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Chlorine photolysis is an advanced oxidation process that relies on the combination of direct chlorination by free available chlorine, direct photolysis, and reactive oxidants to transform contaminants. In waters that contain bromide, free available bromine and reactive bromine species can also form. However, little is known about the underlying mechanisms or formation potential of disinfection byproducts (DBPs) under these conditions. We investigated reactive oxidant generation and DBP formation under dark conditions, chlorine photolysis, and radical-quenched chorine photolysis with variable chlorine (0-10 mg-Cl 2 /L) and bromide (0-2,000 μg/L) concentrations, as well as with free available bromine. Probe loss rates and ozone concentrations increase with chlorine concentration and are minimally impacted by bromide. Radical-mediated processes partially contribute to the formation targeted DBPs (i.e., trihalomethanes, haloacetic acids, haloacetonitriles, chlorate, and bromate), which increase with increasing chlorine concentration. Chlorinated novel DBPs detected by high-resolution mass spectrometry are attributable to a combination of dark chlorination, direct halogenation by reactive chlorine species, and transformation of precursors, whereas novel brominated DBPs are primarily attributable to dark bromination of electron-rich formulas. The formation of targeted and novel DBPs during chlorine photolysis in waters with elevated bromide may limit treatment applications.

Sulfonamide antibiotics (SAs) are ubiquitous in surface water and soil environments, raising considerable concerns about their risk and removal. However, the impacts of various bromide ion (Br - ) concentrations on the phytotoxicity, uptake and fate of SAs in plant growth and physiological metabolism of plants have not been well understood. Our research demonstrated that low concentrations of Br - (0.1, 0.5 mM) promoted the uptake and degradation of sulfadiazine (SDZ) in wheat and attenuated the phytotoxicity of SDZ. Additionally, we proposed a degradation pathway and identified the brominated product of SDZ (SDZ Br ), which attenuated the dihydrofolate synthesis inhibition by SDZ. The primary mechanism was that Br - reduced the level of reactive oxygen radicals (ROS) and alleviated oxidative damage. The production of SDZ Br and the high consumption of H 2 O 2 suggest the potential generation of reactive bromine species, contributing to the degradation of the electron-rich SDZ and thus reducing its toxicity. Moreover, metabolome analysis of wheat roots indicated that low concentrations of Br - stimulated the production of indoleacetic acid under SDZ stress, promoting growth and enhancing the uptake and degradation of SDZ. Conversely, high Br - (1 mM) concentration produced a deleterious effect. These findings provide valuable insights into the mechanisms of antibiotic removal, suggesting a potentially novel approach to plant-based antibiotic remediation., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier B.V. All rights reserved.)

Members of the Gulf Cooperation Council countries Bahrain, Kuwait, Oman, Qatar, Saudi Arabia, and the United Arab Emirates rely on desalination to produce water for domestic use. Desalination produces brine that may intrude into the aquifers to pollute the fresh groundwater because of the concentration gradient and groundwater pumping. Modeling the trends of saltwater intrusion needs theoretical understanding and thorough logical experimentation. The objective of this exercise was to understand the phenomenon of saltwater intrusion using an existing set of data analyzed with the convective-diffusion equation and the two-region mobile-immobile solution model. The objective was achieved by optimizing non-measurable solute transport parameters from an existing set of data generated from a series of logical miscible displacements of potassium bromide through sepiolite minerals and curve-fitting simulations. Assumptions included that solute displacements through sepiolite porous media and the related simulations represented the phenomenon of saltwater intrusion under non-equilibrium conditions of porous media mimicking the aquifers. Miscible displacements of potassium bromide were observed from a column of 2.0-2.8 mm aggregates of sepiolite over 4 ranges of concentration and at 11 displacement speeds under saturated vertical flow deionized water and vice versa. Breakthrough curves of both bromide and potassium ions were analyzed by a curve-fitting technique to optimize transport parameters assuming solute movement was governed (i) by the convective-diffusion equation and (ii) the two-region mobile-immobile solution model. Column Peclet numbers from the two analyses were identical for potassium ions but those for bromide ions were c. 60% greater from the two-region model than from the convective-diffusion equation. For the two-region model, dispersion coefficients were well defined and remained unchanged from the convective-diffusion equation for potassium ions but decreased for bromide ions. Retardation factors for bromide ions were approximately the same, but those for potassium ions, though > 1, were poorly defined. In order to design mitigation strategies for avoiding groundwater contamination, this study's findings may help model groundwater pollution caused by the activities of desalination of seawater, which produces concentrated liquid that intrudes into the coastal aquifer through miscible displacement. However, robust saltwater intrusion models may be considered in future studies to confirm the results of the approach presented in this exercise. Field data on the groundwater contamination levels may be collected to compare with simulated trends drawn from the saltwater intrusion models and the curve-fitting technique used in this work. A comparison of the output from the two types of models may help determine the right option to understand the phenomena of saltwater intrusion into coastal aquifers of various characteristics., (© 2023. The Author(s).)

Oil and gas production generates large amounts of brine wastewater called "produced water" with various geogenic and synthetic contaminants. These brines are generally used in hydraulic fracturing operations to stimulate production. They are characterized by elevated halide levels, particularly geogenic bromide and iodide. Such salt concentrations in produced water may be as high as thousands of mg/L of bromide and tens of mg/L of iodide. Large volumes of produced water are stored, transported, reused in production operations, and ultimately disposed of by deep well injection into saline aquifers. Improper disposal may potentially contaminate shallow freshwater aquifers and impact drinking water sources. Because conventional produced water treatment typically does not remove halides, produced water contamination of groundwater aquifers may cause the formation of brominated and iodinated disinfection by-products (I-DBPs) at municipal water treatment plants. These compounds are of interest because of their higher toxicity relative to their chlorinated counterparts. This study reports a comprehensive analysis of 69 regulated and priority unregulated DBPs in simulated drinking waters fortified with 1 % (v/v) oil and gas wastewater. Impacted waters produced 1.3×-5× higher levels of total DBPs compared to river water after chlorination and chloramination. Individual DBP levels ranged from (<0.1-122 μg/L). Overall, chlorinated waters formed highest levels, including trihalomethanes that would exceed the U.S. EPA regulatory limit of 80 μg/L. Chloraminated waters had more I-DBP formation and highest levels of haloacetamides (23 μg/L) in impacted water. Calculated cytotoxicity and genotoxicity were higher for impacted waters treated with chlorine and chloramine than corresponding treated river waters. Chloraminated impacted waters had the highest calculated cytotoxicity, likely due to higher levels of more toxic I-DBPs and haloacetamides. These findings demonstrate that oil and gas wastewater if discharged to surface waters could adversely impact downstream drinking water supplies and potentially affect public health., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier B.V. All rights reserved.)

In Europe, millions of water samples have been collected from sampling points, especially in the saturated zone to assess the water quality among others to fulfil EU water quality directives. Often water samples are collected from sampling points installed in the subsurface without knowing what the water collected represents in space and time. As such, without detailed knowledge of hydrogeological settings and fluctuations in groundwater levels, it is not possible to assess whether water collected represents a hydraulic active sediment setting or an adjacent isolated sediment body. Collecting water from the latter will hence not reveal by analysis potential contamination in the hydraulic active setting. Based on a detailed three-dimensional sedimentary facies model interpreted from geological and geophysical data combined with groundwater level measurements, this study focuses on delineating the impact of changing solute transport pathways underneath a sandy field (2 ha) exposed to bromide and pesticide applications. Hence, the analyses utilize detections in water samples of bromide, pesticides, and/or their degradation products collected through 19 years at 25 sampling points. A special focus is on the relatively high concentration, long-termed leaching of four degradation products (1,2,4-triazole, CGA108906, PPU, and desethyl-terbuthylazine) through the field. The results show that even for sand, knowledge of the hydrogeological setting and in-situ fate knowledge is imperative to assess the representability of water being sampled from both the variably-saturated and saturated zone of the soil-sediment system. Especially, the sub-horizontal layered sediments with numerous facies shifts facilitate horizontal solute transport, and fluctuations in the groundwater table seem to be decisive for, which solute transport pathways are dominating. Such detailed insights are crucial for accurately assessing sources of contaminants, leaching risk of contaminants through the variably-saturated zone, and improving monitoring procedures in the protection of the water resources and hereby the water quality of the future., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022. Published by Elsevier B.V.)

Combined processes of light-emitting diodes ultraviolet (LED UV) and chlorination (Cl 2 ) are alternative disinfection technologies in drinking water, while the formation of disinfection by-products (DBPs) needs to be evaluated. This study investigated the impacts of critical water matrix factors on the DBP formation in the combined processes. Moreover, the correlation between the degraded natural organic matter (NOM) and the formed DBP was studied. Simultaneous UV/Cl 2 outperformed single Cl 2 and sequential combined processes in degrading humic acids (HA) and resulted in the highest DBP yield. Iodide at 5-20 μg/L and bromide at 0.05-0.2 mg/L slightly affected the degradation of organics, while increased the formation of brominated DBPs up to 36.6 μg/L. pH 6 was regarded as the optimum pH, achieving high efficiency of HA degradation and a lower level of total DBP formation than pH 7 and 8 by 11 % and 24 %, respectively. Compared to HA samples (46.8-103.9 μg/L per mg/L DOC), NOM in canal water were less aromatic and yielded fewer DBPs (19.6 and 21.2 μg/L per mg/L DOC). However, the extremely high bromide in site 1 samples (18.6 mg/L) shifted the chlorinated DBPs to their brominated analogues, posting around 1 order of magnitude higher levels of toxicities than HA samples. The reduction of absorbance at 254 nm (UV 254 ) correlated with all DBP categories in HA samples, while the correlation coefficients were compromised when included in the canal samples. For the first time, this study found that parallel factor analysis (PARAFAC) would neglect the fluorescence change caused by iodide/bromide in UV/Cl 2 , while the changes could be captured by self-organising map (SOM) trained with full fluorescence spectra. Fluorescence Ex/Em pairs were proposed to predict DBP formation, suggesting a potential method to develop an online monitoring system for DBPs., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022 Elsevier B.V. All rights reserved.)

This study aimed to investigate the potential of 1-alkyl-1-methylpiperidinium bromides as fungicides and evaluate their impact on the human respiratory system when spread in the atmosphere. We investigated the behavior of membrane lipids and model membranes in the presence of a series of amphiphilic 1-alkyl-1-methylpiperidinium bromides ([MePipC n ][Br]), differing in the alkyl chain length (n = 4 - 18). The experiments were performed with the Langmuir monolayer technique using 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC) and ergosterol (ERG)-the main components of lung surfactant and fungal plasma membrane, respectively and their mixtures with phospholipids and sterols. The mixtures were chosen as the representatives of target and non-target organisms. The surface pressure-area isotherms were obtained by compressing monolayers in the presence of [MePipC n ][Br] in the subphase. The results were analyzed in terms of area expansion/contraction and compressibility. The surface activity of the studied organic salts was also studied. In addition, the monolayers were deposited on a solid surface and their topography was investigated using atomic force microscopy. This research implies that the studied compounds may destabilize efficiently the fungal plasma membrane. At the same time we demonstrated the significant impact of 1-alkyl-1-methylpiperidinium bromides on the lung surfactant layer. The interaction between [MePipCn][Br] and model membranes depends on the concentration and alkyl chain length of organic salt. The key role of contact time has been also revealed. The results may be helpful in the reasonable development of new agrochemical products aiming at the treatment of fungal infections in plants. In addition, our study indicates the significance of proper safety management while spreading the fungicides in the environment., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022 Elsevier B.V. All rights reserved.)

Background: The presence of inorganic acids in the air poses a threat to the health of workers. Volatile inorganic acids, e.g., hydrochloric acid, hydrobromic acid and nitric acid, may cause respiratory, eye and skin irritation. The presented method uses ion chromatography to determine the concentrations of hydrochloric, hydrobromic and nitric acids in air samples., Material and Methods: The method is based on the collection of airborne volatile acids on impregnated quartz fiber filter, extraction of acids with deionized water, and analysis by ion chromatography with conductivity suppression. The separation was performed on the Dionex IonPac™ AS22 (4 × 250 mm) column for trace anion analysis. The carbonate/bicarbonate eluent was maintained at an isocratic flow rate of 1.2 ml/min. The calibration standard solutions have been covering the range of 0.2-5 mg/l of chloride, bromide and nitrate., Results: The specified chromatographic conditions enable selective measurement of chloride, bromide and nitrate anions. The obtained mass concentration of each anion, having factored in the sample dilution, the conversion factor (to convert anion concentration to acid) and the volume of the air sample, allows the calculation of acid concentrations in the analyzed air., Conclusions: This method makes it possible to determine the concentration of hydrochloric acid, hydrobromic acid and nitric acid in the workplace air within the concentration range corresponding to 0.1-2 times the exposure limit value in Poland. The method meets the criteria for the performance of procedures for the measurement of chemical agents, listed in PN-EN 482. This article discusses the problems of occupational safety and health, which are covered by health sciences and environmental engineering. Med Pr. 2022;73(4):337-47., (This work is available in Open Access model and licensed under a CC BY-NC 3.0 PL license.)

The generation of disinfection by-products during water chlorination is a major concern in water treatment, given the potential health risks that these substances may pose. In particular, nitrogen-containing DBPs are believed to have greater toxicological significance than carbon-based DBPs. Hence, high performance liquid chromatography coupled to high-resolution mass spectrometry (HPLC-HRMS) in positive mode was employed to identify new non-volatile nitrogen containing disinfection by-products (DBPs) and to assess their presence in potable water. Nine water samples were taken in the Llobregat river, in the context of a water reuse trial, near the catchment of a drinking water treatment plant (DWTP) in 2019. River samples were disinfected with chlorine under controlled formation potential tests conditions and analysed with a non-target approach. The peak lists of raw and chlorinated samples were compared exhaustively, resulting in an extensive list of 495 DBPs that include bromine and/or chlorine atoms. 172 of these species were found frequently, in three or more chlorinated samples. The empirical formulae of these DBPs were unambiguously annotated on the basis of accurate m/z measurements, isotopic patterns and common heuristic rules. Most of the annotated species (310) contained bromide, which is consistent with the relatively high bromide content of the Llobregat basin (>0.3 mg/l). Drinking water samples were taken at the outlet of the DWTP during the same sampling period. According to their analysis, a large portion of the DBPs detected after the formation potential tests do not reach real-life drinking water, which suggests that the treatment train successfully removes a significant fraction of DBP precursors. However, 131 DBPs could still be detected in the final product water. A larger sampling was carried in the Barcelona water distribution network, during six consecutive weeks, and it revealed the presence of 78 halogenated DBPs in end-consumer water, most of which were nitrogen-containing. MS/MS fragmentation and retention times were employed to tentatively suggest molecular structure for these recalcitrant DBPs., (Copyright © 2022 The Authors. Published by Elsevier Ltd.. All rights reserved.)

The stability of drinking water disinfectant residuals is known to be influenced by multiple variables. To evaluate the effects of various influencing variables on disinfectant stability, a multivariate analysis of chloramine decay and associated disinfection by-products (DBPs) formation was investigated in a series of bench-scale experiments. Of nine water quality variables previously identified, monochloramine dose, pH, and bromide concentration were selected as key water quality variables based on previous investigations and modelling. Co-effects of these key variables on monochloramine decay and formation of 33 halogenated and nitrogen-containing DBPs were investigated using response surface experimental design. Rechloramination conditions, including monochloramine dose, pH and bromide concentration, were optimised via a 3-factorial multivariate analysis of monochloramine stability in post-treatment drinking water. Effects of influencing variables on disinfectant decay and DBP formation were assessed and graphically presented as response surfaces with minimal experiments using Doehlert matrix experimental design compared to other multivariate experimental designs. Concentrations of trihalomethanes (THMs), haloacetic acids (HAAs), and N-nitrosamines were found to increase with water age, whereas opposite phenomenon was observed in the net production of haloacetonitriles (HANs). Increasing pH was found to stabilise monochloramine but it could cause DBP speciation to shift. Furthermore, increasing bromide concentration elevated Br-DBP formation. In bromide-containing water, pH = 7.8-8.0 should be considered as higher pH increases Br-THMs formations and lower pH increases formations of Br-HAAs and Br-HANs. However, water age or pH has insignificant impacts on DBP formation after significant monochloramine decay or at low initial monochloramine dose. These findings indicate that effective combined control measures to maintain monochloramine stability should include the application of high monochloramine dose (>1.5 mg-Cl 2 .L -1 ) under conditions of moderate to high pH (pH = 7.8-8.0) and minimal bromide concentration. This study provides relevant insights to water utilities aiming to design effective disinfectant residual management strategies for controlling monochloramine decay and DBP formation., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022. Published by Elsevier B.V.)

Bromide in water can form undesirable by-products such as bromate when treated by ozonation during drinking water production. The maximum contaminant level (MCL) for bromate is 10 µg/L in most countries because it is suspected of being carcinogenic. In this paper, the geographical distribution of bromide concentration in Croatian groundwater is presented covering the Pannonian basin and the Dinarides (Adriatic Sea). Groundwater in Croatian wellfields predominantly has a bromide content of less than 50 µg/L and thus belongs to the group with low potential for bromate formation. Waters with higher bromide concentrations were found mainly in the coastal regions of Croatia, probably due to seawater intrusion. In addition, bromide concentration showed a positive correlation of 0.6 with conductivity, chloride, and sodium. In addition, the potential of 123 groundwaters analyzed in this study to form bromate when treated with ozone was evaluated using models available in the literature. Analysis of water from Croatian wellfields indicated that the potential for bromate formation above the MCL during ozonation was relatively low. The models used from the literature predicted quite different values of bromate concentration when applied to the same water, with some values exceeding those theoretically possible. Selected models may be useful as a general warning of possible bromate formation., (© 2022. The Author(s), under exclusive licence to Springer Nature Switzerland AG.)

A fast and automated separation and quantification method for bromide and the artificial nucleoside 5-bromo-2'-deoxyuridine (5-BrdU) via hyphenation of ion exchange chromatography (IC) and inductively coupled plasma-mass spectrometry (ICP-MS) is presented. The analysis of these two species is relevant to monitor the transfer of electrons along metal-mediated DNA base pairs. Charge transfer in DNA is of high interest for the implementation in nanotechnological applications like molecular wires. 5-BrdU as part of the DNA sequence releases bromide upon one electron reduction after efficient electron transfer along the DNA. The concentrations of 5-BrdU and bromide in enzymatically digested DNA samples can therefore be used as a marker for the efficiency of electron transfer along the DNA helix. A large number of samples was analyzed using an automated IC system. This platform enables time-efficient external calibration by inline dilution of a stock solution. Due to the fast separation of the two bromine species in less than 90 s, the developed method is suitable for screening applications with a multitude of samples. Despite the isobaric interferences and a low degree of ionization for bromine detection via ICP-MS the method has a limit of detection (LOD) of 30 ng/L which is approximately an order of magnitude lower than a comparable method using reversed phase high performance liquid chromatography (RP-HPLC) and ICP-MS., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper. The authors declare the following financial interests/personal relationships which may be considered as potential competing interests:, (Copyright © 2021. Published by Elsevier B.V.)

Objective: A selective and sensitive liquid chromatography-tandem mass spectrometer (LC-MS/MS) method has been developed for the quantification of 1,1-dimethyl-3-hydroxy-pyrrolidinium bromide impurity in glycopyrrolate oral solution., Materials and Method: The LC-MS/MS analysis was done on X Bridge HILIC (100 × 4.6 mm, 5 μm) analytical column, and the mobile phase used was10 mM ammonium formate with 0.2% formic acid as mobile phase-A and acetonitrile as mobile phase-B with a gradient programme of 5.0 min. The flow rate used was 1.2 mL/min. Triple quadrupole mass detector coupled to positive electrospray ionization operated in multiple reactions monitoring mode was used for the quantification at m/z 116.10 ± 0.5., Results: Retention time of impurity was found ~3.2 min. The method was validated in terms of specificity, linearity, accuracy, precision, range, limit of detection, limit of quantitation (LOQ) and robustness. Relative standard deviation (RSD) for system suitability was found 1.3%. Calibration plot was linear over the range of 0.050-2.000 μg/mL. Limit of detection and limit of quantification were found 0.017 and 0.051 μg/mL, respectively. The intra- and inter-day precision RSD was 2.3% and the obtained recovery at LOQ to 200% was in between 86.7 and 107.4%., Conclusion: The low RSD values and high recoveries of the method confirm the suitability of the method., (© The Author(s) 2021. Published by Oxford University Press. All rights reserved. For Permissions, please email: journals.permissions@oup.com.)

Microplastics (MPs) are prevalent global pollutants that are being detected in aquatic ecosystems and drinking water sources around the world. In addition to plastic polymers, MPs contain various chemical substances (known as "additives") that can leach and risk water quality. In this paper, we investigated for the first time the potential release of disinfection byproducts (DBPs) precursors when MPs are exposed to hydrolysis and/or degradation by simulated sunlight. Seventeen MPs with seven different polymer types were collected either as commercial products (e.g. drinking water bottles, shopping bags, recycled plastics, etc.) or pure/virgin polymers. Results showed high release of dissolved organic carbon (DOC) from five MP samples and a significant increase in bromide concentrations from four MPs. DBPs formation potential (DBPFP) experiments with MPs' leachates showed higher concentrations of chlorinated trihalomethanes (THMs), haloacetonitriles (HANs), and total organic halogens (TOX) in three samples, while a significant shift to brominated DBPs was observed in samples containing bromide. Extending the leaching experiments to four consecutive cycles showed that the leaching of DOC and DBPs' precursor significantly decreased after the second leaching cycle. Further analysis revealed that the reactivity of the leached DOC - indicated by THMFP yields - was comparable to those of several raw waters that supply drinking water treatment plants. The leached THMs and TOX from MPs that were exposed to UVA irradiation were in general higher than MPs that were run under dark conditions., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier Ltd. All rights reserved.)

This study investigated the speciation of halogen-specific total organic halogen and disinfection byproducts (DBPs) upon chlorination of natural organic matter (NOM) in the presence of iopamidol and bromide (Br - ). Experiments were conducted with low bromide source waters with different NOM characteristics from Northeast Ohio, USA and varied spiked levels of bromide (2-30 μmol/L) and iopamidol (1-5 μmol/L). Iopamidol was found to be a direct precursor to trihalomethane (THM) and haloacetic acid formation, and in the presence of Br - favored brominated analogs. The concentration and speciation of DBPs formed were impacted by iopamidol and bromide concentrations, as well as the presence of NOM. As iopamidol increased the concentration of iodinated DBPs (iodo-DBPs) and THMs increased. However, as Br - concentrations increased, the concentrations of non-brominated iodo- and chloro-DBPs decreased while brominated-DBPs increased. Regardless of the concentration of either iopamidol or bromide, bromochloroiodomethane (CHBrClI) was the most predominant iodo-DBP formed except at the lowest bromide concentration studied. At relevant concentrations of iopamidol (1 μmol/L) and bromide (2 μmol/L), significant quantities of highly toxic iodinated and brominated DBPs were formed. However, the rapid oxidation and incorporation of bromide appear to inhibit iodo-DBP formation under conditions relevant to drinking water treatment., (Copyright © 2019. Published by Elsevier B.V.)

Disinfection byproducts (DBPs) are a ubiquitous source of chemical exposure in drinking water and have been associated with serious health impacts in human epidemiologic studies. While toxicology studies have pinpointed DBPs with the greatest toxic potency, analytical methods have been lacking for quantifying complete classes of most toxic DBPs at sufficiently low quantification limits (ng/L). This new method reports the parts-per-trillion quantification for 61 toxicologically significant DBPs from 7 different chemical classes, including unregulated iodinated haloacetic acids (HAAs) and trihalomethanes (THMs), haloacetaldehydes, haloketones, haloacetonitriles, halonitromethanes, and haloacetamides, in addition to regulated HAAs and THMs. The final optimized method uses salt-assisted liquid-liquid extraction in a single extraction method for a wide range of DBPs, producing the lowest method detection limits to-date for many compounds, including highly toxic iodinated, brominated, and nitrogen-containing DBPs. Extracts were divided for the analysis of the HAAs (including iodinated HAAs) by diazomethane derivatization and analysis using a GC-triple quadrupole mass spectrometer with multiple reaction monitoring, resulting in higher signal-to-noise ratios, greater selectivity, and improved detection of these compounds. The remaining DBPs were analyzed using a GC-single quadrupole mass spectrometer with selected ion monitoring, utilizing a multimode inlet allowed for lower injection temperatures to allow the analysis of thermally labile DBPs. Finally, the use of a specialty-phase GC column (Restek Rtx-200) significantly improved peak shapes, which improved separations and lowered detection limits. Method detection limits for most DBPs were between 15 and 100 ng/L, and relative standard deviations in tap water samples were mostly between 0.2 and 30%. DBP concentrations in real samples ranged from 40 to 17 760 ng/L for this study.

The presence of bromide (Br - ) in water results in the formation of brominated disinfection byproducts (DBPs) after chlorination, which are much more cytotoxic and genotoxic than their chlorinated analogs. Given that conventional water treatment processes (e.g., coagulation, flocculation, and sedimentation) fail to remove Br - effectively, in this study, we systematically tested and compared the performance of different anion exchange resins, particularly two novel Br-selective resins, for the removal of Br - . The resins performance was evaluated under both typical and challenging background water conditions by varying the concentrations of anions and organic matter. The overall Br - removal results followed the trend of Purolite-Br ≥ MIEX-Br > IRA910 ≥ IRA900 > MIEX-Gold > MIEX-DOC. Further evaluation of Purolite-Br resin showed Br - removal efficiencies of 93.5 ± 4.5% for the initial Br - concentration of 0.25 mg/L in the presence of competing anions (i.e., Cl - , NO 3 - , NO 2 - , SO 4 2- , PO 4 3- , and a mixture of all five), alkalinity and organic matter. In addition, experiments under challenging background water conditions confirmed the selectivity of the resins (i.e. Purolite-Br and MIEX-Br) in removing Br - , with SO 4 2- and Cl - exhibiting the greatest influence upon the resin performance followed by NOM concentration, regardless of the NOM characteristic. After Br - removal, both the subsequent formation of brominated DBPs (trihalomethanes, haloacetic acids, and haloacetonitriles), and the total organic halogens (TOX), decreased by ∼90% under the uniform formation conditions. Overall, Br-selective resins represent a promising alternative for the efficient control of Br-DBPs in water treatment plants., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

The bromide concentration in water source (WS) of Yancheng City in China increased unexpectedly due to industrial discharge and saltwater intrusion, which leads to the formation of trihalomethane (THMs) in finished water of water treatment plants (WTP), especially brominated THMs. In Yancheng City, drinking water is supplied by WTP1 and WTP2, primarily sourced by WS1 and WS2, respectively. In this paper, the seasonal variations of bromide in WS1 and WS2 and THMs species in WTP1 and WTP2 were analyzed and compared. The effects of bromide in WS on THMs formation in finished water of WTP in terms of bromine substitution factor (BSF) were simulated by statistical linear model. Although the THMs concentrations in WTP1 were approximate to that in WTP2, the brominated THMs concentrations in WTP1 were higher than that in WTP2 due to higher bromide concentration in WS1 than WS2. The cancer risk analysis indicated that THMs' species of DBCM is the dominant THMs for WTP1 as well as WTP2, which can provide more information for WTPs with higher bromide concentration in water source.

Halides (X - ) in the industrial wastewater are usually thought to adversely affect the degradation kinetics and mineralization rates in several SO 4 - -based advanced oxidation processes. However, their unfavorable effects might be overestimated, particularly the heat/persulfate (PS) system as tested in the present study. Here the degradation of phenol, benzoic acid, coumarin and acid orange 7 (AO7) was examined with the presence of chloride or bromide in a heat/PS process. Cl - was found to have a dual effect (inhibition followed by enhancement) on the decomposition rates of organic pollutants, whereas the effects of Br - are insignificant within the tested concentration (0-0.2 mM). However, some chlorinated or brominated compounds were still identified in this heat/PS system. Unexpectedly, the mineralization rates of AO7, phenol, benzoic acid and coumarin were not apparently inhibited. In addition, the formation of adsorbable organic halogen (AOX) in the heat/PS system was much less than those in the peroxymonosulfate (PMS)/Cl - or PMS/Br - systems. According to the results of kinetic modeling, SO 4 - was the dominating radical for AO7 degradation without Cl - or Br - , but Cl 2 - was the main oxidant in the presence of Cl - , SO 4 - , Br and Br 2 - were responsible for the oxidation of AO7 in the presence of Br - . The present study assumes that X 2 /HOX, rather than halogen radicals, is responsible for the enhanced formation of organohalogens. These findings are meaningful to evaluate the PS-based technologies for the high-salinity wastewater and to develop useful strategies for mitigating the negative effects of halides in advanced oxidation processes (AOPs)., (Copyright © 2019 The Authors. Published by Elsevier Ltd.. All rights reserved.)

Since decades, surface water bodies have been exposed to pesticides from agriculture. In many places, retention systems are regarded as an important mitigation strategy to lower pesticide pollution. Hence, the processes governing the transport of pesticides in and through a retention system have to be understood to achieve sufficient pesticide attenuation. In this study, the temporal dynamics of metazachlor and its transformation products metazachlor-oxalic acid (OA) and -sulphonic acid (ESA) were observed in an agricultural retention pond and hydrologic tracers helped to understand system-inherent processes. Pesticide measurements were carried out for 80 days after their application during transient flow conditions. During a short-term (3 days) experiment, the tracers bromide, uranine and sulphorhodamine B were used to determine hydraulic conditions, residence times and sorption potential. A long-term experiment with sodium naphthionate (2 months) and isotopes (12 months) provided information about inputs via interflow and surface-groundwater interactions. During transient conditions, high concentration pulses of up to 35 μg L -1 metazachlor, 14.7 μg L -1 OA and 22.5 μg L -1 ESA were quantified that enduringly raised solute concentrations in the pond. Mean residence time in the system accounted for approximately 4 h showing first tracer breakthrough after 5 min and last tracer concentrations 72 h after injection. While input via interflow was confirmed, no evidence for surface-groundwater interaction was found. Different tracers illustrated potentials for sorption and photolytic degradation inside the system. This study shows that high-resolution sampling is essential to obtain robust results about retention efficiency and that hydrological tracers may be used to determine the governing processes.

Background: A fast and sensitive method for the simultaneous analysis of iodine and bromine species in infant formula was developed using HPLC-inductively coupled plasma-MS (HPLC-ICP-MS). Method: To determine the four halogen species [iodide (I - ), iodate ( IO 3 - ) , bromide (Br - ), and bromate ( BrO 3 - ) ] in a milk-based Standard Reference Material and four commercially available infant formula products. Results: The four halogen species were baseline separated in less than 6.5 min using an anion exchange resin column and 5.0 mM NaH₂PO₄ / 15.0 mM Na₂SO₄ / 5.0 mM EDTA (pH 7.0) mobile phase. Following separation, the halogen species were detected by measuring m/z 79 for Br and m/z 127 for I using a triple quadrupole-ICP-MS. The instrument was operated in single quadrupole mode with helium cell gas. Excellent linearity (R = 0.9999 or better) was obtained for all four species with calibration standards ranging from 0 to 100 ppb. The LOD for I - , IO 3 - , Br - , and BrO 3 - were all less than 0.67 μg/kg. To test the suitability of the method for the accurate determination of low concentrations of the four species in infant formula samples, a spike recovery test was carried out at 20 and 40 μg/kg into the diluted infant formula samples. Conclusions: Total elemental determinations of iodine and bromine were also performed using the triple quadrupole-ICP-MS without HPLC.

Concerns regarding disinfection by-product (DBP) formation during drinking water treatment have led water utilities to apply treatment processes to reduce the concentration of DBP precursor natural organic matter (NOM). However, these processes often do not remove bromide, leading to high bromide to dissolved organic carbon (DOC) ratios after treatment, which can increase the formation of more toxic brominated DBPs. In the current study, we investigated the formation and effect of DBPs in a matrix of synthetic water samples containing different concentrations of bromide and DOC after disinfection with chlorine. Trihalomethanes and haloacetic acids were analysed by chemical analysis, while effect was evaluated using in vitro bioassays indicative of the oxidative stress response and bacterial toxicity. While the addition of increasing bromide concentrations did not alter the sum molar concentration of DBPs formed, the speciation changed, with greater bromine incorporation with an increasing Br:DOC ratio. However, the observed effect did not correlate with the Br:DOC ratio, but instead, effect increased with increasing DOC concentration. Water samples with low DOC and high bromide did not exceed the available oxidative stress response effect-based trigger value (EBT), while all samples with high DOC, irrespective of the bromide concentration, exceeded the EBT. This suggests that treatment processes that remove NOM can improve drinking water quality, even if they are unable to remove bromide. Further, iceberg modelling showed that detected DBPs only explained a small fraction of the oxidative stress response, supporting the application of both chemical analysis and bioanalysis for monitoring DBP formation.

Nitrate and bromide ions are generally considered indicators of anthropogenic pollution and seawater intrusion, respectively, in the groundwater of coastal territories. The analysis of these species is generally carried out with routine chromatographic analyses which generally afford partially merged or poorly resolved peaks. In the present paper a simple method for the correct evaluation of their concentration in water is reported. This method does not imply utilization of other instruments or technologies, only the mathematical elaboration of the data obtained from routine analysis of standard solutions containing the two species. Standard binary solutions of nitrate and bromide ions at different concentrations, ranging between 0.1 and 2 mM, were analyzed by means of ion chromatography. Splitting two partially merged chromatographic peaks and considering each resulting area as originating from a single species produces "measured" concentration values which differ from the nominal ones. Such a procedure generates errors (one per species) which can be written as a function of the above mentioned "measured" concentrations and which can be graphically represented by means of a surface in a three-dimensional (3D) space. In this way, "measured" concentrations of bromide and nitrate ions can be corrected by calculating the errors generated under the experimental conditions at which the chromatographic separation is performed. Notably, this is analogous with the two-dimensional (2D) calibration normally carried out for analytical purposes. Indeed, both methods allow estimation of the unknown concentration of species in solution by correlating the instrumental response with the concentration of standard solutions., Competing Interests: The authors declare no conflict of interest.

A facile and sustainable electrochemical umpolung of bromide ion protocol was developed under mild reaction conditions. Transition metal catalysts and exogenous chemical oxidants were obviated for the bromination of C⁻H bond. Notably, graphite rod, which is commercially available at supermarkets and is inexpensive, was employed as the electrode material. This operationally easy and environmentally friendly approach accomplished the synthesis of 3-bromoindole in excellent yield and regioselectivity.

Management of turfgrass on golf courses and athletic fields often involves application of plant protection products to maintain or enhance turfgrass health and performance. However, the transport of fertilizer and pesticides with runoff to adjacent surface waters can enhance algal blooms, promote eutrophication and may have negative impacts on sensitive aquatic organisms and ecosystems. Thus, we evaluated the effectiveness of chemical application setbacks to reduce the off-site transport of chemicals with storm runoff. Experiments with water soluble tracer compounds confirmed an increase in application setback distance resulted in a significant increase in the volume of runoff measured before first off-site chemical detection, as well as a significant reduction in the total percentage of applied chemical transported with the storm runoff. For example, implementation of a 6.1 m application setback reduced the total percentage of an applied water soluble tracer by 43%, from 18.5% of applied to 10.5% of applied. Evaluation of chemographs revealed the efficacy of application setbacks could be observed with storms resulting in lesser (e.g. 100 L) and greater (e.g. > 300 L) quantities of runoff. Application setbacks offer turfgrass managers a mitigation approach that requires no additional resources or time inputs and may serve as an alternative practice when buffers are less appropriate for land management objectives or site conditions. Characterizing potential contamination of surface waters and developing strategies to safeguard water quality will help protect the environment and improve water resource security. This information is useful to grounds superintendents for designing chemical application strategies to maximize environmental stewardship. The data will also be useful to scientists and regulators working with chemical transport and risk models., (Copyright © 2018. Published by Elsevier Inc.)

This work reports a simple voltammetric method for the determination of chloride, bromide, and iodide ions using screen-printed carbon electrodes modified with silver nanoparticles electrochemically deposited on the working electrode surface. UV/Vis absorption spectroelectrochemistry was used to study the electrodeposition of silver nanoparticles on the working carbon electrode on PET or Gore-Tex ® supports, and their subsequent oxidation in the presence of halide ions. The main figures of merit of the developed sensors, such as reproducibility and detection limit, have been calculated. Reproducibility values of 2.22%, 2.83% and 3.23% were obtained for chloride, bromide and iodide determinations, respectively. Additionally, the lowest detected amount of chloride, bromide and iodide ions were 3.0·10 -6  M, 5.0·10 -6  M and 5.0·10 -6  M, respectively. Taking into account the relevance of the determination of chloride ion concentration in sweat, the voltammetric method for the determination of halides has been successfully transferred to a Gore-Tex ® support to build a first approach to a wearable sensor that facilitates the quantification of this ion in sweat samples. The Gore-Tex ® sensor provides a good reproducibility (RSD = 1.61%)., (Copyright © 2018. Published by Elsevier B.V.)

This study systematically investigated the degradation of tetrabromobisphenol A (TBBPA) by ferrate (VI) oxidation. The reaction kinetics between ferrate (VI) with TBBPA were studied under pseudo-first-order conditions in the pH range 5.5-10.5. Then, a series of batch experiments were carried out to investigate other factors, including the ferrate (VI) dosage, temperature and interfering ions. Additionally, the generation of inorganic products (bromide ion and bromate) was evaluated. The organic intermediates were identified, and possible pathways were proposed. In addition, the toxicity variation was analyzed with marine luminous bacteria (V. fischeri). Degradation of TBBPA by ferrate (VI) oxidation was confirmed to be an effective and environmentally friendly technique. The reaction was fitted with a second-order rate model. With a ferrate (VI) dosage of 25.25 μmol/L, TBBPA concentration of 1.84 μmol/L, an initial pH of 7.0, and a temperature of 25 °C, a 99.06% TBBPA removal was achieved within 30 min. The evaluation of inorganic products showed that the capacity of ferrate (VI) oxidation to yield bromide ions was relatively strong and could prevent the formation of bromate compared to photocatalytic and mechanochemical techniques. Eleven intermediates were identified, and the proposed degradation pathway indicated that TBBPA might undergo debromination, beta scission, substitution, deprotonation and oxidation. The results of toxicity testing showed that ferrate (VI) could effectively control the toxicity of the treated samples, although the toxicity increased in the initial reaction stage due to the accumulation and destruction of more toxic intermediates., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

The characteristics of dissolved organic matter (DOM) and bromide ion concentration have a significant influence on the formation of disinfection by-products (DBPs). In order to identify the main DBP precursors, DOM was divided into five fractions based on molecular weight (MW), trihalomethane formation potential and haloacetic acid formation potential were determined for fractions, and the change in contents of different fractions and total DBPs during treatment processes (pre-chlorination, coagulation, sand filtration, disinfection) were studied. Moreover, the relationship between bromide concentration and DBP generation characteristics in processes was also analyzed. The results showed that the main DBP precursors were the fraction with MW <1kDa and fraction with MW 3-10kDa, and the DBP's generation ability of lower molecular weight DOM (<10kDa) was higher than that of higher molecular weight DOM. During different processes, pre-chlorination and disinfection had limited effect on removing organics but could alter the MW distribution, and coagulation and filtration could effectively remove organics with higher MW. For DBPs, trihalomethanes (THMs) were mainly generated in pre-chlorination and disinfection, while haloacetic acids (HAAs) were mostly generated during pre-chlorination; coagulation and sand filtration had little effect on THMs but resulted in a slight removal of HAAs. In addition, the results of ANOVA tests suggested that molecular sizes and treatment processes have significant influence on DBP formation. With increasing bromide concentration, the brominated DBPs significantly increased, but the bromine incorporation factor in the processes was basically consistent at each concentration., (Copyright © 2017. Published by Elsevier B.V.)

This article has been retracted: please see Elsevier Policy on Article Withdrawal (https://www.elsevier.com/about/our-business/policies/article-withdrawal). This article has been retracted at the request of the authors due to the results of a detailed investigation of the data quality conducted by the Central Analytical Laboratory (CAL) after relocation to the University of Wisconsin (UW) – Wisconsin State Laboratory of Hygiene. Using a subset of the 30 samples with the highest bromide ion (Br-) concentrations, the CAL at UW found 6 samples that could not be verified or were incorrect. Because the extent of the incorrect data is unknown, the NADP Executive Committee voted unanimously in May 2019 to discontinue public access to these data, and they decided to sequester all Br- data prior to June 2018. These issues were not obvious to the authors when the paper was written. The authors apologize for the inconvenience caused., (Published by Elsevier Ltd.)

When a bromide-containing water is treated by the ultraviolet (UV)/chlorine process, hydroxyl radicals (HO) and halogen radicals such as Cl or Br are formed due to the UV photolysis of free halogens. These reactive species may induce the formation of bromate, which is a probable human carcinogen. Bromate formation in the UV/chlorine process using low pressure (LP) and medium pressure (MP) lamps in the presence of bromide was investigated in the present study. The UV/chlorine process significantly enhanced bromate formation as compared to dark chlorination. The bromate formation was elevated with increasing UV fluence, bromide concentration, and pH values under both LP and MP UV irradiations. It was significantly enhanced at pH 9 compared to those at pH 6 and 7 with MP UV irradiation, while it was slightly enhanced at pH 9 with LP UV. The formation by UV/chlorine process started with the formation of free bromine (HOBr/OBr - ) through the reaction of chlorine and bromide, followed by a subsequent oxidation of free bromine and formation of BrO and bromate by reacting with radicals., (Copyright © 2017 Elsevier Ltd. All rights reserved.)

We studied the formation of four nitrogenous DBPs (N-DBPs) classes (haloacetonitriles, halonitromethanes, haloacetamides, and N-nitrosamines), as well as trihalomethanes and total organic halogen (TOX), after chlorination or chloramination of source waters. We also evaluated the relative and additive toxicity of N-DBPs and water treatment options for minimisation of N-DBPs. The formation of halonitromethanes, haloacetamides, and N-nitrosamines was higher after chloramination and positively correlated with dissolved organic nitrogen or total nitrogen. N-DBPs were major contributors to the toxicity of both chlorinated and chloraminated waters. The strong correlation between bromide concentration and the overall calculated DBP additive toxicity for both chlorinated and chloraminated source waters demonstrated that formation of brominated haloacetonitriles was the main contributor to toxicity. Ozone-biological activated carbon treatment was not effective in removing N-DBP precursors. The occurrence and formation of N-DBPs should be investigated on a case-by-case basis, especially where advanced water treatment processes are being considered to minimise their formation in drinking waters, and where chloramination is used for final disinfection., (Copyright © 2017. Published by Elsevier B.V.)

This paper describes a programme of research investigating horizontal fluid flow and solute transport through saturated municipal solid waste (MSW) landfill. The purpose is to inform engineering strategies for future contaminant flushing. Solute transport between injection/abstraction well pairs (doublets) is investigated using three tracers over five separate tests at well separations between 5m and 20m. Two inorganic tracers (lithium and bromide) were used, plus the fluorescent dye tracer, rhodamine-WT. There was no evidence for persistent preferential horizons or pathways at the inter-well scale. The time for tracer movement to the abstraction wells varied with well spacing as predicted for a homogeneous isotropic continuum. The time for tracer movement to remote observation wells was also as expected. Mobile porosity was estimated as ~0.02 (~4% of total porosity). Good fits to the tracer breakthrough data were achieved using a dual-porosity model, with immobile regions characterised by block diffusion timescales in the range of about one to ten years. This implies that diffusional exchanges are likely to be very significant for engineering of whole-site contaminant flushing and possibly rate-limiting., (Copyright © 2017. Published by Elsevier B.V.)

Natural and anthropogenic factors can alter bromide concentrations in drinking water sources. Increasing source water bromide concentrations increases the formation and alters the speciation of disinfection byproducts (DBPs) formed during drinking water treatment. Brominated DBPs are more toxic than their chlorinated analogs, and thus have a greater impact on human health. However, DBPs are regulated based on the mass sum of DBPs within a given class (e.g., trihalomethanes and haloacetic acids), not based on species-specific risk or extent of bromine incorporation. The regulated surrogate measures are intended to protect against not only the species they directly represent, but also against unregulated DBPs that are not routinely measured. Surrogates that do not incorporate effects of increasing bromide may not adequately capture human health risk associated with drinking water when source water bromide is elevated. The present study analyzes trihalomethanes (THMs), measured as TTHM, with varying source water bromide concentrations, and assesses its correlation with brominated THM, TTHM risk and species-specific THM concentrations and associated risk. Alternative potential surrogates are evaluated to assess their ability to capture THM risk under different source water bromide concentration conditions. The results of the present study indicate that TTHM does not adequately capture risk of the regulated species when source water bromide concentrations are elevated, and thus would also likely be an inadequate surrogate for many unregulated brominated species. Alternative surrogate measures, including THM 3 and the bromodichloromethane concentration, are more robust surrogates for species-specific THM risk at varying source water bromide concentrations., (Copyright © 2017. Published by Elsevier B.V.)

Coiled tubing corrosion was investigated for 16 field water samples (S5 to S20) from a Canadian shale gas field. Weight loss corrosion rates of carbon steel beads incubated with these field water samples averaged 0.2 mm/yr, but injection water sample S19 had 1.25±0.07 mm/yr. S19 had a most probable number of zero acid-producing bacteria and incubation of S19 with carbon steel beads or coupons did not lead to big changes in microbial community composition. In contrast other field water samples had most probable numbers of APB of 102/mL to 107/mL and incubation of these field water samples with carbon steel beads or coupons often gave large changes in microbial community composition. HPLC analysis indicated that all field water samples had elevated concentrations of bromide (average 1.6 mM), which may be derived from bronopol, which was used as a biocide. S19 had the highest bromide concentration (4.2 mM) and was the only water sample with a high concentration of active bronopol (13.8 mM, 2760 ppm). Corrosion rates increased linearly with bronopol concentration, as determined by weight loss of carbon steel beads, for experiments with S19, with filtered S19 and with bronopol dissolved in defined medium. This indicated that the high corrosion rate found for S19 was due to its high bronopol concentration. The corrosion rate of coiled tubing coupons also increased linearly with bronopol concentration as determined by electrochemical methods. Profilometry measurements also showed formation of multiple pits on the surface of coiled tubing coupon with an average pit depth of 60 μm after 1 week of incubation with 1 mM bronopol. At the recommended dosage of 100 ppm the corrosiveness of bronopol towards carbon steel beads was modest (0.011 mm/yr). Higher concentrations, resulting if biocide is added repeatedly as commonly done in shale gas operations, are more corrosive and should be avoided. Overdosing may be avoided by assaying the presence of residual biocide by HPLC, rather than by assaying the presence of residual surviving bacteria.

A tracer test was conducted to aid in the investigation of water movement and solute transport at a crude-oil spill site near Bemidji, Minnesota. Time of travel was measured using breakthrough curves for rhodamine WT and bromide tracers moving from the soil surface through oil-contaminated and oil-free unsaturated zones to the saturated zone. Results indicate that the rates of tracer movement were similar in the oil-free unsaturated and saturated zones compared to the oily zones. These results are somewhat surprising given the oil contamination in the unsaturated and saturated zones. Rhodamine tracer breakthrough in the unsaturated and saturated zones in general was delayed in comparison to bromide tracer breakthrough. Peak tracer concentrations for the lysimeters and wells in the oily zone were much greater than at the corresponding depths in the oil-free zone. Water and tracer movement in the oily zone was complicated by soil hydrophobicity and decreased oil saturations toward the periphery of the oil. Preferential flow resulted in reduced tracer interaction with the soil, adsorption, and dispersion and faster tracer movement in the oily zone than expected. Tracers were freely transported through the oily zone to the water table. Recharge calculations support the idea that the oil does not substantially affect recharge in the oily zone. This is an important result indicating that previous model-based assumptions of decreased recharge beneath the oil were incorrect. Results have important implications for modeling the fate and transport of dissolved contaminants at hydrocarbon spill sites., (Published by Elsevier B.V.)

The quality of drinking water sources can decrease when contaminants are transported by overland and subsurface flow and discharged into surface waters following rainfall events. Increases in organic contaminants such as road salts and organic matter may occur and potentially modify disinfection by-products (DBPs) concentration and speciation. This study investigated the effects of various spring rainfall events on the quality of treated waters at a large water treatment plant through the implementation of intensive water quality monitoring of raw, filtered and treated waters during different rainfall events. DBPs (four trihalomethanes and six haloacetic acids) and their explanatory variables (pH, turbidity, water temperature, specific ultraviolet absorbance, total and dissolved organic carbon, bromide and chlorine dose) were measured during four rainfall events. The results showed that water quality degrades during and following rainfall, leading to small increases in trihalomethanes (THM4) and haloacetic acids (HAA6) in treated waters. While THM4 and HAA6 levels remained low during the pre-rainfall period (<9 μg/L) for the four sampling campaigns, small increases in THM4 and HAA6 during and after spring rainfall events were observed. During the rainfall and post-rainfall periods, concentration peaks corresponding to 3-fold and 2-fold increases (respectively 27.5 μg/L for THM4 and 12.6 μg/L for HAA6) compared to pre-rainfall levels were also measured. A slight decrease in harmful brominated THM and HAA proportion was also observed following rainfall events., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

The objective of this study was to analyze the behavior of a new material, silver-doped polymeric cloth (Ag-cloth), in the removal of bromide and iodide from waters. Silver is immobilized on the cloth, guaranteeing selective adsorption of the halide ions as retained silver halides that therefore do not pass into the solution. Results indicate that Ag 0 reacts with H 2 O 2 in the first phases of the process, yielding Ag + and superoxide radical; however, as the process advances, this radical favors Ag + reduction. Increases in the concentration of H 2 O 2 augment the capacity of the Ag-cloth to remove halides from the medium up to a maximum concentration (55μM), above which the removal capacity remains constant (Xm≅1.3-1.8mg halide/g Ag-cloth). Thus, when there is excess H 2 O 2 in the medium, secondary competitive reactions that take place in the process guarantee a constant Ag + concentration, which defines the maximum adsorption capacity of Ag-cloth, reducing its ability to remove halides. Ag-cloth has a higher capacity to remove iodide than bromide, and the presence of organic matter or chloride reduces its capacity to remove iodide or bromide from water. The results obtained shown that the capacity of Ag 0 with H 2 O 2 significantly varies as a function of the medium pH from 1mg Br - /g Ag-cloth at very low pH to 1.6mg/g Ag-cloth at pH9., (Copyright © 2016 Elsevier B.V. All rights reserved.)

Previous studies have documented the occurrence of veterinary sulfonamide antibiotics in groundwater and rivers located far from pollution sources, although their transport and fate is relatively unknown. In mountainous agricultural fields, the transport behaviour can be influenced by climate, slope and physico-chemical properties of the sulfonamides. The objective of this research is to describe the transport behaviour of three sulfonamide antibiotics (sulfamethoxazole, sulfadimethoxine and sulfamethazine) in sloped agricultural fields located in the Haean catchment, South Korea. During dry and monsoon seasons, a solute transport experiment was conducted in two typical sandy loam agricultural fields after application of antibiotics and potassium bromide as conservative tracers. Field measurement and modelling revealed that frequency and amount of runoff generation indicate a relation between slope and rain intensity during monsoon season. Since the steepness of slope influenced partitioning of precipitation between runoff and subsurface flow, higher loss of sulfonamide antibiotics and bromide by runoff was observed at the steeper sloped field. Bromide on topsoil rapidly infiltrated at high infiltration rates. On the contrary, the sulfonamides were relatively retarded in the upper soil layer due to adsorption onto soil particles. Presence of furrows and ridges affected the distribution of sulfonamide antibiotics in the subsurface due to gradient from wetter furrows to drier ridges induced by topography. Modelling results with HydroGeoSphere matched with background studies that describe physico-chemical properties of the sulfonamides interaction between soil and the antibiotic group, solute transport through vadose zone and runoff generation by storm events.

Poor performance of the amphipod Hyalella azteca has been observed in exposures using reconstituted waters. Previous studies have reported success in H. azteca water-only exposures with the addition of relatively high concentrations of bromide. The present study evaluated the influence of lower environmentally representative concentrations of bromide on the response of H. azteca in 42-d water-only exposures. Improved performance of H. azteca was observed in reconstituted waters with >0.02 mg Br/L. Environ Toxicol Chem 2016;35:2425-2429. Published 2016 Wiley Periodicals Inc. on behalf of SETAC. This article is a US Government work and, as such, is in the public domain in the United States of America., (Published 2016 Wiley Periodicals Inc. on behalf of SETAC. This article is a US Government work and, as such, is in the public domain in the United States of America.)

Road salt used as a deicing agent in winter months has become an emerging contaminant to streams and groundwater. In central New York, road salts are applied heavily during winter months. Recognizing potential sources of salinity to a river may reveal processes controlling the salinization of freshwater systems, with implications for future management practices. The Tioughnioga River, located in central New York, is a headwater of the Susquehanna River, which flows into the Chesapeake Bay. Salinity of the Tioughnioga River water has been increasing since the late 1930s. In this study, water samples were collected weekly at the East and West Branches of the Tioughnioga River from 2012 to 2014. We characterize natural and anthropogenic sources of salinity in the Tioughnioga River, using two independent approaches: (1) chloride to bromide ratios (Cl/Br) and (2) linear discriminant analysis. Ratios of Cl/Br suggest that road salt runoff influence is notable in both branches, but is more significant in the West Branch, consistent with a greater area of urban land. Linear discriminant analysis confirms the results of Cl/Br in the West Branch and further indicates presence of Appalachian Basin Brines in the East Branch, although their contribution may be volumetrically small. Longitudinal stream Cl concentration profiles indicate that sources of pollution are particularly concentrated around urban areas. Residence time of Cl in the watershed is estimated to be approximately 20 to 30years using a mixing model, suggesting that stream Cl concentrations likely will continue to rise for several decades., (Copyright © 2016 Elsevier B.V. All rights reserved.)

Pesticide transport from seed dressings toward subsurface tile drains is still poorly understood. We monitored the neonicotinoid insecticides imidacloprid and thiamethoxam from sugar beet seed dressings in flow-proportional drainage water samples, together with spray applications of bromide and the herbicide S-metolachlor in spring and the fungicides epoxiconazole and kresoxim-methyl in summer. Event-driven, high first concentration maxima up to 2830 and 1290 ng/L for thiamethoxam and imidacloprid, respectively, were followed by an extended period of tailing and suggested preferential flow. Nevertheless, mass recoveries declined in agreement with the degradation and sorption properties collated in the groundwater ubiquity score, following the order bromide (4.9%), thiamethoxam (1.2%), imidacloprid (0.48%), kresoxim-methyl acid (0.17%), S-metolachlor (0.032%), epoxiconazole (0.013%), and kresoxim-methyl (0.003%), and indicated increased leaching from seed dressings compared to spray applications. Measured concentrations and mass recoveries indicate that subsurface tile drains contribute to surface water contamination with neonicotinoids from seed dressings.

Monitoring total bromine and bromide concentrations in soils is significant in many environmental studies. Thus fast analytical methodologies that entail simple sample preparation and low-cost analyses are desired. In the present work, the possibilities and drawbacks of low-power total reflection X-ray fluorescence spectrometry (TXRF) for the determination of total bromine and bromide contents in soils were evaluated. The direct analysis of a solid suspension using 20 mg of fine ground soil (<63 μm) gave a 3.7 mg kg(-1) limit of detection for bromine which, in most cases, was suitable for monitoring total bromine content in soils (Br content range in soils = 5-40 mg kg(-1)). Information about bromide determination in soils is also possible by analyzing the Br content in water soil extracts. In this case, the TXRF analysis can be directly performed by depositing 10 μL of the internal standardized soil extract sample on a quartz glass reflector in a measuring time of 1500 s. The bromide limit of detection by this approach was 10 μg L(-1). Good agreement was obtained between the TXRF results for the total bromine and bromide determinations in soils and those obtained by other popular analytical techniques, e.g. energy dispersive X-ray fluorescence spectrometry (total bromine) and ionic chromatography (bromide). As a study case, the TXRF method was applied to study bromine accumulation in two agricultural soils fumigated with a methyl bromide pesticide and irrigated with regenerated waste water., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

Gold-plated silver nanoparticles have been developed to undergo morphological changes that enhance the surface plasmon resonance (SPR) sensing response. These morphological changes were realized through thin-frame gold plating that both reinforces the nanoparticle edges and enables partial silver etching upon exposure to several biological molecules, including thiols and amines.

Ferrate (VI) is traditionally recognized as a safe oxidant without production of disinfection byproducts (DBPs). However, here we detected probable carcinogenic bromate (BrO3(-)) during ferrate(VI) oxidation of bromide (Br(-))-containing water, and evaluated the effects of pH, ferrate(VI) dose, initial Br(-) concentration, and co-existing anions on the BrO3(-) formation. BrO3(-) was produced at a moderately-weakly acidic pH condition and in the absence of phosphate that was commonly applied as a buffer and stabilizing agent in previous ferrate(VI) studies. At pH 5.0, the produced BrO3(-) was increased from 12.5 to 273.8 μg/L with the increasing initial Br(-) concentration from 200 to 1000 μg/L at 10 mg/L Fe(VI), corresponding to an increase in the molar conversion ([BrO3(-)]/initial [Br(-)]) from 2.3% to 10.3%, in a bicarbonate-buffered solution. As pH increased to 7.0, the BrO3(-) concentration gradually dropped. The BrO3(-) production appeared to be associated with the oxidation by high valence iron species (i.e. Fe(VI), Fe(V) and Fe(IV)). Two key intermediate products (i.e. hypobromous acid/hypobromite (HOBr/OBr(-)) and hydrogen peroxide (H2O2)) relevant to the bromate formation were identified. The production of HOBr, a requisite intermediate for the ensuing bromate formation, was indirectly validated through identification of bromine-containing trihalomethanes and haloacetic acids during ferrate oxidation in a natural water, though these bromo-organic DBPs produced were insignificant. Furthermore, the inhibition effects of various anions on the formation of BrO3(-) followed chloride < sulfate < silicate < phosphate. More H2O2 was detected at higher phosphate concentration. It could reduce HOBr to Br(-), thereby inhibiting the bromate formation., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

The water in and air above swimming pools often contain high levels of disinfection byproducts (DBPs) due to chemical reactions between chlorine- or bromine-based disinfectants and organic/inorganic matter in the source water and released from swimmers. Exposure to these DBPs, though inevitable, can pose health threats to humans. In this study, DBPs in tap water (S1), and water from a chlorinated indoor swimming pool before (S2) and after swimming (S3) were measured. The brominated species constituted the majority of DBPs formed in S1, S2, and S3. Trihalomethanes (THMs) in S3 was 6.9 (range 2.9-11.1) and 1.4 (range 0.52-2.9) times those in S1 and S2, respectively; and the haloacetic acids (HAAs) in S3 was 4.2 (range 2.5-7.5) and 1.2 (range 0.6-2.6) times those in S1 and S2, respectively. The mean THMs in air above the swimming pool before (S2-A) and after swimming (S3-A) were 72.2 and 93.0 μg/m(3), respectively, and their ranges were 36.3-105.8 and 44.1-133.6 μg/m(3), respectively. The average percentages of bromide incorporation (BI) into THMs in S1, S2, and S3 were 3.0, 9.3, and 10.6 %, respectively; and the BI into HAAs in S1, S2, and S3 were 6.6, 12.0, and 12.2 %, respectively. Several models were trained for predicting the BI into THMs and HAAs. The results indicate that additional information is required to develop predictive models for BI in swimming pools.

in groundwaters from 145 wells across central West Bengal, India, those from Pleistocene aquifers at depths >70 m beneath paleo-interfluves contain <10 μg/L As. Pleistocene aquifers beneath deep paleo-channels typically host groundwaters containing 10-100 μg/L As at depths between 120 and 180 m. The depth profiles of As and SO4 and the conservative tracers Cl/Br, δ(18)O, and δ(2)H show that the As in Pleistocene groundwater beneath deep paleo-channels is relict and does not arise from migration downward of As-polluted groundwater in overlying aquifers. We postulate that the As was liberated in situ by reduction of minimal iron oxyhydroxides in the gray Pleistocene sands by organic matter infiltrating from riverbeds during late Pleistocene or earliest Holocene times. Mitigation of the widespread As-pollution in shallow aquifers through exploitation of deep Pleistocene aquifers would improve if guided by an understanding of the distribution of buried paleo-channels and paleo-interfluves and the knowledge that As may be present naturally in groundwater at depths >150 m beneath deep paleo-channels.

Linear alkylbenzene sulfonates (LAS) are an important group of organic pollutants in urban wastewater effluents. The practice of using seawater for toilet flushing results in saline wastewater effluents, which contain high levels of bromide ions. Chlorine is most commonly used in wastewater disinfection. During chlorination of freshwater or saline wastewater effluents, some halogenated disinfection byproducts (DBPs) resulting from LAS could be formed. In this study, the overall formation of halogenated DBPs resulting from LAS was quantified by total organic halogen (TOX) measurement. Polar halogenated DBPs resulting from LAS were detected with a novel precursor ion scan method. The structures and formation pathways of the major ones were tentatively proposed. The overall toxicity of different scenarios of LAS samples was evaluated with embryos of a marine polychaete Platynereis dumerilii. The results demonstrate that chlorinated DBPs were generated during chlorination of LAS without bromide, while brominated DBPs were generated during chlorination of LAS with bromide. The TOX concentrations were relatively low, indicating that LAS were not quite reactive with halogen. The major polar chlorinated and brominated DBPs resulting from LAS were proposed to be 2,6-dichloro-3,5-dihydroxy-4-dodecylbenzenesulfonic acid and 2,6-dibromo-3,5-dihydroxy-4-dodecylbenzenesulfonic acid, which belong to a group of DBPs with similar structures but different halogen atoms, and their formation pathways were tentatively proposed. The results also reveal that the undisinfected LAS sample was the least toxic, followed by the chlorinated LAS sample without bromide, and the chlorinated LAS sample with bromide was the most toxic., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

Porting is a powerful methodology to recalibrate an existing database of ion chromatography (IC) retention times by reflecting the changes of column behavior resulting from either batch-to-batch variability in the production of the column or the manufacture of new versions of a column. This approach has been employed to update extensive databases of retention data of inorganic and organic anions forming part of the "Virtual Column" software marketed by Thermo Fisher Scientific, which is the only available commercial optimization tool for IC separation. The current porting process is accomplished by performing three isocratic separations with two representative analyte ions in order to derive a porting equation which expresses the relationship between old and new data. Although the accuracy of retention prediction is generally enhanced on new columns, errors were observed on some columns. In this work, the porting methodology was modified in order to address this issue, where the porting equation is now derived by using six representative analyte ions (chloride, bromide, iodide, perchlorate, sulfate, and thiosulfate). Additionally, the updated porting methodology has been applied on three Thermo Fisher Scientific columns (AS20, AS19, and AS11HC). The proposed approach showed that the new porting methodology can provide more accurate and robust retention prediction on a wide range of columns, where average errors in retention times for ten test anions under three eluent conditions were less than 1.5%. Moreover, the retention prediction using this new approach provided an acceptable level of accuracy on a used column exhibiting changes in ion-exchange capacity., (Crown Copyright © 2016. Published by Elsevier B.V. All rights reserved.)

Exchange of water and solutes between contaminated soil matrix and bulk solution in preferential flow paths has been shown to contribute to the long-term release of dissolved contaminants in the subsurface, but whether and how this exchange can affect the release of colloids in a soil are unclear. To examine this, we applied rainfall solutions of different ionic strength on an intact soil core and compared the resulting changes in effluent colloid concentration through multiple sampling ports. The exchange of water between soil matrix and the preferential flow paths leading to each port was characterized on the basis of the bromide (conservative tracer) breakthrough time at the port. At individual ports, two rainfalls of a certain ionic strength mobilized different amounts of colloids when the soil was pre-exposed to a solution of lower or higher ionic strength. This result indicates that colloid mobilization depended on rainfall solution history, which is referred as colloid mobilization hysteresis. The extent of hysteresis was increased with increases in exchange of pore water and solutes between preferential flow paths and matrix. The results indicate that the soil matrix exchanged the old water from the previous infiltration with new infiltrating water during successive infiltration and changed the pore water chemistry in the preferential flow paths, which in turn affected the release of soil colloids. Therefore, rainfall solution history and soil heterogeneity must be considered to assess colloid mobilization in the subsurface. These findings have implications for the release of colloids, colloid-associated contaminants, and pathogens from soils.

It had been reported that alumina nanoshell coating could be obtained on the external surface of various substrates in one-nanometer precision in aqueous solution. In this work, alumina nanoshell coated mesoporous silica microbeads (nanoAl2O3/mesoSiO2) were prepared with the similar method, and were successfully applied to inorganic anions separation. As the mass transfer speed is largely constrained in the mesopore compared with that on the open surface, it was found that a complete alumina nanoshell coating could be obtained within the mesopore until the five-time coating was carried out. After characterization by BET, SEM and FTIR, it was found that the obtained nanoAl2O3/mesoSiO2 particles are smooth and well dispersed, and the mesopores are well reserved. In addition, the full coverage of nanoAl2O3 shell in mesopores was also confirmed by the binding capacity experiments with berberine. Finally, the nanoAl2O3/mesoSiO2 particles were packed in silica capillary for the separation of inorganic anions I(-), SCN(-), Br(-), NO2(-) and NO3(-) with ion chromatography (IC), and a column efficiency of 3.8 × 10(4) plates per meter was obtained for I(-)., (Copyright © 2016. Published by Elsevier B.V.)