-crosslinked SA (MX-ZrSA) beads were synthesized and their phosphate adsorption performance under different conditions was assessed. Investigations using SEM/EDS, XRD, BET, TGA and contact angle meter reveal that the addition of Ti 3 C 2 -MXene enhanced the thermal stability, mechanical strength, hydrophilicity, and formed loose network-like mesoporous inner structure with large surface area. The theoretical maximum adsorption capacity was 492.55 mg P/g and was well fitted by Freundlich and optimized Langmuir models. The Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy analysis showed that chemisorption was involved, and the formation of Zr-O-P and Ti-O-P complexes accounted for high selectivity and affinity to phosphate. The adsorption experiments in real waters and lab-scale continuous flow Anaerobic-Anoxic-Oxic reactor further indicated the application potential of MX-ZrSA beads. Our study will provide insight into MXene and SA aerogel synergistic adsorption of aquatic contaminants and help with the removal and recovery of finite phosphorus resource., Competing Interests: Declaration of competing interest The authors declare the following financial interests/personal relationships which may be considered as potential competing interests: Jun Nan has patent #202210394911.1 pending to China National Intellectual Property Administration., (Copyright © 2023 Elsevier Ltd. All rights reserved.)

The effect of glucose content on the electrochemical corrosion behavior of the Ti/ZrO 2 brazing joint in simulated body fluid (SBF) was researched by the means of SEM morphologies, electrochemical and XPS analyses. Herein, pitting is observed to be a dominating corrosion model under the investigated glucose content. The pitting corrosion of the joint in 200 mg/dL SBF is minimal. In addition, the joint in 200 mg/dL SBF manifests the best corrosion resistance by electrochemical analyses, which indicates that glucose content has a bidirectional effect on corrosion of the Ti/ZrO 2 brazing joint. Additionally, the corrosion current value and impedance of titanium and brazing joint are close, which indicates that their corrosion resistance is similar. Finally, the OH - , Cl - , Sn 2+ /Sn 4+ and -COOH on the joint surface are found by XPS analysis, and the mechanism of Ti/ZrO 2 brazing joint corrosion is elucidated. The study provides a novel understanding of the corrosion behavior and relevant corrosion mechanism of the Ti/ZrO 2 brazing joint in body fluids with different glucose content.

Background: Humans are exposed to exogenous sources of titanium-containing particles that can enter the body mainly by inhalation, ingestion, or dermal absorption. Given the widespread use of biomaterials in medicine, the surface of a titanium (Ti) biomedical device is a potential endogenous source of Ti ions and/or Ti-containing particles, such as TiO 2 micro-(MPs) and nano-particles (NPs), resulting from biotribocorrosion processes. Ti ions or Ti-containing particles may deposit in epithelial cells of the oral mucosa, and the latter may therefore serve as bioindicators of short and long-term systemic Ti contamination. The aim of the present study was to histologically and quantitatively evaluate the presence of Ti traces in cells exfoliated from the oral mucosa as possible bioindicators of systemic contamination with this metal at short and long-term experimental time points METHODS: Thirty Wistar rats were intraperitoneally injected with a suspension of titanium dioxide (TiO 2 ) (0.16 g/100 g body weight of TiO 2 in 5 ml of NaCl 0.9%) using 5 nm NPs (Group: TiO 2 -NP5; n = 10), 45 µm MPs (Group: TiO 2 -MP45; n = 10), or vehicle alone (Control group; n = 10). At one and six months post-injection, right-cheek mucosa cells were obtained by exfoliative cytology using a cytobrush; they were spray fixed and stained using Safranin or the Papanicolaou technique. The smears were cytologically evaluated (light microscopy) to determine the presence of particulate material, which was also analyzed microchemically (SEM-EDS). Left-cheek mucosa cells were similarly obtained and re-suspended in 5 ml of PBS (pH: 7.2-7.4); the samples corresponding to each group were pooled together and analyzed spectrometrically (ICP-MS) to determine Ti concentration in each of the studied groups. Blood samples were obtained for histological determination of the presence of particulate material on Safranin-stained blood smears and determination of plasma concentration of Ti by ICP-MS RESULTS: Different size and shape metal-like particles were observed inside and outside epithelial cells in TiO 2 -NP5 and TiO 2 -MP45 cytological smears at both one and six months post-injection. EDS analysis showed the presence of Ti in the particles. ICP-MS revealed higher Ti concentrations in both TiO 2 injected groups compared to the control group. In addition, Ti concentration did not vary with time or particle size. Monocytes containing particles were observed in blood smears of TiO 2 -exposed animals one- and six-months post-injection. Plasma levels of Ti were significantly higher in TiO 2 -NP5- and TiO 2 -MP45- exposed animals than in controls (p < 0.05), and Ti concentration was significantly higher at one month than at six months in both TiO 2 -exposed groups (p < 0.05)., Conclusions: Cells exfoliated from the oral mucosa could be used as bioindicators of short- and long-term systemic contamination with Ti. Exfoliative cytology could be used as a simple, non-invasive, and inexpensive diagnostic method for monitoring biotribocorrosion of Ti implants and patient clinical follow-up., 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 GmbH. All rights reserved.)

The development of effective electrochemical methods for the determination of pesticide residues is highly desirable for food safety requirements. Herein, a novel electrochemical sensing strategy for indirect detection of thiabendazole (TBZ) was achieved by monitoring the anodic stripping peak signal change of media Cu 2+ induced by a significant activity difference between active Cu 2+ and inactive Cu 2+ -TBZ complexes. In this sensing system, a heterostructured Ti 3 C 2 T x -TiO 2 composite synthesized via a simple in-situ-oxidization strategy is used as the electrode material to boost the anodic stripping peak signal. After optimizing various conditions, the developed sensor presents satisfactory analytical performance for TBZ assay with a linear range from 0.3 to 100.0 nM and a limit of detection as low as 0.1 nM (S/N = 3). Furthermore, the proposed sensing platform also exhibits outstanding anti-interference, repeatability, and stability, which is effective for the determination of TBZ in fruit and water samples., 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 role of metallic nano- and microparticles in the development of inflammation has not yet been investigated. Soft tissue biopsy specimens of the bone bed taken during surgical revisions, as well as supernatants obtained from the surface of the orthopedic structures and dental implants (control), were examined. Investigations were performed using X-ray microtomography, X-ray fluorescence analysis, and scanning electron microscopy. Histological studies of the bone bed tissues were performed. Nanoscale and microscale metallic particles were identified as participants in the inflammatory process in tissues. Supernatants containing nanoscale particles were obtained from the surfaces of 20 units of new dental implants. Early and late apoptosis and necrosis of immunocompetent cells after co-culture and induction by lipopolysaccharide and human venous blood serum were studied in an experiment with staging on the THP-1 (human monocytic) cell line using visualizing cytometry. As a result, it was found that nano- and microparticles emitted from the surface of the oxide layer of medical devices impregnated soft tissue biopsy specimens. By using different methods to analyze the cell-molecule interactions of nano- and microparticles both from a clinical perspective and an experimental research perspective, the possibility of forming a chronic immunopathological endogenous inflammatory process with an autoimmune component in the tissues was revealed.

In this work photocatalytic ethylene degradation (TiO 2 -UV) was applied in green cherry tomatoes with the aim to control biochemical and physiological changes during ripening. Photocatalytic process was performed at 18 °C  ±  2 °C and 85% HR for 10 days using continuous air flux. Ethylene, O 2 and CO 2 concentration from cherry tomatoes under TiO 2 -UV and control (c) fruits, were measured by GC-MS for 10 days. After that, the tomatoes were stored for 20 days. During the photocatalysis process, ethylene was completely degraded and control fruits, the ethylene was 28.73 nL/g. Respiration rate was lower for fruits under TiO 2 -UV than control. During storage period, cherry tomatoes treated by TiO 2 -UV, showed lower ethylene concentration, respiration rate, total soluble solid, lycopene, sugar and organic acid content than control showing that the fruits treated with photocatalysis did not reach the full maturity. In addition, all the cherry tomatoes showed different maturity stages. Fungal incidence was higher in control fruits than fruits treated with photocatalysis. This research showed for the first time that photocatalytic technology preserved the physiological quality of cherry tomatoes for 30 days of storage, being a promised technology to preserve cherries tomatoes.

Background: The objective of this study was to evaluate the accumulation of ions in blood and organs caused by titanium (Ti) metal particles in a mandibular defect in rats, together with a description of the local reaction of oral tissues to this Ti alloy debris., Methods: Twenty Sprague-Dawley rats were randomly distributed into three groups: an experimental group with a mandibular bone defect filled with metallic debris obtained by implantoplasty; a positive control group; and a negative control group. Thirty days after surgery, the rats were euthanized and perilesional tissue surrounding the mandibular defect was removed, together with the lungs, spleen, liver, and brain. Two blood samples were collected: immediately before surgery and before euthanasia. The perilesional tissue was histologically analyzed using hematoxylin-eosin staining, and Ti, aluminum, and vanadium ion concentrations in blood and organs were measured by TQ-ICP-MS. Descriptive and bivariate analyses of the data were performed., Results: All rats with implanted metal debris showed metal particles and a bone fracture callus on the osseous defect. The metal particles were surrounded by a foreign body reaction characterized by the presence of histiocytes and multinucleated giant cells (MNGCs). The experimental group had a significant higher concentration of Ti ions in all studied organs except lung tissue (p < 0.05). In addition, there were more V ions in the brain in the experimental group (p = 0.008)., Conclusions: Although further studies are required to confirm the clinical relevance of these results, Ti metal particles in the jaw might increase the concentration of metal ions in vital organs and induce a foreign body reaction., (© 2022 American Academy of Periodontology.)

Chromium (VI) removal is crucial to the safety of water resources, but there is still a lack of effective and fast dislodge methods, especially the on-site rapid remediation and emergency removal technology. Herein, the monolayer (ML) Ti 3 C 2 T x nanosheets (NSs) were prepared to remove Cr (VI) from water. The solution sample of the two-dimensional (2D) Ti 3 C 2 T x NSs demonstrate ultrafast adsorption kinetics (the concentration decreasing from 300 to 3 mg L -1 in 10 min) and impressively high capacity (1483 mg g -1 ), which is several times higher than that of the most reported Cr (VI) adsorption by Ti 3 C 2 T x . The analysis of the adsorption kinetics and isotherm models indicates that the adsorption reaction is endothermic, with physical and chemical adsorption coexisting (mainly monolayer chemical adsorption). The joint study of the experimental analysis and theoretical calculation based on the density functional theory (DFT) demonstrates that the extraordinary removal performance of Cr (VI) is due to the synergetic effect of reduction reaction removal and electrostatic adsorption. It is found that the Cr (VI) is mainly reduced by the OH- terminals on Ti 3 C 2 , and the detoxified Cr (III) is anchored on the surface of Ti 3 C 2 T x through complexation reaction with O terminal. The advantages of ultrafast adsorption kinetics and extra-high adsorption capacity of the single-layered Ti 3 C 2 T x for Cr (VI) removal make it a remarkable candidate for rapid and urgent removal of Cr (VI) wastewater., 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.)

While atmospheric microplastics have attracted scientific attention as a significant source of microplastic contamination in the environment, studies in large population centers remain sparse. Here we present the first report on the occurrence and distribution of atmospheric microplastics in Mexico City (Latin America's second most densely populated city), collected using PM 10 and PM 2.5 active samplers at seven monitoring stations (urban, residential, and industrial) during the dry and wet seasons of 2020. The results showed that microplastics were detected in all of the samples examined, with mean microplastic concentrations (items m -3 ) of 0.205 ± 0.061 and 0.110 ± 0.055 in PM 10 and PM 2.5 , respectively. The spatial distribution of microplastics showed seasonal variation, with greater abundances in locations closer to industrial and urban centers. There was also a significant difference in microplastic concentrations in PM 10 and PM 2.5 between the dry and wet seasons. The mean PM 2.5 /PM 10 ratio was 0.576, implying that microplastics were partitioned more towards PM 2.5 than PM 10 in Mexico City. Fibers were the most prominent shape (>75 %), and blue was the most common color (>60 %). The size characteristics indicated microplastics of varying lengths, ranging from 39 to 5000 μm, with 66 % being <500 μm. Metal contaminants such as aluminum, iron, and titanium were detected using SEM-EDX on randomly selected microplastics. The microplastics were identified as cellophane, polyethylene, polyethylene terephthalate, polyamide, and cellulose (rayon) using ATR-FTIR spectral analysis. Our findings unravel the extent and characteristics of atmospheric microplastics in the Mexico City metropolitan area, which will aid future research to better understand their fate, transport, and potential health risks, demanding more investigations and close monitoring., 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 B.V. All rights reserved.)

Excessive iron and manganese presented in groundwater sources may cause harm to human health that needs to be solved urgently. This research aims to develop high-performance Mn/Ti-modified zeolites using sol-gel method and hydrothermal synthesis method to remove Fe 2+ and Mn 2+ simultaneously. The preparation parameters were optimized by response surface methodology, and the results confirmed that the optimal preparation conditions were as follows: mass ratio of MnO 2 -TiO 2 /zeolite = 1, hydrothermal temperature = 200°C, and calcination temperature = 500°C. The results of batch adsorption experiments showed that the best removal rate of Fe 2+ and Mn 2+ by modified zeolite materials which was prepared under the optimum conditions reached 96.8% and 94.4%, respectively, at which the saturated adsorption capacity was 2.80 mg/g and 1.86 mg/g. Through the adsorption kinetics, thermodynamics, internal diffusion, and isothermal adsorption analyses, it is confirmed that the adsorption process of Fe 2+ and Mn 2+ by the modified zeolite is mainly chemical adsorption. The results of the Weber-Morris internal diffusion model prove that internal diffusion is not the only step that controls the adsorption process. In addition, combined with the characterization of the composite-modified zeolite and the adsorption experimental study, it shows that there is an autocatalytic reaction in the adsorption process., (© 2022. The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature.)

An automated and high-throughput (36 h -1 ) method for extremely sensitive determination of the two main tellurium species in the environment, namely, tellurite (Te IV ) and tellurate (Te VI ), was developed. Flow injection hydride generation was interfaced for the first time with inductively coupled plasma triple quadrupole mass spectrometry (ICP-MS/MS) detection to assure interference-free tellurium analysis. ICP-MS/MS conditions were studied in detail. Using a mixture of He + O 2 gases in the reaction cell, the background signals significantly dropped and Xe isobaric interference was eliminated, allowing measurement with the most abundant Te isotopes, that is, 128 Te and 130 Te, and offering a huge increase in sensitivity. Volatile H 2 Te was selectively generated by a HCl/NaBH 4 reaction from Te IV or from both Te IV and Te VI (Te IV+VI ) after pre-reduction of Te VI by a TiCl 3 solution. The optimum conditions for TiCl 3 as a pre-reductant and the pre-reduction kinetics were also investigated. Different reduction rates were found depending on the sample stabilization media (HCl, HNO 3 , or EDTA). The same sensitivity was found for Te IV and Te VI , measured after pre-reduction, and no significant matrix effect was observed in both fresh and seawaters. Therefore, external calibration was used for quantification in real samples. Under optimal conditions, this method reached an unprecedented limit of detection of 0.07 ng L -1 for both Te IV and Te IV+VI and an intra-day repeatability of 5.2% at the 5 ng L -1 level. The methodology was successfully applied to the speciation analyses in commercially available certified reference materials of river water and seawater, and in bottled water and lake water samples.

Continuous release of nanoparticles (NPs) into marine coastal environments results in an increased risk of exposure to complex NP mixtures for marine organisms. However, to date, the information on the effects at molecular and biochemical levels induced by the exposure to NPs, singly and as a mixture, is still scant. The present work aimed at exploring the independent and combined effects and the mechanism(s) of action induced by 7-days exposure to 1 μg/L nZnO, 1 μg/L nTiO 2 and 1 μg/L FC 60 fullerene in the Manila clam Ruditapes philippinarum, using a battery of immunological and oxidative stress biomarkers in haemolymph, gills and digestive gland. In addition, proteomics analyses were performed in gills and the digestive gland, where NP bioaccumulation was also assessed. Increased bioaccumulation of single NPs and the mixture was linked with increased oxidative stress and higher damage to proteins, lipids and DNA in all tissues analysed. The proteomics approach highlighted protein modulation in terms of abundance and damage (higher redox-thiol and carbonylated groups content). In particular, the modulated proteins (16 in gills and 18 in digestive gland) were mostly related to cytoskeleton and energetic metabolism. The digestive gland was the tissue more affected. For all biomarkers measured, increased detrimental effects were observed in the mixture compared to single NP exposures., 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 B.V. All rights reserved.)

The TiO 2 @MOF-919(Fe-Cu) solid-phase extraction material was prepared by growing MOF-919(Fe-Cu) in situ on three-dimensional radial TiO 2 microspheres by a simple solvothermal method. This combination drew on both the resources of good single dispersion and extraction rate, which made it a better extraction material. It was accompanied with high-performance liquid chromatography (SPE-HPLC) for the separation and determination of four benzoylurea pesticides (triflumuron, chlorbenzuron, teflubenzuron and diflubenzuron) in afforestation irrigation water and juice samples (grape, peach and apple juices). Under the optimal conditions, the linearity of the method ranged from 1 to 400 μg L -1 with a correlation coefficient ( R 2 ) ≥ 0.9994, while the detection limit was in the range of 0.40-0.56 μg L -1 for the four pesticides. The adopted material showed good reusability and can be used no less than 10 times. The intra-day and inter-day precision were in the range of 1.78-3.24% and 4.06-5.08%, respectively. The proposed method was then successfully applied for the detection of benzoylurea pesticides in the spiked samples with good recoveries (72.3-108.4%) and good precision (5.15%) due to π-π and hydrophobic interactions between the analytes and adsorbent. The results show that the composite had the potential to be used as a SPE adsorbent for the enrichment and extraction of benzene ring structures containing imide groups in actual samples.

The analysis of natural and anthropogenic nanomaterials (NMs) in the environment is challenging and requires methods capable to identify and characterise structures on the nanoscale regarding particle number concentrations (PNCs), elemental composition, size, and mass distributions. In this study, we employed single particle inductively coupled plasma-mass spectrometry (SP ICP-MS) to investigate the occurrence of NMs in the Melbourne area (Australia) across 63 locations. Poisson statistics were used to discriminate between signals from nanoparticulate matter and ionic background. TiO 2 -based NMs were frequently detected and corresponding NM signals were calibated with an automated data processing platform. Additionally, a method utilising a larger mass bandpass was developed to screen for particulate high-mass elements. This procedure identified Pb-based NMs in various samples. The effects of different environmental matrices consisting of fresh, brackish, or seawater were mitigated with an aerosol dilution method reducing the introduction of salt into the plasma and avoiding signal drift. Signals from TiO 2 - and Pb-based NMs were counted, integrated, and subsequently calibrated to determine PNCs as well as mass and size distributions. PNCs, mean sizes, particulate masses, and ionic background levels were compared across different locations and environments., (© 2022. The Author(s).)

It is imperative to search the eco-friendly and cost-effective technologies for degrading contaminants. Coupling the effect of Ti/PbO 2 at the anode with heterogeneous electro-Fenton was an efficient method. Industrial pyrite waste slag characterized by a variety of methods had catalytic performance and stable performance to activate hydrogen peroxide (H 2 O 2 ) into hydroxyl radical (∙OH). Meanwhile, the processing conditions, the malachite green wastewater concentration, the current density, the pH range, and the dosage of industrial pyrite waste slag were emphatically optimized. Herein, the total organic carbon (TOC) removal efficiency reached 97.70%, the mineralization current efficiency (MCE) was 0.392%, and the energy consumption (E C ) was 1.942 kWh/m 3 after 240 min. Heterogeneous Ti/PbO 2 -electro-Fenton using industrial pyrite waste slag as catalyst was an environmentally friendly technology and provided a recycling method with traditional wastes. Finally, catalytic mechanisms and possible pathways were represented according to the results of quantum chemistry calculations and gas chromatography-mass spectrometry (GCMS)., (© 2022. The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature.)

The techniques used in oral implantology to remove bacterial biofilm from the surface of implants by machining the titanium surface (implantoplasty) or by placing rough dental implants through friction with the cortical bone generate a large release of particles. In this work, we performed a simulation of particle generation following clinical protocols. The particles were characterized for commercially pure titanium with particle sizes of 5, 10, 15, and 30 μm. The aim was to determine the effect of particle size and chemical composition of the implant on the immune response. For this purpose, their morphology and possible contamination were characterized by scanning electron microscopy and X-ray microanalysis. In addition, the granulometry, specific surface area, release of metal ions into the medium, and studies of cytocompatibility, gene expression, and cytokine release linked to the inflammatory process were studied. The release of ions for titanium particles showed levels below 800 ppb for all sizes. Smaller particle sizes showed less cytotoxicity, although particles of 15 μm presented higher levels of cytocompatibility. In addition, inflammatory markers (TNFα and Il-1β) were higher compared to larger titanium. Specifically, particles of 15 μm presented a lower proinflammatory and higher anti-inflammatory response as characterized by gene expression and cytokine release, compared to control or smaller particles. Therefore, in general, there is a greater tendency for smaller particles to produce greater toxicity and a greater proinflammatory response.

Purpose: To present a selective analytical Inductively Coupled Plasma-Atomic Emission Spectroscopy (ICP-AES) method developed and validated for the quantitation of tablet film coatings containing titanium. Methods: Tablet samples were decomposed by either digestion or dry ashing. The amount of film tablet coating was calculated based on titanium content of the sample. Results: The reported ICP-AES method was accurate, precise, sensitive and linear for determination of titanium concentrations from 2.9 to 8.6 ppm. Conclusion: This method provides an accurate determination of the amount of coating on a tablet and has general applicability for a variety of coating formulations containing different elements. [Copyright &y& Elsevier]

Sweat pH is a critical indicator for evaluating human health. With the extensive attention on the wearable and flexible biosensing devices, the technology for the monitoring of human sweat can be realized. In this study, a sensitive, miniaturized, and flexible electrochemical sweat pH sensor was developed for the continuous and real-time monitoring of the hydrogen-ion concentration in human sweat. A flexible electrode was fabricated on the poly(ethylene terephthalate) (PET) substrate by a simple and low-cost screen-printing technology, which was based on the integration of fluoroalkyl silane-functionalized Ti 3 C 2 T x (F-Ti 3 C 2 T x ) and the polyaniline (PANI) membrane technology instead of the traditional ion-sensitive membrane. The surface functionalization strategy for Ti 3 C 2 T x with perfluorodecyltrichlorosilane can provide environmental stability. Functionalized Ti 3 C 2 T x (F-Ti 3 C 2 T x ) was doped with PANI to obtain improved responsiveness, sensitivity, and reversibility. The constructed microsize, portable, and wearable F-Ti 3 C 2 T x /PANI pH sensor aimed to real-time monitor the pH value of human sweat during exercise. On-body sweat pH monitoring for females and males, respectively, exhibited high accuracy and continuous stability compared with ex situ analyses. This study thus offers a facile and practical solution for developing a highly reliable MXene-based mini-type pH sensor to realize the online monitoring of human sweat pH.

Ammonium as the major reduction intermediate has always been the limitation of nitrate reduction by cathodic reduction or nano zero-valent iron (nZVI). In this work, we report the electrochemical nitrate removal by magnetically immobilized nZVI anode on RuO 2 -IrO 2 /Ti plate with ammonia-oxidizing function. This system shows maximum nitrate removal efficiency of 94.6% and nitrogen selectivity up to 72.8% at pH of 3.0, and it has also high nitrate removal efficiency (90.2%) and nitrogen selectivity (70.6%) near neutral medium (pH = 6). As the increase of the applied anodic potentials, both nitrate removal efficiency (from 27.2% to 94.6%) and nitrogen selectivity (70.4%-72.8%) increase. The incorpration of RuO 2 -IrO 2 /Ti plate with ammonia-oxidizing function on the nZVI anode enhances the nitrate reduction. The dosage of nZVI on RuO 2 -IrO 2 /Ti plate (from 0.2 g to 0.6 g) has a slight effect (the variance is no more than 10.0%) on the removal performance. Cyclic voltammetry, Tafel analysis and electrochemical impedance spectroscopy (EIS) were further used to investigate the reaction mechanisms occurring on the nZVI surfaces in terms of CV curve area, corrosion voltage, corrosion current density and charge-transfer resistance. In conclusion, high nitrate removal performance of magnetically immobilized nZVI anode coupled with RuO 2 -IrO 2 /Ti plate may guide the design of improved electrochemical reduction by nZVI-based anode for practical nitrate remediation., (Copyright © 2022 Elsevier Ltd. All rights reserved.)

A new instrumental neutron activation analysis (INAA) for the simultaneous determination of titanium (TiO 2 ) and silica (SiO 2 ) dioxide as UV-filters in sunscreens is described. Samples are encapsulated, neutron irradiated (30 s) and after a suitable decay (3 min), the induced 51 Ti (T 1/2  = 5.76 min) and 29 Al (T 1/2  = 6.56 min) radionuclides are measured for the emitted γ-ray fingerprint. Three applications were carried out: (i) screening study (analysis of commercial sunscreens in combination with single particle inductively coupled plasma mass spectrometry (sp-ICP-MS); (ii) research study (development of innovative UV-filters such as titanium dioxide or bismuth titanate loaded inorganic mesoporous silica nanoparticles, MSN); (iii) validation study (intercalibration of a spectrochemical method - inductively coupled plasma optical emission spectrometry, ICP-OES). Collectively, the nuclear method appears a powerful tool adequate for quantifying TiO 2 and SiO 2 in the above studies. The limited accessibility at the nuclear reactor for neutron activation is probably one of the reasons why the excellent characteristics of the nuclear technique are not always fully known and exploited in the industrial and research chemical world., Competing Interests: Declaration of competing interest The authors declare the following financial interests/personal relationships which may be considered as potential competing interests: Riccardo Magarini and Renato Riscassi have an actual competing financial interest as employed in Perkin Elmer Italia, a company committed to commercializing the sp-ICP-MS and ICP-OES technology., (Copyright © 2022 Elsevier B.V. All rights reserved.)

Objectives: To perform a retrospective, descriptive, histopathological study of peri-implant tissue pathologies associated with titanium dental implants (TDI), and to evaluate the presence of metallic particles in samples from a single diagnostic center., Methods: Sixty-eight cases of TDI-associated lesions were retrieved from the Surgical Pathology Laboratory archives, School of Dentistry, University of Buenos Aires (UBA) (1990-2018). The study included re-examining the histopathological features of the biopsy samples, analyzing the inflammatory infiltrate, and examining the samples to detect metallic particles whose chemical composition was determined spectrophotometrically (EDS). Available clinical and radiographic data were also reviewed., Results: The retrieved cases ranged from lesions of inflammatory origin to neoplastic lesions. Metallic particles were observed in 36 cases (52.9%), all of which showed inflammation. Particle length ranged from 2 to 85µm. EDS analysis of the particles/deposits observed in the tissues showed the presence of aluminum, titanium, iron, and nickel, among other elements., Conclusions: A significant number of TDI-associated lesions, including cases not reported to date and diagnosed at a single diagnostic center, are shown here. Cases showing particles exhibited an inflammatory response, irrespective of the histopathological diagnosis. The role of metallic particles in the development of TDI-associated lesion is yet to be established., (© 2021 Wiley Periodicals LLC.)

Titanium (Ti) is an element beneficial to plant growth. Application of titanium to roots or leaves at low concentrations can improve crop yield and performance. However, the effect of titanium ions on the bulk soil microbial community of planted crops remains unclear. This study aimed to explore the effects of titanium on soil bacterial and fungal communities. Field surveys were conducted to determine the effect of titanium ions on bulk soil microbial communities in pitaya and grape plantations of Panzhihua and Xichang areas, respectively. Full-length 16S rRNA and internal transcribed spacer ( ITS ) amplicon sequencing were performed using PacBio Sequel to further explore the composition and structure of soil microbiota. The application of titanium ions significantly altered the composition and structure of soil microbiota. Root irrigation with titanium ions in pitaya gardens reduced the diversity of soil fungi and bacteria. However, the decline in bacterial diversity was not statistically significant. Meanwhile, foliar spray of titanium ions on grapes greatly reduced the soil microbial diversity. The bulk soil microbiota had a core of conserved taxa, and titanium ions significantly altered their relative abundances. Furthermore, the application of titanium increased the interaction network of soil fungi and bacteria compared with the control group. Thus, titanium ions potentially improve the stability of the soil microbial community. IMPORTANCE Pitaya and grape are important cash crops in the Panzhihua and Xichang areas, respectively, where they are well adapted. Titanium is a plant growth-promoting element, but the interaction between titanium and soil microorganisms is poorly understood. Titanium ions are still not widely used for growing pitaya and grape in the two regions. Thus, we investigated the effects of titanium ions on soil microbial communities of the two fruit crops in these two regions. Microbial diversity decreased, and the community structure changed; however, the addition of titanium ions enhanced cooccurrence relationships and improved the stability of the community. This study provides a basis for the importance of titanium ion application in crop cultivation.

Although titanium dioxide (TiO 2 ) is a suspected human carcinogen when inhaled, fiber-grade TiO 2 (nano)particles were demonstrated in synthetic textile fibers of face masks intended for the general public. STEM-EDX analysis on sections of a variety of single use and reusable face masks visualized agglomerated near-spherical TiO 2 particles in non-woven fabrics, polyester, polyamide and bi-component fibers. Median sizes of constituent particles ranged from 89 to 184 nm, implying an important fraction of nano-sized particles (< 100 nm). The total TiO 2 mass determined by ICP-OES ranged from 791 to 152,345 µg per mask. The estimated TiO 2 mass at the fiber surface ranged from 17 to 4394 µg, and systematically exceeded the acceptable exposure level to TiO 2 by inhalation (3.6 µg), determined based on a scenario where face masks are worn intensively. No assumptions were made about the likelihood of the release of TiO 2 particles itself, since direct measurement of release and inhalation uptake when face masks are worn could not be assessed. The importance of wearing face masks against COVID-19 is unquestionable. Even so, these results urge for in depth research of (nano)technology applications in textiles to avoid possible future consequences caused by a poorly regulated use and to implement regulatory standards phasing out or limiting the amount of TiO 2 particles, following the safe-by-design principle., (© 2022. The Author(s).)

With the growth of the economy, the number of automobiles on the road is fast growing, resulting in substantial environmental pollution from exhaust gas emissions. In the automobile factory, some improvements have been achieved by constructing devices to degrade automobile exhaust. However, although most of the vehicle exhaust emissions have met the national standards, the exhaust gas is superimposed at the same time period due to the increasing traffic volume, making the exhaust emissions seriously reduce the air quality. Therefore, the scholars in the road field began to study new road materials to degrade vehicle exhaust, which has gradually become one of the effective ways to reduce automobile exhaust. Photocatalyst materials have been widely concerned because of their ability to oxidize harmful gases by solar photocatalysis. Yet, the effect has been not satisfactory because of the small light response range of photocatalyst material, which restricts the catalytic effect. In this study, this paper attempts to use Fe3+ to modify the TiO2, which is one of the main photocatalytic materials, to expand the range of light reaction band and to improve the degradation effect of automobile exhaust. The degradation effects of ordinary TiO2 and modified TiO2 on automobile exhaust were compared by test system in the laboratory. The results show that the modified TiO2 can effectively improve the performance of vehicle exhaust degradation. Moreover, the molecular dynamics method was used to establish the channel model of TiO2, and the dynamic process of automobile exhaust diffusion and absorption was simulated. The diffusion law and adsorption process of different types of automobile exhaust gas such as NO, CO, and CO2 in the TiO2 channel were analyzed from the molecular scale through the radial concentration distribution and adsorption energy., Competing Interests: The authors have declared that no competing interests exist.

Investigations were carried out to analyze the role of anatase nanoparticles in inducing genetic variability in lentils (Lens culinaris Medik.) for yield improvement and subsequent involvement in development, quality, and biochemical response of second-generation seedlings through their lifecycle. Trans-generational alterations in the morphological and biochemical pool of the plant system were evaluated over a range of concentrations (25-200 µg/mL). Analysis of F 2 seedlings showed an increase in yield parameters at the lowest concentration (25 µg/mL). Biochemical studies revealed that the F 2 plants experienced lower oxidative stress as compared with previous generation plants. Quality analysis of seeds revealed a slight positive shift in the mean values of seed protein content at the lowest concentration. The effect of nanoparticles on the growth parameters was antagonistic except at the lowest concentration, where the growth parameters were found to be slightly higher than in the controls. The variability present in different traits in the F 2 populations was quantified as phenotypic variability and its components, which is a measure of the transmissibility of variations of the so-called mutated populations as a result of nanoparticle application.

Nanoparticles are the magic bullets and at the leading edge in the field of nanotechnology, and their unique properties make these materials indispensable and superior in many areas, including the electronic field. Extensive applications of nanomaterials are incontrovertibly entering our living system. The increasing use of nanomaterials into the ecosystem is one of the crucial environmental factors that human being is facing. Nanomaterials raise noticeable toxicological concerns; particularly their accumulation in plants and the resultant toxicity may affect the food chain. Here, we analyzed the characterization of nanomaterials, such as graphene, Al 2 O 3 , TiO 2 , and semi-insulating or conducting nanoparticles. Quantitative evaluation of the nanomaterials was conducted and their commercialization aspects were discussed. Various characterization techniques, scanning electron microscopy, X-ray diffraction, and ultraviolet rays were utilized to identify the morphology, phase, absorbance, and crystallinity. In addition, we analyzed the effects of nanomaterials on plants. The toxicity of nanoparticles has severe effects on loss of morphology of the plants. Potential mechanisms including physical and physiological effects were analyzed. In future studies, it is indispensable to assess widely accepted toxicity evaluation for safe production and use of nanomaterials., (© 2020 International Union of Biochemistry and Molecular Biology, Inc.)

Titanium dioxide (TiO 2 ) is commonly contained in many commercial products and there are concerns about its release into the aquatic environment after use. This study was designed to characterize the distribution of Ti-containing nanoparticulates (NPs) in the water of the Tamsuei River Basin in northern Taiwan. Water samples were collected from the upstream, mid-stream, and downstream areas of the Tamsuei River Basin and analyzed with single-particle ICPMS to profile the Ti-containing NPs in terms of mass concentration, number concentration and particulate size. The lowest mass concentration of Ti-containing NPs, 1.04 ± 0.04 μg/L, was found in the upstream water samples, while the highest mass concentration, 31.7 ± 0.6 μg/L, was observed in downstream samples; there was an increasing trend from upstream to downstream. The highest particulate number concentration, 479 ± 163 × 10 3 /mL, was observed for the downstream samples, but the lowest concentration, 45.4 ± 5.6 × 10 3 /mL, was found in the mid-stream water samples taken from Site C. Moreover, the average mode values for particulate sizes were approximately 50 nm for all samples, although a relatively larger average mode value of 62 ± 5.7 nm was observed in the mid-stream samples from Site A. Increasing mass concentrations and particulate number concentrations from upstream to downstream implied that these NPs might have originally resulted from anthropogenic activities involving the use of TiO 2 NPs-containing products. Surprisingly, however, the lowest number concentrations for Ti-containing NPs in the mid-stream samples can probably be attributed to the fact that the corresponding sampling sites were located in the water preservation zone, which exhibits a particle-settling effect. Additionally, the sizes of Ti-containing NPs in downstream samples were not significantly larger than those in the upstream and mid-stream samples, as expected, which was probably due to the steric effects resulting from the presence of large amounts of macromolecule polymers in aquatic environments., Competing Interests: Declaration of competing interest This research did not receive any specific grant from funding agencies in the public, commercial, or not-for-profit sectors. The authors declare no conflict of interest and all the contents, including any opinions and/or conclusions expressed, are solely those of the authors., (Copyright © 2021 Elsevier B.V. All rights reserved.)

Titanium dioxide (TiO 2 ) is one of the most commonly used pharmaceutical excipients. It is widely used as a white pigment in tablet and pellet coatings. However, it has recently been under massive criticism as a number of studies suggest a cancerogenic potential. It can therefore no longer be taken for granted that TiO 2 will continue to be universally available for drug products. Finding suitable alternatives is hence of special relevance. In this study, a number of different pigments were coated on tablets and their covering potential analyzed. None of the alternative pigments showed comparable effectiveness and efficiency to TiO 2 , though the CaCO 3 /CaHPO 4 -based coating showed the second-best results. Regarding the ability to protect photosensitive active ingredients, ZnO showed a comparable potential as TiO 2 , while all other pigments failed. Using the alternative pigments as markers for in-line Raman spectroscopy as a process analytical technology was challenging and led to increased prediction errors. Again, the CaCO 3 /CaHPO 4 -based coating was the only of the tested alternatives with satisfying results, while all other pigments led to unacceptably high prediction errors.