Showing papers on "Chlorine published in 2012"

Graphene quantum dot as a green and facile sensor for free chlorine in drinking water.

Abstract: Free chlorine was found to be able to destroy the passivated surface of the graphene quantum dots (GQDs) obtained by pyrolyzing citric acid, resulting in significant quenching of their fluorescence (FL) signal. After optimizing some experimental conditions (including response time, concentration of GQDs, and pH value of solution), a green and facile sensing system has been developed for the detection of free residual chlorine in water based on FL quenching of GQDs. The sensing system exhibits many advantages, such as short response time, excellent selectivity, wide linear response range, and high sensitivity. The linear response range of free chlorine (R2 = 0.992) was from 0.05 to 10 μM. The detection limit (S/N = 3) was as low as 0.05 μM, which is much lower than that of the most widely used N-N-diethyl-p-phenylenediamine (DPD) colorimetric method. This sensing system was finally used to detect free residual chlorine in local tap water samples. The result agreed well with that by the DPD colorimetric met...

Degradation of Polyamide Nanofiltration and Reverse Osmosis Membranes by Hypochlorite

Abstract: The degradation of polyamide (PA) nanofiltration and reverse osmosis membranes by chlorine needs to be understood in order to develop chlorine-resistant membranes. Coated and uncoated fully aromatic (FA) and piperazine (PIP) semi-aromatic PA membranes were treated with hypochlorite solution and analyzed by X-ray photoelectron spectroscopy (XPS) and Fourier transform infrared (FTIR). XPS results showed that in chlorine treated FA PA membranes the ratio of bound chlorine to surface nitrogen was 1:1 whereas it was only 1:6 in the case of PIP PA membranes. Surface oxygen of uncoated FA and PIP membranes increased with increasing hypochlorite concentration whereas it decreased for coated FA membranes. High resolution XPS data support that chlorination increased the number of carboxylic groups on the PA surface, which appear to form by hydrolysis of the amide bonds (C(O)–N). FTIR data indicated the disappearance of the amide II band (1541 cm–1) and aromatic amide peak (1609 cm–1) in both coated and uncoated chl...

Effects of Chlorine Exposure Conditions on Physiochemical Properties and Performance of a Polyamide Membrane—Mechanisms and Implications

Abstract: Understanding the effects of chlorine exposure on polyamide (PA) based membranes is essential in membrane lifespan improvement. In this study, NF90 nanofiltration membrane was treated with sodium hypochlorite at different concentrations, pHs and durations. The changes in membrane elemental composition and bonding chemistry obtained from XPS and ATR-FTIR revealed the impacts of two competing mechanisms: N-chlorination and chlorination-promoted hydrolysis. More chlorine was incorporated into the PA matrix at pH 7 with abundant hydroxyl groups. The membrane surface became more hydrophobic when chlorination was dominant, which in turn caused the water permeability of chlorinated membrane to decrease. Meanwhile, membrane became more hydrophilic and less cross-linked when hydrolysis effects were governing, which made the membrane more permeable for water. Rejection of charged solutes [NaCl, As(V)] improved in most chlori...

Study on Transformation of Natural Organic Matter in Source Water during Chlorination and Its Chlorinated Products using Ultrahigh Resolution Mass Spectrometry

Abstract: Natural organic matter (NOM) can affect the performance of water treatment processes, and serves as a main precursor for the formation of disinfection byproduct (DBPs) during chlorination. To minimize such undesirable effects, a better understanding of its structural information and reactivity toward chlorine is necessary. In this study, electrospray ionization coupled to Fourier transform ion cyclotron resonance mass spectrometry (ESI FT-ICR MS) was used to study the molecular composition of NOM in source water. More than four thousand NOM components were resolved in the sample. NOM molecules with a low degree of oxidation (low O/C ratio) were found to be more reactive toward chlorine than those with high O/C ratio. Totally, 659 one-chlorine containing products and 348 two-chlorine containing products were detected in the chlorinated sample at a high confidence level. The chlorinated products can be arranged into series, which indicate they were originated from precursor compounds in series related by the replacement of CH(4) against oxygen. Of the 1007 chlorine-containing products observed in this study, only 7 molecular formulas can be found in previous studies, showing the distinct difference from previous studies. This study explored the reactivity of NOM toward chlorine on a molecular level, which was previously explained on the level of whole mixtures or fractions of NOM, and the identified chlorinated products may contribute to our knowledge of the unknown total organic halide (TOX).

Iodate and Iodo-Trihalomethane Formation during Chlorination of Iodide-Containing Waters: Role of Bromide

Abstract: The kinetics of iodate formation is a critical factor in mitigation of the formation of potentially toxic and off flavor causing iodoorganic compounds during chlorination. This study demonstrates that the formation of bromine through the oxidation of bromide by chlorine significantly enhances the oxidation of iodide to iodate in a bromide-catalyzed process. The pH-dependent kinetics revealed species specific rate constants of k(HOBr + IO–) = 1.9 × 106 M–1 s–1, k(BrO– + IO–) = 1.8 × 103 M–1 s–1, and k(HOBr + HOI) < 1 M–1 s–1. The kinetics and the yield of iodate formation in natural waters depend mainly on the naturally occurring bromide and the type and concentration of dissolved organic matter (DOM). The process of free chlorine exposure followed by ammonia addition revealed that the formation of iodo-trihalomethanes (I-THMs), especially iodoform, was greatly reduced by an increase of free chlorine exposure and an increase of the Br–/I– ratio. In water from the Great Southern River (with a bromide concen...

Examining the impact of heterogeneous nitryl chloride production on air quality across the United States

Abstract: . The heterogeneous hydrolysis of dinitrogen pentoxide (N2O5) has typically been modeled as only producing nitric acid. However, recent field studies have confirmed that the presence of particulate chloride alters the reaction product to produce nitryl chloride (ClNO2) which undergoes photolysis to generate chlorine atoms and nitrogen dioxide (NO2). Both chlorine and NO2 affect atmospheric chemistry and air quality. We present an updated gas-phase chlorine mechanism that can be combined with the Carbon Bond 05 mechanism and incorporate the combined mechanism into the Community Multiscale Air Quality (CMAQ) modeling system. We then update the current model treatment of heterogeneous hydrolysis of N2O5 to include ClNO2 as a product. The model, in combination with a comprehensive inventory of chlorine compounds, reactive nitrogen, particulate matter, and organic compounds, is used to evaluate the impact of the heterogeneous ClNO2 production on air quality across the United States for the months of February and September in 2006. The heterogeneous production increases ClNO2 in coastal as well as many in-land areas in the United States. Particulate chloride derived from sea-salts, anthropogenic sources, and forest fires activates the heterogeneous production of ClNO2. With current estimates of tropospheric emissions, it modestly enhances monthly mean 8-h ozone (up to 1–2 ppbv or 3–4%) but causes large increases (up to 13 ppbv) in isolated episodes. This chemistry also substantially reduces the mean total nitrate by up to 0.8–2.0 μg m−3 or 11–21%. Modeled ClNO2 accounts for up to 6% of the monthly mean total reactive nitrogen. Sensitivity results of the model suggest that heterogeneous production of ClNO2 can further increase O3 and reduce TNO3 if elevated particulate-chloride levels are present in the atmosphere.

Colorimetric determination of hypochlorite with unmodified gold nanoparticles through the oxidation of a stabilizer thiol compound.

Abstract: In this article, we report a colorimetric approach for the determination of hypochlorite (OCl−) with gold nanoparticles (Au NPs). The test proceeds as two individual steps and selectivity is developed based on the strong oxidizing ability of hypochlorite. In concentrated phosphate buffer (PB), the red solution of citrate-capped Au NPs could be stabilized by the chemisorption of 11-mercaptoundecanoic acid (MUA), without which the colloidal suspension turned blue because of salt-induced particles aggregation. However, by its oxidizing power, OCl− converted the alkanethiol to a sulfonate derivative, which could not protect Au NPs from aggregation, thereby a blue solution was observed after the subsequent addition of Au suspension. With this method and under the optimal conditions (28 nm Au NP, 50 mM PB, pH 7.0, and 10 min for the colorimetric response), 1.5 μM of OCl− can be easily visualized by the naked eye. This sensitive and selective colorimetric assay opens up a fresh insight of facile, rapid, and reliable detection of OCl−, and may find its future application in the monitoring of OCl−/HOCl in waters sanitized by chlorine or hypochlorite compounds.

Reversible chemical storage of halogens in few-layer graphene

Abstract: Few-layer graphene can be chlorinated up to 56 wt.% by irradiation with UV light in a liquid chlorine medium. The chlorinated sample decomposes on heating or on laser irradiation releasing all the chlorine. Similar results have been obtained with the bromination of few-layer graphene.

Direct Investigation of Covalently Bound Chlorine in Organic Compounds by Solid‐State 35Cl NMR Spectroscopy and Exact Spectral Line‐Shape Simulations

Abstract: 35/37Cl NMR spectroscopy studies of organic systems are very rare, with only a few neat liquids having been studied.1 The lack of chlorine NMR spectroscopy data may be explained by the fact that 35Cl and 37Cl are quadrupolar (spin I=3/2) and low-frequency isotopes. The quadrupole moments of the chlorine nuclei couple with the electric field gradient (EFG) tensor at the nuclei; this phenomenon is known as the quadrupolar interaction (QI). The quadrupolar coupling constant, CQ, and the quadrupolar asymmetry parameter, ηQ, describe the magnitude and asymmetry of the QI. In solution, one of the consequences of the QI is fast relaxation, which means that the 35/37Cl NMR signals for covalently bound chlorines are very broad and are of low intensity.1 For these reasons, chemically distinct chlorine sites are very difficult to distinguish with solution NMR spectroscopy. However, in the solid state, nuclear spin relaxation is typically slower, thus enabling higher quality 35Cl NMR spectra to be collected, at least in principle. Unfortunately, the magnitude of the QI for covalently bound chlorines is very large because of the substantial, anisotropic EFG at the Cl atom, owing mainly to its electronic configuration when it forms a chlorine–carbon bond. Conventional wisdom is that such chlorine sites cannot be studied in powders by solid-state NMR spectroscopy as the central transition (CT; mI=1/2↔−1/2) can span tens of megahertz in typical commercially available magnetic fields. For this reason, only ionic chlorides2 and inorganic chlorides3 have been studied, as the EFG at these chlorides is often an order of magnitude smaller than at covalently bound chlorine atoms in organic molecules. The bonding environments for these types of chlorine atoms are substantially different from the environments in those chloride-containing molecules that have been studied previously.2, 3 A partial 35Cl NMR spectrum for hexachlorophene has been briefly mentioned in the literature.4 On the other hand, most of the interesting chlorine chemistry occurs when Cl is covalently bound to a carbon atom, where the chlorine atom often acts as a leaving group. Chlorine atoms are also important in many organic pharmaceuticals as well as in crystal design applications where they can form halogen bonds.5 Recent studies show that covalently bound chlorine is also important in biological chemistry where, for example, the tryptophan 7-halogenase was found to selectively chlorinate tryptophan moieties.6

Silicon nanocrystal production through non-thermal plasma synthesis: a comparative study between silicon tetrachloride and silane precursors.

Abstract: Silicon nanocrystals with sizes between 5 and 10 nm have been produced in a non-thermal plasma reactor using silicon tetrachloride as precursor. We demonstrate that high-quality material can be produced with this method and that production rates as high as 140 mg h(-1) can be obtained, with a maximum precursor utilization rate of roughly 50%. Compared to the case in which particles are produced using silane as the main precursor, the gas composition needs to be modified and hydrogen needs to be added to the mixture to enable the nucleation and growth of the powder. The presence of chlorine in the system leads to the production of nanoparticles with a chlorine terminated surface which is significantly less robust against oxidation in air compared to the case of a hydrogen terminated surface. We also observe that significantly higher power input is needed to guarantee the formation of crystalline particles, which is a consequence not only of the different gas-phase composition, but also of the influence of chlorine on the stability of the crystalline structure.

Effects of carbonate on the electrolytic removal of ammonia and urea from urine with thermally prepared IrO2 electrodes

Abstract: Recent studies have shown that electrolysis can be an efficient process for nitrogen removal from urine. These studies have been conducted with urea solutions or fresh urine, but urine collected in NoMix toilets and urinals has a substantially different composition, because bacteria hydrolyse urea quickly to ammonia and carbonate. In this study, we compared electrochemical removal of nitrogen from synthetic solutions of fresh and stored urine using IrO2 anodes. We could show that in fresh urine both ammonia and urea are efficiently eliminated, mainly through chlorine-mediated oxidation. However, in stored urine the presence of carbonate, arising from urea hydrolysis, leads to an inhibition of ammonia oxidation. We suggest two parallel mechanisms to explain this effect: the competition between chloride and carbonate oxidation at the anode and the competition between chlorate formation, enhanced by the buffering effect of carbonate, and ammonia oxidation for the consumption of active chlorine in the bulk. However, further experiments are needed to support the latter mechanism. In conclusion, this study highlights the negative consequences of the presence of carbonate in urine solutions, but also in other wastewaters, when subjected to an electrolytic treatment on IrO2 in alkaline media.

Reactivity of chlorine dioxide with amino acids, peptides, and proteins

Abstract: Amino acids, proteins, and peptides are found ubiquitously in waters. They can form harmful byproducts during water treatment by reaction with disinfectants. Chlorination and chloramination of water containing natural organic matter is known to result in the production of toxic substances, often referred to as disinfection byproducts. The main advantage of using chlorine dioxide (ClO2) over other known chlorine-containing disinfectants is the minimization of the formation of harmful trihalomethanes. Because ClO2 is a promising alternative to other chlorine-containing disinfectants, the chemistry of ClO2 interactions with amino acids, proteins, and peptides should be understood to ensure the safety of potable water supplies. Here, we present an overview of the aqueous chemistry of ClO2 and its reactivity with amino acids, peptides, and proteins. The kinetics and products of the reactions are reviewed. Only a few amino acids have been reported to be reactive with ClO2, and they have been found to follow second-order kinetics for the overall reaction. The rate constants vary from 10−2 to 107 M−1 s−1 and follow an order of reactivity: cysteine > tyrosine > tryptophan > histidine > proline. For reactions of histidine, tryptophan, and tyrosine with ClO2, products vary depending largely on the molar ratios of ClO2 with the specific amino acid. Products of ClO2 oxidation differ with the presence or absence of oxygen in the reaction mixture. Excess molar amounts of ClO2 relative to amino acids are associated with the production of low molecular weight compounds. The oxidation of the biochemically important compounds bovine serum albumin and glucose-6-phosphate dehydrogenase by ClO2 suggests a denaturing of proteins by ClO2 by an attack on tryptophan and tyrosine residues and relates to the inactivation of microbes by ClO2.

Oxidation of CrIII to CrVI during chlorination of drinking water

Abstract: Drinking water treatment typically uses strong oxidants such as chlorine which are capable of converting CrIII to CrVI. The rates and extent of CrIII oxidation by chlorine are not well established. CrIII oxidation experiments were therefore conducted in distilled deionized water and New York City tap water dosed initially with CrIII and supplemented with sodium hypochlorite to increase free chlorine residual. Reaction progress was monitored using capillary electrophoresis which quenched reactions and allowed for quantification of CrVI. Three different forms of CrIII were used as reactants: a CrIII nitrate salt, CrIII–EDTA, and CrIII hydroxide. Rates of CrVI production for all three forms of CrIII were rapid, on the order of hours. However, oxidation rates slowed and a plateau in CrVI concentrations was reached. This resulted in less than 100% conversion of CrIII to CrVI even at relatively high chlorine doses (10 to 100 mg L−1 as Cl2). The loss of free chlorine due to a non-Cr chlorine demand, the precipitation of CrIII to Cr(OH)3(s), and the partial oxidation of CrIII to intermediate oxidation states (i.e. CrIV and CrV) were examined and eliminated as possible explanations for this behavior. Consumption of chlorine via reaction with intermediate oxidation states of Cr is therefore offered as a possible explanation for the plateau in CrVI concentrations.