Bromine Content Research Articles

Efficient wide-bandgap perovskite photovoltaics with homogeneous halogen-phase distribution

Wide-bandgap (WBG) perovskite solar cells (PSCs) are employed as top cells of tandem cells to break through the theoretical limits of single-junction photovoltaic devices. However, WBG PSCs exhibit severe open-circuit voltage (Voc) loss with increasing bromine content. Herein, inhomogeneous halogen-phase distribution is pointed out to be the reason, which hinders efficient extraction of carriers. We thus propose to form homogeneous halogen-phase distribution to address the issue. With the help of density functional theory, we construct a double-layer structure (D-2P) based on 2-(9H-Carbazol-9-yl)ethyl]phosphonic acid molecules to provide nucleation sites for perovskite crystallization. Homogeneous perovskite phase is achieved through bottom-up templated crystallization of halogen component. The efficient carrier extraction reduces the Shockley-Read-Hall recombination, resulting in a high Voc of 1.32 V. As a result, D-2P-treated device (1.75 eV) achieves a record power conversion efficiency of 20.80% (certified 20.70%), which is the highest value reported for WBG (more than 1.74 eV) PSCs.

Extremely high levels of PBDEs in children’s toys from European markets: causes and implications for the circular economy

BackgroundWith the high influx of low-cost plastic toys on the market, there is growing concern about the safety of such toys. Some of these plastic toys contains hazardous chemicals like polybrominated diphenyl ethers (PBDEs) due to the use of recycled plastics in new toy manufacturing. Here, we investigated if toys marketed in Europe are compliant with EU directives to assess the safety of currently used children's toys and identify implications of PBDE content in toys.ResultsEighty-four toys purchased from international toy retailers were screened for bromine using X-ray fluorescence (XRF), and 11 of those with bromine content higher than 500 µg/g were analyzed for ten PBDEs using GC–HRMS. PBDEs were detected in all 11 toys. Ʃ10PBDE concentrations ranged up to 23.5 mg/g (with a median concentration of 8.61 mg/g), with BDE-209 being the most abundant compound (4.40 mg/g). Eight samples exceeded the EU’s Low POP Content Limit (LPCL) of 500 µg/g for the Ʃ10PBDEs by 6–47 times and the Unintentional Trace Contaminant (UTC) limits of 10 µg/g for Deca-BDE by 12–800 times.ConclusionsPBDEs were up to percent levels, suggesting direct recycling of flame retarded plastic, e.g., e-waste plastics, into toy components. This is a call for concern and requires intervention from all stakeholders involved in the toy market. Overall, the occurrence of non-compliant toys in the EU market, as indicated in this study is primarily attributed to gaps in regulations, inadequate legislation for recycled plastics, the rise of online sales, complexities in global and national supply chains, and economic challenges. Failure to address these issues will hinder the efforts of the plastics industry to transition into a circular economy. This suggests that more actions are needed to address gaps in cross-border enforcement, and stricter sanctions are required for toy manufacturers who fail to adhere to regulations and safety standards.

Research on mercury re-release model in wet flue gas desulfurization (WFGD) in coal-fired power plants

Mercury (Hg), a toxic heavy metal, has triggered regulations for emission control from coal-fired power plants. It has been found that mercury re-release occurs in WFGD slurry, which is affected by WFGD process parameters. The coal co-combustion with bromide technology proves to be an efficient approach for enhancing mercury removal ratio but the accumulation of introduced bromine in WFGD slurry would impact the re-emission behavior of mercury significantly. Model study is efficient method to reveal the physicochemical processes in WFGD systems. However, previous model studies were carried out under Hg2+ contained simulated slurry systems without consideration of Hg2+ transformation process from gas to liquid phase, and co-combustion with bromide technology was not considered. Here, a model which encompasses droplets motion sub-model, gas–liquid heat transfer sub-model, gas–liquid mass transfer sub-model and the mercury re-release kinetic sub-model is developed and validated against experimental data. The effects of bromine concentration, slurry temperature, pH value and S(IV) concentration were investigated. It was found that introduced bromine has significant inhibitory effects on the re-release of mercury. When the slurry temperature is higher, the absorption rate of Hg2+ is lower and more Hg0 is released. Moreover, the increase in the slurry pH value and S(IV) concentration has certain inhibitory effects on the re-release of Hg0 in WFGD. Above all, the developed model has high prediction accuracy for the absorption of Hg2+ and the re-release of Hg0 in WFGD which is expected to be beneficial for guiding the operation of WFGD systems.

Experimental verification of solubilization effect of soil bromine by waterlogging reduction

ABSTRACT Although the concentration of bromine in the Earth’s crust is only approximately 2 µg g−1, it is one of the most crucial elements in daily human life. On the Earth’s surface, bromine is thought to be widely transported and circulated in the hydrosphere, atmosphere, lithosphere, and biosphere. However, little is known regarding the dynamics of bromine in the terrestrial environments. In this study, waterlogging incubation tests were conducted on two soil types, Lowland soil and Andosol, to verify the solubilization effect of waterlogging on soil bromine. The amount of bromine in the soil extracts increased considerably with incubation time in Lowland soil and Andosol, proving that the soil reduction caused by waterlogging enhanced the solubilization of soil bromine. The amount of bromine solubilized by soil reduction tended to be higher in Andosols, which had a higher total bromine concentration than Lowland soil. The amount by soil reduction during the 28 days period ranged from 0.18 to 1.14 µg g−1 for the Lowland soil group and from 0.20 to 30.2 µg g−1 for the Andosol group. Solubilized bromine could not remain in the soil, and most of it leached out with the percolation water, as shown by the soil-filled column tests. To estimate the amount of bromine leached from a rice paddy field under waterlogged conditions, a percolation test was conducted using Wagner pot-cropped paddy rice plants. The results showed that 531 to 544 mg of bromine per square meter of soil surface leached during one growing season. The amount of bromine leached from the soil was much higher than the previously reported annual amount of bromine addition to land from atmospheric deposition.

Determination of sodium, chlorine, and bromine concentrations in breast milk using neutron activation: Correlation, regression, and machine learning predictions

Breast milk plays a vital role in infant health, providing essential nutrients that directly impact nutrition and development. Understanding its elemental composition, as well as the relationships among these elements, is crucial for assessing its nutritional adequacy. This study focused on determining the concentrations of sodium (Na), chlorine (Cl), and bromine (Br) in the breast milk of lactating mothers in Tehran, Iran, during early lactation. The primary objectives were to analyze the concentrations of these elements, investigate their interrelationships, and employ machine-learning techniques to predict their concentrations in breast milk. Neutron activation analysis (NAA) was used to precisely measure the levels of Na, Cl, and Br, while statistical methods, including correlation and regression analyses, were applied to further explore these relationships. Machine-learning models, specifically Random Forest and Linear Regression, were utilized to predict the concentrations of these elements based on their interdependencies. The study revealed mean concentrations of 5.12 mg/g for Na, 8.14 mg/g for Cl, and 11.84 mg/kg for Br in the breast milk samples. A strong positive correlation was observed between Na and Cl (r = 0.976, p < 0.001), while moderate positive correlations were found between Na and Br (r = 0.558, p < 0.001) and Cl and Br (r = 0.606, p < 0.001). Multiple regression models showed that 94.7 % of the variance in Na concentration could be explained by Cl and Br levels (R-squared = 0.947), with a strong positive association between Cl and Na, and a slight inverse relationship between Br and Na. A similar model for Cl concentrations showed strong predictive power, with Na being a significant predictor. However, the model for Br concentrations explained a smaller proportion of variance (R-squared = 0.318), suggesting that additional factors influencing Br levels were not captured in this study. Furthermore, multicollinearity was observed between Na and Cl (VIF = 20.675), indicating potential interactions between these elements. This study highlights the significant correlations between Na, Cl, and Br in breast milk, with particularly strong predictive models for Na and Cl concentrations. The findings also suggest the need for further investigation into the factors affecting Br concentrations. Overall, this research provides valuable insights into the elemental composition of breast milk and its implications for infant nutrition and health.

Chemical Recycling of Mixed Polyolefin Post-Consumer Plastic Waste Sorting Residues (MPO323)-Auto-Catalytic Reforming and Decontamination with Pyrolysis Char as an Active Material.

Mixed plastic packaging waste sorting residue (MPO323) was treated by thermal pyrolysis to utilize pyrolysis oil and char. The pyrolysis oil was found to contain aromatic and aliphatic hydrocarbons. The chlorine and bromine contents were as high as 40,000 mg/kg and 200 mg/kg, respectively. Additionally, other elements like sulfur, phosphorous, iron, aluminum, and lead were detected, which can be interpreted as impurities relating to the utilization of oils for chemical recycling. The pyrolysis char showed high contents of potentially active species like silicon, calcium, aluminum, iron, and others. To enhance the content of aromatic hydrocarbons and to reduce the level of contaminants, pyrolysis oil was reformed with the corresponding pyrolysis char to act as an active material in a fixed bed. The temperature of the reactor and the flow rate of the pyrolysis oil feed were varied to gain insights on the cracking and reforming reactions, as well as on performance with regard to decontamination.

Effect of bromine on the formation of δ-CsPbI3 in Cs0.22FA0.78Pb(I1-xBrx)3 perovskite solar cells

Applying CsxFA1-xPbI3 perovskite is a useful strategy for synthesizing high-efficiency organic-inorganic lead halide perovskite solar cells because it improves the stability of the perovskite structure. High concentration of cesium (Cs) in CsFAPbI3 synthesized under ambient conditions typically lead to phase separation due to δ-CsPbI3 formation and moisture, thereby reducing light absorption and increasing non-radiative recombination. To counter this, we fabricated the mixed halide Cs0.22FA0.78Pb(I1-xBrx)3 perovskite films. Introducing bromine (Br) content effectively reduced the δ-CsPbI3 formation and grain boundaries, thus suppressing the non-radiative recombination between perovskite and charge transport layers. Employing this approach, our perovskite solar cells with a 10 % Br concentration achieved a power conversion efficiency of 15.81 %. This demonstrates the potential of Br incorporation in enhancing the stability and efficiency of perovskite solar cells.

Advancements in bandgap engineering: bromide-doped cesium lead perovskite thin films

Perovskite materials have emerged as promising candidates for next-generation photovoltaic devices due to their unique optoelectronic properties. In this study, we investigate the incorporation of bromine into cesium lead mixed iodide and bromide perovskites (CsPbI3(1-x)Br3x) to enhance their performance. By depositing films with varying bromine concentrations (x = 0, 0.25, 0.5, 0.75), we employ a combination of structural and optical characterization techniques, including X-ray diffraction (XRD), scanning electron microscopy (SEM), UV–visible spectroscopy, and photoluminescence. Our analysis reveals that introducing bromine leads to structural modifications, influencing the perovskite films’ optical properties and energy gap. Specifically, we observe semiconductor behavior with a tunable energy gap controlled by the intercalation of bromine atoms into the CsPbI3 lattice. Furthermore, heat treatment induces phase transitions in the perovskite films, affecting their optical responses and crystalline quality. SCAPS-1D simulations confirm the improved stability and efficiency of bromine-doped CsPbI3 films compared to undoped counterparts. Our findings demonstrate that bromine incorporation facilitates the formation of highly crystalline perovskite films with reduced trap defects and enhanced carrier transport properties. These results underscore the potential of bromine-doped CsPbI3 perovskites as promising materials for high-performance photovoltaic applications, paving the way for further optimization and device integration.

Method development for multielement determination of halogens and sulfur in teas

Abstract Microwave-induced combustion was evaluated as a sample preparation method for several types of tea (black, green, lemon balm, boldo, and mint) for further determination of bromine, chlorine, fluorine, iodine, and sulfur by ion chromatography. Parameters such as the sample mass efficiently decomposed and the most suitable absorbing solution (ultrapure water and 25, 50, 100, and 150 mmol L−1 NH4OH) were evaluated, considering the characteristics of the analytes and the determination technique used. The maximum sample mass possible to be decomposed was 900 mg of milled tea in the form of pellets, and the absorbing solution chosen was 100 mmol L−1 NH4OH, which provided suitable stabilization of the analytes (recoveries between 95 % and 103 %). To assess the accuracy of the proposed method, a certified reference material (BCR 060, aquatic plant) was analyzed. Agreements with the certified values ranged from 101 % to 107 %. The proposed method was used to analyze tea samples and the concentrations ranged from 549 to 2,549 mg kg−1 for chlorine, 223 to 828 mg kg−1 for fluorine, and 786 to 4,023 mg kg−1 for sulfur; bromine and iodine concentrations were below the limits of quantification (42 and 80 mg kg−1, respectively) in all evaluated samples.

Thermal-oxidative stability of PVC compositions modified with a bromine-containing plasticizer-flame retardant

The possibility of creating polymer compositions based on polyvinyl chloride plasticized with a bromine-containing flameretarding plasticizer has been investigated. Their thermostability at introduction of plasticizer with different bromine content was evaluated. The optimal concentrations of bromine in the flame-retarding plasticizer to increase the thermal stability of the polymer composition have been established. It is noted that increasing the concentration of bromine in the flame-retarding plasticizer increases the rate of elimination of hydrogen bromide and slows down the thermal destruction of the polymer matrix. It is shown that during thermo-oxidative degradation of plasticized PVC composite, hydrogen bromide is first eliminated from flame-retarding plasticizer, which accelerates the process of polyene formation and additional cross-linking of polymer macromolecules. An increase in the tensile strength of plasticized compositions at the introduction of optimal dosages of flame-retarding plasticizer was observed.

Phase-stable wide-bandgap perovskites enabled by suppressed ion migration

Wide-bandgap (>1.7 eV) perovskites suffer from severe light-induced phase segregation due to high bromine content, causing irreversible damage to devices stability. However, the strategies of suppressing photoinduced phase segregation and related mechanisms have not been fully disclosed. Here, we report a new passivation agent 4-aminotetrahydrothiopyran hydrochloride (4-ATpHCl) with multifunctional groups for the interface treatment of a 1.77-eV wide-bandgap perovskite film. 4-ATpH+ impeded halogen ion migration by anchoring on the perovskite surface, leading to the inhibition of phase segregation and thus the passivation of defects, which is ascribed to the interaction of 4-ATpH+ with perovskite and the formation of low-dimensional perovskites. Finally, the champion device achieved an efficiency of 19.32% with an open-circuit voltage (VOC) of 1.314 V and a fill factor of 83.32%. Moreover, 4-ATpHCl modified device exhibited significant improved stability as compared with control one. The target device maintained 80% of its initial efficiency after 519 h of maximum power output (MPP) tracking under 1 sun illumination, however, the control device showed a rapid decrease in efficiency after 267 h. Finally, an efficiency of 27.38% of the champion 4-terminal all-perovskite tandem solar cell was achieved by mechanically stacking this wide-bandgap top subcell with a 1.25-eV low-bandgap perovskite bottom subcell.

Primary and residual impacts of phosphoric acid modified biochar on growth and concentrations of essential and non-essential elements in lettuce and second crop arugula

The study aimed to explore how phosphoric acid-modified rice husk biochar (PBC) affects the growth and concentrations of essential and non-essential elements in two crops: lettuce as the primary crop and arugula as the secondary crop. The treatments consisted of a no P fertilized control and 250 mg P kg−1 sourced either from PBC, triple super phosphate (TSP) or phosphoric acid (PA). When subjected to phosphorus (P) sources, both lettuce and arugula exhibited a noteworthy rise in their dry weights compared to the control plants. PBC treatments significantly increased P concentration in both plants. Although the PBC treatment decreased lettuce nitrogen (N) concentration, it had no impact on arugula N concentration. Phosphorus treatments resulted in a decrease in lettuce K concentration, whereas it increased in arugula. Calcium (Ca), magnesium (Mg) and sulfur (S) concentrations in both plants were not affected by P sources. The zinc (Zn) concentrations of the plants notably decreased with P treatments. Moreover, P treatments led to a reduction in manganese (Mn) concentration specifically in arugula. PBC significantly increased the silicon (Si) concentrations of lettuce plants. The application of PA significantly increased the vanadium (V) concentration in arugula. Phosphoric acid treatments resulted in an increase in the plant bromine (Br) concentrations. To conclude, PBC may serve as an alternative P source, potentially being as effective as or even more effective than other P sources in influencing plant nutrition, without causing an undesirable elevation of non-essential elements in plants.

Anthropogenic Influence on Tropospheric Reactive Bromine Since the Pre‐industrial: Implications for Arctic Ice‐Core Bromine Trends

AbstractTropospheric reactive bromine (Bry) influences the oxidation capacity of the atmosphere by acting as a sink for ozone and nitrogen oxides. Aerosol acidity plays a crucial role in Bry abundances through acid‐catalyzed debromination from sea‐salt‐aerosol, the largest global source. Bromine concentrations in a Russian Arctic ice‐core, Akademii Nauk, show a 3.5‐fold increase from pre‐industrial (PI) to the 1970s (peak acidity, PA), and decreased by half to 1999 (present day, PD). Ice‐core acidity mirrors this trend, showing robust correlation with bromine, especially after 1940 (r = 0.9). Model simulations considering anthropogenic emission changes alone show that atmospheric acidity is the main driver of Bry changes, consistent with the observed relationship between acidity and bromine. The influence of atmospheric acidity on Bry should be considered in interpretation of ice‐core bromine trends.

Spatial and temporal variability analysis of snow cover parameters according to the urbanized area profile system

The purpose of the study is to analyze the spatial and temporal variability of snow cover parameters in the urbanized area of the city of Irkutsk and its adjacent areas according to the system of profiles reflecting the features of the area microrelief. Field surveys were conducted in accordance with standard recommendations for snow and geochemical surveys. Snow sampling was carried out at the entire snow depth, with the exception of the snow depth of 0.5-1 cm. Sampling points located at least 25 meters away from the roads. Snow sampling in the residential areas of the city was carried out in the places with undisturbed snow cover and free from extraneous snow banks and landfills. Global Mapper, Golden Software Surfer, Statistica software were used to carry out statistical analysis, build the models of profile sections and obtain the diagrams of snow cover parameter distribution. A 3D relief model was obtained on the basis of radar topographic survey data, which revealed a multiple formation relief of the studied area featuring mountains, high plains with undulating flat gently sloping watersheds, valleys, hollows and depressions. The height difference is up to 230 m. The diagrams of snow depth distribution built with regard to the profiles made it possible to identify the territories with the deepest snow cover. A geochemical analysis of the melt water filtrate was carried out over a three-year period. In 2021 a high correlation with electrical conductivity was found for the contents of tungsten, sodium, bromine, calcium, molybdenum, sulfur, barium, magnesium, antimony, tantalum, cesium, titanium, chromium, and silicon. The average correlation level with electrical conductivity was recorded for arsenic, copper, and lead. The analysis data obtained indicate a different contamination level of the area as a result of atmospheric precipitation in those years due to the activity of industrial facilities. The distribution patterns of the pH snow index have been revealed. It is shown that zones with pH&lt;6 are mostly confined to the Irkutsk aluminum smelter. The zones with pH &gt;6 are caused by the influence of the power plants using hydrocarbon fuels: gasoline, kerosene, fuel oil, diesel fuel, coal. The snow cover was subjected to field and laboratory studies using GIS technologies and physico-chemical methods. The distribution and migration of pollutants in various spatial and temporal aspects have been revealed taking into account the terrain relief. The conducted study opens up opportunities for modeling the landscape structure, taking into account meteorological parameters, phenological processes and snow cover state for the purposes of the national economy and the location of construction of various facilities.

Thermal pyrolysis of a real plastic sample from small WEEE and characterization of the produced oil in view of fuel or feedstock uses

The possibilities of valorizing by pyrolysis a plastic fraction from small waste from electrical and electronic equipment (WEEE-R4) rejected by a material recovery facility have been assessed. The characterization revealed that WEEE-R4 was mainly composed of acrylonitrile–butadiene–styrene (ABS) and blends of polycarbonate (PC)-ABS (75 and 25 wt%, respectively) and had good physicochemical properties as feed for pyrolysis processes: high values for volatile matter (95 wt%) and low heating value (LHV, 35 MJ/kg) and low ash and moisture content (2.5 and 0.33 wt%, respectively). On the contrary, the high content of heteroatoms, in particular Br from brominated flame retardants, arose as source of concern. Thermal analysis coupled with evolved gas Fourier transform Infrared (FTIR) spectroscopy showed that WEEE-R4 degraded in two steps in the range 310–460 °C and mainly to the monoaromatic compounds phenol and styrene. Thermal pyrolysis at 400 °C was carried out in a bench-scale reactor and the yields of the products were 18 wt% solids, 58 wt% light oil, 16 wt% tar and 8 wt% gas. The gaseous fraction was composed mainly of CO2 (60 wt%), originating from the thermal degradation of PC. After removing CO2, the gas had a good LHV (32.5 MJ/kg) such to contribute for the 66 % to the energy required for the pyrolysis process of WEEE-R4. The properties of the light oil were evaluated by means of the same standard tests used for commercial fuels or crude oils. The results were interesting but far from the more refined gasoline and diesel oil, with the concentration of nitrogen and bromine even higher than the typical composition of petroleum. Nevertheless, this study shows that pyrolysis followed by a refining treatment such as, distillation is capable of producing monoaromatic hydrocarbon in significant amount (>30 wt%).

EVALUATION OF THE THERMAL-OXIDATIVE STABILITY OF A HALOGEN-CONTAINING PLASTICIZER-FIRE RETARDANT

The importance of assessing the indicators of thermal-oxidative stability of plasticizers that are part of polymer compositions for ensuring high performance indicators during their processing and operation of finished products is noted. When using brominated organic compounds of the aromatic series, a short burning time of polymer compositions and a significant smoldering time have been established. The use of flame retardants containing a halogen in the aliphatic radical leads to a decrease in the smoldering time and an increase in the duration of combustion due to a decrease in the thermal stability of the material at the stage of decomposition. It is indicated that bromine-containing compounds give the best inhibition effect compared to chlorine-containing compounds due to a decrease in the carbon-bromine bond breaking energy compared to the carbon-chlorine bond energy. The decomposition parameters of the brominated plasticizer-fire retardant have been established. It is shown that the thermal decomposition of the brominated plasticizer occurs in two stages, corresponding to the elimination of bromine from the aliphatic radical in the temperature range 473 K – 573 K and the decomposition of phthalic acid esters in the range 603 K – 623 K. The beginning of intensive decomposition corresponds to 443 K. The maximum of the first stage of decomposition is at the point corresponding to 501 K, the second - 606-623 K. It was noted that the bromine-free plasticizer decomposes intensively, starting from 503 K and reaches the maximum decomposition rate at 611 K. The maximum loss of the bromine-free plasticizer was established at 27%, brominated - 50.9% of the mass of the sample. It has been confirmed that the presence of bromine atoms in the plasticizer adversely affects its thermal stability. The influence of the degree of halogenation of an unsaturated plasticizer on the nature of its thermal-oxidative degradation in the temperature range corresponding to the technological parameters of processing polymeric materials at elevated temperatures of 413-443 K has been studied. It is shown that an increase in the content of bromine in the plasticizer when performing technological operations for the processing of polymer compositions in the specified temperature range and the duration of exposure to elevated temperatures within one hour does not significantly affect the mass fraction of bromine in the plasticizer. A kinetic equation for the reaction of thermal decomposition of a bromine-containing plasticizer-flame retardant of the phthalate type, accompanied by the elimination of hydrogen bromide, is proposed. The activation parameters of the hydrogen bromide evolution reaction were determined for the temperature range of maximum decomposition of a brominated phthalate plasticizer with a bromine content in the range of 5% – 25%. It is shown that the activation energy of hydrogen bromide elimination depends on the bromine content in the plasticizer and decreases by 23% with an increase in the degree of bromination. It is shown that the temperature range of maximum decomposition of the brominated fire retardant plasticizer, corresponding to 473 K – 573 K, allows using it as a secondary plasticizer for polyvinyl chloride without reducing the thermal stability of the base.

Optimizing ionic transport in argyrodites: a unified view on the role of sulfur/halide distribution and local environments.

Understanding diffusion mechanisms in solid electrolytes is crucial for advancing solid-state battery technologies. This study investigates the role of structural disorder in Li7-x PS6-x Br x argyrodites using ab initio molecular dynamics, focusing on the correlation between key structural descriptors and Li-ion conductivity. Commonly suggested parameters, such as configurational entropy, bromide site occupancy, and bromine content, correlate with Li-ion diffusivity but do not consistently explain conductivity trends. We find that a uniform distribution of bromine and sulfur ions across the 4a and 4d sublattices is critical for achieving high conductivity by facilitating optimal lithium jump activation energies, anion-lithium distances, and charge distribution. Additionally, we introduce the ionic potential as a simple descriptor that predicts argyrodite conductivity by assessing the interaction strength between cations and anions. By analyzing the correlation between ionic potential and conductivity for a range of argyrodite compositions published over the past decade, we demonstrate its broad applicability. Minimizing and equalizing ionic potentials across both sublattices enhances conductivity by reducing the strength of anion-lithium interactions. Our analysis of local environments coordinating Li jumps reveals that balancing high and low-energy pathways is crucial for enabling macroscopic diffusion, supported by investigating percolating pathways. This study highlights the significance of the anionic framework in lithium mobility and informs the design of solid electrolytes for improved energy storage systems.

Exposure and Toxicity of Polybrominated Diphenyl Ethers: A Mini Review

Polybrominated Diphenyl Ethers (PBDEs), recognized as persistent organic pollutants by the United Nations Environment Programme, are a class of brominated flame retardants that pose significant environmental and health risks. These compounds, consisting of two aromatic rings with up to 10 bromine atom substitutions, are categorized into penta-BDE, octa-BDE, and deca-BDE based on their bromine content, each exhibiting distinct environmental behaviors. PBDEs with fewer bromine atoms are more volatile and prone to bioaccumulation, raising significant health concerns. These compounds, often added physically to products, can leach into the environment, leading to pollution during production and after the parent polymer degrades. The transformation of higher brominated diphenyl ethers into less brominated forms in the environment further complicates their impact, with mono-brominated BDE-3 being particularly concerning due to its extended atmospheric photolysis lifetime and increased bioavailability. The management of PBDEs is challenging due to their persistence and transformation in the environment. As endocrine disruptors, they are linked to various acute and chronic toxicological effects, including neurodevelopmental toxicity, teratogenicity, and potential carcinogenicity. Their structural similarity to thyroid hormones allows them to disrupt thyroid hormone balance, leading to further health complications. The subject of this review is to summarize the current body of knowledge that is essential to understand their long-term effects on ecosystems and human health and to develop strategies to mitigate their adverse impacts.

Second-order calibration high-resolution continuum source graphite furnace molecular absorption spectrometry-based determination of bromine and fluorine

In this study, we report the simultaneous determination of bromine and fluorine using Second-Order Calibration High-Resolution Continuum Source Graphite Furnace Molecular Absorption Spectrometry (HR CS MAS). The instrumental data acquired correspond to the time versus wavelength matrix per sample that were analyzed using Parallel Factor Analysis (PARAFAC), along with Unfold and N-way Partial Least Squares combined with a post-calibration step known as Residual Bilinearization (U and N PLS/RBL). Despite the significant difference in sensitivity between bromine and fluorine, all approaches provided reasonably accurate results when predicting both analytes in synthetic mixtures within a controlled environment. The relative prediction error (REP) values for bromine were 29.8 % (PARAFAC), 23.6 % (N-PLS/RBL), and 13.1 % (U-PLS/RBL), while for fluorine, the REP values were 3.4 % (PARAFAC), 3.5 % (N-PLS/RBL), and 3.2 % (U-PLS/RBL). When applying this approach to predict unknown samples, a comparison was made between the estimated nominal concentrations of fluorine and bromine obtained using either a reference method or based on labeled values or spiked mass, and those obtained using the proposed method. It was observed that PARAFAC was unable to predict the samples accurately, whereas the REP values for the prediction of bromine and fluorine using N-PLS/RBL and U-PLS/RBL methods were 19.3 %/19.2 % and 13.6 %/13.1 %, respectively.

Evaluating the photochemical reactivity of disinfection byproducts formed during seawater desalination processes

Reverse osmosis (RO) is widely used for seawater desalination but pre-chlorination of intake water produces halogenated disinfection byproducts (DBPs). The fate and environmental impacts associated with the discharge of DBP-containing RO brine wastewater are unknown. Therefore, to evaluate if photochemistry plays a role in DBP degradation in seawater, we collected samples at a desalination plant, which were desalted and concentrated using two-inline solid phase extraction (SPE) techniques combining reverse-phase polymeric (PPL) and weak anion exchange (WAX) resins. Both filtered water samples and SPE samples (extracts reconstituted in open ocean seawater) were exposed to simulated sunlight in a custom-built flow-through system. Optical property analysis during irradiation experiments did not provide distinguishing features between intake water and RO reject water (brine). Extractable organic bromine (organoBr) concentrations were low in intake water samples (7.8 μg Br L−1) and did not change significantly due to irradiation. OrganoBr concentrations in laboratory-chlorinated raw water were much higher (135 μg Br L−1) and on average decreased by 42 % after 24 h irradiation. However, while organoBr concentrations were highest in RO reject water (473 μg Br L−1), changes in organoBr concentrations in PPL SPE samples after 24 h irradiation were variable, ranging from a 1–46 % loss. Furthermore, most bromine-containing molecular ions identified by high resolution mass spectrometry that were present in RO reject water before irradiation were also found after both 24 h and 50 h exposures. Although only one RO reject water sample was tested in this study, results highlight that hundreds of yet to be identified brominated DBPs in RO reject water could be resistant to photodegradation or phototransform into existing DBPs in the environment. Future work examining the biolability of DBPs in RO reject water, as well as the interplay between photochemical and biological DBP cycling, is warranted.