Bromide Levels Research Articles

Metabolomics profiling for identification of potential biomarkers in chickens infected with avian leukosis virus subgroup J (ALV-J)

There are currently no vaccines or effective drugs to prevent the disorders caused by avian leukosis virus subgroup J (ALV-J). Hence, it is critical to identify potential biomarkers in ALV-J-infected chickens to prevent ALV-J-induced disorders. We hypothesized that ALV-J infection alters metabolic profile in chickens. In the present study, a nontargeted metabolomics approach based on liquid chromatography coupled with mass spectrometry (LC-MS) was used to find differential metabolites in plasma samples from ALV-J-infected chickens and healthy controls. The parametric statistical test (Student's t-test) and fold change analysis were used for univariate analysis. Multivariate statistical analyses included principal component analysis (PCA) and partial least squares-discriminant analysis (PLS-DA). The levels of methyl bromide, pyraclonil, hexaflumuron, lythidathion, 3-phosphoglycerol-glutathione, bis-4-nitrophenyl phosphate, 4-ketocyclophosphamide, oxidized photinus luciferin, phenyl sulfate, and aryl sulfate significantly decreased, whereas the levels of 2-methylthiobenzothiazole, irinotecan, methadone, 3-o-ethyl-l-ascorbic acid, and o-acetylneuraminic acid markedly increased in ALV-J-infected chickens as compared to those in healthy controls. These data provide metabolic evidence and potential biomarkers for ALV-J-induced alterations in plasma metabolism.

Bromide toxicosis (bromism) secondary to a decreased chloride intake after dietary transition in a dog with idiopathic epilepsy: a case report

BackgroundBromide is a halide ion of the element bromine usually administered in the form of potassium salt as monotherapy or add-on treatment in epileptic dogs. It is excreted unchanged in the urine and undergoes tubular reabsorption in competition with chloride. Thus, dietary chloride content affects serum bromide concentrations. This is the first published clinical report of bromide toxicosis secondary to a dietary modification of chloride content in an epileptic dog treated with potassium bromide.Case presentationA 3-year-old 55-kg neutered male Tibetan Mastiff was evaluated because of a 1-month history of progressive signs including ataxia, lethargy and behaviour changes. The dog was successfully treated for idiopathic epilepsy since the age of 1-year-old with phenobarbital and potassium bromide. Two months prior to presentation, the owners decided to change the dog’s diet without veterinary advice. Physical examination was unremarkable. A 12-kg weight gain was recorded since last follow-up (8 months). Neurological examination revealed severe symmetric 4-limbs ataxia with altered vigilance and intermittent episodes of hyperactivity and aggressive behaviour without significant abnormality of cranial nerves. Serum bromide concentration was high and increased by 103 % since last follow-up. Nutritional evaluation revealed a 53 % decrease of chloride content in the diet before and after dietary transition. Bromide toxicosis was suspected, due to bromide reduced clearance secondary to the decreased dietary chloride content. Potassium bromide treatment was lowered by 15 % without further dietary changes. Neurologic signs progressively improved over the next month, without any seizure. After two months, the serum bromide concentration lowered to the same level measured before dietary modification. After four months, neurological examination was unremarkable.ConclusionsDietary chloride content can directly influence serum bromide concentrations, therefore affecting seizure control or contributing to unexpected adverse effects. In the present case, a reduction in chloride intake markedly increased serum bromide concentrations causing bromism. Dietary changes should be avoided in dogs treated with potassium bromide to maintain stable serum bromide levels.

Tracking Br-DBPs and bromine substitution factors by two-stage differential characterization of water matrix and NOM during chlorination

Tracking disinfection byproducts (DBPs) upon chlorination becomes challenging whenever bromides occur because they alter DBP formation from chlorinated to brominated DBPs (Br-DBPs). Although epidemiological studies have emphasized the need to control Br-DBPs because of their notable carcinogen effects, work on Br-DBP monitoring is timely, since limited attention has to date been paid to this. This study proposes a two-stage differential characterization approach to a water matrix and natural organic matter (NOM) surrogates as a more robust way to trace Br-DBP precursors and bromine substitution factors (BSF). This two-stage approach monitors the differential variations (Δ) of both inorganic and organic precursors, e.g., dissolved organic carbon (DOC), bromide levels, Cl2 content, specific ultraviolet absorbance (SUVA), fluorescent spectra, before and after chlorination. To mimic practical conditions, chlorination experiments were conducted with two principle NOMs, including Suwannee River fulvic (SW) and M. aeruginosa organic matter (MA), with Br− levels from 0 to 2000 μg/L and chlorination times from 15 min-24 h. When Br− levels increased, all Br-DBP yields and BSF values correspondingly magnified, accounted for 70–90% of the total DBP yields from chlorinated SW or MA water. At each Br− level, prolonging chlorination time also increased the overall Br-DBPs and varied BSF values, but these differences were of no significance (p > 0.05). Correlation tests highlighted the significant insufficiency of the conventionally-used DBP surrogates (initial DOC, Cl2 dose, and SUVA) for Br-DBPs and BSF monitoring. By contrast, our two-stage characterization parameters are superior, with correlation coefficients ρ > 0.8 (p < 0.01), especially for those parameters including ΔBr as a numerator. Accordingly, regression models of Br-DBPs and BSFs built by our two-stage tertiary parameters exhibited high adjusted R2 values mostly >0.7 and >0.8 (n = 60), indicating a promising application for effective Br-DBPs and BSF monitoring.

DBP formation and toxicity alteration during UV/chlorine treatment of wastewater and the effects of ammonia and bromide

The UV/chlorine process is efficient for the abatement of micropollutants; yet, the formation of disinfection by-products (DBPs) and the toxicity can be altered during the treatment. This study investigated effluent organic matter characterization, DBP formation and toxicity alteration after the UV/chlorine treatment of wastewater; particularly, typical water matrix components in wastewater, namely, ammonia and bromide, were studied. The raw wastewater contained low levels of ammonia (3 µM) and bromide (0.5 µM). The UV/chlorine treatment efficiently eliminated 90 – 94% of fluorescent components. Compared with chlorination alone, a 20 min UV/chlorine treatment increased the formation of trihalomethanes (THMs), haloacetic acids (HAAs), chloral hydrate (CH), haloacetonitriles (HANs), trichloronitromethane (TCNM) and haloacetamides (HAcAms) by 90 – 508%. In post-chlorination after the UV/chlorine treatment, the formation of CH, HANs, TCNM and HAcAms increased by 77 – 274%, whereas the formation of both THMs and HAAs increased slightly by 11%. Meanwhile, the calculated cytotoxicity and genotoxicity of DBPs increased considerably after the UV/chlorine treatment and in post-chlorination, primarily due to the increased formation of HAAs and nitrogenous DBPs (N-DBPs). However, the acute toxicity of the wastewater to Vibrio fischeri and genotoxicity determined by the umu test decreased by 19% and 76%, respectively, after the 20 min UV/chlorine treatment. An additional 200 µM ammonia decreased the formation of all detected DBPs during the UV/chlorine treatment and 24 h post-chlorination, except that TCNM formation increased by 11% during post-chlorination. The acute toxicity of wastewater spiked with 200 µM ammonia was 32% lower than that of raw wastewater after the UV/chlorine treatment, but the genotoxicity was 58% higher. The addition of 1 mg/L bromide to the UV/chlorine process dramatically increased the formation of brominated DBPs and the overall calculated cytotoxicity and genotoxicity of DBPs. However, the acute toxicity and genotoxicity of the wastewater decreased by 7% and 100%, respectively, when bromide was added to the UV/chlorine treatment. This study illuminated that UV/chlorine treatment can decrease acute and geno- toxicities of wastewater efficiently.

Toxicity of chlorinated algal-impacted waters: Formation of disinfection byproducts vs. reduction of cyanotoxins

Seasonal algal blooms in surface waters can impact water quality through an input of algal organic matter (AOM) to the pool of dissolved organic matter as well as the release of cyanotoxins. The formation and speciation of disinfection byproducts (DBPs) during chlorination of algal-impacted waters, collected from growth of Microcystis aeruginosa were studied. Second-order rate constants for the reactions of microcystins (MCs) with chlorine and bromine were determined. Finally, the toxicity of chlorinated algal-impacted waters was evaluated by Chinese hamster ovary (CHO) cytotoxicity and genotoxicity assays. Under practical water treatment conditions, algal-impacted waters produced less regulated trihalomethanes (THMs) and haloacetic acids (HAAs), haloacetonitriles (HANs), and total organic halogen (TOX) than natural organic matter (NOM). For example, the weight ratios of DBP formation from AOM to NOM (median levels) were approximately 1:5, 1:3, 1:2 and 1:3 for THMs, HAAs, HANs, and TOX, respectively. Increasing initial bromide level significantly enhanced THM and HAN concentrations, and therefore unknown TOX decreased. The second-order rate constant for the reactions of MC-LR (the most common MC species) with chlorine was 60 M−1 s−1 at pH 7.5 and 21 °C, and the rate constants for MC congeners follow the order: MC-WR > MC-LW > MC-YR > MC-LY > MC-LR ≈ MC-RR. The reaction rate constant of bromine with MC-LR is two orders of magnitude higher than that of chlorine. Unchlorinated algal-impacted waters were toxic owning to the presence of MCs, and chlorination enhanced their cytotoxicity and genotoxicity due to the formation of toxic halogenated DBPs. However, the toxicity of treated waters depended on the evolution of cyanotoxins and formation of DBPs (particularly unknown or emerging DBPs).

The new water soluble zinc(II) phthalocyanines substituted with morpholine groups- synthesis and optical properties

Two new tetra- or octa-substituted zinc(II) phthalocyanines (1 and 2) bearing 3-(morpholinomethyl)phenyl groups were synthesized via Suzuki-Miyaura coupling method. These phthalocyanines (1 and 2) were converted to their water-soluble derivatives (1Q and 2Q) by quaternization of nitrogen atoms on the morpholine groups. The photochemical and photophysical properties of the non-ionic zinc(II) phthalocyanines (1 and 2) were explored in DMSO. On the other hand, these properties of the quaternized cationic derivatives (1Q and 2Q) were studied in both DMSO and aqueous solutions for determination of their photosensitizing capabilities in photodynamic therapy. The ct-DNA interaction of synthesized 1Q and 2Q were investigated and binding constants were found as 6.3 × 104 and 1.5 × 105 M, respectively. The binding constant values were found at similar levels of ethidium bromide (EB), which is a well-known intercalator. The spontaneous and exothermic nature of binding mechanisms were proved according to the calculated thermodynamic constants. Strong interactions of 1Q and 2Q with ct-DNA were also found with EB displacement assay and gel electrophoresis. Additionally, the bovine serum albumin (BSA) binding behavior of the new compounds (1Q and 2Q) were determined in water solution to verify the transporting capability of these phthalocyanines in the circulatory system and these values were found as 7.0 × 105 and 1.6 × 107 M−1 for 1Q and 2Q, respectively.

Use of spectroscopic indicators for the monitoring of bromate generation in ozonated wastewater containing variable concentrations of bromide

Time-resolved monitoring of bromate and other by-products formed into effluents treated with ozone or advanced oxidation processes in wastewater treatment plants (WWTPs) is time-consuming and expensive. This study examined whether concentrations of bromate formed in wastewater after ozonation in the presence of widely varying bromide levels (from ca. 0.7–21.2 mg/L) can be quantified based on measurements of changes in optical properties (differential UV absorbance (ΔUVA), spectral slopes, total or regional fluorescence) of the ozonated samples. Batch ozonation was carried out using a secondary effluent produced at a major wastewater treatment plant located in the Metropolitan Seattle Area. The tests involved raw and bromide-spiked samples treated with ozone doses from 0.1 to 1 mg O3/mg DOC. Measurements of the absorbance at 254 nm (UVA254), fluorescence and bromate concentrations were performed on the treated samples.In the ozonated wastewater the concentration of bromate increased approximately linearly, from <10 ppb to ca. 200 ppb, without showing the lag phase characteristic for lower ozone doses (<0.4 mg O3/mg DOC) that was observed in previous studies carried out with concentrations of bromide in the range of 0.05–0.5 mg/L. The highest bromide concentrations used in this study (>10 mg/L) tended to inhibit the generation of bromate. Relative reduction of UVA254 and total fluorescence (TF) were found to be good predictors of bromate generation. Specifically, exponential curves could adequately fit the non-linear relationships found to exist between the concentrations of bromate and the relative reductions of the UV254 and TF, for any initial bromide concentrations used in this study. Little formation of bromate was found to occur for reduction ranges for UVA254 and TF of 30–40% and 70–80% respectively. Conversely, rapid increases in bromate generation were observed when the decrease of UVA254 or TF exceeded these threshold values.

Formation of Disinfection Byproducts from Algal Organic Matter Exposed to Monochloramine: Effects of Monochloramine Dosages, pH, and Bromide Concentrations

The formation of volatile DBPs and haloacetic acids (HAAs) from algal organic matter (AOM) in different chloramination conditions (i.e., different monochloramine (NH2Cl) dosages, pH values, and bromide concentrations) was studied. In chloramination of AOM, HAAs were the major DBP species, followed by trihalomethanes (THMs), haloacetonitriles (HANs), and haloketones (HKs). The levels of THMs, HAAs, HKs, and HANs generated in chloramination were 75%, 69%, 68%, and 122% of those in chlorination, respectively. The concentrations of THMs and HAAs both doubled as the NH2Cl dosage doubled. The proportions of bromodichloromethane and dibromochloromethane in THMs and the proportions of dichloroacetic acid and trichloroacetic acid in HAAs increased with the NH2Cl dosage. Accelerating the pH value enhanced the formation of THMs, HAAs, and HANs, respectively, and favored the formation of brominated THMs. The HAN species distribution was unaffected by the NH2Cl dosage and pH. Increasing bromide levels slightly increased the yield of THMs and slightly decreased the yields of HAAs and HKs. The species shift from the chlorinated to the brominated was more significant for THMs and HANs than for HAAs. The THM-BSF and dichloroacetonitrile-BSF values were lower in chloramination than in chlorination. The high pH value and bromide level significantly accelerated the THM-BSFs. The maximum values of THM-BSFs and dichloroacetonitrile-BSF were 0.6 and 0.5.

Physicochemical and Toxicological Assay of Leachate from Malt Spent Rootlets Biochar

The aim of this study was to characterize the leachate derived from biochar produced from malt spent rootlets (MSR) and to evaluate the required washing level in order to provide water free from inorganic substances. MSR biochar was placed in a column and subjected to six serial washes with distilled water, and the leachate was analysed for main anions and heavy metals. The 1st wash aliquot contained increased levels of mainly phosphates (980 mg/L) and chlorides (760 mg/L), and lower levels of nitrates, sulfates, fluoride and bromide, which were decreased over washes. Zero concentrations were observed after three washes for most anions. The increased levels of Zn, Be, Cs, Mn, V and Se determined in the 1st wash aliquot were eliminated in the successive washes. The toxic potency of each wash aliquot, determined by the use of the fairy shrimp Thamnocephalus platyurus showed that the 1st and 2nd MSR biochar leachates were toxic with 4.52 and 1.46 toxic units (TU), respectively, followed by a significant elimination of toxicity after further washes.

Highly Efficient Bromide Removal from Shale Gas Produced Water by Unactivated Peroxymonosulfate for Controlling Disinfection Byproduct Formation in Impacted Water Supplies.

Shale gas extraction processes generate a large amount of hypersaline wastewater, whose spills or discharges may significantly increase the bromide levels in downstream water supplies and result in the formation of brominated disinfection byproducts (DBPs) upon chlorination. Although a few studies have investigated selective bromide removal from produced water, the low removal efficiencies and complex system setups are not desirable. In this study, we examined a simple cost-effective approach for selective bromide removal from produced water relying on the oxidation by unactivated peroxymonosulfate. More than 95% of bromide was removed as Br2(g) in less than 10 min under weakly acidic conditions without significant formation of Cl2(g) even when the chloride concentration was more than 2 orders of magnitude higher. A kinetic model considering the involved reactions was then developed to describe the process well under various reaction conditions. The organic compounds in the produced water neither noticeably lowered the bromide removal efficiency nor reacted with the halogen species to form halogenated byproducts. The tests in batch and continuously stirred tank reactor systems suggested that it was feasible to achieve both high bromide removal and neutral effluent pH such that further pH adjustment was not necessary before discharge. After the treatment, the effect of the produced water on DBP formation was largely eliminated.

Identification, formation and control of polar brominated disinfection byproducts during cooking with edible salt, organic matter and simulated tap water

Edible salt is essential to the health of humans and serves as a seasoning universally. Besides chloride, edible salt also contains other anions such as bromide, fluoride, sulfate, and carbonate due to incomplete removal during raw salt refinement. In a household cooking (e.g., soup making) process, a chlorine/monochloramine residual in tap water could react with bromide in edible salt and organic matter in food (e.g., rice, wheat) to form numerous brominated disinfection byproducts (Br-DBPs) at significant levels, which might induce adverse health effects to human beings. In this study, we solicited 20 edible salts of different types (i.e., sea salts, well and rock salts, lake salts, and bamboo salts) from nine countries and determined their bromide levels to be 67–375 mg/kg, with an average level of 173 mg/kg. A total of 25 polar Br-DBPs were detected and identified with structures/formulae in cooking water samples using ultra performance liquid chromatography/electrospray ionization-triple quadruple mass spectrometry (UPLC/ESI-tqMS) and high-resolution mass spectrometry. Effects of cooking conditions (e.g., disinfectant type and level, edible salt dose, organic matter type and dose, sequence and time interval of adding organic matter and salt, etc.) on the formation of polar Br-DBPs were investigated, and optimized cooking conditions with minimized formation of polar Br-DBPs were determined. Further aided with an Hep G2 cell cytotoxicity assay, it was found that the overall cytotoxicity of chlorinated and chloraminated cooking water samples prepared after cooking condition optimization was reduced by 57% and 22%, respectively, compared with those prepared before cooking condition optimization.

The formation of disinfection by-products from the chlorination and chloramination of amides

This study examined the potential of six aliphatic and aromatic amides, commonly found in natural waters or used as chemical aids in water treatment, to act as organic precursors for nine haloacetamides (HAcAms), five haloacetonitriles (HANs), regulated trihalomethanes (THMs) and haloacetic acids (HAAs) upon chlorination and chloramination. The impact of key experimental conditions, representative of drinking water, including pH (7 & 8), retention time (4 & 24 h) and bromide levels (0 & 100 μg/L), on the generation of the target DBPs was investigated. The highest aggregate DBP yields upon chlor(am)ination were reported for the aromatic and hydrophobic hydroxybenzamide; 2.7% ± 0.1% M/M (chlorination) and 1.7% M/M (chloramination). Increased reactivity was observed in aliphatic and hydrophilic compounds, acrylamide (2.5 ± 0.2% M/M) and acetamide (1.3 ± 0.2% M/M), in chlorination and chloramination, respectively. The addition of bromide increased average DBP yields by 50–70%. Relative to chlorination, the application of chloramines reduced DBP formation by 66.5% (without Br−) and by 46.4% (with Br−). However, bromine incorporation in HAAs and HAcAms was enhanced following chloramination, of concern due to the higher toxicological potency of brominated compounds.

Treating water containing elevated bromide and iodide levels with granular activated carbon and free chlorine: impacts on disinfection byproduct formation and calculated toxicity

Granular activated carbon effectively controlled disinfection byproduct formation and calculated toxicity, especially at high influent bromide levels.

Drivers of disinfection byproduct formation and speciation in small, chlorinated coastal groundwater systems: relative roles of bromide and organic matter, and the need for improved source water characterization and monitoring

Small, chlorinated coastal groundwater systems are uniquely susceptible to elevated (especially brominated) DBP formation, due to the potential for high bromide and DOM levels, technical and resource constraints, and limited regulatory oversight.

Disinfection byproducts and halogen-specific total organic halogen speciation in chlorinated source waters – The impact of iopamidol and bromide

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.

Elevated concentrations of bromate in Drinking water and groundwater from Kuwait and associated exposure and health risks

Drinking water is an important source of human exposure to bromate, an ubiquitous environmental contaminant and a suspect human carcinogen. Nevertheless, little is known with regard to bromate exposure from water produced by thermal desalination of seawater. The purpose of this study was to determine the occurrence of bromate in desalinated drinking water and groundwater from Kuwait and estimate associated exposure and health risks to consumers. In this study, 194 tap and ground water samples collected from Kuwait were analyzed for the presence of bromate and bromide (reduced form of bromine). Bromate was found in almost all tap water samples with a mean concentration of 19.6 μg/L, which is higher than the maximum acceptable contaminant level (MCL) of 10 μg/L. The mean concentration of bromide in tap water samples was 46.2 μg/L. In bottled water, lower mean bromate concentration was found (2.89 μg/L) with mean bromide levels at 76.1 μg/L. Saline brackish water had bromate concentration at 9.48 μg/L while bromate was not detected in saline groundwater/well water samples. The mean estimated daily intake (EDI) of bromate by the Kuwaiti population through tap water and commonly consumed bottled water was 21.7 μg/d and 3.21 μg/d, respectively. Among the five age groups, 3 to 5-year-old children had the highest EDI of bromate at 15.4 μg/d. The excess cancer risk due to ingestion of bromate in tap water was estimated to be 3.92 × 10−4, which is approximately one order of magnitude higher than the maximum acceptable level of risk (2× 10−5). This study highlights the significance of desalinated water as a source of bromate exposure.

Anion-exchange resin adsorption followed by electrolysis: A new disinfection approach to control halogenated disinfection byproducts in drinking water

Bromide and natural organic matter (NOM) are both precursors of halogenated disinfection byproducts (DBPs) in drinking water. During drinking water treatment process, chloride-form anion-exchange resin adsorption is expected to be capable of removing these DBP precursors and in the meantime releasing chloride ions. The released chloride as well as the chloride initially present in source water could be oxidized through electrolysis to generate free chlorine for disinfection. Based on the above assumptions, we developed a new disinfection approach using chloride-form anion-exchange resin adsorption followed by electrolysis to control halogenated DBPs. Parameter setup and optimization were performed for resin adsorption and electrolysis processes. Results showed that 93.7% of NOM and 90% of bromide could be removed at a resin dose of 20 mL per 2 L of simulated source water sample with a contact time of 1 h. Meanwhile, 49.5 mg/L of chloride was released from the resin to the water sample via anion-exchange, and the released chloride was further oxidized by electrolysis (Ti/RuO2–IrO2 anode and graphite cathode, current intensity of 0.4 A) to generate free chlorine (5 mg/L as Cl2) within 192 s. With this new approach, formation of total organic halogen, four trihalomethanes, and five haloacetic acids was reduced by 86.4%, 98.5%, and 93.2%, respectively, compared with chemical chlorination alone. Although the new approach might enhance the formation of some phenolic DBPs by decreasing bromide levels in source water, the overall cytotoxicity of the water samples treated with the new approach was significantly decreased by 68.8% according to a human hepatoma cell cytotoxicity assay. Notably, disinfection ability evaluation showed that the new approach achieved 3.36-log10 reductions of three seeded bacteria (Escherichia coli, Pseudomonas aeruginosa, and Staphylococcus aureus) in 19 s, suggesting that it was not only effective to E. coli but also effective to the chlorine-resistant bacteria (P. aeruginosa and S. aureus).

Occurrence and spatio-temporal variability of halogenated acetaldehydes in full-scale drinking water systems

As the third largest group of identified disinfection by-products (DBPs) by weight, halogenated acetaldehydes (HALs), were monitored for one year at numerous locations in two full-scale drinking water systems applying an ozone-chlorine sequential disinfection strategy. The HALs that were targeted included four trihalogenated acetaldehydes (THALs): chloral hydrate (CH), bromodichloroacetaldehyde (BDCAL), dibromochloroacetaldehyde (DBCAL) and tribromoacetaldehyde (TBAL). Three dihalogenated acetaldehydes (DHALs) were also included: dichloroacetaldehyde (DCAL), bromochloroacetaldehyde (BCAL) and dibromoacetaldehyde(DBAL). In addition to various sampling points in two distribution networks, this study also investigated the formation of HALs during water treatment and for the first time, reports the formation of DBAL before chlorine is applied. Low bromide levels in source waters from both systems resulted in the rare detection of DBAL and TBAL. CH accounted for >50% of total HALs (HAL7) with DHALs accounting for as little as 10% of HAL7, presumably due to the use of ozone-chlorine instead of ozone-chloramine. In the presence of chlorine residuals and with increasing water residence times, most HALs continued to form, more readily in warm water than in cold water. However, the spatial and temporal patterns for each HAL differed depending on speciation (THAL vs. DHAL) and water temperature. Compared to the relatively stable bromine incorporation factor (BIF) of THMs in the distribution systems, the decreasing BIFs of HALs according to water residence time increases suggested that bromine-containing THMs are more stable than their corresponding HALs. Re-chlorination at the extremities of the distribution networks demonstrated a significant impact on the occurrence and speciation of DBPs. In both full-scale systems, water temperature was shown to be the biggest contributing factor to HAL formation. The strong correlations between THM levels and THAL levels make it possible to predict the occurrence of THALs based on THMs.

Integrated control of CX3R-type DBP formation by coupling thermally activated persulfate pre-oxidation and chloramination

The alternative disinfectant chloramine can lower the formation of carbonaceous DBPs (C-DBPs) but promote the formation of nitrogenous DBPs (N-DBPs), which are more cytotoxic and genotoxic. In this study, the combination of thermally activated persulfate pre-oxidation and post-chloramination (TA/PS-NH2Cl) was proposed to control the formation and reduce the toxicity of both C-DBPs and N-DBPs. The formation, speciation and toxicity of trihalomethanes, haloacetic acids, haloaldehydes, haloacetonitriles, halonitromethanes and haloacetamides, collectively defined as CX3R-type DBPs, under TA/PS-NH2Cl process were compared with processes of chlorination alone (Cl2), chloramination alone (NH2Cl) and coupled thermally activated persulfate pre-oxidation with post-chlorination (TA/PS-Cl2). Results showed that chloramination could reduce formation of C-DBPs and total organic halogen (TOX) while increase N-DBP formation, and the introduction of TA/PS pretreatment process slightly increased the formation of C-DBPs and TOX but sharply reduced the formation of N-DBPs with higher toxicity as well as brominated CX3R-type DBPs that are more toxic than their chlorinated analogues. By comprehensive toxicity calculation, an outright decline of both cytotoxicity and genotoxicity risk of CX3R-type DBPs was observed during TA/PS-NH2Cl process compared with Cl2, NH2Cl, and TA/PS-Cl2 processes. In summary, TA/PS-NH2Cl process was a potential effective method for integrally controlling the formation of CX3R-type DBPs and their toxicity and is suggested to be used to treat raw waters containing no bromide or low levels of bromide considering bromate caused by TA/PS pre-oxidation. The study may provide a feasible and economical method for DBP control on the background of global warming.

Effects of long-term exposure to colloidal gold nanorods on freshwater microalgae

Gold nanorods have shown to pose adverse effects to biota. Whether these effects may be potentiated through prolonged exposure has been rarely studied. Therefore, this work aimed at evaluating the effects of long-term exposure to sublethal levels of cetyltrimethylammonium bromide (CTAB) coated gold nanorods (Au-NR) on two freshwater microalgae: Chlorella vulgaris and Raphidocelis subcapitata. These algae were exposed to several concentrations of Au-NR for 72 h and, afterwards, to the corresponding EC5,72h, for growth, during 16 days. The sensitivity of the two algae to Au-NR was assessed at days 0, 4, 8, 12 and 16 (D0, D4, D8, D12 and D16, respectively) after a 72-h exposure to several concentrations of Au-NR. At the end of the assays, effects on yield and population growth rate were evaluated. Raphidocelis subcapitata was slightly more sensitive to Au-NR than C. vulgaris: EC50,72h,D0 for yield were 48.1 (35.3–60.9) and 70.5 (52.4–88.6) μg/L Au-NR, respectively while for population growth rate were above the highest tested concentrations (53 and 90 μg/L, respectively). For R. subcapitata the long-term exposure to Au-NR increased its sensitivity to this type of nanostructures. For C. vulgaris, a decrease on the effects caused by Au-NR occurred over time, with no significant effects being observed for yield or population growth rate at D12 and D16. The capping agent CTAB caused reductions in yield above 30% (D0) for both algae at the concentration matching the one at the highest Au-NR tested concentration. When exposed to CTAB, the highest inhibition values were 69% (D4) and 21.3% (D8) for R. subcapitata, and 64% (D12) and 21% (D16) to C. vulgaris, for yield and population growth rate, respectively. These results suggested long-term exposures should be included in ecological risk assessments since short-term standard toxicity may either under- or overestimate the risk posed by Au-NR.