Release Of Metals Research Articles

Use of Electropolishing in Orthodontic Appliances: An Option to Reduce the Risk of Metal Hypersensitivity.

Electropolishing is a common treatment in the industry; however, how it behaves in the mouth and what benefits it can bring over metal dental attachments have not yet been established. Thus, the aim of this study was to determine the levels of corrosion, the released metal ions, and the changes in structural composition in metallic orthodontic appliances following electropolishing treatment. This study included 56 orthodontic brackets and 28 archwires. The samples were subjected to a pH cycle to simulate an oral environment. Using UV-Vis spectrophotometry, the release of metallic particles was evaluated, and using scanning electron microscopy, the structural and composition changes were evaluated. Groups were compared using Student's t-tests with a value of p ≤ 0.05. The cyclical pH solutions showed variations between groups and days (1, 3, 5, 7 and 15), reaching the highest acidification in the self-ligating brackets; the absorbance between solutions did not differ significantly. As seen from the SEM results, the experimental group showed minor irregularities compared with the control groups. The experimental brackets decreased in iron and increased in chromium after electropolishing, while for the NiTi archwires, they decreased in nickel. Therefore, electropolishing treatments in metallic orthodontic attachments improve their surface structure and corrosion resistance could reduce the risk of metal hypersensitivity, mainly from nickel.

Predicting the Metal Ion Release From CoCrMo Alloy–UHMWPE Tribocorrosion Contacts

Predicting the Metal Ion Release From CoCrMo Alloy–UHMWPE Tribocorrosion Contacts

Corrosion phenomena and deposits in ITER Neutral Beam Test Facility primary cooling circuits

The ITER Neutral Beam Test Facility (NBTF) is hosted in Padua and includes two experiments: MITICA, the 1 MeV full-scale prototype of the ITER HNB injector, and SPIDER, the 100 keV full-size ITER Radio Frequency (RF) negative ion source. SPIDER and MITICA experiments are actively cooled by Ultrapure Water (UPW) to electrically insulate in-vessel components that are biased to high voltage levels. Water conductivity is an important monitored parameter to ensure components' insulation by limiting the leakage current of active cooled equipment. A very low conductivity water is especially important in MITICA, where components need to operate up to 1 MVdc, an insulation level beyond the actual industrial standard. Careful selection of suitable materials for any in-vessel (vacuum insulation) and out-vessel component (air insulation) is of utmost importance, as their interaction with water and different environment may affect their chemical and mechanical properties. Additionally, materials selection can severely influence water chemical characteristics: cooling circuits are made of metals (copper, aluminium, steel) and insulating materials (plastic, rubber) when connecting parts at different electric potentials.During the first years of cooling plant exploitation, it was shown that water degrades more quickly than estimated by design. The Primary Circuits (PCs) that showed the most severe water degradation during operation are SPIDER and MITICA power supply ones, respectively called PC01 and PC08. This paper describes the results of specific experimental tests performed on MITICA PC08 to evaluate possible causes of water degradation and detect sources of contaminants that might compromise future experimental campaigns. The cooling circuit was subdivided in different sections and water circulation tests were performed at constant temperature and flowrate. Water samples were collected and Inductively Coupled Plasma Mass Spectrometry (ICP-MS) analyses were performed to quantify the type and amount of metals released. Moreover, components samples collected along their cooling circuits were characterized by Scanning Electron Microscope (SEM) technique to detect undesired contaminants and immersed in UPW to study their corrosion behaviour using metal release tests.

Investigating the Feasibility and Performance of Hybrid Overmolded UHMWPE 3D-Printed PEEK Structural Composites for Orthopedic Implant Applications: A Pilot Study.

Ultra-high-molecular-weight polyethylene (UHMWPE) components for orthopedic implants have historically been integrated into metal backings by direct-compression molding (DCM). However, metal backings are costly, stiffer than cortical bone, and may be associated with medical imaging distortion and metal release. Hybrid-manufactured DCM UHMWPE overmolded additively manufactured polyetheretherketone (PEEK) structural components could offer an alternative solution, but are yet to be explored. In this study, five different porous topologies (grid, triangular, honeycomb, octahedral, and gyroid) and three surface feature sizes (low, medium, and high) were implemented into the top surface of digital cylindrical specimens prior to being 3D printed in PEEK and then overmolded with UHMWPE. Separation forces were recorded as 1.97-3.86 kN, therefore matching and bettering the historical industry values (2-3 kN) recorded for DCM UHMWPE metal components. Infill topology affected failure mechanism (Type 1 or 2) and obtained separation forces, with shapes having greater sidewall numbers (honeycomb-60%) and interconnectivity (gyroid-30%) through their builds, tolerating higher transmitted forces. Surface feature size also had an impact on applied load, whereby those with low infill-%s generally recorded lower levels of performance vs. medium and high infill strategies. These preliminary findings suggest that hybrid-manufactured structural composites could replace metal backings and produce orthopedic implants with high-performing polymer-polymer interfaces.

Investigation of the adsorption performance and mechanism of multi-source mineral composite calcination materials on heavy metal ions

To address the challenges of plume generation and the release of heavy metal ions caused by deep-sea mining operations, this study utilized multi-source minerals, including steel slag (SS), oceanic manganese nodules (OMN), attapulgite (AT), and sawdust (SD), to fabricate a multi-source mineral composite calcination material (MMCCM) through a sintering process, and then the preliminary heavy metal ion adsorption experiment was carried out. The results indicated that both Langmuir and Freundlich models can describe the adsorption behavior of Cu2+ in a single system, while the Freundlich model was more applicable in competitive systems. The adsorption of Co2+ and Ni2+ consistently aligned with the Langmuir model across all systems. The adsorptive behavior conformed to pseudo-second-order kinetics, indicating that chemisorption played a leading role. The intraparticle diffusion was the principal rate-limiting step, and the adsorption process was spontaneous. BET, TG-DTG, SEM-EDS, XRD, FT-IR and XPS elucidated that surface physical adsorption, ion exchange, complexation with functional groups, electrostatic attraction, and co-precipitation, which were the predominant adsorption mechanisms for MMCCM. Evaluations of regenerability, economy, security, and suitability demonstrated that MMCCM is an eco-friendly adsorbent, which provides materials and data support for future heavy metal marine sewage treatment, especially for immobilizing heavy metal in deep-sea sediments.

Evolution of physicochemical and leaching characteristics of municipal solid waste incineration fly ash in China under ultra-low emission standard

The physical and chemical characteristics of fly ash has changed significantly under ultra-low emission system and the current leaching system is no longer suitable for high alkalinity fly ash. This work investigated the pH values and evolution of physical and chemical characteristics of fly ash from 24 typical municipal solid waste incineration plants in China. The pH value of the leaching solution obtained by HJ/T 300–2007 presented two different acid and alkali characteristics, where high and low alkalinity fly ash accounted for 54.17% and 45.83%, respectively. The alkali content in fly ash increased significantly after ultra-low emission standard, increasing by 18.24% compared with before the implementation of GB 18485-2014. The leaching behavior of high alkalinity fly ash showed the illusion that they could enter the landfill only by the addition of a small amount of chelating agent or even without stabilization treatment, and its long-term landfill risk is significant. The phase change of high alkalinity fly ash and pH value change of the leaching solution after carbonation were the key factors for the leaching concentration change of heavy metals. Therefore, it is recommended to improve the existing leaching system or conduct accelerated carbonization experiments to scientifically evaluate the long-term leaching characteristics of high alkalinity fly ash, and to reduce the risk of heavy metal release from high alkalinity FA after entering the landfill site.

Cement-mortar lining failure and metal release caused by electrochemical corrosion of ductile iron pipes in drinking water distribution systems

The electrochemical corrosion of ductile pipes (DPs) in drinking water distribution systems (DWDS) has a crucial impact on cement-mortar lining (CML) failure and metal release, potentially leading to drinking water quality deterioration and posing a risk to public health. An in-situ scanning vibrating electrode technique (SVET) with micron-scale resolution, microscopic scale detection and water quality analysis were used to investigate the corrosion behavior and metal release from DPs throughout the whole CML failure process. Metal pollutants release occurred at three different stages of CML failure process, and there are potential risks of water quality deterioration exceeding the maximum allowable levels set by national standards in the partial failure stage and lining peeling stage. Furthermore, the effects of water chemistry (Cl−, SO42−, NO3−, and Ca2+) on corrosion scale growth and iron release activity, were investigated during the CML partial failure stage. Results showed that the CML failure process in DPs was accelerated by the autocatalysis of localized corrosion. Cl− was found to damage the uncorroded metal surface, while SO42− mainly dissolved the corrosion scale surface, increasing iron release. Both the oxidation of NO3− and selective sedimentation of Ca2+ were found to enhance the stability of corrosion scales and inhibit iron release.

Mineralogy and environmental stability of metallurgical slags from the Euronickel smelter, Vozarci, North Macedonia

The laterite Ni-smelting operations at Vozarci, Republic North Macedonia have produced large amounts of smelting wastes dumped in the close vicinity of the smelter. We examined phase composition and chemistry of the various types of slags (electric furnace slags, converter slag, magnetic slag) with the special focus on the phases containing potentially toxic elements in terms of their mineralogy, chemical composition, and responses to weathering. Electric furnace slags contain between 35 and 47 wt.% SiO2, 21–40 wt.% Fe2O3, and 13–23 wt.% MgO; converter and magnetic slags are Fe-rich (76–77 wt.% of Fe2O3) with significant amounts of Ca (7.6–8.4 wt.% CaO) and S-portion (2–2.5 wt.% SO3). All slags contain substantial amounts of the potentially toxic elements: Co (20–87 ppm), Cr (9600–17400 ppm), Ni (170–730 ppm), and Zn (150–380 ppm). Further mineralogical analyses showed that the slags consist of silicate glass, synthetic equivalents of olivines, orthopyroxenes, clinopyroxenes, and subordinate spinel-group phases, sulfides, and intermetallic compounds. Some of the slags had been subject to weathering since their dumping in 1982. The weathering results in the release of metals from primary slag phases, particularly from glass, and the partial immobilization of these metals in secondary soluble and insoluble minerals in the slag heaps (hydroxy-iron oxides, gypsum, anhydrite, syngenite, aphthitalite). The majority of slag samples exhibited increased leaching under conditions of lower pH (2.9) compared to higher pH (4.9). The contrast between leaching treatments was particularly evident for nickel (Ni), with leaching at a low pH of 2.9 reaching up to 135 times higher (MS) than at pH 4.9. At lower pH conditions, other contaminants of interest were leached out at a rate 4 to 76 times faster compared to the leaching achieved at pH 4.9, because they are the major source of potentially toxic elements.

Assessment of heavy metal pollution in soils of Jebba Area, Nigeria: Concentrations, source analysis and implications for ecological and human health risks

This comprehensive research investigates heavy metal contamination in the rapidly developing town of Jebba in north-central Nigeria, which is essential to the nation's economy due to its agro-allied and non-agro-allied businesses. The research focuses on soil samples, collecting and analyzing 137 surface soil samples to assess the presence of 25 distinct metals. After statistical analysis and simple mathematical models are applied to the data, the amounts of harmful metals and their probable causes are revealed. The study identifies geogenic and anthropogenic origins of toxic metals, with some elements exceeding average crustal concentrations. Non-homogeneous metal dispersion is shown in the region by spatial distribution maps. The geo-accumulation index reflects various amounts of contamination, with particular metals posing significant threats to the ecosystem. Additionally, the study compares results with worldwide studies, revealing distinct pollution patterns in Jebba. The research delves into weathering processes, employing chemical indices to quantify the level of soil weathering and uncovering a prominent role of geogenic activities in metal release. Bivariate correlation and principal component analysis indicate links and possibly common sources among heavy metals, emphasizing anthropogenic contributions. In addition, assessments of ecological and medical risks are conducted, indicating possible threats to human wellness and the ecosystem. Children, in particular, are regarded as especially vulnerable to non-carcinogenic health concerns, with various heavy metals posing potential threats through diverse exposure routes. The study emphasizes the need to implement remediation procedures to address the risks to public health and the environment related to metal pollution.

Exploring Heavy Metal and Metalloid Exposure in Children: A Pilot Biomonitoring Study near a Sugarcane Mill.

Sugarcane production has been linked to the release of heavy metals and metalloids (HM/MTs) into the environment, raising concerns about potential health risks. This study aimed to assess the levels of 19 HM/MTs in children living near a sugarcane mill through a pilot biomonitoring investigation. We investigated sex-related differences in these element levels and their correlations. A cross-sectional study was conducted, analyzing data from 20 children in the latter part of 2023. Spearman correlation coefficients with 95% confidence intervals (CIs) were used to assess the relationships between urinary HM/MT levels. Detectable levels of 17 out of the 19 HM/MTs were found across the entire study sample, with arsenic and copper detectable in 95% of the children. Titanium exhibited higher levels in boys compared to girls (p = 0.017). We identified 56 statistically significant correlations, with 51 of them being positive, while the remaining coefficients indicated negative relationships. This study characterized HM/MT levels in school-aged children residing near a sugarcane mill through a pilot biomonitoring investigation. Further research employing larger sample sizes and longitudinal assessments would enhance our understanding of the dynamics and health impacts of HM/MT exposure in this vulnerable population.

Self-Sustained-Release Strategy Realizes Colloid Oriented Assembly to Fabricate Prussian Blue with Hierarchical Structure.

The controlled self-assembly of nanomaterials has been a great challenge in nanosynthesis, especially for hierarchical architectures with high complexity. Particularly, the structural design of Prussian blue (PB) series materials with robustness and fast nucleation is even more difficult. Herein, a self-sustained-release strategy based on the slow release of metal ions from coordination ions is proposed to guide the assembly of PB crystals. The key to this strategy is the slow release by ligand, which can create ultra-low concentrations of metal ions so as to provide the possibility to realize the surface charge manipulation of PB primary colloids. By adding electrolyte or changing the polarity of the solution, the surface charge regulation of PB colloid is realized, and the PB hierarchical structures with branch fractal structure (PB-BS), octahedral fractal structure, and spherical fractal structure are effectively constructed. This work not only achieves the designability of the PB structure, but also synchronizes the functionalization during the PB assembly growth process by in situ encapsulation of the effective catalytic active component L-Ascorbic acid. As a result, the assembled PB-BS exhibits greatly enhanced catalytic activity and selectivity in styrene oxidation with the selectivity of oxidized styrene increasing from 35.6% (PB) to 80.5% (PB-BS).

Fe/Mn (oxyhydr)oxides reductive dissolution promoted by cyanobacterial algal bloom-derived dissolved organic matter caused sediment W release during an algal bloom in Taihu Lake

Tungsten (W) can be toxic to aquatic organisms. However, the spatiotemporal characteristics and controlling factors of W mobility during harmful algal blooms (HABs) have rarely been investigated. In this study, simultaneous changes in soluble W, iron (Fe), manganese (Mn), and ultraviolet absorbance (UV254) in the sediment-water interface (SWI) were measured monthly using high-resolution peeper (HR-Peeper) devices. Laboratory experiments were conducted to verify the effects of environmental factors on W release. From May 2021 to October 2021, the concentration and flux of soluble W were higher than in other months. In addition, from May to October, DMAX (the depth at which the maximum concentration occurs on each profile) was 30–50 mm below the SWI, rather than the maximum depth. Principal component analysis (PCA) also divided the year into two periods, designated W-stable (December 2020, January, March, April and November 2021 with low soluble W concentration) and W-active periods (from May 2021 to October 2021 with high soluble W concentration). Laboratory experiments showed that both warming and anoxic conditions caused simultaneous release of soluble W, Fe(II), Mn, and dissolved organic matter (DOM), with strong correlations among soluble W, Fe(II), Mn. Partial least squares path modeling (PLS-PM) and random forest model showed that DOM directly affected W release or indirectly affected W release through promoting ferromanganese (oxyhydr)oxides reduction under warming and anaerobic conditions. The results of the field investigation showed that, in the W-stable period with low T, high DO, and an oxic SWI, the concentrations of soluble W, Fe, Mn, and DOM were low. The redundancy analysis (RDA) showed that these months were mainly affected by water DO. The significant and strong positive correlation among soluble W, Fe and Mn indicated that soluble W was probably scavenged by Fe/Mn (oxyhydr)oxides in the oxic water during the W-stable period. The W-active period corresponded to the cyanobacterial HABs (cyanoHABs) outbreak, with higher T, lower DO, and a more anoxic SWI. During this period, the concentrations of soluble W, Fe, Mn, and DOM were high and their correlations were stronger. RDA showed that these months were mainly affected by T, UV254, soluble Fe and Mn. These results indicated that reductive dissolution of Fe/Mn (oxyhydr)oxides driven by DOM generated in W-active period, especially cyanoHAB-derived DOM, mainly caused soluble W release. These results reveal the coupling relationship between cyanoHABs and W release and emphasize the need for prevention and control of heavy metal release in eutrophic lakes.

Integrating HYDRUS-2D and Bayesian Networks for simulating long-term sludge land application: Uncovering heavy metal mobility and pollution risk in the soil-groundwater environment

The release of sludge-derived heavy metals (HMs) to soil and their subsequent migration into groundwater poses a significant challenge for safe and low-carbon sludge land application. This study developed a predictive framework to simulate 60-year sludge land application, evaluating the risk of HMs pollution in the soil-groundwater environment and assessing the influence of soil and water properties. HYDRUS-2D simulations revealed that highly mobile Cu, Ni, and Zn penetrated a 10 m soil layer over a 60-year period, contributing to groundwater pollution. In contrast, Cr was easily sequestered within the topsoil layer after 5-years continuous operation. The non-equilibrium parameter α could serve as an indicator for assessing their potential risk. Furthermore, the limited soil adsorption sites for Pb (f = 0.02772) led to short-term (1-year) groundwater pollution at a 0.5 m-depth. Bayesian Networks model outcomes indicated that humic-like organics crucially influenced HMs transformation, enhancing the desorption of Cd, Cu, Ni, Pb, and Zn, while inhibiting the desorption for Cr. Additionally, electrical conductivity promoted the release of most HMs, in contrast to the Mn mineralogy in soil. This study bridges the gap between the macro-level HMs migration trends and the micro-level adsorption-desorption characteristics, providing guidance for the safe land application of sewage sludge. Environmental ImplicationThis study introduces a framework integrating HYDRUS-2D simulations with Bayesian Networks to assess the risks of groundwater pollution by heavy metals (HMs) over a 60-year sludge application. Sludge-derived Cu, Ni, and Zn are found to penetrate soil up to 10 m and exceed safety limits, with the non-equilibrium parameter α serving as an indicator for pollution risk. The importance of nutrients from sludge-amended soil for the transformation of HMs in the subsurface environment highlights the need for enhanced sludge management, specifically through more detailed regulation of nutrient composition. These findings contribute to developing precise strategies for the long-term sludge land application.

The effect of heavy precipitation on the leaching of heavy metals from tropical coastal legacy tailings

The continued growth in demand for mineral resources has led to a large amount of mining wastes, which is a major challenge in the context of carbon neutrality and climate change. In this study, runoff migration, batch leaching, and column experiments were used to investigate the short-, medium-, and long-term leaching of heavy metals from legacy tailings, respectively; the cumulative metal release kinetic equations were established, and the long-term effects of tailings leaching were verified by HYDRUS-1D. In runoff migration experiments, surface dissolution of tailings and the co-migration of adsorbed soil particles by erosion were the main carriers in the early stages of leachate formation (Mn ∼ 65 mg/L and SO42- up to 2697.2 mg/L). Batch leaching tests showed that the concentration of heavy metals in soil leached by acid rain were 0.1 ∼ 22.0 μg/L for Cr, 0.7 ∼ 26.0 μg/L for Cu, 4.8 ∼ 5646.0 μg/L for Mn, 0.3 ∼ 232.4 μg/L for Ni, and 1.3 ∼ 448.0 μg/L for Zn. The results of column experiments indicated that some soluble components and metals with high mobility showed a significant decreasing trend at cumulative L/S ≤ 2. Additionally, the metals have higher leaching rates under TCLP conditions, as shown by Mn > Co > Zn > Cd > Ni > Cu > Pb > Cr. The fitting results of Langmuir equation were closer to the cumulative release of metals in the real case, and the release amounts of Mn, Zn, Co, and Ni were higher with 55, 5.84, 2.66, and 2.51 mg/kg, respectively. The water flow within tailings affects the spatial distribution of metals, which mainly exist in relatively stable chemical fractions (F3 + F4 + F5 > 90 %) after leaching. Numerical simulation verified that Mn in leachate has reached 8 mg/L at a scale of up to 100 years. The research results are expected to provide technical basis for realizing the resource utilization of tailings in the future.

Metals in coastal groundwater systems under anthropogenic pressure: a synthesis of behavior, drivers, and emerging threats

AbstractSubmarine groundwater discharge (SGD) dynamically links land‐ and ocean‐derived chemical constituents, such as metals, in the coastal ocean. While many metals are sediment‐bound, changing environmental conditions, particularly along the coast, may lead to increased release of metals to their dissolved and more bioavailable form. Here, we review metal behavior, speciation, and drivers of mobilization in the coastal environment under anthropogenic influence. We also model global metal contamination risk to the coastal ocean via SGD considering anthropogenic and hydrogeologic pressures, where tropical regions with high population density, SGD, and acid sulfate soils (4% of the global coast) present the highest risk. Although most SGD studies focus on other analytes, such as nutrients, this review demonstrates the importance of considering SGD as a critical pathway for metals to reach the coastal ocean under rapidly changing environmental conditions.

Investigating the distribution of microplastics in soils from e-waste dismantling sites and their adsorption of heavy metals.

Microplastics are characterized by strong hydrophobicity, large specific surface area. In addition to the pollutant they contain, the heavy metals adsorbed on the surface of microplastics can migrate or be transformed with them into the environmental medium, which is potentially harmful to humans. The distribution characteristics of microplastics in contaminated soil at the e-waste dismantling site were studied. The study investigated the adsorption characteristics of polyvinyl chloride (PVC), polypropylene (PP) and acrylonitrile-butadiene-styrene (ABS) on copper (Cu), zinc (Zn) and lead (Pb). It analysed the influence of various factors on the adsorption process of heavy metals, the adsorption law of microplastics on some of the heavy metals in the environment, and the risk of heavy metal release from microplastics to soil. The results showed that ABS and PP were the main microplastics in the contaminated soil. Among them, black, white and transparent microplastics accounted for 89.91%. The shape of microplastics is mainly granular, and microplastics with a particle size of 1-2 mm accounted for the largest proportion. Further studies showed that plastic particles made of ABS, PP and PVC also have the adsorption capacity for different types of heavy metals in soil, and the trends of adsorption capacity are: PP>PVC>ABS. When PP does not reach adsorption equilibrium in the adsorption process, the smaller the particle size and the more added amount, the greater the adsorption capacity. This is because the smaller the particle size of the microplastic is, the more adsorption points it can provide, increasing its ability to adsorb heavy metal ions.

Boosting organics degradation via sulfite activation by Fe/Mn@CF composite electrode: Performance and mechanism

Sulfite has been proven to promote advanced oxidation processes (AOPs) to achieve low-cost and efficient degradation of contaminants, serving as an alternative to persulfate. In this study, a novel composite Fe/Mn@carbon felt (CF) electrode was successfully constructed to remove carbamazepine (CBZ). The capacity of the Fe/Mn@CF anode to activate sulfite was evaluated under various electrode preparation conditions and operating parameters. Results clearly indicated that the complete removal of CBZ was achieved in Fe/Mn@CF anode activated sulfite system under the specific conditions including Na2SO4 electrolyte concentration of 50 mM, sulfite dosage of 1 mM, initial pH of 7, and current density of 1 mA/cm2. The capacity of Fe/Mn@CF anode for sulfite activation was further presented by its excellent reusability and stability in terms of CBZ removal and metal ion release. Both radical and non-radical pathways were significantly contributed to the CBZ removal, including OH, SO4·-, O2·-, 1O2, and other reasons. Density functional theory (DFT) calculations demonstrated that Fe-Mn bimetals effectively promoted sulfite activation, with the electric field further boosting the process of Fe-Mn valence cycle and oxidation. Overall, the novel Fe/Mn@CF activated sulfite system exhibited outstanding performance and had great potential for sustainable use in removing organics.

Quantitative and qualitative analysis of metallic ion release of orthodontic brackets in three different pH conditions - An invitro study

BackgroundFluoridated mouth rinses improve anti-cariogenic environment but decrease oral pH below critical value, affecting orthodontic bracket surface topography and causing corrosive changes over prolonged use. This invitro study aimed to quantitatively and qualitatively assess the surface topography and metallic ion release of the stainless steel (SS) brackets at varying acidic and alkaline pH. Materials and methodsForty unused SS brackets were divided into four groups (Group A, B, C, D) and immersed for 48- hours in solutions of artificial saliva and sodium fluoride (0.2 %) mouth rinse at varying pH of 5.5,6.7,7 and 8. The surface morphologic changes were analyzed under scanning electron microscope (SEM) at 50×, 150×, and 500× magnification. The changes in slot area were scored using the customized scale. The Energy Dispersive Xray Spectroscopy Analysis (EDAX) was used to estimate the probed elements' atomic and weight percentage. ResultsThe mean score of the scale was 3.4 for the brackets immersed in the acidic solution which was statistically significant (p = 0.00)and for alkaline and neutral solutions (p = 0.00). Chromium was found to be significantly higher in the alkaline solution (p = 0.016) followed by the neutral solution. Carbon was found excess in acidic solution than the neutral and alkaline solution. ConclusionQuantitative and qualitative analysis of the ion release in stainless steel brackets using SEM and EDAX revealed the corrosive effect of fluoride ion causing maximum surface changes in acidic medium and chromium release in alkaline pH.

Hybrid copper-polyelectrolyte nanoaggregates obtained with smart block copolymers based on 4-[(hydroxyimino)aldehyde]butyl methacrylate (HIABMA) in water and acetonitrile

The AB multi-stimuli-responsive block copolymer pTEGMA-b-pHIABMA (TEGMA: tetra(ethyleneglycol) methyl ether methacrylate; HIABMA: 4-[(hydroxyimino)aldehyde]butyl methacrylate) comprises a hydrophilic and thermoresponsive PTEGMA block linked to the hydrophobic PHIABMA chain. The latter is endowed with slightly acidic oxime groups that potentially form complexes with metal ions. Here we investigate the formation of hybrid Cu(II)-polymer nanoaggregates both in water and in acetonitrile. Cu(II) ions are quantitatively and rapidly incorporated, in the presence of a base, into pre-formed polymeric core-shell micelles (30 nm diameter by DLS) in water up to 1:2 metal-to-ligand stoichiometry. The pKa of the polymer is decreased from ≅11.2 to 4.65 due to interaction with Cu(II) and the complex is shown to involve oximate ions. The thermoresponsivity of the polymeric micelles remains unchanged with Cu(II) complexation and allows an easy separation by flocculation of the hybrid complex. Moreover, nanoaggregates (D = 20 nm) form in acetonitrile from the fully solubilized copolymer interacting with Cu(OAc)2. The 1:2 Cu(II)/ligand stoichiometry is confirmed with the Job graphical method. Characterization of the hybrid micelles was carried out by UV–Vis spectrometry, DLS, TEM, STEM and SAXS. Quantitative release of Cu(II) in acidic conditions is demonstrated both in water and in acetonitrile. Full recovery of the free metal ions and of intact polymeric micelles is achieved through centrifugal filtration of the aqueous preparation, as a proof-of-concept for a recyclable system for metal uptake and release. Furthermore, Cu0 nanoparticles of 5–10 nm are obtained through reduction of Cu(II) within the micelles with ascorbic acid in aqueous solution.

Fragmentation of polypropylene into microplastics promoted by photo-aging; release of metals, toxicity and inhibition of biodegradability

The widespread presence of microplastics (MP) in water represents an environmental problem, not only because of the harmful effects of their size and potential to vector other pollutants, but also because of the release of additives, degradation products and residues contained in the polymer matrix. The latter includes metallic catalysts, which are often overlooked. This study focuses on the photo-aging of polypropylene (PP) and the resulting structural changes that promote its fragmentation microplastics (PP-MPs) and release of metals, as well as the resulting toxicity of leachates and their potential to inhibit biodegradation of organics in water. The pristine, photo-aged and waste PP are ground under the same regime to assess susceptibility to fragmentation. Obtained PP-MPs are submitted to leaching tests; the release of organics and metals is monitored by Total Organic Carbon (TOC) and Inductively Coupled Plasma Mass Spectrometry (ICP-MS) analysis, respectively. The leachates are assessed for their toxicity against Vibrio fischeri, Daphnia magna and Pseudokirchneriella subcapitata and their influence on the biodegradability of the glucose solution. Photo-aging induced changes in the crystallinity and morphology of the PP and manifested in the abundance of smaller MPs, as revealed by the particle size distribution. In the case of pristine PP, all particles were > 100 μm in size, while aged PP yielded significant mass fraction of MPs <100 μm. The toxicity of leachates from aged PP-MPs is higher than that of pristine and exhibits a positive correlation with portion of metals released. The biodegradability of glucose is strongly inhibited by PP-MPs leachates containing a mixture of metals in trace concentrations.