Bromide Ion Effect on <i>N</i>-Nitrosodimethylamine Formation by Monochloramine

<i>N</i>-Nitrosodimethylamine (NDMA) formation experiments conducted in phosphate buffer demonstrated that in waters containing monochloramine, the presence of bromide ion enhanced NDMA formation at the relatively high pH values of 8 and 9 after 24 h of reaction time, which was consistent with literature results. However, at relatively low to neutral pH (6 to 7), the presence of bromide resulted in lower NDMA formation as compared to results obtained in the absence of bromide. The hypothesis that bromamines were the species directly responsible for enhanced NDMA formation at high pH was tested and was shown not to be valid. Additional active bromine species were also tested, including hypobromous acid, hypobromite ion, and tribromide ion, with no species showing an ability to directly enhance NDMA formation. Analysis of the UV spectral data corresponding to the NDMA experiments suggest that the mechanism by which bromide enhances NDMA formation lies in the formation of a haloamine compound, possibly the mixed dihaloamine bromochloramine

Kinetics of Bromochloramine Formation and Decomposition

Batch experiments were performed to study the kinetics of bromochloramine formation and decomposition from the reaction of monochloramine and bromide ion. The effects of pH, initial monochloramine and bromide ion concentrations, phosphate buffer concentration, and excess ammonia were evaluated. Results showed that the monochloramine decay rate increased with decreasing pH and increasing bromide ion concentration, and the concentration of bromochloramine increased to a maximum before decreasing gradually. The maximum bromochloramine concentration reached was found to decrease with increasing phosphate and ammonia concentrations. Previous models in the literature were not able to capture the decay of bromochloramine, and therefore we proposed an extended model consisting of reactions for monochloramine autodecomposition, the decay of bromamines in the presence of bromide, bromochloramine formation, and bromochloramine decomposition. Reaction rate constants were obtained through least-squares fitting to 11 data sets representing the effect of pH, bromide, monochloramine, phosphate, and excess ammonia. The reaction rate constants were then used to predict monochloramine and bromochloramine concentration profiles for all experimental conditions tested. In general, the modeled lines were found to provide good agreement with the experimental data under most conditions tested, with deviations occurring at low pH and high bromide concentrations

Toxicity of Drinking Water Disinfection Byproducts: Cell Cycle Alterations Induced by the Monohaloacetonitriles

Haloacetonitriles (HANs) are a chemical class of drinking water disinfection byproducts (DBPs) that form from reactions between disinfectants and nitrogen-containing precursors, the latter more prevalent in water sources impacted by algae bloom and municipal wastewater effluent discharge. HANs, previously demonstrated to be genotoxic, were investigated for their effects on the mammalian cell cycle. Treating Chinese hamster ovary (CHO) cells with monoHANs followed by the release from the chemical treatment resulted in the accumulation of abnormally high DNA content in cells over time (hyperploid). The potency for the cell cycle alteration followed the order: iodoacetonitrile (IAN) > bromoacetonitrile (BAN) ≫ chloroacetonitrile (CAN). Exposure to 6 μM IAN, 12 μM BAN and 900 μM CAN after 26 h post-treatment incubation resulted in DNA repair; however, subsequent cell cycle alteration effects were observed. Cell proliferation of HAN-treated cells was suppressed for as long as 43 to 52 h. Enlarged cell size was observed after 52 h post-treatment incubation without the induction of cytotoxicity. The HAN-mediated cell cycle alteration was mitosis- and proliferation-dependent, which suggests that HAN treatment induced mitosis override, and that HAN-treated cells proceeded into S phase and directly into the next cell cycle. Cells with multiples genomes would result in aneuploidy (state of abnormal chromosome number and DNA content) at the next mitosis since extra centrosomes could compromise the assembly of bipolar spindles. There is accumulating evidence of a transient tetraploid state proceeding to aneuploidy in cancer progression. Biological self-defense systems to ensure genomic stability and to eliminate tetraploid cells exist in eukaryotic cells. A key tumor suppressor gene, p53, is oftentimes mutated in various types of human cancer. It is possible that HAN disruption of the normal cell cycle and the generation of aberrant cells with an abnormal number of chromosomes may contribute to cancer induction and perhaps be involved in the induction of adverse pregnancy outcomes associated with long-term consumption of disinfected water. Here we present the first observation of the induction of hyperploidy by a class of DBPs

Characterizing Bacteriophage PR772 as a Potential Surrogate for Adenovirus in Water Disinfection: A Comparative Analysis of Inactivation Kinetics and Replication Cycle Inhibition by Free Chlorine

Elucidating mechanisms by which pathogenic waterborne viruses become inactivated by drinking water disinfectants would facilitate the development of sensors to detect infectious viruses and novel disinfection strategies to provide safe water. Using bacteriophages as surrogates for human pathogenic viruses could assist in elucidating these mechanisms; however, an appropriate viral surrogate for human adenovirus (HAdV), a medium-sized virus with a double-stranded DNA genome, needs to be identified. Here, we characterized the inactivation kinetics of bacteriophage PR772, a member of the <i>Tectiviridae</i> family with many similarities in structure and replication to HAdV. The inactivation of PR772 and HAdV by free chlorine had similar kinetics that could be represented with a model previously developed for HAdV type 2 (HAdV-2). We developed and tested a quantitative assay to analyze several steps in the PR772 replication cycle to determine if both viruses being inactivated at similar rates resulted from similar replication cycle events being inhibited. Like HAdV-2, we observed that PR772 inactivated by free chlorine still attached to host cells, and viral DNA synthesis and early and late gene transcription were inhibited. Consequently, free chlorine exposure inhibited a replication cycle event that was post-binding but took place prior to early gene synthesis for both PR772 and HAdV-2

Analysis of the Viral Replication Cycle of Adenovirus Serotype 2 after Inactivation by Free Chlorine

Free chlorine is effective at inactivating a wide range of waterborne viral pathogens including human adenovirus (HAdV), but the mechanisms by which free chlorine inactivates HAdV and other human viruses remain to be elucidated. Such advances in fundamental knowledge are key for development of new disinfection technologies and novel sensors to detect infectious viruses in drinking water. We developed and tested a quantitative assay to analyze several steps in the HAdV replication cycle upon increasing free chlorine exposure. We used quantitative polymerase chain reaction (qPCR) to detect HAdV genomic DNA as a means to quantify attachment and genome replication of untreated and treated virions. Also, we used quantitative reverse-transcription PCR (RT-qPCR) to quantify the transcription of E1A (first early protein) and hexon mRNA. We compared these replication cycle events to virus inactivation kinetics to determine what stage of the virus replication cycle was inhibited as a function of free chlorine exposure. We observed that adenovirus inactivated at levels up to 99.99% by free chlorine still attached to host cells; however, viral DNA synthesis and early E1A and late hexon gene transcription were inhibited. We conclude that free chlorine exposure interferes with a replication cycle event occurring postbinding but prior to early viral protein synthesis

Modeling the Effect of Charge Density in the Active Layers of Reverse Osmosis and Nanofiltration Membranes on the Rejection of Arsenic(III) and Potassium Iodide

We used an extended solution-diffusion model that incorporates Donnan electrostatic exclusion of ions and unhindered advection due to imperfections, and measurements of charge density in the polyamide active layers of reverse osmosis (RO) and nanofiltration (NF) membranes, to predict the rejection of a strong electrolyte (i.e., potassium iodide) and a weak acid (i.e., arsenious acid) as a function of the pH of the feed aqueous solution. Predictions of solute rejection were in agreement with experimental data indicating that (i) the extended solution-diffusion model taking into account Donnan exclusion and unhindered advection due to imperfections satisfactorily describes the effect of pH on solute rejection by RO/NF membranes and (ii) measurement of charge density in active layers provides a valuable characterization of RO/NF membranes. Our results and analysis also indicate that independent ions, and not ion pairs, dominate the permeation of salts

Development and Performance Characterization of a Polyimine Covalent Organic Framework Thin-Film Composite Nanofiltration Membrane

Two-dimensional covalent organic frameworks (COFs) were used to create the first asymmetric, thin-film composite (TFC) nanofiltration (NF) membrane with a COF active layer. NF membrane active layers of polyimine COF were synthesized via the interfacial polymerization (IP) of terephthalaldehyde and tris­(4-aminophenyl)­benzene monomers on top of a poly­(ether sulfone) (PES) ultrafiltration membrane support. Rutherford backscattering spectrometry and Fourier transform infrared spectroscopy analyses confirmed the presence of an imine-linked film with a thickness of ∼10 nm that was formed reproducibly. The rejection efficiencies of the COF NF membrane for a model organic compound, Rhodamine-WT, and a background electrolyte, NaCl, were higher than those of the PES support without the COF film. This enhanced solute rejection is the first successful demonstration of a TFC membrane with a thin COF active layer. However, this work also demonstrates the need for COF NF membranes with smaller active layer pores and alternative support materials. The former should result in greater solute rejection, and the latter is key because the PES used for support in the COF membranes is incompatible with the organic solvents used for the COF IP process

Adenovirus Replication Cycle Disruption from Exposure to Polychromatic Ultraviolet Irradiation

Polychromatic ultraviolet (UV) light with bandwidth of 20 nm and peak emission centered at 224, 254, or 280 nm (UV₂₂₄, UV₂₅₄, and UV₂₈₀, respectively) were used to inactivate human adenovirus type 2 (HAdV-2). Quantitative polymerase chain reaction (qPCR) and reverse transcriptase qPCR assays were used to elucidate the step in the HAdV-2 replication cycle that was disrupted after UV exposure. UV treatment at any of the wavelengths analyzed did not inhibit association of HAdV-2 to the host cells even after exposure to a fluence (UV dose) that would produce a virus inactivation efficiency, measured by plaque assay, greater than 99.99%. In contrast, UV irradiation at all three peak emissions disrupted early E1A gene transcription and viral DNA replication, but different mechanisms appeared to be dominating such disruptions. UV₂₂₄ seemed to have little effect on the integrity of the viral genome but produced a structural transformation of the viral capsid that may inhibit the delivery of viral genome into the host cell nucleus. On the other hand, UV₂₅₄ and UV₂₈₀ did not affect the integrity of the viral capsid, but the mutations they produced on the viral genome might cause the inhibition of the early gene transcription and DNA replication after the viral genome successfully translocated into the host cell nucleus

Chloroacetonitrile and <i>N</i>,2-Dichloroacetamide Formation from the Reaction of Chloroacetaldehyde and Monochloramine in Water

Combined chlorine is increasingly being used as an alternative disinfectant to free chlorine to maintain a residual in drinking water distribution systems mainly because it would reduce the formation of regulated disinfection byproducts (DBPs) trihalomethanes and haloacetic acids. However, the use of combined chlorine could promote the formation of currently unregulated nitrogenous DBPs (N-DBPs) such as haloacetonitriles and haloacetamides that are found to be more cyto- and genotoxic than regulated DBPs. Monochloramine quickly reacts with chloroacetaldehyde, a DBP formed during primary disinfection with free chlorine, forming and reaching pseudoequilibrium (equilibrium constant <i>K</i>₁ = 1.87 × 10³ M^–1) with the carbinolamine 2-chloro-1-(chloroamino)­ethanol. 2-Chloro-1-(chloroamino)­ethanol undergoes slow dehydration to form the imine 1-chloro-2-(chloroimino)­ethane that decomposes at a faster rate to chloroacetonitrile. 2-Chloro-1-(chloroamino)­ethanol is also oxidized by monochloramine to produce the previously unreported DBP <i>N</i>,2-dichloroacetamide. The carbinolamine dehydration step was found to be acid/base catalyzed (<i>k</i>₂⁰ = 3.30 × 10^–6 s^–1, <i>k</i>₂^H = 2.43 M^–1 s^–1, <i>k</i>₂^OH = 3.90 M^–1 s^–1). In contrast, <i>N</i>,2-dichloroacetamide formation was observed to be only base catalyzed (<i>k</i>₃^OH = 3.03 × 10⁴ M^–2 s^–1). <i>N</i>,2-dichloroacetamide cytotoxicity (LC₅₀ = 2.56 × 10^–4 M) was found to be slightly lower compared to that reported for chloroacetamide but higher than those of di- and trichloroacetamide

Changes in Physicochemical and Transport Properties of a Reverse Osmosis Membrane Exposed to Chloraminated Seawater

This study contributed to improving our understanding of how disinfectants, applied to control biofouling of reverse osmosis (RO) membranes, result in membrane performance degradation. We investigated changes in physicochemical properties and permeation performance of a RO membrane with fully aromatic polyamide (PA) active layer. Membrane samples were exposed to varying concentrations of monochloramine, bromide, and iodide in both synthetic and natural seawater. Elemental analysis of the membrane active layer by Rutherford backscattering spectrometry (RBS) revealed the incorporation of bromine and iodine into the polyamide. The kinetics of polyamide bromination were first order with respect to the concentration of the secondary oxidizing agent Br₂ for the conditions investigated. Halogenated membranes were characterized after treatment with a reducing agent and heavy ion probes to reveal the occurrence of irreversible ring halogenation and an increase in carboxylic groups, the latter produced as a result of amide bond cleavage. Finally, permeation experiments revealed increases in both water permeability and salt passage as a result of oxidative damage