Bromine Research Articles

Dual Role of Aerosols on Reactive Bromine Recycling in Extrapolar Marine and Continental Regions

AbstractReactive bromine species play important roles in atmospheric chemistry and influence the abundance of climate‐ and air quality‐relevant trace gases. While extensive studies have focused on bromine chemistry in polar regions, the bromine species in extrapolar regions, particularly regarding pollution‐related bromine recycling, have received less attention. In this study, we examine the factors influencing the bromine recycling at a clean marine site of the North Atlantic (Cape Verde, CVAO), a semipolluted coastal site of the South China Sea (Hok Tsui, HT), and a polluted continental site of North China (Wangdu, WD), using an observation‐based model combined with updated halogen chemistry. Our results indicate that aerosol‐related multiphase processes significantly affect bromine recycling in these extrapolar sites. Nitrate photodissociation efficiently recycled bromide into the gas phase in regions characterized by strong aerosol acidity (HT) or high aerosol concentrations (WD). Concurrently, bromine species are lost from the gas phase toward aerosol surfaces, with this process being more effective at higher liquid water content (WD > HT > CVAO). In semipolluted and polluted sites, the aerosol‐related processes resulted in elevated bromine levels in the daytime compared to nighttime, leading to larger effects of bromine species on ozone than previously thought. Our study suggests the need for a better understanding of the complex effects of aerosols on reactive halogen chemistry.

Microvasculature and Trabecular Bone in Beagle Proximal Femur: Microstructural Insights

Avascular necrosis of femoral head and malunion are frequent post-operative complications of femoral neck fractures. To optimize surgical techniques, this study aims to provide a microstructural understanding of intraosseous microvasculature and the trabecular bone of the femoral head and neck. This anatomical study analyzed twenty-eight femora from fourteen cadaveric beagles. Common iliac arteries were infused with colored silicone-resin for vascular visualization, followed by non-decalcified hard tissue processing using the EXAKT®, and Masson's trichrome staining. Morphology and histomorphometric analysis were performed by Nikon NIS Elements BR and ImageJ-fiji. Histomorphometry revealed thin, elongated trabeculae with high vascularity aligned parallel in the neck; numerous intraosseous anastomoses at the neck-shaft and head-neck junctions; thick trabeculae with smaller marrow cavities and dense, branching vascular networks near the cortex in the head. Quantitative analysis showed an inverse correlation between trabecular density and mean vascular density/vascular length density, with no significant sex or side differences. Dense connective tissue fibers maintained the microvasculature and trabeculae structure. The femoral neck displayed an outside-in microvascular pattern via retinacular branches. Conversely, the femoral head had an inside-out pattern through epiphyseal branches reinforced by medullary branches. Dense intraosseous microvasculature aligned sub-cortically. The study identified a potential anatomical safe zone for screwing in femoral neck fractures in beagles. These findings provide an anatomical basis for translational research in joint preservation techniques for humans.

Synthesis of Stable Hypervalent Bromine(III) Complexes by in Situ Oxidation with Lewis Acids Containing sp-Hybridized Nitrogen.

Stable hypervalent bromine(III) compounds were synthesized via aryl bromine oxidation with sp-hybridized nitrogen cations generated by oxime N-O bond cleavage in trifluoroacetic acid. The resulting intramolecular N-Br hypervalent bond is effectively stabilized by the planar xanthone structure. The structures and physicochemical properties of these λ3-bromanes were characterized by X-ray crystallography, cyclic voltammetry, UV-vis spectroscopy, and computational analysis.

Predicting reaction kinetics of reactive bromine species with organic compounds by machine learning: Feature combination and knowledge transfer with reactive chlorine species

Reactive bromine species (RBS) such as bromine atom (Br•) and dibromine radical (Br2•−) are important oxidative species accounting for the transformation of organic compounds in bromide-containing water. This study developed quantitative structure−activity relationship (QSAR) models to predict second order rate constants (k) of RBS by machine learning (ML) and conducted knowledge transfer between RBS and reactive chlorine species (RCS, e.g., Cl• and Cl2•−) to improve model performance. The ML-based models (RMSEtest = 0.476 −0.712) outperformed the multiple linear regression-based models (RMSEtest = 0.572 −3.68) for predicting k of RBS. In addition, the combination of molecular fingerprints (MFs) and quantum descriptors (QDs) as input features improved the performance of ML-based models (RMSEtest = 0.476 −0.712) compared to those developed by MFs (RMSEtest = 0.524 −0.834) or QDs (RMSEtest = 0.572 −0.806) alone. EHOMO and Egap were identified to be the most important features affecting k of RBS based on SHAP analysis. A unified model integrating the datasets of four reactive halogen species (RHS, e.g., Br•, Br2•−, Cl• and Cl2•−) was further developed (R2test = 0.802), which showed better predictive performance than the individual models (R2test = 0.521 −0.776). Meanwhile, the model performance changed differently by employing knowledge transfer among RHS, which was improved for Br•/Cl•, mixed for Br•/Br2•− and Cl•/Cl2•−, but worse for Br2•−/Cl2•−. This study provides useful tools for predicting k of RHS in aqueous environments.

A hydrogeochemical and isotopic approach for assessing the origin, recharge and mixing process of geothermal water in the Yinchuan Basin

The hydrogeochemistry of geothermal fluids is fundamental to reveal the genesis, recharge mechanism and circulation pattern of geothermal water. However, the origin and hydrogeochemical process of geothermal water in deep aquifer system still remain unclear. In this study, 17 water samples were analyzed to study the origin, recharge and mixing process of geothermal water in the Yinchuan basin by using a hydrogeochemical and isotopic approach. The results showed that the concentrations of major ions (SO42−, Na+, Cl−, TDS, Ca2+, K+, Mg2+ and NH4+) and trace elements (Li, F−, Br−, I−, Sr and Mn) in geothermal water are significantly greater than those in shallow water, hot spring and cold spring in the study area. The hydrochemical type of geothermal water is dominated by Cl·SO4-Na, which is mainly influenced by dissolution of halides, chlorides and sulfates under strong fluid-rock interactions. The isotope analysis demonstrated that the atmospheric precipitation in the Helan Mountain area is the major recharge source of geothermal water, the recharge elevation is 1118 m–1133 m, and the deep geothermal water is formed by a mixing process of ancient precipitation and modern precipitation. The silica-enthalpy mixing model suggested that the reservoir temperature of deep geothermal fluid is between 110 °C and 175 °C, and the mixing ratio of cold water is about 54 % to 92 %. The present study sheds some light on the genesis, recharge mechanism and hydrogeochemical evolution of geothermal water in deep aquifers, which are vital for sustainable exploitation and utilization of geothermal resources.

Light-dependent Br-org production in terrestrial plants under acetaminophen stress and the bromination mechanisms mediated by photosystem

Due to the endocrine toxicity, neurotoxic, and reproductive toxicity to organisms, the sources and risks of brominated organic pollutants have attracted widespread attention. However, knowledge gaps remain in the bromination processes of emerging phenolic pollutants in plants, which may increase the potential health risk associated with food exposure. Our study discovered that light induced generation and accumulation of more toxic brominated organic compounds (Br-org) in lettuce leaves under the stress of acetaminophen (ACE) than that without light, as evidenced by an increase in C-Br bond intensity in FTIR analysis. This result can be explained by the oxidation of bromide ions (Br-) by reactive species (ROS and 3Chl*) of chloroplast into reactive bromine species (RBS). The main mechanism is that the redox of Br- reduced the oxidative damage of ACE to the structure and function of chloroplasts, providing good conditions for light energy uptake and utilization and promoting the increase of pigments and active species. Compared with the dark group exposed to 5 mg/L Br-, the pigment content, H2O2 and 1O2 level of the light group increased by 56%, 84% and 69%, respectively. On the other hand, RBS attacks certain electrophilic organic compounds in leaves to generate Br-org. Triple excited state of chlorophyll (3Chl*) was the dominant species for the transformation of ACE, while RBS is a key factor in the generation of Br-org in the Br-/light/chlorophyll system. A total of six transformation products were identified by HPLC-MS/MS, which were involved in three transformation pathways: methylation, hydroxyl oxidation and hydroxylation followed by bromination. This is the first report that Br- could enter the chloroplast and improved chloroplast structure under ACE stress, and elucidated the bromination mechanism of organics in terrestrial plant involving of biophotochemical bromination in chloroplast besides enzyme-catalyzed bromination. This study is beneficial for risk assessment and prevention of emerging phenolic pollutants.

K, Sr isotopes, and trace element to constrain potash origin in the Simao Basin, southwestern China, and insight into K isotope geochemical behavior in evaporite

With the advancement of emerging potassium isotope testing techniques, the characteristics of δ41K in evaporite have garnered increasing attention. Its application in constraining the genesis of potash deposits and tracing the process of potash mineralization holds significant prospects. A comprehensive analysis of the geochemical characteristics of K, Sr isotopes, and trace elements provides an opportunity to address the ongoing debate regarding the mineralization mechanism of potash in the Simao Basin. In this study, we collected 64 potash samples from the Simao and Khorat basins. The analytical results revealed that the major ions in the samples consist of Na+, K+, Mg2+, Ca2+, Cl−, and SO2- 4, while the trace elements Br, Sr, Rb, B, Li, V, Cr, Mn, Ba, As, and Zn are relatively enriched. The δ41K values range from − 0.12 ‰ to 0.20 ‰ with an average of 0.01 ‰. The 87Sr/86Sr ratios range from 0.707553 to 0.708565 with an average of 0.708020, which is lower than that of the river water in the drainage basin. Additionally, the Br content ranges from 316.3 × 10−6 to 1709.1 × 10−6, with an average of 633.8 × 10−6. These data indicate that the Early Cretaceous Albian-Middle Jurassic Bajocian seawater serves as an important source of potassium for potash deposition in the Simao Basin. The characteristics of the ratios of the Br/Cl (mmol/mol), K/Cl (mmol/mol), Rb/Sr (mol/mol), along with the contents of the Br and Rb, indicate that the most of potash in the Simao Basin is primary origin. Moreover, we have also provided new insight into the geochemical behaviors of K isotopes during the evolution of the evaporites. The precipitation of potash may be accompanied by K isotope fractionation, as evidenced by the lighter K isotope composition of carnallite compared to that of sylvinite. K isotope fractionation occurs between the secondary sylvite and its parent source, and newly precipitated solids are characterized by relatively light K isotope Episodic freshwater inflow into the evaporative basin stimulates microbial activity, leading to fluctuations in K isotopes in the precipitated potash during the same evaporation stage. Therefore, this work not only provided direct evidence from the K isotopes for determining the origin of the potash in the Simao Basin but also further perceived the geochemical behaviors of K isotopes during the evolution of evaporite.

The Flammability and Thermal Stability of Filling Epoxy Foam Plastics for Construction Purposes.

An effective type of polymer heat-insulating material (foams) based on reactive oligomers is casting epoxy foams with high technological and operational parameters. However, polyepoxide foams are highly flammable, which significantly restrains their application in the construction industry. The aim of this work was to develop effective methods for reducing the flammability of filling epoxy foams. In order to achieve the objective, the following objectives were addressed: determining the influence of the chemical nature and content of additive and reactive bromine- and phosphorus-containing compounds on the thermal stability, flammability and operational properties of filling epoxy foams, and the development of polyepoxy foams of reduced flammability with high-quality physical and mechanical characteristics. When estimating the flammability of epoxy foams, we used both state-approved methods and the methods described in scientific and technical literature. The thermal properties of epoxy foams were studied with the help of multimodular thermoanalytical complex DuPont-9900. The data on the influence of the apparent density of foams and oxygen concentration in the oxidant flow on the flame propagation speed on the horizontal surface of polyepoxy foams are presented. It was revealed that the chemical nature of amine hardeners does not affect the thermal stability and flammability of epoxy foams. It was established that phosphate plasticizers are ineffective flame retardants of foamed epoxy resin, and the chemical structure of additive organobromic flame retardants insignificantly affects their efficiency. It was shown that microencapsulated flame retardants are inferior in flame retardant efficiency to additive flame retardants. It was found that effective flame retardants for casting polyepoxy foams are phosphorus-containing oligoether methacrylate and epoxidized waste from the production of tetrabromodiphenylpropane. The results of this research will form the basis for the production of an experimental industrial batch of samples of pouring epoxy foams of reduced flammability.

Visualizing and Understanding the Ionic Liquid-Mediated Polybromide Electrochemistry for Aqueous Zinc-Bromine Redox Batteries.

Aqueous zinc-bromine redox systems possess multiple merits for scalable energy storage. Applying bromine complexing agents shows effectiveness in alleviating the key challenge of ubiquitous crossover of reactive liquid bromine species, while the underlying microscopic mechanism requires a deep understanding to engineer better complexing electrochemistry. Herein, taking a series of quaternary ammonium ionic liquids (methyl4NBr, ethyl4NBr, propyl4NBr, and butyl4NBr) as a redox mediator model, operando optical monitoring was used to visualize the dynamic electrochemical behaviors, unveiling the ionic liquid-mediated polybromide electrochemistry with a distinct chain length effect. A longer chain length possesses a stronger electrostatic interaction in the complexing product to effectively capture Br2. Operando results reveal the liquid nature of the reversibly electrogenerated polybromide microdroplets in the butyl4NBr-added redox system, which promoted the Br3-/Br- conversion kinetics and alleviated the self-discharge for improved battery performance. This work provides direct evidence and new insights into complexing electrochemistry for advancing Zn-Br2 batteries.

First report of metals and metalloids on bone and claw tissues of Humboldt penguins (Spheniscus humboldti)

Samples of bones (humerus) and claws of adult Humboldt penguins (Spheniscus humboldti) were opportunistically obtained from twenty-seven carcasses at two important nesting sites in northern Chile: Chañaral Island (CHI) and Pan de Azúcar Island (PAI). The concentrations of trace elements (Cu, Zn, Pb, Ni, Fe, Se, As, Br, Mn and Cr) were determined by X-ray fluorescence. The highest levels (mean ± standard deviation, micrograms/g dry weight) of Cu (26.57 ± 4.08), Zn (163.9 ± 42.7), Pb (1.86 ± 1.53), Ni (0.31 ± 0.03), Se (7.70 ± 4.87) and Cr (0.25 ± 0.24) were detected in bones, whereas the highest levels of Fe (3,162 ± 1,579), As (6.75 ± 4.21), Br (0.12 ± 0.06) and Mn (76.7 ± 47.9) were found in claws. In bones, Se and Ni levels were higher (P < 0.05) in CHI than in PAI. In claws, the contents of Pb, Fe, and Mn were higher at CHI than those at PAI, whereas only As exhibited higher contents at PAI than those found at CHI. The trace element content in the claws and bones found herein may be the result of either acute or chronic exposure to penguins, respectively. These findings may serve as a baseline for further studies to design adequate and opportune plans to protect this vulnerable species.

Simultaneous Oxidation of Bromide and Dissolution of Manganese Oxide Induced by Freezing.

This study demonstrates that the oxidation of bromide by birnessite (δ-MnO2) results in the concurrent production of soluble manganese (Mn(II)) and reactive bromine (RBr) species in frozen solutions, a process not observed in aqueous solutions. This enhanced oxidation in ice is attributed to the concentration of protons, birnessite, or bromide in the ice grain boundary region. Furthermore, different types of commercial manganese oxides can also oxidize bromide to RBr and release Mn(II) in ice. The presence of fulvic acid (FA) further increases the simultaneous production of RBr and Mn(II) in ice, accompanying the formation of organobromine compounds (OBCs). In frozen δ-MnO2/Br-/FA system, a significant increase in OBCs, mainly highly unsaturated and phenolic compounds, was detected using Fourier transform ion cyclotron resonance mass spectrometry. A marked contrast was observed in the number of OBCs formed in frozen solutions (853 and 415 OBCs at initial pH 3.0 and 5.8, respectively) compared to their aqueous counterparts (11 and 23 OBCs). These findings introduce a new pathway for the formation of RBr, Mn(II), and OBCs in ice, highlighting the need for further research on the environmental fate of bromide and manganese.

Spontaneous Molecular Bromine Production in Sea-Salt Aerosols.

Bromine chemistry is responsible for the catalytic ozone destruction in the atmosphere. The heterogeneous reactions of sea-salt aerosols are the main abiotic sources of reactive bromine in the atmosphere. Here, we present a novel mechanism for the activation of bromide ions (Br-) by O2 and H2O in the absence of additional oxidants. The laboratory and theoretical calculation results demonstrated that under dark conditions, Br-, O2 and H3O+ could spontaneously generate Br and HO2 radicals through a proton-electron transfer process at the air-water interface and in the liquid phase. Our results also showed that light and acidity could significantly promote the activation of Br- and the production of Br2. The estimated gaseous Br2 production rate was up to 1.55×1010 molecules cm-2 ⋅ s-1 under light and acidic conditions; these results showed a significant contribution to the atmospheric reactive bromine budget. The reactive oxygen species (ROS) generated during Br- activation could promote the multiphase oxidation of SO2 to produce sulfuric acid, while the increase in acidity had a positive feedback effect on Br- activation. Our findings highlight the crucial role of the proton-electron transfer process in Br2 production; here, H3O+ facilitates the activation of Br- by O2, serves as a significant source of atmospheric reactive bromine and exerts a profound impact on the atmospheric oxidation capacity.

Spontaneous Molecular Bromine Production in Sea‐Salt Aerosols

AbstractBromine chemistry is responsible for the catalytic ozone destruction in the atmosphere. The heterogeneous reactions of sea‐salt aerosols are the main abiotic sources of reactive bromine in the atmosphere. Here, we present a novel mechanism for the activation of bromide ions (Br−) by O2 and H2O in the absence of additional oxidants. The laboratory and theoretical calculation results demonstrated that under dark conditions, Br−, O2 and H3O+ could spontaneously generate Br and HO2 radicals through a proton–electron transfer process at the air–water interface and in the liquid phase. Our results also showed that light and acidity could significantly promote the activation of Br− and the production of Br2. The estimated gaseous Br2 production rate was up to 1.55×1010 molecules cm−2 ⋅ s−1 under light and acidic conditions; these results showed a significant contribution to the atmospheric reactive bromine budget. The reactive oxygen species (ROS) generated during Br− activation could promote the multiphase oxidation of SO2 to produce sulfuric acid, while the increase in acidity had a positive feedback effect on Br− activation. Our findings highlight the crucial role of the proton‐electron transfer process in Br2 production; here, H3O+ facilitates the activation of Br− by O2, serves as a significant source of atmospheric reactive bromine and exerts a profound impact on the atmospheric oxidation capacity.

Investigation of metal non-opaque foreign bodies of firearm origin by radiation methods

Background. The purpose is to investigate metal non-opaque foreign bodies of firearm origin. Materials and methods. Five cases of removing soft tissue foreign bodies of gunshot origin were investigated, when radiography of the limb soft tissues didn’t detect foreign bodies, but they were removed during the primary surgical wound debridement. X-ray of soft tissue gunshot wounds found no foreign bodies. To study radiographic density, foreign bodies were placed in a foam model with subsequent multislice computed tomography. For spectral analysis of metal foreign bodies, we used wavelengths unconventional for X-ray, which allowed to conduct X-ray fluorescence and X-ray structural studies. Results. Radiographic density of metal foreign bodies ranged from 989 to 2123 HU. Given the different thickness of foreign bodies, from 0.4 to 3.2 mm, the average was 1700 ± 189 HU. The foam had radiographic density of –969 HU with model dimensions of 200 × 100 × 50 mm. When examining samples of foreign bodies, it was found that they are deformed, have different thicknesses. One of the samples is light and smooth on one side, and dark and rough on the other. X-ray fluorescence results: composition on the light side (% by mass): Al — base, Mn — 0.8, Fe — 0.3, Zn — 0.1, Cr — 0.05, Ti — 0.2, corresponding to Al-Mn alloy. The dark side is an oxidized Al-Mn alloy. In the spectrum of the dark side of the sample, the Br-Kα line was detected, which indicates the participation of bromine compounds in the oxidation process. From the smooth side of the sample, the spectrum of this line is not determined. Conclusions. Non-opaque metal foreign bodies of gunshot origin are a rare phenomenon. Metal foreign bodies with low radiographic density are non-ferromagnetic, the use of modern magnetic surgical instruments will not be effective. Visualization of metal foreign bodies, which are not determined by radiography, is possible with the help of multislice computed tomography. The use of the wavelength of primary radiation, which is unconventional for X-ray spectral analysis, and original X-ray optical schemes allows for quantitative determination of the composition and structure of any metal foreign bodies.

Freezing-induced acidification of sea ice brine

The acidity of sea ice and snow plays a key role in the chemistry of the cryosphere; an important example lies in the photochemical catalytic release of reactive bromine in polar regions, facilitated at pHs below 6.5. We apply in-situ acid-base indicators to probe the microscopic acidity of the brine within the ice matrix in artificial sea water at a range of concentrations (0.35–70 PPT) and initial pHs (6–9). The results are supported by analogous measurements of the most abundant salts in seawater: NaCl, Na2SO4, and CaCO3. In the research herein, the acidity is expressed in terms of the Hammett acidity function, H2−. The obtained results show a pronounced acidity increase in sea water after freezing at −15 °C and during the subsequent cooling down to −50 °C. Importantly, we did not observe any significant hysteresis; the values of acidity upon warming markedly resembled those at the corresponding temperatures at cooling. The acidity increase is attributed to the minerals' crystallization, which is accompanied by a loss of the buffering capacity. Our observations show that lower salinity sea water samples (≤ 3.5 PPT) reach pH values below 6.5 at the temperature of −15 °C, whereas higher salinity ices attain such values only at −30 °C. The ensuing implications for polar chemistry and the relevance to the field measurements are discussed.

Significant roles of reactive bromine intermediates on organic co-contaminants degradation during bromate reduction in electrochemically activated (bi)sulfite process

(Bi)sulfite radical-based advanced reduction process (HSO3/SO3−-ARP) was an emerging technology to simultaneously reduce BrO3− and oxidize organic co-contaminants. However, the evolution of reactive bromine intermediates (RBrIs) and their role on degradation of organics has not been investigated. This study utilized an electrochemically activated (bi)sulfite process, a novel HSO3/SO3−-ARP for BrO3− reduction (EA-S (IV)-BrO3− process), to confirm the generation of RBrIs and elaborate the degradation mechanism of organic contaminants. Firstly, the generated RBrIs responsible for organic pollutants degradation were bromine dioxide (BrO2), bromine monoxide (BrO) and free bromine (HBrO/BrO−). Then, the species-specific second-order rate constants for RBrIs reacting with structurally diverse phenolic contaminants (PCs) (kBrO2, PCs = 107−1010 M−1 s−1 and kBrO, PCs = 106−1010 M−1 s−1) were obtained by fitting with the experimental data using a first-principle-based kinetic model of EA-S (IV)-BrO3− process in anaerobic condition. Notably, at pH 2 and 6, HSO3 (33–95 %) and BrO2 (5–66 %) dominated PCs degradation. Conversely, at pH 10, BrO (48–66 %), SO3− (27–42 %) and BrO2 (5–12 %) were the major radicals due to high reaction rates between RBrIs and dissociated PCs. The role of HBrO/BrO− was minimal (<1 %). Finally, negative linear relationships between kBrO2/BrO/HBrO, PCs and Hammett constants (Σσ+) indicated that PCs with electron-donating groups were more sensitive to RBrIs. BrO and BrO2 dominated oxidation of PCs via electron transfer, hydroxylation and ketonization, while the formation of brominated products attributed to HOBr/BrO− were negligible. This study advanced the understanding of BrO3− reduction process and the significant role of RBrIs on degradation of organic co-contaminants.

Surface snow bromide and nitrate at Eureka, Canada, in early spring and implications for polar boundary layer chemistry

Abstract. This study explores the role of snowpack in polar boundary layer chemistry, especially as a direct source of reactive bromine (BrOx = BrO + Br) and nitrogen (NOx = NO + NO2) in the Arctic springtime. Surface snow samples were collected daily from a Canadian high Arctic location at Eureka, Nunavut (80° N, 86° W) from the end of February to the end of March in 2018 and 2019. The snow was sampled at several sites representing distinct environments: sea ice, inland close to sea level, and a hilltop ∼ 600 m above sea level (a.s.l.). At the inland sites, surface snow salinity has a double-peak distribution with the first and lowest peak at 0.001–0.002 practical salinity unit (psu), which corresponds to the precipitation effect, and the second peak at 0.01–0.04 psu, which is likely related to the salt accumulation effect (due to loss of water vapour by sublimation). Snow salinity on sea ice has a triple-peak distribution; its first and second peaks overlap with the inland peaks, and the third peak at 0.2–0.4 psu is likely due to the sea water effect (a result of upward migration of brine). At all sites, snow sodium and chloride concentrations increase by almost 10-fold from the top 0.2 to ∼ 1.5 cm. Surface snow bromide at sea level is significantly enriched, indicating a net sink of atmospheric bromine. Moreover, surface snow bromide at sea level has an increasing trend over the measurement period, with mean slopes of 0.024 µM d−1 in the 0–0.2 cm layer and 0.016 µM d−1 in the 0.2–0.5 cm layer. Surface snow nitrate at sea level also shows a significant increasing trend, with mean slopes of 0.27, 0.20, and 0.07 µM d−1 in the top 0.2, 0.2–0.5, and 0.5–1.5 cm layers, respectively. Using these trends, an integrated net deposition flux of bromide of (1.01 ± 0.48) × 107 molec.cm-2s-1 and an integrated net deposition flux of nitrate of (2.6 ± 0.37) × 108 molec.cm-2s-1 were derived. In addition, the surface snow nitrate and bromide at inland sites were found to be significantly correlated (R = 0.48–0.76) with the [NO3-]/[Br-] ratio of 4–7 indicating a possible acceleration effect of reactive bromine in atmospheric NOx-to-nitrate conversion. This is the first time such an effect has been seen in snow chemistry data obtained with a sampling frequency as short as 1 d. BrO partial column (0–4 km) data measured by MAX-DOAS show a decreasing trend in early spring, which generally agrees with the derived surface snow bromide deposition flux indicating that bromine in Eureka atmosphere and surface snow did not reach a photochemical equilibrium state. Through mass balance analysis, we conclude that the average release flux of reactive bromine from snow over the campaign period must be smaller than the derived bromide deposition flux of ∼ 1 × 107 molec.cm-2s-1. Note that the net mean fluxes observed do not completely rule out larger bidirectional fluxes over shorter timescales.

Do bromine and surface-active substances influence the coastal atmospheric particle growth?

New particle formation (NPF) is considered a major source of aerosol particles and cloud condensation nuclei (CCN); however, our understanding of NPF and the subsequent particle growth mechanisms in coastal areas remains limited. This study provides evidence of frequent NPF events followed by particle growth in the middle Adriatic Sea during the summer months at the coastal station of Rogoznica in Croatia. To our knowledge, this is the first study to report such events in this region. Our research aims to improve the understanding of NPF by investigating particle growth through detailed physicochemical characterization and event classification. We used a combination of online measurements and offline particle collection, followed by a thorough chemical analysis. Our results suggest the role of bromine in the particle growth process and provide evidence for its involvement in combination with organic compounds. In addition, we demonstrated the significant influence of surface-active substances (SAS) on particle growth. NPF and particle growth events have been observed in air masses originating from the Adriatic Sea, which can serve as an important source of volatile organic compounds (VOC). Our study shows an intricate interplay between bromine, organic carbon (OC), and SAS in atmospheric particle growth, contributing to a better understanding of coastal NPF processes. In this context, we also introduced a new approach using the semi-empirical 1st derivative method to determine the growth rate for each time point that is not sensitive to the nonlinear behavior of the particle growth over time. We observed that during NPF and particle growth event days, the OC concentration measured in the ultrafine mode particle fraction was higher compared to non-event days. Moreover, in contrast to non-event days, bromine compounds were detected in the ultrafine mode atmospheric particle fraction on nearly all NPF and particle growth event days. Regarding sulfuric acid, the measured sulfate concentration in the ultrafine mode atmospheric particle fraction on both NPF event and non-event days showed no significant differences. This suggests that sulfuric acid may not be the primary factor influencing the appearance of NPF and the particle growth process in the coastal region of Rogoznica.

Myocardial SERCA2 Protects Against Cardiac Damage and Dysfunction Caused by Inhaled Bromine.

Myocardial sarcoendoplasmic reticulum calcium ATPase 2 (SERCA2) activity is critical for heart function. We have demonstrated that inhaled halogen (chlorine or bromine) gases inactivate SERCA2, impair calcium homeostasis, increase proteolysis, and damage the myocardium ultimately leading to cardiac dysfunction. To further elucidate the mechanistic role of SERCA2 in halogen-induced myocardial damage, we used bromine-exposed cardiac-specific SERCA2 knockout (KO) mice [tamoxifen-administered SERCA2 (flox/flox) Tg (αMHC-MerCreMer) mice] and compared them to the oil-administered controls. We performed echocardiography and hemodynamic analysis to investigate cardiac function 24 hours after bromine (600 ppm for 30 minutes) exposure and measured cardiac injury markers in plasma and proteolytic activity in cardiac tissue and performed electron microscopy of the left ventricle (LV). Cardiac-specific SERCA2 knockout mice demonstrated enhanced toxicity to bromine. Bromine exposure increased ultrastructural damage, perturbed LV shape geometry, and demonstrated acutely increased phosphorylation of phospholamban in the KO mice. Bromine-exposed KO mice revealed significantly enhanced mean arterial pressure and sphericity index and decreased LV end diastolic diameter and LV end systolic pressure when compared with the bromine-exposed control FF mice. Strain analysis showed loss of synchronicity, evidenced by an irregular endocardial shape in systole and irregular vector orientation of contractile motion across different segments of the LV in KO mice, both at baseline and after bromine exposure. These studies underscore the critical role of myocardial SERCA2 in preserving cardiac ultrastructure and function during toxic halogen gas exposures. SIGNIFICANCE STATEMENT: Due to their increased industrial production and transportation, halogens such as chlorine and bromine pose an enhanced risk of exposure to the public. Our studies have demonstrated that inhalation of these halogens leads to the inactivation of cardiopulmonary SERCA2 and results in calcium overload. Using cardiac-specific SERCA2 KO mice, these studies further validated the role of SERCA2 in bromine-induced myocardial injury. These studies highlight the increased susceptibility of individuals with pathological loss of cardiac SERCA2 to the effects of bromine.

Unveiling distinct influencing mechanisms of Br- on NDMA formation during ozonation of actual water Matrixes: Identification of precursors and brominated substance

Bromide ion (Br-) in water sources has been found to affect the formation of carcinogenic non-brominated N-nitrosodimethylamine (NDMA) during ozonation of typical amines. The increasing bromide levels bring more concern due to climate change and industrial discharge, but its effects on actual water matrixes were still unclear. In this study, NDMA formation from three actual water matrixes during ozonation as the Br- concentration increased from 0 to 100 µM were investigated (promotion (100.4 ∼ 231.6 ng/L), promotion then inhibition (399.5 ∼ 461.2 ∼ 428.2 ng/L), and subtle influence (51.9 ± 6.9 ng/L)); from which the NDMA precursors were screened and 8 precursors were selected for exploring the influencing mechanisms. The results indicated that the roles of Br- on NDMA formation significantly depended on the water characteristics of actual matrixes. A total of 16 typical NDMA precursors, which were mainly derived from industrial, agricultural and pharmaceutical sources, were identified. Moreover, 6 brominated substance (Br-DMA, Br-UDMH, Br-DMSC, Br-DMS, Br-TMDS, Br2-TMDS), which were thought to play a crucial role in promoting NDMA formation, were also identified in actual water by precursor ion scan (PIS) method. Hypobromous acid (HOBr), which has been proved to be the culprit to the generation of brominated substances, tend to attack the electron-donating groups of amines, such as acylamino (–NHCO-R) or amidogen (–NH2) groups. However, the reactive bromine species (∙Br and ∙Br2-) was inclined to attack the aromatic and anti-oxidant moieties then result in Br- release, as no bromine substitution but free radical transfer reaction occurs. Therefore, decreasing HOBr formation is the crucial step to reduce NDMA generation. This work would provide technical guide for NDMA risks control during ozonation of Br--amines co-containing water matrixes.