Chlorination Kinetics of Titanium Nitride for Production of Titanium Tetrachloride from Nitrided Ilmenite

NASA Astrophysics Data System (ADS)

Ahmadi, Eltefat; Rezan, Sheikh Abdul; Baharun, Norlia; Ramakrishnan, Sivakumar; Fauzi, Ahmad; Zhang, Guangqing

2017-10-01

The kinetics of chlorination of titanium nitride (TiN) was investigated in the temperature range of 523 K to 673 K (250 °C to 400 °C). The results showed that the extent of chlorination slightly increased with increasing temperature and decreasing particle size of titanium nitride at constant flow rate of N2-Cl2 gas mixture. At 523 K (250 °C), the extent of chlorination was 85.6 pct in 60 minutes whereas at 673 K (400 °C), it was 97.7 pct investigated by weight loss measurement and confirmed by ICP analyses. The experimental results indicated that a shrinking unreacted core model with mixed-control mechanism governed the chlorination rate. It was observed that the surface chemical reaction of chlorine gas on the surface of TiN particles was rate controlling in the initial stage and, during later stage, internal (pore) diffusion through the intermediate product layer was rate controlling step. Overall the process follows the mixed-control model incorporating both chemical reaction and internal diffusion control. The activation energy for the chlorination of TiN was found to be about 10.97 kJ mol-1. In processing TiCl4 from TiN and TiO0.02C0.13N0.85, the solids involved in the chlorination process were characterized by X-ray diffraction (XRD), Scanning electron microscopy (SEM) and Energy-dispersive X-ray spectrometer (EDX). The SEM/EDX results demonstrated the consumption of TiN particles with extent of chlorination that showed shrinking core behavior.

Chlorination Revisited: Does Cl- Serve as a Catalyst in the Chlorination of Phenols?

PubMed

Lau, Stephanie S; Abraham, Sonali M; Roberts, A Lynn

2016-12-20

The aqueous chlorination of (chloro)phenols is one of the best-studied reactions in the environmental literature. Previous researchers have attributed these reactions to two chlorine species: HOCl (at circum-neutral and high pH) and H 2 OCl + (at low pH). In this study, we seek to examine the roles that two largely overlooked chlorine species, Cl 2 and Cl 2 O, may play in the chlorination of (chloro)phenols. Solution pH, chloride concentration, and chlorine dose were systematically varied in order to assess the importance of different chlorine species as chlorinating agents. Our findings indicate that chlorination rates at pH < 6 increase substantially when chloride is present, attributed to the formation of Cl 2 . At pH 6.0 and a chlorine dose representative of drinking water treatment, Cl 2 O is predicted to have at best a minor impact on chlorination reactions, whereas Cl 2 may contribute more than 80% to the overall chlorination rate depending on the (chloro)phenol identity and chloride concentration. While it is not possible to preclude H 2 OCl + as a chlorinating agent, we were able to model our low-pH data by considering Cl 2 only. Even traces of chloride can generate sufficient Cl 2 to influence chlorination kinetics, highlighting the role of chloride as a catalyst in chlorination reactions.

Highly selective transformation of ammonia nitrogen to N2 based on a novel solar-driven photoelectrocatalytic-chlorine radical reactions system.

PubMed

Ji, Youzhi; Bai, Jing; Li, Jinhua; Luo, Tao; Qiao, Li; Zeng, Qingyi; Zhou, Baoxue

2017-11-15

A highly selective method for transforming ammonia nitrogen to N 2 was proposed, based on a novel solar-driven photoelectrocatalytic-chlorine radical reactions (PEC-chlorine) system. The PEC-chlorine system was facilitated by a visible light response WO 3 nanoplate array (NPA) electrode in an ammonia solution containing chloride ions (Cl - ). Under illumination, photoholes from WO 3 promote the oxidation of Cl - to chlorine radical (Cl). This radical can selectively transform ammonia nitrogen to N 2 (79.9%) and NO 3 - (19.2%), similar to the breakpoint chlorination reaction. The ammonia nitrogen removal efficiency increased from 10.6% (PEC without Cl - ) to 99.9% with the PEC-chlorine system within 90 min operation, which can be attributed to the cyclic reactions between Cl - /Cl and the reaction intermediates (NH 2 , NHCl, etc.) that expand the degradation reactions from the surface of the electrodes to the whole solution system. Moreover, Cl is the main radical species contributing to the transformation of ammonia nitrogen to N 2 , which is confirmed by the tBuOH capture experiment. Compared to conventional breakpoint chlorination, the PEC-chlorine system is a more economical and efficient means for ammonia nitrogen degradation because of the fast removal rate, no additional chlorine cost, and its use of clean energy (since it is solar-driven). Copyright © 2017 Elsevier Ltd. All rights reserved.

Selective recovery of uranium from Ca-Mg uranates by chlorination

NASA Astrophysics Data System (ADS)

Pomiro, Federico J.; Gaviría, Juan P.; Quinteros, Raúl D.; Bohé, Ana E.

2017-07-01

A chlorination process is proposed for the uranium extraction and separation using Calciumsbnd Magnesium uranates such as starting reactants which were obtained by precipitation from uranyl nitrate solutions with calcium hydroxide. The study is based on thermodynamic and reaction analysis using chlorine gas as chlorination agent. The results showed that the chlorination reaction of Ca uranate is more feasible to occur than the Mg uranate. The products obtained after chlorination reactions were washed with deionized water to remove the chlorides produced and analyzed. The XRD patterns of the washed products indicated that the chlorination between 400 and 500 °C result in a single phase of calcium uranate (CaUO4) as reaction product. The formation of U3O8 and MgU3O10 was observed at temperatures between 600 °C and 700 °C for 8 hs. The optimal conditions to recover uranium were 3 l h-1 of chlorine and 10 hs of reaction at 700 °C being U3O8 the single uranium product obtained.

Assessment of benzophenone-4 reactivity with free chlorine by liquid chromatography quadrupole time-of-flight mass spectrometry.

PubMed

Negreira, N; Rodríguez, I; Rodil, R; Cela, R

2012-09-19

The stability of the UV filter benzophenone-4 (BP-4) in free chlorine-containing water was investigated, for the first time, by liquid chromatography quadrupole time-of-flight mass spectrometry (LC-QqTOF-MS). High mass accuracy and resolution capabilities of this hybrid mass spectrometer were used for the reliable assignation of empirical formulae and chemical structures of BP-4 derivatives. Time-course profiles of the parent compound and its by-products were simultaneously recorded by direct injection of sample aliquots, after quenching the excess of chlorine, in the LC-QqTOF-MS system. At neutral pHs, in excess of chlorine, BP-4 showed a limited stability fitting a pseudo-first-order degradation kinetics. A noticeable reduction in the half-lives of BP-4 was observed when increasing the sample pH between 6 and 8 units and also in presence of bromide traces. The reaction pathway of this UV filter involved a first electrophilic substitution of hydrogen per chlorine (or bromide) in the phenolic ring, followed by oxidation of the carbonyl moiety to an ester group, which induced a further electrophilic substitution in the same aromatic ring. Above reactions were also noticed when mixing a BP-4 containing personal care product with chlorinated tap water and in chlorinated swimming pool and sewage water, previously spiked with a BP-4 standard. Copyright © 2012 Elsevier B.V. All rights reserved.

Mechanistic insights into the one-pot synthesis of propargylamines from terminal alkynes and amines in chlorinated solvents catalyzed by gold compounds and nanoparticles.

PubMed

Aguilar, David; Contel, Maria; Urriolabeitia, Esteban P

2010-08-09

Propargylamines can be obtained from secondary amines and terminal alkynes in chlorinated solvents by a three- and two-component synthesis catalyzed by gold compounds and nanoparticles (Au-NP) under mild conditions. The use of dichloromethane allows for the activation of two C-Cl bonds and a clean transfer of the methylene fragment to the final product. The scope of the reaction as well as the influence of different gold(III) cycloaurated complexes and salts has been investigated. The involvement of gold nanoparticles generated in situ in the process is discussed and a plausible reaction mechanism is proposed on the basis of the data obtained.

Enhanced elemental mercury removal from coal-fired flue gas by sulfur-chlorine compounds.

PubMed

Yan, Nai-Qiang; Qu, Zan; Chi, Yao; Qiao, Shao-Hua; Dod, Ray L; Chang, Shih-Ger; Miller, Charles

2009-07-15

Oxidation of Hg(0) with any oxidant or converting itto a particle-bound form can facilitate its removal. Two sulfur-chlorine compounds, sulfur dichloride (SCl2) and sulfur monochloride (S2Cl2), were investigated as oxidants for Hg(0) by gas-phase reaction and by surface-involved reactions in the presence of flyash or activated carbon. The gas-phase reaction between Hg(0) and SCl2 is shown to be more rapid than the gas-phase reaction with chlorine, and the second order rate constant was 9.1 (+/- 0.5) x 10(-18) mL-molecules(-1) x s(-1) at 373 K. The presence of flyash or powdered activated carbon in flue gas can substantially accelerate the reaction. The predicted Hg(0) removal is about 90% with 5 ppm SCl2 or S2Cl2 and 40 g/m3 of flyash in flue gas. The combination of activated carbon and sulfur-chlorine compounds is an effective alternative. We estimate that coinjection of 3-5 ppm of SCl2 (or S2Cl2) with 2-3 Lb/MMacf of untreated Darco-KB is comparable in efficiency to the injection of 2-3 Lb/MMacf Darco-Hg-LH. Extrapolation of kinetic results also indicates that 90% of Hg(0) can be removed if 3 Lb/MMacf of Darco-KB pretreated with 3% of SCl2 or S2Cl2 is used. Mercuric sulfide was identified as one of the principal products of the Hg(0)/SCl2 or Hg(0)/S2Cl2 reactions. Additionally, about 8% of SCl2 or S2Cl2 in aqueous solutions is converted to sulfide ions, which would precipitate mercuric ion from FGD solution.

Research in Chemical Kinetics. Annual Report, 1993

DOE R&D Accomplishments Database

Rowland, F. S.

1993-01-01

Progress on the seven projects under this contract is reported. The projects are: (1) Chlorine atom reactions with vinyl bromide. Mass spectrometric investigations of the anti-Markownikoff rule. (2) Chlorine atom reactions with CF{sub 2}{double_bond}CFBr. (3) Gas phase thermal {sup 38}Cl reactions with (CH{sub 2}{double_bond}CH){sub n}M (M=Sn, Si, n=4; M=Sb, n=3; M=Hg, n=2). (4) Gas phase reactions of thermal chlorine atoms with (CH{sub 3}){sub 4}M (M=C, Si, Ge, Sn, Pb). (5) Hydrogen abstraction reactions by thermal chlorine atoms with HFCs, HCFCs, and halomethanes. (6) Half-stabilization pressure of chlorine atoms plus ethylene in a nitrogen bath. (7) {sup 14}C content of atmospheric OCS, C{sub 2}H{sub 6} and C{sub 3}H{sub 8}.

Chemical fate and changes in mutagenic activity of antibiotics nitrofurazone and furazolidone during aqueous chlorination.

PubMed

Nakamura, Hitomi; Kawakami, Tsuyoshi; Niino, Tatsuhiro; Takahashi, Yasuo; Onodera, Sukeo

2008-12-01

Reactions of nitrofuran antibiotics (nitrofurazone (NFZ) and frazolidone (FZD)) with hypochlorite in aqueous solution were investigated under the conditions that simulate wastewater disinfection. The chlorination byproducts were determined by high performance liquid chromatography. At the levels of 5 microM, NFZ reacted rapidly with free chlorine in neutral pH (7.0), while the FZD-hypochlorite reaction was reasonably slow under the same pH. Nevertheless, the strong mutagenic parents disappeared completely after the hypochlorite reactions, and the chlorination byproducts were observed to exert a weak mutagenic effect on Salmonella typhimurium TA100 without S9-mix. The extent of the reactions depended on the chlorine dose, solution pH and compound structures.

Reaction of chlorine nitrate with hydrogen chloride and water at Antarctic stratospheric temperatures

NASA Technical Reports Server (NTRS)

Tolbert, Margaret A.; Rossi, Michel J.; Malhotra, Ripudaman; Golden, David M.

1987-01-01

Laboratory studies of heterogeneous reactions important for ozone depletion over Antarctica are reported. The reaction of chlorine nitrate (ClONO2) with H2O and HCl on surfacers that simulate polar stratospheric clouds are studied at temperatures relevant to the Antarctic stratosphere. The gaseous products of the resulting reactions, HOCl, Cl2O, and Cl2, could readily photolyze in the Antarctic spring to produce active chlorine for ozone depletion. Furthermore, the additional formation of condensed-phase HNO3 could serve as a sink for odd nitrogen species that would otherwise scavenge the active chlorine.

Application of direct thermometric analysis in iodometry.

PubMed

Marik-Korda, P; Erdey, L

1970-12-01

Elementary chlorine was determined by a thermometric method using potassium iodide as reagent. The temperature rise corresponding to the heat of reaction was proportional to the chlorine content. Iodine formed in the reaction was also determined with sodium thiosulphate. The heat of the chlorine-iodide reaction is about five times that of the iodine-thiosulphate reaction. Direct determination with potassium iodide is simpler and more rapid than the indirect one.

In Situ Treatment of Chlorinated Ethene-Contaminated Groundwater Using horizontal Flow Treatment Wells.

DTIC Science & Technology

2000-03-01

groundwater, Environmental Science and Technology, 30 (12): 536A-539A, 1996. Arnold, W. A. and A. L. Roberts, Pathways of chlorinated ethylene and...chlorinated acetylene reaction with Zn(0), Environmental Science and Technology, 32 (19): 3017-3025, 1998. Arnold, W. A. and A. L. Roberts, Pathways and...kinetics of chlorinated ethylene and chlorinated acetylene reaction with Fe(0) particles, Environmental Science and Technology, in press, 2000

Chlorination kinetics of glyphosate and its by-products: modeling approach.

PubMed

Brosillon, Stephan; Wolbert, Dominique; Lemasle, Marguerite; Roche, Pascal; Mehrsheikh, Akbar

2006-06-01

Chlorination reactions of glyphosate, glycine, and sodium cyanate were conducted in well-agitated reactors to generate experimental kinetic measurements for the simulation of chlorination kinetics under the conditions of industrial water purification plants. The contribution of different by-products to the overall degradation of glyphosate during chlorination has been identified. The kinetic rate constants for the chlorination of glyphosate and its main degradation products were either obtained by calculation according to experimental data or taken from published literature. The fit of the kinetic constants with experimental data allowed us to predict consistently the concentration of the majority of the transitory and terminal chlorination products identified in the course of the glyphosate chlorination process. The simulation results conducted at varying aqueous chlorine/glyphosate molar ratios have shown that glyphosate is expected to degrade in fraction of a second under industrial aqueous chlorination conditions. Glyphosate chlorination products are not stable under the conditions of drinking water chlorination and are degraded to small molecules common to the degradation of amino acids and other naturally occurring substances in raw water. The kinetic studies of the chlorination reaction of glyphosate, together with calculations based on kinetic modeling in conditions close to those at real water treatment plants, confirm the reaction mechanism that we have previously suggested for glyphosate chlorination.

Conditions affecting the formation of chlorinated carbon compounds during carbochlorination

NASA Astrophysics Data System (ADS)

Landsberg, A.; Wilson, R. D.; Burns, W.

1988-06-01

The Bureau of Mines, United States Department of the Interior, has conducted an extensive study of the relationship between various metal oxide carbochlorination reactions and carbon compound byproducts. Experiments in which oxides of titanium, zirconium, and aluminum with graphite, charcoal, metallurgical coke, and pctroleum coke were chlorinated at 600° to 1000 °C produced 136 identified and quantified carbon byproduct compounds. The 20 most abundant of these compounds were correlated with reactants and reaction conditions. Experimental results support a proposed carbochlorination reaction with an initial chlorine-carbon step followed by a reaction between the resulting chlorine-carbon products and the metal oxide.

Chlorination and oxidation of sulfonamides by free chlorine: Identification and behaviour of reaction products by UPLC-MS/MS.

PubMed

Gaffney, Vanessa de Jesus; Cardoso, Vitor Vale; Benoliel, Maria João; Almeida, Cristina M M

2016-01-15

Sulfonamides (SAs) are one class of the most widely used antibiotics around the world and have been frequently detected in municipal wastewater and surface water in recent years. Their transformation in waste water treatment plants (WWTP) and in water treatment plants (WTP), as well as, their fate and transport in the aquatic environment are of concern. The reaction of six sulfonamides (sulfamethoxazole, sulfapyridine, sulfamethazine, sulfamerazine, sulfathiazole and sulfadiazine) with free chlorine was investigated at a laboratory scale in order to identify the main chlorination by-products. A previously validated method, liquid chromatography/mass spectrometry, was used to analyse SAs and their chlorination by-products. At room temperature, pH 6-7, reaction times of up to 2 h and an initial concentration of 2 mg/L of free chlorine, the majority of SAs suffered degradation of around 65%, with the exception of sulfamethoxazole and sulfathiazole (20%). The main reaction of SAs with free chlorine occurred in the first minute. Copyright © 2015 Elsevier Ltd. All rights reserved.

Reaction of Cl- ions in electrolyte solution induced electrical discharge plasma in the presence of argon fine bubbles

NASA Astrophysics Data System (ADS)

Hayashi, Yui; Takada, Noriharu; Wahyudiono, Kanda, Hideki; Goto, Motonobu

2017-05-01

Active chlorine species such as chlorine molecules and hypochlorous acid have been known as high performance sanitizers. They would act more reactive on chemical and biological substances when an electrical discharge was introduced in water containing an electrolyte substance. Here, the reaction of chloride (Cl-) ions were examined by introducing of a pulsed discharge plasma in sodium chloride (NaCl) solution as an electrolyte solution at room temperature. The results show that a large electrical current generated by the pulsed discharge plasma affected the reaction of Cl- ions to result available chlorine. The reaction pathway for available chlorine production was assumed similar with the reaction pathway as electrolysis. A pulsed discharge plasma in NaCl solution in the presence of argon (Ar) fine bubbles exhibited intense emissions and high electron density compared to when no Ar fine bubbles were introduced. At these conditions, the dissociation reaction rate of water increased drastically leads to the formation of 0 atoms. As a result, the reaction of Cl- ions and the available chlorine generation were also increased.

CHLORINE DIOXIDE CHEMISTRY, REACTIONS, AND DISINFECTION BY-PRODUCTS

EPA Science Inventory

This chapter contains two main sections-the first section describes the chemistry and reactions of chlorine dioxide, and the second describes the disinfection by-products (DBPs) of chlorine dioxide and their control. A short section on Research Needs completes this chapter. The...

REACTION PRODUCTS FROM THE CHLORINATION OF SEAWATER

EPA Science Inventory

Chemical treatment of natural waters, in particular the use of chlorine as a biocide, modifies the chemistry of these waters in ways that are not fully understood. The research described in this report examined both inorganic and organic reaction products from the chlorination of...

Identification of reaction products from reactions of free chlorine with the lipid-regulator gemfibrozil.

PubMed

Krkošek, Wendy H; Koziar, Stephen A; White, Robert L; Gagnon, Graham A

2011-01-01

High global consumption rates have led to the occurrence of pharmaceutically active compounds (PhACs) in wastewater. The use of chlorine to disinfect wastewater prior to release into the environment may convert PhACs into uncharacterized chlorinated by-products. In this investigation, chlorination of a common pharmaceutical, the antihyperlipidemic agent gemfibrozil, was documented. Gemfibrozil (2,2-dimethyl-5-(2,5-dimethylphenoxy)pentanoic acid) was reacted with sodium hypochlorite and product formation was monitored by gas chromatography-mass spectrometry (GC-MS). The incorporation of one, two or three chlorine atoms into the aromatic region of gemfibrozil was demonstrated using negative-ion electrospray ionization mass spectrometry (ESI-MS) and tandem mass spectrometry (ESI-MS/MS). Further analysis using (1)H nuclear magnetic resonance (NMR) spectroscopy identified the reaction products as 4'-ClGem (5-(4-chloro-2,5-dimethylphenoxy)-2,2-dimethylpentanoic acid) 4',6'-diClGem (5-(4,6-dichloro-2,5-dimethylphenoxy)-2,2-dimethylpentanoic acid), and 3',4',6'-triClGem (5-(3,4,6-trichloro-2,5-dimethylphenoxy)-2,2-dimethylpentanoic acid), products consistent with electrophilic aromatic substitution reactions. The rapid reaction of gemfibrozil with free chlorine at pH conditions relevant to water treatment indicates that a mixture of chlorinated gemfibrozils is likely to be found in wastewater disinfected with chlorine. Copyright © 2010 Elsevier Ltd. All rights reserved.

UV-induced effects on chlorination of creatinine.

PubMed

Weng, Shih Chi; Li, Jing; Wood, Karl V; Kenttämaa, Hilkka I; Williams, Peggy E; Amundson, Lucas M; Blatchley, Ernest R

2013-09-15

Ultraviolet (UV) irradiation is commonly employed for water treatment in swimming pools to complement conventional chlorination, and to reduce the concentration of inorganic chloramine compounds. The approach of combining UV irradiation and chlorination has the potential to improve water quality, as defined by microbial composition. However, relatively little is known about the effects of this process on water chemistry. To address this issue, experiments were conducted to examine the effects of sequential UV254 irradiation/chlorination, as will occur in recirculating system of swimming pools, on disinfection byproduct (DBP) formation. Creatinine, which is present in human sweat and urine, was selected as the target precursor for these experiments. Enhanced formation of dichloromethylamine (CH3NCl2) and inorganic chloramines was observed to result from post-chlorination of UV-irradiated samples. Chlorocreatinine was found to be more sensitive to UV254 irradiation than creatinine; UV254 irradiation of chlorocreatinine resulted in opening of the ring structure, thereby yielding a series of intermediates that were more susceptible to free chlorine attack than their parent compound. The quantum yields for photodegradation of creatinine and chlorocreatinine at 254 nm were estimated at 0.011 ± 0.002 mol/E and 0.144 ± 0.011 mol/E, respectively. The N-Cl bond was found to be common to UV-sensitive chlorinated compounds (e.g., inorganic chloramines, CH3NCl2, and chlorocreatinine); compounds that were less susceptible to UV-based attack generally lacked the N-Cl bond. This suggested that the N-Cl bond is susceptible to UV254 irradiation, and cleavage of the N-Cl bond appears to open or promote reaction pathways that involve free chlorine, thereby enhancing formation of some DBPs and promoting loss of free chlorine. Proposed reaction mechanisms to describe this behavior based on creatinine as a precursor are presented. Copyright © 2013 Elsevier Ltd. All rights reserved.

Mechanism of chemical activation of sodium chloride in the presence of amino acids.

PubMed

Rahn, Anja K K; Yaylayan, Varoujan A

2015-01-01

Sodium chloride has been shown to promote chlorination of glycerol during thermal processing. However, the detailed mechanism of this reaction is not well understood. Preliminary experiments have indicated that the reaction mixture should contain an amino acid and it should be dissolved thoroughly in water in order to induce chlorination. These observations are consistent with the process of dissociation of sodium chloride and its re-association with amino acid and eventual formation of the chlorinating agent in the form of the hydrochloride salt. Release of HCl from this salt can be manifested in chlorination and hydrolytic reactions occurring during thermal processing. The generation of HCl at room temperature from a mixture of sodium chloride and glycine was confirmed through spectrophotometric monitoring of the pH. Hydrolytic and chlorination reactions were demonstrated through monitoring of formation of HMF and chlorinated products under pyrolytic conditions using glucose or sucrose and amino acid mixtures. Copyright © 2014 Elsevier Ltd. All rights reserved.

Room-temperature Pd-catalyzed C-H chlorination by weak coordination: one-pot synthesis of 2-chlorophenols with excellent regioselectivity.

PubMed

Sun, Xiuyun; Sun, Yonghui; Zhang, Chao; Rao, Yu

2014-02-07

A room-temperature Pd(II)-catalyzed regioselective chlorination reaction has been developed for a facile one-pot synthesis of a broad range of 2-chlorophenols. The reaction demonstrates an excellent regioselectivity and reactivity for C-H chlorination. This reaction represents one of the rare examples of mild C-H functionalization at ambient temperature.

Transformation of pharmaceuticals during oxidation/disinfection processes in drinking water treatment.

PubMed

Postigo, Cristina; Richardson, Susan D

2014-08-30

Pharmaceuticals are emerging contaminants of concern and are widespread in the environment. While the levels of these substances in finished drinking waters are generally considered too low for human health concern, there are now concerns about their disinfection by-products (DBPs) that can form during drinking water treatment, which in some cases have been proven to be more toxic than the parent compounds. The present manuscript reviews the transformation products of pharmaceuticals generated in water during different disinfection processes, i.e. chlorination, ozonation, chloramination, chlorine dioxide, UV, and UV/hydrogen peroxide, and the main reaction pathways taking place. Most of the findings considered for this review come from controlled laboratory studies involving reactions of pharmaceuticals with these oxidants used in drinking water treatment. Copyright © 2014 Elsevier B.V. All rights reserved.

Chlorine dioxide reactions with indoor materials during building disinfection: surface uptake.

PubMed

Hubbard, Heidi; Poppendieck, Dustin; Corsi, Richard L

2009-03-01

Chlorine dioxide received attention as a building disinfectant in the wake of Bacillus anthracis contamination of several large buildings in the fall of 2001. It is increasingly used for the disinfection of homes and other indoor environments afflicted by mold. However, little is known regarding the interaction of chlorine dioxide and indoor materials, particularly as related to the removal of chlorine dioxide from air. Such removal may be undesirable with respect to the subsequent formation of localized zones of depleted disinfectant concentrations and potential reductions in disinfection effectiveness in a building. The focus of this paper is on chlorine dioxide removal from air to each of 24 different indoor materials. Experiments were completed with materials housed in flow-through 48-L stainless steel chambers under standard conditions of 700 ppm chlorine dioxide inlet concentration, 75% relative humidity, 24 degrees C, and 0.5 h(-1) air changes. Chlorine dioxide concentration profiles, deposition velocities, and reaction probabilities are described in this paper. Deposition velocities and reaction probabilities varied over approximately 2 orders of magnitude across all materials. For most materials, deposition velocity decreased significantly over a 16-h disinfection period; that is, materials became smaller sinks for chlorine dioxide with time. Four materials (office partition, ceiling tile, medium density fiberboard, and gypsum wallboard) accounted for the most short- and long-term consumption of chlorine dioxide. Deposition velocity was observed to be a strong function of chlorine dioxide inlet concentration, suggesting the potential importance of chemical reactions on or within test materials.

Development of a Portable Binary Chlorine Dioxide Generator for Decontamination

DTIC Science & Technology

2010-03-01

chlorine dioxide forms slowly from chlorite solutions through either acid release or a radical chain reaction that we observed at neutral pH. Task 7... Chlorine dioxide and water in methanol - no agent control F. 5.25% Bleach G. Methanol only 3.0 PROCEDURES 3.1 METHOD VALIDATION The reaction...error range in gas chromatography measurements. For the chlorine dioxide containing samples, mass spectra were analyzed to determine potential

Ferrate(VI) oxidation of polychlorinated diphenyl sulfides: Kinetics, degradation, and oxidized products.

PubMed

Chen, Jing; Xu, Xinxin; Zeng, Xiaolan; Feng, Mingbao; Qu, Ruijuan; Wang, Zunyao; Nesnas, Nasri; Sharma, Virender K

2018-06-13

This paper presents oxidation of polychlorinated diphenyl sulfides (PCDPSs), dioxin-like compounds, by ferrate(VI) (Fe VI O 4 2- , Fe(VI)). Kinetics of the reactions of Fe(VI) with seventeen PCDPSs, differ in number and positions of chlorine atoms (from 2 to 7), were investigated at pH 8.0. The second-order rate constants (k, M -1 s -1 ) of the reactions varied with the numbers and positions of chlorine atoms and appeared to be related with standard Gibbs free energy of formation (Δ f G 0 ) of PCDPSs. Degradation experiments in the presence of ions and humic acid demonstrated complete removal of PeCDPS by Fe(VI) in minutes. Pathways of the reaction were investigated by identifying oxidized products (OPs) of the reaction between Fe(VI) and 2,2',3',4,5-pentachlorodiphenyl sulfide (PeCDPS) at pH 8.0. Pathways of oxidation involved major pathway of attack on sulfur(II) by Fe(VI) in steps to yield sulfoxide type products, and subsequent breakage of C-S bond with the formation of sulfonic acid-containing trichloro compound. Minor pathways were hydroxylation of benzene ring and substitution of chlorine atom with hydroxyl group. Estimation of toxicity of OPs of the oxidation of PeCDPS by Fe(VI) suggested the decreased toxicity from the parent contaminant. Copyright © 2018. Published by Elsevier Ltd.

MODELING CHLORINE RESIDUALS IN DRINKING-WATER DISTRIBUTION SYSTEMS

EPA Science Inventory

A mass-transfer-based model is developed for predicting chlorine decay in drinking-water distribution networks. The model considers first-order reactions of chlorine to occur both in the bulk flow and at the pipe wall. The overall rate of the wall reaction is a function of the ...

MODELING CHLORINE RESIDUALS IN DRINKING-WATER DISTRIBUTION SYSTEMS

EPA Science Inventory

A mass transfer-based model is developed for predicting chlorine decay in drinking water distribution networks. he model considers first order reactions of chlorine to occur both in the bulk flow and at the pipe wall. he overall rate of the wall reaction is a function of the rate...

Alternative synthesis of 3-acetyl, 3-epoxy, and 3-formyl chlorins from a 3-vinyl chlorin, methyl pyropheophorbide-a, via iodination.

PubMed

Oba, Toru; Masuya, Takuto; Yasuda, Satoru; Ito, Satoshi

2015-08-01

We developed novel methods to convert the C3-vinyl group of a chlorophyll derivative, methyl pyropheophorbide-a, into an acetyl group, an epoxy group, and a formyl group via iodination with I2 and phenyliodine(III) bis(trifluoroacetate). Reaction of the iodinated intermediate with ethylene glycol and subsequent treatment with base led to formation of the C3-acetyl chlorin. Reaction of the iodinated intermediate with ethylenediamine afforded the C3-oxiranyl chlorin. The C3-formyl chlorin was readily derived from the epoxide without hazardous reagents such as OsO4. These reactions were facile and useful alternatives to the previous methods. Copyright © 2015 Elsevier Ltd. All rights reserved.

Dominant Overall Chemical Reaction in a Chlorine Trifluoride Silicon Nitrogen System at Atmospheric Pressure

NASA Astrophysics Data System (ADS)

Habuka, Hitoshi; Otsuka, Toru; Qu, Wei-Feng

1999-11-01

This study evaluates the overall chemical reaction in a chlorine trifluoride silicon nitrogen system at atmospheric pressure, based on the observation of the dominant chemical species in the gas phase using a quadrupole mass spectra analyzer coupled with a horizontal cold-wall single-wafer epitaxial reactor. Chlorine trifluoride gas etches the silicon surface, producing two major products, silicon tetrafluoride gas and chlorine gas, at room temperature and 530 K. The production of chlorosilanes was not observed in this study. The results obtained in this study indicate that the dominant overall chemical reaction in a chlorine trifluoride silicon nitrogen system is 3Si + 4ClF3 →3SiF4 ↑+ 2Cl2 ↑.

Chlorine dioxide-induced and Congo red-inhibited Marangoni effect on the chlorite-trithionate reaction front

NASA Astrophysics Data System (ADS)

Liu, Yang; Ren, Xingfeng; Pan, Changwei; Zheng, Ting; Yuan, Ling; Zheng, Juhua; Gao, Qingyu

2017-10-01

Hydrodynamic flows can exert multiple effects on an exothermal autocatalytic reaction, such as buoyancy and the Marangoni convection, which can change the structure and velocity of chemical waves. Here we report that in the chlorite-trithionate reaction, the production and consumption of chlorine dioxide can induce and inhibit Marangoni flow, respectively, leading to different chemo-hydrodynamic patterns. The horizontal propagation of a reaction-diffusion-convection front was investigated with the upper surface open to the air. The Marangoni convection, induced by gaseous chlorine dioxide on the surface, produced from chlorite disproportionation after the proton autocatalysis, has the same effect as the heat convection. When the Marangoni effect is removed by the reaction of chlorine dioxide with the Congo red (CR) indicator, an oscillatory propagation of the front tip is observed under suitable conditions. Replacing CR with bromophenol blue (BPB) distinctly enhanced the floating, resulting in multiple vortexes, owing to the coexistence between BPB and chlorine dioxide. Using the incompressible Navier-Stokes equations coupled with reaction-diffusion and heat conduction equations, we numerically obtain various experimental scenarios of front instability for the exothermic autocatalytic reaction coupled with buoyancy-driven convection and Marangoni convection.

Chlorine dioxide as a post-disinfectant for Dutch drinking water.

PubMed

Wondergem, E; van Dijk-Looijaard, A M

1991-02-01

Chlorine dioxide has some important advantages over chlorine with respect to water quality (no formation of trihalomethanes, no impairment of taste and no odor) and stability when used for oxidation/disinfection of drinking water. In this paper, results are presented of experiments into the consumption and reaction kinetics of chlorine dioxide in a number of (drinking) waters in The Netherlands. It was found that chlorine dioxide consumption is related to the dissolved oxygen content (DOC) of the water and the reaction time. Water samples from a plant that applied ozonation and activated carbon filtration had a very low chlorine dioxide consumption. Other water quality parameters, including pH and CO3(2-), did not have any influence on consumption. The temporary advised Dutch guidelines of 0.2 mg l-1 (dosage) is sufficient for activated carbon treated water. For other Dutch drinking waters, however, none of the 0.2 mg l-1 chlorine dioxide remained after a reaction time of 10 min, as was also found for the water of Dutch pumping stations where chlorine dioxide is at present used for disinfection.

Preliminary GRS Measurement of Chlorine Distribution on Surface of Mars

NASA Astrophysics Data System (ADS)

Keller, J. M.; Boynton, W. V.; Taylor, G. J.; Hamara, D.; Janes, D. M.; Kerry, K.

2003-12-01

Ongoing measurements with the Gamma Ray Spectrometer (GRS) aboard Mars Odyssey provide preliminary detection of chlorine at the surface of Mars. Summing all data since boom deployment and using a forward calculation model, we estimate values for chlorine concentration at 5° resolution. Rebinning this data and smoothing with a 15-degree-radius boxcar filter reveal regions of noticeable chlorine enrichment at scales larger than the original 5° resolution and allow for preliminary comparison with previous Mars datasets. Analyzing chlorine concentrations within 30 degrees of the equator, we find a negative correlation with thermal inertia (R2=0.55) and positive correlation with albedo (R2=0.52), indicating that chlorine is associated with fine, non-rock surface materials. Although possibly a smoothing artifact, the spatial correlation is more noticeable in the region covering Tharsis and Amazonis than around Arabia and Elysium. Additionally, a noticeable region of chlorine enrichment appears west of Tharsis Montes ( ˜0 to 20N, ˜110 to 150W) and chlorine concentration is estimated to vary in the equatorial region by over a factor of two. A simplified two-component model involving chlorine-poor rocks and a homogenous chlorine-rich fine material requires rock abundance to vary from zero to over 50%, a result inconsistent with previous measurements and models. In addition to variations in rock composition and distribution, substantial variations in chlorine content of various types of fine materials including dust, sand, and duricrust appear important in explaining this preliminary observation. Surprisingly, visual comparison of surface units mapped by Christensen and Moore (1992) does not show enrichment in chlorine associated with regions of indurated surfaces, where cementation has been proposed. Rather, Tharsis, a region of active deposition with proposed mantling of 0.1 to 2 meters of recent dust (Christensen 1986), shows the greatest chlorine signal. In light of suggested fine material formation mechanisms, this preliminary result is intriguing. Tentative models involving venting of chlorine from hydrothermal systems (Newsom 1999), enrichment of chlorine through volcanic aerosols (Settle 1979) or acid fog reactions (Banin et al 1997), and preferential deposition of a proposed salt component in Mars fines (Clark 1993), if more easily mobilized from the Martian duricrust, are viable. Finally, this preliminary measurement will be improved through further data collection by Mars Odyssey and comparisons with MER and future missions.

Kinetics and mechanism of styrene epoxidation by chlorite: role of chlorine dioxide.

PubMed

Leigh, Jessica K; Rajput, Jonathan; Richardson, David E

2014-07-07

An investigation of the kinetics and mechanism for epoxidation of styrene and para-substituted styrenes by chlorite at 25 °C in the pH range of 5-6 is described. The proposed mechanism in water and water/acetonitrile includes seven oxidation states of chlorine (-I, 0, I, II, III, IV, and V) to account for the observed kinetics and product distributions. The model provides an unusually detailed quantitative mechanism for the complex reactions that occur in mixtures of chlorine species and organic substrates, particularly when the strong oxidant chlorite is employed. Kinetic control of the reaction is achieved by the addition of chlorine dioxide to the reaction mixture, thereby eliminating a substantial induction period observed when chlorite is used alone. The epoxidation agent is identified as chlorine dioxide, which is continually formed by the reaction of chlorite with hypochlorous acid that results from ClO produced by the epoxidation reaction. The overall stoichiometry is the result of two competing chain reactions in which the reactive intermediate ClO reacts with either chlorine dioxide or chlorite ion to produce hypochlorous acid and chlorate or chloride, respectively. At high chlorite ion concentrations, HOCl is rapidly eliminated by reaction with chlorite, minimizing side reactions between HOCl and Cl2 with the starting material. Epoxide selectivity (>90% under optimal conditions) is accurately predicted by the kinetic model. The model rate constant for direct reaction of styrene with ClO2(aq) to produce epoxide is (1.16 ± 0.07) × 10(-2) M(-1) s(-1) for 60:40 water/acetonitrile with 0.20 M acetate buffer. Rate constants for para substituted styrenes (R = -SO3(-), -OMe, -Me, -Cl, -H, and -NO2) with ClO2 were determined. The results support the radical addition/elimination mechanism originally proposed by Kolar and Lindgren to account for the formation of styrene oxide in the reaction of styrene with chlorine dioxide.

Unique metabolites of Pestalotiopsis fici suggest a biosynthetic hypothesis involving a Diels-Alder reaction and then mechanistic diversification.

PubMed

Liu, Ling; Niu, Shubin; Lu, Xinhua; Chen, Xulin; Zhang, Hua; Guo, Liangdong; Che, Yongsheng

2010-01-21

Chloropupukeanolides A (1) and B (2), unprecedented spiroketal peroxides, and chloropupukeanone A (3), three highly functionalized metabolites featuring a chlorinated pupukeanane core, were isolated from an endophytic fungus Pestalotiopsis fici, with 1 showing significant anti-HIV-1 and cytotoxic effects.

Investigation of the mechanism of chlorination of glyphosate and glycine in water.

PubMed

Mehrsheikh, Akbar; Bleeke, Marian; Brosillon, Stephan; Laplanche, Alain; Roche, Pascal

2006-09-01

The chlorination reactions of glyphosate and glycine in water were thoroughly studied. Utilizing isotopically enriched (13C and 15N) samples of glycine and glyphosate and 1H, 13C, 31P, and 15N NMR spectroscopy we were able to identify all significant terminal chlorination products of glycine and glyphosate, and show that glyphosate degradation closely parallels that of glycine. We have determined that the C1 carboxylic acid carbon of glycine/glyphosate is quantitatively converted to CO2 upon chlorination. The C2 methylene carbon of glycine/glyphosate is converted to CO2 and methanediol. The relative abundance of these two products is a function of the pH of the chlorination reactions. Under near neutral to basic reaction conditions (pH 6-9), CO2 is the predominant product, whereas, under acidic reaction conditions (pH < 6) the formation of methanediol is favored. The C3 phosphonomethylene carbon of glyphosate is quantitatively converted to methanediol under all conditions tested. The nitrogen atom of glycine/glyphosate is transformed into nitrogen gas and nitrate, and the phosphorus moiety of glyphosate produces phosphoric acid upon chlorination. In addition to these terminal chlorination products, a number of labile intermediates were also identified including N-chloromethanimine, N-chloroaminomethanol, and cyanogen chloride. The chlorination products identified in this study are not unique to glyphosate and are similar to those expected from chlorination of amino acids, proteins, peptides, and many other natural organic matters present in drinking water.

Degradation of sulfamethoxazole using ozone and chlorine dioxide - Compound-specific stable isotope analysis, transformation product analysis and mechanistic aspects.

PubMed

Willach, Sarah; Lutze, Holger V; Eckey, Kevin; Löppenberg, Katja; Lüling, Michelle; Terhalle, Jens; Wolbert, Jens-Benjamin; Jochmann, Maik A; Karst, Uwe; Schmidt, Torsten C

2017-10-01

The sulfonamide antibiotic sulfamethoxazole (SMX) is a widely detected micropollutant in surface and groundwaters. Oxidative treatment with e.g. ozone or chlorine dioxide is regularly applied for disinfection purposes at the same time exhibiting a high potential for removal of micropollutants. Especially for nitrogen containing compounds such as SMX, the related reaction mechanisms are largely unknown. In this study, we systematically investigated reaction stoichiometry, product formation and reaction mechanisms in reactions of SMX with ozone and chlorine dioxide. To this end, the neutral and anionic SMX species, which may occur at typical pH-values of water treatment were studied. Two moles of chlorine dioxide and approximately three moles of ozone were consumed per mole SMX degraded. Oxidation of SMX with ozone and chlorine dioxide leads in both cases to six major transformation products (TPs) as revealed by high-resolution mass spectrometry (HRMS). Tentatively formulated TP structures from other studies could partly be confirmed by compound-specific stable isotope analysis (CSIA). However, for one TP, a hydroxylated SMX, it was not possible by HRMS alone to identify whether hydroxylation occurred at the aromatic ring, as suggested in literature before, or at the anilinic nitrogen. By means of CSIA and an analytical standard it was possible to identify sulfamethoxazole hydroxylamine unequivocally as one of the TPs of the reaction of SMX with ozone as well as with chlorine dioxide. H-abstraction and electron transfer at the anilinic nitrogen are suggested as likely initial reactions of ozone and chlorine dioxide, respectively, leading to its formation. Oxidation of anionic SMX with ozone did not show any significant isotopic fractionation whereas the other reactions studied resulted in a significant carbon isotope fractionation. Copyright © 2017 Elsevier Ltd. All rights reserved.

A Simple Photochemical Conversion of Perfluoroalkyl Hydrides to Perfluoroalkyl Bromides Using Interhalogen Compounds.

DTIC Science & Technology

1983-05-31

slower (100 hrs) than the ambient temperature chlorination of that compound (10 minutes). The reaction was followed by gas phase infrared spectroscopy...excess of bromine to chlorine and a slightly shorter (254 hrs) reaction time slightly increases the yield of bromo-F-neopentane. The 19F NMR data (Table... chlorination products, however, optimal bromina- tion (4.4:1) occurred for reaction 4 which produced predominately 1-bromo-3- hydryl-F-neopentane (48%). It

Arenium ions are not obligatory intermediates in electrophilic aromatic substitution

PubMed Central

Galabov, Boris; Koleva, Gergana; Simova, Svetlana; Hadjieva, Boriana; Schaefer, Henry F.; Schleyer, Paul von Ragué

2014-01-01

Our computational and experimental investigation of the reaction of anisole with Cl2 in nonpolar CCl4 solution challenges two fundamental tenets of the traditional SEAr (arenium ion) mechanism of aromatic electrophilic substitution. Instead of this direct substitution process, the alternative addition–elimination (AE) pathway is favored energetically. This AE mechanism rationalizes the preferred ortho and para substitution orientation of anisole easily. Moreover, neither the SEAr nor the AE mechanisms involve the formation of a σ-complex (Wheland-type) intermediate in the rate-controlling stage. Contrary to the conventional interpretations, the substitution (SEAr) mechanism proceeds concertedly via a single transition state. Experimental NMR investigations of the anisole chlorination reaction course at various temperatures reveal the formation of tetrachloro addition by-products and thus support the computed addition–elimination mechanism of anisole chlorination in nonpolar media. The important autocatalytic effect of the HCl reaction product was confirmed by spectroscopic (UV-visible) investigations and by HCl-augmented computational modeling. PMID:24972792

On the relevance of the methane oxidation cycle to ozone hole chemistry

NASA Technical Reports Server (NTRS)

Mueller, Rolf; Crutzen, Paul J.

1994-01-01

High concentrations of active chlorine are clearly responsible for the observed ozone depletion during the Antarctic polar spring. However, the mechanism behind the activation of chlorine from the reservoirs species HCl and ClONO2 and the maintenance of extremely high levels of active chlorine after polar sunrise is less well understood. Here, we focus on the influence of the methane oxidation cycle on 'ozone hole' chemistry through its effect on HOx and ClOx radicals. We demonstrate the great potential importance of the heterogeneous reaction HCl + HOCl yields Cl2 + H2O and the gasphase reaction ClO + CH3O2 yields ClOO + CH3O under sunlight conditions in polar spring. Under these conditions, the heterogeneous reaction is the main sink for HOx radicals. Through this channel, the HCl reservoir may be almost completely depleted. The gas phase reaction may control the levels of the CH3O2 radical, provided that high levels of ClO exist. Otherwise this radical initiates a sequence of reactions leading to a considerable loss of active chlorine. Moreover, the production of HOx radicals is reduced, and thereby the efficiency of the heterogeneous reaction limited. The two reactions together may accomplish the complete conversion of HCl into active chlorine, thereby leading to a rapid destruction of ozone.

The occurrence of chlorine in serpentine minerals

USGS Publications Warehouse

Miura, Y.; Rucklidge, J.; Nord, G.L.

1981-01-01

Partially serpentinized dunites containing small amounts of Chlorine (< 0.5%) from Dumont, Quebec, and Horoman, Hokkaido, Japan, and one containing less than 0.05% Chlorine from Higashi-Akaishi-Yama, Ehime, Japan have been examined using the electron probe microanalyzer and scanning transmission electron microscope with X-ray analytical capabilities. Chlorine was found together with Si, Mg, Ca and Fe in the serpentine minerals of the Dumont and Hokkaido dunites but not in the Ehime dunite. Chlorine is found associated only with the most finely crystalline facies of the serpentine (grain size less than 10 nm). The Ehime dunite contained no such fine grained serpentine, and was thus effectively chlorine-free, as are the coarser grained serpentines of the other samples. The finegrained chlorine-bearing serpentine also has a much higher concentration of Fe, and can contain smaller amounts of Ca, Ni and Mn than the coarse-grained variety as well as minute awaruite (FeNi3) grains. This fine-grained serpentine probably represents an early stage in the transformation of olivine to serpentine, with chlorine from hydrothermal solutions assisting the necessary chemical changes. The Cl increases the reaction rate by lowering the activation barrier to reaction by the introduction of reaction steps. ?? 1981 Springer-Verlag.

Tests of stratospheric models - The reactions of atomic chlorine with O3 and CH4 at low temperature

NASA Technical Reports Server (NTRS)

Demore, W. B.

1991-01-01

The rate-constant ratio of the photochemical reactions of atomic chlorine with O3 and CH4 was determined using data from laboratory experiments on competitive chlorination of O3/CH4 mixtures at stratospheric temperatures (197-217 K). Two experimental approaches were used: (1) measuring the k1/k2 ratio for the reactions of atomic chlorine with ozone and methane and (2) testing for some of the ClO/CH3O2 chemistry. The chlorine and ozone concentrations were monitored by UV-Vis spectroscopy, and the CH3Cl concentration was measured by FTIR. The results on the k1/k2 ratio are in excellent agreement with the current NASA recommendation (DeMore et al., 1990), being only 12 percent higher. On the other hand, results on the ClO + CH3O2 reaction do not support the rate constant suggested by Simon et al. (1989).

XAFS Study on Chlorination of Y2O3 in LiCl-KCl-ZrCl4 Melt

NASA Astrophysics Data System (ADS)

Okamoto, Yoshihiro; Yaita, Tsuyoshi; Shiwaku, Hideaki; Suzuki, Shinichi

2008-11-01

The chlorination reaction of Y2O3 with ZrCl4 in LiCl-KCl eutectic melt was investigated by X-ray absorption fine structure (XAFS) technique. The chlorination reaction was observed between 773 K and 823 K as the 1st peak shift of the Fourier transform magnitude function |FT(k3χ(k))|. The peak corresponding to the nearest Y3+-Cl- correlation was observed in the XAFS analysis at 823 K as the result of the chlorination. It was confirmed that the mixture melts after the reaction is almost equivalent to a molten 5% YCl3-(LiCl-KCl eutectic) mixture.

[Degradation Kinetics and Formation of Disinfection By-products During Linuron Chlorination in Drinking Water].

PubMed

Ling, Xiao; Hu, Chen-yan; Cheng, Ming; Gu, Jian

2015-05-01

Chlorination degradation of linuron was studied using the common disinfectant sodium hypochlorite, the effects of chlorine dosage, pH value, bromine ion concentrationand temperature were systematically investigated, and the formation characteristics of disinfection by-products (DBPs) during the chlorination reaction was analyzed. The results showed that the chlorination degradation kinetics of linuron by sodium hypochlorite could be well described by the second-order kinetic model. Moreover, pH values had a great impact on the degradation reaction, and the rate constant reached the maximum level at pH 7, and the base elementary reaction rate constants of HOCl and OCl- with linuron were 4.84 x 10(2) L · (mol · h)(-1) and 3.80 x 10(2) L · (mol · h)(-1), respectively. The reaction rate decreased with the addition of bromide ion and increased with increasing temperature. Furthermore, many kinds of disinfection by- products were produced during the chlorination degradation of linuron, including CF, DCAN, TCNM and halogen acetone. Under conditions of different solution pH and different bromide ion concentrations, there would be significant difference in the types and concentrations of disinfection by-products.

Kinetics of aqueous chlorination of some pharmaceuticals and their elimination from water matrices.

PubMed

Acero, Juan L; Benitez, F Javier; Real, Francisco J; Roldan, Gloria

2010-07-01

Apparent rate constants for the reactions of four selected pharmaceutical compounds (metoprolol, naproxen, amoxicillin, and phenacetin) with chlorine in ultra-pure (UP) water were determined as a function of the pH. It was found that amoxicillin (in the whole pH range 3-12), and naproxen (in the low pH range 2-4) presented high reaction rates, while naproxen (in the pH range 5-9), and phenacetin and metoprolol (in the pH range 2.5-12 for phenacetin, and 3-10 for metoprolol) followed intermediate and slow reaction rates. A mechanism is proposed for the chlorination reaction, which allowed the evaluation of the intrinsic rate constants for the elementary reactions of the ionized and un-ionized species of each selected pharmaceutical with chlorine. An excellent agreement is obtained between experimental and calculated rate constants by this mechanism.The elimination of these substances in several waters (a groundwater, a surface water from a public reservoir, and two effluents from municipal wastewater treatment plants) was also investigated at neutral pH. The efficiency of the chlorination process with respect to the pharmaceuticals elimination and the formation THMs was also established. It is generally observed that the increasing presence of organic and inorganic matter in the water matrices demand more oxidant agent (chlorine), and therefore, less chlorine is available for the oxidation of these compounds. Finally, half-life times and oxidant exposures (CT) required for the removal of 99% of the four pharmaceuticals are also evaluated. These parameters are useful for the establishment of safety chlorine doses in oxidation or disinfection stages of pharmaceuticals in treatment plants.

Bromine-Chlorine Coupling in the Antarctic Ozone Hole

NASA Technical Reports Server (NTRS)

Danilin, Michael Y.; Sze, Nien-Dak; Ko, Malcolm K. W.; Rodriquez, Jose M.; Prather, Michael J.

1996-01-01

The contribution from the chlorine and bromine species in the formation of the Antarctic ozone hole is evaluated. Since chlorine and bromine compounds are of different industrial origin, it is desirable, from a policy point of view, to be able to attribute chlorine-catalyzed loss of ozone with those reactions directly involving chlorine species, and likewise for bromine-catalyzed loss. In the stratosphere, however, most of the chemical families are highly coupled, and, for example, changes in the chlorine abundance will alter the partitioninig in other families and thus the rate of ozone loss. This modeling study examines formation of the Antarctic ozone hole for a wide range of bromine concentrations (5 - 25 pptv) and for chlorine concentrations typical of the last two decades (1.5, 2.5 and 3.5 ppbv). We follow the photochemical evolution of a single parcel of air, typical of the inner Antarctic vortex (50 mbar, 70 deg. S, NO(sub y) = 2 ppbv, with Polar Stratospheric Clouds(PSC)) from August 1 to November 1. For all of these ranges of chlorine and bromine loading, we would predict a substantial ozone hole (local depletion greater than 90%) within the de-nitrified, PSC- perturbed vortex. The contributions of the different catalytic cycles responsible for ozone loss are tabulated. The deep minimum in ozone is driven primarily by the chlorine abundance. As bromine levels decrease, the magnitude of the chlorine-catalyzed ozone loss increases to take up the slack. This is because bromine suppresses ClO by accelerating the conversion of ClO an Cl2O2 back to HCI. For this range of conditions, the local relative efficiency of ozone destruction per bromine atom to that per chlorine atom (alpha-factor) ranges from 33 to 55, decreasing with increase of bromine.

EOS CHEM: A Mission to Study Ozone and Climate

NASA Technical Reports Server (NTRS)

Schoeberl, Mark

1998-01-01

The Earth's stratosphere contains the ozone layer, which shields us from the Sun@ harmful ultraviolet (UV) radiation. Ozone is destroyed through chemical reactions involving natural and man-made nitrogen, hydrogen, bromine, and chlorine compounds. The release of chlorofluoro-carbons CFCs) has caused a dramatic decrease in the protective stratospheric ozone layer during the last two decades. Detection of stratospheric ozone depletion led to regulation and phase-out of CFC production worldwide. As a result, man-made chlorine levels in the atmosphere are slowly beginning to decrease. CHEM will be able to determine whether the stratospheric ozone layer is now recovering, as predicted by scientific models.

Using Iron to Treat Chlorohydrocarbon-Contaminated Soil

NASA Technical Reports Server (NTRS)

Hitchens, G. Duncan; Hodko, Dalibor; Kim, Heekyung; Rogers, Tom; Singh, Waheguru Pal; Giletto, Anthony; Cisar, Alan

2004-01-01

A method of in situ remediation of soil contaminated with chlorinated hydrocarbon solvents involves injection of nanometer-size iron particles. The present method exploits a combination of prompt chemical remediation followed by longer-term enhanced bioremediation and, optionally, is practiced in conjunction with the method of bioremediation described earlier. Newly injected iron particles chemically reduce chlorinated hydrocarbons upon contact. Thereafter, in the presence of groundwater, the particles slowly corrode via chemical reactions that effect sustained release of dissolved hydrogen. The hydrogen serves as an electron donor, increasing the metabolic activity of the anaerobic bacteria and thereby sustaining bioremediation at a rate higher than the natural rate.

Heterogeneous Reaction gaseous chlorine nitrate and solid sodium chloride

NASA Technical Reports Server (NTRS)

Timonen, Raimo S.; Chu, Liang T.; Leu, Ming-Taun

1994-01-01

The heterogeneous reaction of gaseous chlorine nitrate and solid sodium chloride was investigated over a temperature range of 220 - 300 K in a flow-tube reactor interfaced with a differentially pumped quadrupole mass spectrometer.

Rapid plasma quenching for the production of ultrafine metal and ceramic powders

NASA Astrophysics Data System (ADS)

Donaldson, Alan; Cordes, Ronald A.

2005-04-01

The rapid plasma quench concept used to produce ultrafine titanium hydride, magnesium, and aluminum powders involves the thermal dissociation of liquid reactants into gaseous components followed by rapid quenching of the products of the subject reaction to prevent back reactions. For example, in the case of titanium hydride powder production, titanium tetrachloride dissociates into titanium and chlorine atoms at 5,000 K. Expansion through a Delaval nozzle accelerates the gas to supersonic speed, cooling it very rapidly at rates as high as 710 K/s. Injected hydrogen reacts with condensed titanium particles to form titanium hydride and with the chlorine to form hydrogen chloride. Titanium powder has been produced at 20 kg/h in a continuous reactor. Costs are projected to be lower than the Kroll process at a sufficiently large scale. Magnesium and aluminum production based upon the rapid plasma quench concept are also discussed.

Chlorine isotope fractionation between chloride (Cl-) and dichlorine (Cl2)

NASA Astrophysics Data System (ADS)

Giunta, Thomas; Labidi, Jabrane; Eggenkamp, Hans G. M.

2017-09-01

The use of chlorine stable isotopes (35Cl and 37Cl) can help to constrain natural processes that involve chlorine species with different oxidation states. Theoretical studies based on thermodynamic and quantum mechanical approaches predict large isotope fractionation during redox reactions but to date, these reactions have not been studied experimentally. Here, we explore the chlorine isotope fractionation during the oxidation of hydrated Cl- (redox state of -I) to Cl2 (redox state of 0) at 25 °C and at 0 °C. Our apparatus consists of a sealed glass reactor where liquid HCl is mixed with liquid H2O2, a strong oxidant. Following complex reaction pathways, this mixture ultimately leads to the oxidation of Cl- and to the formation of Cl2 gas. As long as it is degassing, the Cl2 gas is flushed out of solution using N2 as a vector-gas from the glass-reactor to a potassium hydroxide (KOH) solution (pH 14) where it disproportionates into soluble species: Cl- and ClO-. After each experiment, the chlorine isotopic composition was measured in the recovered KOH-trap solution, as well as in the residual HCl solution. Consistent with theoretical predictions, the produced Cl2 gas is always enriched in the heavier 37Cl as compared to the initial Cl-reservoir. The following isotope fractionation factors are obtained: At 0 °C the isotopic fractionation 1000ln α(Cl2-Cl-) is 4.51 (+1.65/-0.49)‰ At 25 °C the isotopic fractionation 1000ln α(Cl2-Cl-) is 3.94 (+0.69/-0.18)‰. From the obtained data it is suggested that the production of Cl2 gas in our experiments is best described by a closed-system distillation. Our results are in agreement with published theoretical ab-initio calculations.

Aromatic fluorine compounds. VI. Displacement of aryl fluorine in diazonium salts

USGS Publications Warehouse

Finger, G.C.; Oesterling, R.E.

1956-01-01

Several chlorofluorobenzenes have been isolated from the Schiemann synthesis of fluorobenzenes. These have been shown to be the products of two side reactions occurring during thermal decomposition of the dry benzenediazonium fluoborate salt containing coprecipitated sodium chloride, an unavoidable contaminant in large preparations involving the use of hydrochloric acid and sodium fluoborate. The major side reaction and its chloro product were unexpected; a unique displacement of fluorine ortho to the diazonium group was observed. Replacement of the diazo group with chlorine was the predicted side reaction which proved to be minor. Conditions causing the side reactions and the isolation and identification of the products are described.

Palliative effects of H2 on SOFCs operating with carbon containing fuels

NASA Astrophysics Data System (ADS)

Reeping, Kyle W.; Bohn, Jessie M.; Walker, Robert A.

2017-12-01

Chlorine can accelerate degradation of solid oxide fuel cell (SOFC) Ni-based anodes operating on carbon containing fuels through several different mechanisms. However, supplementing the fuel with a small percentage of excess molecular hydrogen effectively masks the degradation to the catalytic activity of the Ni and carbon fuel cracking reaction reactions. Experiments described in this work explore the chemistry behind the "palliative" effect of hydrogen on SOFCs operating with chlorine-contaminated, carbon-containing fuels using a suite of independent, complementary techniques. Operando Raman spectroscopy is used to monitor carbon accumulation and, by inference, Ni catalytic activity while electrochemical techniques including electrochemical impedance spectroscopy and voltammetry are used to monitor overall cell performance. Briefly, hydrogen not only completely hides degradation observed with chlorine-contaminated carbon-containing fuels, but also actively removes adsorbed chlorine from the surface of the Ni, allowing for the methane cracking reaction to continue, albeit at a slower rate. When hydrogen is removed from the fuel stream the cell fails immediately due to chlorine occupation of methane/biogas reaction sites.

[Comparative evaluation of health hazards associated with industrial chemicals and their derivates forming during water chlorination].

PubMed

Zholdakova, Z I; Poliakova, E E; Lebedev, A T

2006-01-01

Many industrial chemicals found in waste waters are able to form organochlorine by-products during water disinfection. The transformation of seven model compounds, cyclohexene, n-butanol, diphenylmethane, acetophenone, aniline, 1-methylnaphthalene, and phenylxylylethane during a reaction with active chlorine was studied. Aqueous chlorine and sodium hypochlorite were used as chlorinating agents. The products of the reaction were analyzed by means of chromatomass-spectrometry. A schematic model of diphenylmethane transformation was proposed. Comparative evaluation of hazards associated with the model chemicals and their derivates confirmed that chlorination products can be more toxic and dangerous than the initial compounds, and may possess mutagenic and cancerigenic properties.

A covalent modification for graphene by adamantane groups through two-step chlorination-Grignard reactions

NASA Astrophysics Data System (ADS)

Sun, Xuzhuo; Li, Bo; Lu, Mingxia

2017-07-01

Chemical modification of graphene is a promising approach to manipulate its properties for its end applications. Herein we designed a two-step route through chlorination-Grignard reactions to covalently decorate the surface of graphene with adamantane groups. The chemically modified graphene was characterized by Raman spectroscopy, atomic force microscopy, and X-ray photoelectron spectroscopy. Chlorination of graphene occurred rapidly, and the substitution of chlorine atoms on chlorinated graphene by adamantane Grignard reagent afforded adamantane graphene in almost quantitative yield. Adamantane groups were found to be covalently bonded to the graphene carbons. The present two-step procedure may provide an effective and facile route for graphene modification with varieties of organic functional groups.

Imidazole catalyzes chlorination by unreactive primary chloramines

PubMed Central

Roemeling, Margo D.; Williams, Jared; Beckman, Joseph S.; Hurst, James K.

2015-01-01

Hypochlorous acid and simple chloramines (RNHCl) are stable biologically-derived chlorinating agents. In general, the chlorination potential of HOCl is much greater than that of RNHCl, allowing it to oxidize or chlorinate a much wider variety of reaction partners. However, in this study we demonstrate by kinetic analysis that the reactivity of RNHCl can be dramatically promoted by imidazole and histidyl model compounds via intermediary formation of the corresponding imidazole chloramines. Two biologically relevant reactions were investigated—loss of imidazole-catalyzed chlorinating capacity and phenolic ring chlorination using fluorescein and the tyrosine analog, 4-hydroxyphenylacetic acid (HPA). HOCl reacted stoichiometrically with imidazole, N-acetylhistidine (NAH), or imidazoleacetic acid to generate the corresponding imidazole chloramines which subsequently decomposed. Chloramine (NH2Cl) also underwent a markedly accelerated loss in chlorinating capacity when NAH was present, although in this case NAHCl did not accumulate, indicating that the catalytic intermediate must be highly reactive. Mixing HOCl with 1-methylimidazole (MeIm) led to very rapid loss in chlorinating capacity via formation of a highly reactive chlorinium ion (MeImCl+) intermediate; this behavior suggests that the reactive forms of the analogous imidazole chloramines are their conjugate acids, e.g., the imidazolechlorinium ion (HImCl+). HOCl-generated imidazole chloramine (ImCl) reacted rapidly with fluorescein in a specific acid-catalyzed second order reaction to give 3′-monochloro and 3′,5′-dichloro products. Equilibrium constants for the transchlorination reactions: HOCl + HIm = H2O + ImCl and NH2Cl + HIm = NH3 + ImCl were estimated from the dependence of the rate constants upon [HIm]/[HOCl] and literature data. Acid catalysis again suggests that the actual chlorinating agent is HImCl+; consistent with this interpretation, MeIm markedly catalyzed fluorescein chlorination by HOCl. Time-dependent imidazole-catalyzed HPA chlorination by NH2Cl was also demonstrated by product analyses. Quantitative assessment of the data suggests that physiological levels of histidyl groups will react with primary chloramines to generate a flux of imidazole chloramine sufficient to catalyze biological chlorination via HImCl+, particularly in environments that generate high concentrations of HOCl such as the neutrophil phagosome. PMID:25660996

Triple-element compound-specific stable isotope analysis of 1,2-dichloroethane for characterization of the underlying dehalogenation reaction in two Dehalococcoides mccartyi strains.

PubMed

Franke, Steffi; Lihl, Christina; Renpenning, Julian; Elsner, Martin; Nijenhuis, Ivonne

2017-12-01

Chlorinated ethanes belong to the most common groundwater and soil contaminants. Of these, 1,2-dichloroethane (1,2-DCA) is a man-made, persistent and toxic contaminant, released due to improper waste treatment at versatile production sites. This study investigated the anaerobic transformation of 1,2-DCA by Dehalococcoides mccartyi strain 195 and strain BTF08 using triple-element compound-specific stable isotope analysis of carbon, chlorine and hydrogen for the first time. Isotope fractionation patterns for carbon (εCBTF08 = -28.4 ± 3.7‰; εC195 = -30.9 ± 3.6‰) and chlorine (εClBTF08 = -4.6 ± 0.7‰; εCl195 = -4.2 ± 0.5‰) within both investigated D. mccartyi strains, as well as the dual-element analysis (ΛBTF08 = 6.9 ± 1.2; Λ195 = 7.1 ± 0.2), supported identical reaction mechanisms for dehalogenation of 1,2-DCA. Hydrogen isotope fractionation analysis revealed dihaloelimination as prevalent reaction mechanism. Vinyl chloride as major intermediate could be excluded by performing the experiment in deuterated aqueous media. Furthermore, evaluation of the derived apparent kinetic isotope effects (AKIECBTF08 = 1.029/AKIEC195 = 1.031; AKIEClBTF08 = 1.005/AKIECl195 = 1.004) pointed towards simultaneous abstraction of both involved chlorine-substituents in a concerted matter. It was shown that D. mccartyi strain BTF08 and strain 195 are capable of complete, direct dihaloelimination of 1,2-DCA to ethene. © FEMS 2017. All rights reserved. For permissions, please e-mail: journals.permissions@oup.com.

Reaction of benzophenone UV filters in the presence of aqueous chlorine: kinetics and chloroform formation.

PubMed

Duirk, Stephen E; Bridenstine, David R; Leslie, Daniel C

2013-02-01

The transformation of two benzophenone UV filters (Oxybenzone and Dioxybenzone) was examined over the pH range 6-11 in the presence of excess aqueous chlorine. Under these conditions, both UV filters were rapidly transformed by aqueous chlorine just above circumneutral pH while transformation rates were significantly lower near the extremes of the pH range investigated. Observed first-order rate coefficients (k(obs)) were obtained at each pH for aqueous chlorine concentrations ranging from 10 to 75 μM. The k(obs) were used to determine the apparent second-order rate coefficient (k(app)) at each pH investigated as well as determine the reaction order of aqueous chlorine with each UV filter. The reaction of aqueous chlorine with either UV filter was found to be an overall second-order reaction, first-order with respect to each reactant. Assuming elemental stoichiometry described the reaction between aqueous chlorine and each UV filter, models were developed to determine intrinsic rate coefficients (k(int)) from the k(app) as a function of pH for both UV filters. The rate coefficients for the reaction of HOCl with 3-methoxyphenol moieties of oxybenzone (OXY) and dioxybenzone (DiOXY) were k(1,OxY) = 306 ± 81 M⁻¹s⁻¹ and k(1,DiOxY) = 154 ± 76 M⁻¹s⁻¹, respectively. The k(int) for the reaction of aqueous chlorine with the 3-methoxyphenolate forms were orders of magnitude greater than the un-ionized species, k(2,OxY) = 1.03(±0.52) × 10⁶ M⁻¹s⁻¹ and k(2_1,DiOxY) = 4.14(±0.68) × 10⁵ M⁻¹s⁻¹. Also, k(int) for the reaction of aqueous chlorine with the DiOXY ortho-substituted phenolate moiety was k(2_2,DiOxY) = 2.17(±0.30) × 10³ M⁻¹s⁻¹. Finally, chloroform formation potential for OXY and DiOXY was assessed over the pH range 6-10. While chloroform formation decreased as pH increased for OXY, chloroform formation increased as pH increased from 6 to 10 for DiOXY. Ultimate molar yields of chloroform per mole of UV filter were pH dependent; however, chloroform to UV filter molar yields at pH 8 were 0.221 CHCl₃/OXY and 0.212 CHCl₃/DiOXY. Copyright © 2012 Elsevier Ltd. All rights reserved.

Role of drinking water biofilms on residual chlorine decay and trihalomethane formation: An experimental and modeling study.

PubMed

Xu, Jianeng; Huang, Conghui; Shi, Xiaoyang; Dong, Shengkun; Yuan, Baoling; Nguyen, Thanh H

2018-06-13

PVC pipe loops were constructed to simulate household premise plumbing. These pipe loops were exposed to water treated by physical processes at three water treatment plants in Xiamen, China from August 2016 to June 2017. After the biofilms were allowed to develop inside the pipes, these pipes were deconstructed and exposed to organic-free chlorine solution buffered at pH 6.8 ± 0.2 for 48 h. The decay of chlorine by these biofilms was higher than by the effluent waters that were used to grow the biofilms. A chlorine consumption mass balance model elucidated the role of both the diffusion of chlorine into the biofilm and the reaction of chlorine with the biofilm matrix. Comparable concentrations of trihalomethanes were quantified from the reaction between chlorine and source water organic matters, and chlorine and the biofilm, further emphasizing the role of biofilms in the safety of disinfected drinking water. These findings imply that when chlorine is used in the drinking water distribution system, the ubiquitous presence of biofilms may cause the depletion of chlorine and the formation of non-negligible levels of toxic disinfection byproducts. Copyright © 2018 Elsevier B.V. All rights reserved.

PHOTOCHEMICAL REACTIONS AMONG FORMALDEHYDE, CHLORINE, AND NITROGEN DIOXIDE IN AIR

EPA Science Inventory

Photochemical reactions among chlorine, nitrogen dioxide, and formaldehyde were studied, using parts-per-million concentrations in 1 atm of air. The reactant mixtures were irradiated by ultraviolet fluorescent lamps and simultaneously analyzed by the Fourier transform infrared te...

Degradation of Nicotine in Chlorinated Water: Pathways and ...

EPA Pesticide Factsheets

Report The objective of the study is to illustrate how drinking water would affect alkaloid pesticides, and to address the issue by (a) investigating the fate of nicotine in chlorinated drinking water and deionized water, (b) determining the reaction rate and pathway of the reaction between nicotine and aqueous chlorine, (c) identifying nicotine’s degradation products, and (d) providing data that can be used to assess the potential threat from nicotine in drinking water.

Chlorination of tramadol: Reaction kinetics, mechanism and genotoxicity evaluation.

PubMed

Cheng, Hanyang; Song, Dean; Chang, Yangyang; Liu, Huijuan; Qu, Jiuhui

2015-12-01

Tramadol (TRA) is one of the most detected analgesics in environmental matrices, and it is of high significance to study the reactivity of TRA during chlorination considering its potential toxicity to the environment. The chlorine/TRA reaction is first order with respect to the TRA concentration, and a combination of first-order and second-order with respect to chlorine concentration. The pH dependence of the observed rate constants (kobs) showed that the TRA oxidation reactivity increased with increasing pH. kobs can be quantitatively described by considering all active species including Cl2, Cl2O and HOCl, and the individual rate constants of HOCl/TRA(0), HOCl/TRAH(+), Cl2/TRA and Cl2O/TRA reactions were calculated to be (2.61±0.29)×10(3)M(-1)s(-1), 14.73±4.17M(-1)s(-1), (3.93±0.34)×10(5)M(-1)s(-1) and (5.66±1.83)×10(6)M(-1)s(-1), respectively. Eleven degradation products were detected with UPLC-Q-TOF-MS, and the corresponding structures of eight products found under various pH conditions were proposed. The amine group was proposed to be the initial attack site under alkaline pH conditions, where reaction of the deprotonated amine group with HOCl is favorable. Under acidic and neutral pH conditions, however, two possible reaction pathways were proposed. One is an electrophilic substitution on the aromatic ring, and another is an electrophilic substitution on the nitrogen, leading to an N-chlorinated intermediate, which can be further oxidized. Finally, the SOS/umu test showed that the genotoxicity of TRA chlorination products increased with increasing dosage of chlorine, which was mostly attributed to the formation of some chlorine substitution products. Copyright © 2015 Elsevier Ltd. All rights reserved.

Theoretical study of the kinetics of chlorine atom abstraction from chloromethanes by atomic chlorine.

PubMed

Brudnik, Katarzyna; Twarda, Maria; Sarzyński, Dariusz; Jodkowski, Jerzy T

2013-10-01

Ab initio calculations at the G3 level were used in a theoretical description of the kinetics and mechanism of the chlorine abstraction reactions from mono-, di-, tri- and tetra-chloromethane by chlorine atoms. The calculated profiles of the potential energy surface of the reaction systems show that the mechanism of the studied reactions is complex and the Cl-abstraction proceeds via the formation of intermediate complexes. The multi-step reaction mechanism consists of two elementary steps in the case of CCl4 + Cl, and three for the other reactions. Rate constants were calculated using the theoretical method based on the RRKM theory and the simplified version of the statistical adiabatic channel model. The temperature dependencies of the calculated rate constants can be expressed, in temperature range of 200-3,000 K as [Formula: see text]. The rate constants for the reverse reactions CH3/CH2Cl/CHCl2/CCl3 + Cl2 were calculated via the equilibrium constants derived theoretically. The kinetic equations [Formula: see text] allow a very good description of the reaction kinetics. The derived expressions are a substantial supplement to the kinetic data necessary to describe and model the complex gas-phase reactions of importance in combustion and atmospheric chemistry.

Antarctic stratospheric chemistry of chlorine nitrate, hydrogen chloride, and ice - Release of active chlorine

NASA Technical Reports Server (NTRS)

Molina, Mario J.; Tso, Tai-Ly; Molina, Luisa T.; Wang, Frank C.-Y.

1987-01-01

The reaction rate between atmospheric hydrogen chloride (HCl) and chlorine nitrate (ClONO2) is greatly enhanced in the presence of ice particles; HCl dissolves readily into ice, and the collisional reaction probability for ClONO2 on the surface of ice with HCl in the mole fraction range from about 0.003 to 0.010 is in the range from about 0.05 to 0.1 for temperatures near 200 K. Chlorine is released into the gas phase on a time scale of at most a few milliseconds, whereas nitric acid (HNO3), the other product, remains in the condensed phase. This reaction could play an important role in explaining the observed depletion of ozone over Antarctica; it releases photolytically active chlorine from its most abundant reservoir species, and it promotes the formation of HNO3 and thus removes nitrogen dioxide from the gas phase. Hence it establishes the necessary conditions for the efficient catalytic destruction of ozone by halogenated free radicals.

Dechlorination and Decolorization of Organics in Bleach Plant E-1 Effluent by Photochemical Processes

NASA Astrophysics Data System (ADS)

Xie, Tianyan

1994-01-01

Photochemical study of the dechlorination of four model compounds, 4,5-dichloroguaiacol, 2,4,6-trichlorophenol, 2,3,4,5-tetrachlorophenol, and tetrachloroguaiacol in aqueous solutions under UV radiation was conducted using ArF (193 nm) and KrF (248 nm) excimer laser to explore the response of chlorinated phenolics present in the E_1 effluent from conventional chlorine bleaching of softwood kraft pulp towards photo-oxidation processes. Kinetic study show that the overall dechlorination reaction follow the first order rate law. The factors affecting the dechlorination were investigated. The quantum yield of chloride ion formation was found to be dependent on pH of the reaction mixture, and orignal chlorine content of the compounds. The effect of the substituents on the aromatic ring on the reactivity of the compounds was studied. The mechanism for the dechlorination was proposed involving homolytic photo-dissociation, heterolytic cleavage of carbon-chlorine bonds and substitution reactions of hydroxyl radicals. It was found that the dechlorination under formation to chloride is influenced by the amount of organically bound chlorine in the starting material. Dechlorination reaction favors high pH. Guaiacols more easily undergo dechlorination than phenols. Four fractions of high relative molecular-mass chloro-organics or polychlorinated oxylignin (PCOL) were isolated from an E_1 effluent by combination of ultrafiltration, and purified by repeated precipitation. The fractions were analysed by classical functional group analysis and spectrophotometric methods. The analytical data indicated that the major structural differences between PCOL fractions and kraft lignin preparations are with regard to the content of founctional groups such as carboxyl content, methoxyl and hydroxyl contents. In addition, IR, ^1H and ^{13 }C NMR spectral analyses revealed an almost complete absence of absorption attributable to aromatic structures in PCOLs. These results and others led to the conclusion that the PCOL fractions are comprised mainly of non-aromatic lignin oxidation products containing a considerable amount of organically bound chlorine as well as unsaturated aliphatic carbon bonded to either oxygen or chlorine. The PCOL fractions were subjected to 193 nm UV -Excimer laser photolysis in presence and absence of oxygen with and without hydrogen peroxide. Kinetic study showed that they readily undergo dechlorination and decolorization on UV ArF-excimer laser (193 nm) photolysis under both oxygen and nitrogen atmosphere. About 60% dechlorination could be achieved by 3 hours irradiation. However, the relative molecular-mass of the PCOL fractions were not changed during the photolysis. Addition of small amount (2-8% w/w) of hydrogen peroxide lead to a signifiant reduction of color and relative molecular-mass. Thus, hydrogen peroxide play very important role in degradation and decolorization of PCOLs. The possible reaction mechanism for the UV-Excimer laser photolysis of PCOLs are discussed on the basis of the observed results.

Adsorption of phenolic compound by aged-refuse.

PubMed

Xiaoli, Chai; Youcai, Zhao

2006-09-01

The adsorption of phenol, 2-chlorophenol, 4-chlorophenol and 2,4-dichlorophenol by aged-refuse has been studied. Adsorption isotherms have been determined for phenol, 2-chlorophenol, 4-chlorophenol and 2,4-dichlorophenol and the data fits well to the Freundlich equation. The chlorinated phenols are absorbed more strongly than the phenol and the adsorption capacity has an oblivious relationship with the numbers and the position of chlorine subsistent. The experiment data suggests that both the partition function and the chemical adsorption involve in the adsorption process. Pseudo-first-order and pseudo-second-order model were applied to investigate the kinetics of the adsorption and the results show that it fit the pseudo-second-order model. More than one step involves in the adsorption process and the overall rate of the adsorption process appears to be controlled by the chemical reaction. The thermodynamic analysis indicates that the adsorption is spontaneous and endothermic.

Formation kinetics of gemfibrozil chlorination reaction products: analysis and application.

PubMed

Krkosek, Wendy H; Peldszus, Sigrid; Huck, Peter M; Gagnon, Graham A

2014-07-01

Aqueous chlorination kinetics of the lipid regulator gemfibrozil and the formation of reaction products were investigated in deionized water over the pH range 3 to 9, and in two wastewater matrices. Chlorine oxidation of gemfibrozil was found to be highly dependent on pH. No statistically significant degradation of gemfibrozil was observed at pH values greater than 7. Gemfibrozil oxidation between pH 4 and 7 was best represented by first order kinetics. At pH 3, formation of three reaction products was observed. 4'-C1Gem was the only reaction product formed from pH 4-7 and was modeled with zero order kinetics. Chlorine oxidation of gemfibrozil in two wastewater matrices followed second order kinetics. 4'-C1Gem was only formed in wastewater with pH below 7. Deionized water rate kinetic models were applied to two wastewater effluents with gemfibrozil concentrations reported in literature in order to calculate potential mass loading rates of 4'C1Gem to the receiving water.

Absolute rate of the reaction of Cl(p-2) with molecular hydrogen from 200 - 500 K

NASA Technical Reports Server (NTRS)

Whytock, D. A.; Lee, J. H.; Michael, J. V.; Payne, W. A.; Stief, L. J.

1976-01-01

Rate constants for the reaction of atomic chlorine with hydrogen are measured from 200 - 500 K using the flash photolysis-resonance fluorescence technique. The results are compared with previous work and are discussed with particular reference to the equilibrium constant for the reaction and to relative rate data for chlorine atom reactions. Theoretical calculations, using the BEBO method with tunneling, give excellent agreement with experiment.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lei, Yu; Liu, Bin; Lu, Junling

The effect of residue chlorine on the synthesis of well-dispersed Pd nanoparticles on TiO2 supports using Pd atomic layer deposition (ALD) was investigated. The dispersion of Pd nanoparticles was compared over chlorine-containing and chlorine-free TiO2 supports prepared by selecting proper precursors. The detailed X-ray photoelectron spectroscopy and scanning transmission electron microscopy characterizations showed that higher dispersion of Pd nanoparticles was achieved on the chlorine-containing TiO2 surface than the chlorine-free TiO2. The preparation of TiO2 thin films and Pd nanoparticles was characterized by in situ FT-IR. The temperature required for complete deligation of palladium hexafluoroacetylacetonate decreased from 175 to 100 degreesmore » C with the presence of chlorine on the TiO2 surface. Density functional theory calculations confirm that Pdligand bond strength could be weakened as Pd binds to the Cl sites. The water-gas-shift reaction was chosen as the model reaction, and the catalytic performance of the ALD Pd catalysts was discussed. Compared to reported catalysts, the Pd nanocatalysts supported by TiO2/SiO2 mixed oxides showed promising performance in the low-temperature water-gas-shift reaction.« less

Aqueous chlorination of mefenamic acid: kinetics, transformation by-products and ecotoxicity assessment.

PubMed

Adira Wan Khalit, Wan Nor; Tay, Kheng Soo

2016-05-18

Mefenamic acid (Mfe) is one of the most frequently detected nonsteroidal anti-inflammatory drugs in the environment. This study investigated the kinetics and the transformation by-products of Mfe during aqueous chlorination. The potential ecotoxicity of the transformation by-products was also evaluated. In the kinetic study, the second-order rate constant (kapp) for the reaction between Mfe and free available chlorine (FAC) was determined at 25 ± 0.1 °C. The result indicated that the degradation of Mfe by FAC is highly pH-dependent. When the pH was increased from 6 to 8, it was found that the kapp for the reaction between Mfe and FAC was decreased from 16.44 to 4.4 M(-1) s(-1). Characterization of the transformation by-products formed during the chlorination of Mfe was carried out using liquid chromatography-quadrupole time-of-flight accurate mass spectrometry. Four major transformation by-products were identified. These transformation by-products were mainly formed through hydroxylation, chlorination and oxidation reactions. Ecotoxicity assessment revealed that transformation by-products, particularly monohydroxylated Mfe which is more toxic than Mfe, can be formed during aqueous chlorination.

Indium-catalyzed direct chlorination of alcohols using chlorodimethylsilane-benzil as a selective and mild system.

PubMed

Yasuda, Makoto; Yamasaki, Satoshi; Onishi, Yoshiyuki; Baba, Akio

2004-06-16

The InCl3-catalyzed reaction of alcohols with chlorodimethylsilane (HSiMe2Cl) in the presence of benzil gave the corresponding organic chlorides under mild conditions. Benzil significantly changes the reaction course because the reducing product through dehydroxyhydration was obtained in the absence of benzil. The secondary or tertiary alcohols were effectively chlorinated. The substrates bearing acid-sensitive functional groups were also applied to this system. The highly selective chlorination of the tertiary site was observed in the competitive reaction between tertiary and primary alcohols. The highly coordinated hydrosilane generated from benzil and HSiMe2Cl is an important intermediate.

Monte Carlo analysis of uncertainty propagation in a stratospheric model. 2: Uncertainties due to reaction rates

NASA Technical Reports Server (NTRS)

Stolarski, R. S.; Butler, D. M.; Rundel, R. D.

1977-01-01

A concise stratospheric model was used in a Monte-Carlo analysis of the propagation of reaction rate uncertainties through the calculation of an ozone perturbation due to the addition of chlorine. Two thousand Monte-Carlo cases were run with 55 reaction rates being varied. Excellent convergence was obtained in the output distributions because the model is sensitive to the uncertainties in only about 10 reactions. For a 1 ppby chlorine perturbation added to a 1.5 ppby chlorine background, the resultant 1 sigma uncertainty on the ozone perturbation is a factor of 1.69 on the high side and 1.80 on the low side. The corresponding 2 sigma factors are 2.86 and 3.23. Results are also given for the uncertainties, due to reaction rates, in the ambient concentrations of stratospheric species.

Degradation of Organic UV filters in Chlorinated Seawater Swimming Pools: Transformation Pathways and Bromoform Formation.

PubMed

Manasfi, Tarek; Coulomb, Bruno; Ravier, Sylvain; Boudenne, Jean-Luc

2017-12-05

Organic ultraviolet (UV) filters are used in sunscreens and other personal-care products to protect against harmful effects of exposure to UV solar radiation. Little is known about the fate of UV filters in seawater swimming pools disinfected with chlorine. The present study investigated the occurrence and fate of five commonly used organic UV filters, namely dioxybenzone, oxybenzone, avobenzone, 2-ethylhexyl-4-methoxycinnamate, and octocrylene, in chlorinated seawater swimming pools. Pool samples were collected to monitor the variation of UV filter concentrations during pool opening hours. Furthermore, laboratory-controlled chlorination experiments were conducted in seawater spiked with UV filters to investigate the reactivity of UV filters. Extracts of chlorination reaction samples were analyzed using high-resolution mass spectrometry and electron-capture detection to identify the potentially formed byproducts. In the collected pool samples, all the UV filters except dioxybenzone were detected. Chlorination reactions showed that only octocrylene was stable in chlorinated seawater. The four reactive UV filters generated brominated transformation products and disinfection byproducts. This formation of brominated products resulted from reactions between the reactive UV filters and bromine, which is formed rapidly when chlorine is added to seawater. Based on the identified byproducts, the transformation pathways of the reactive UV filters were proposed for the first time. Bromoform was generated by all the reactive UV filters at different yields. Bromal hydrate was also detected as one of the byproducts generated by oxybenzone and dioxybenzone.

Anaerobic reductive dechlorination of tetrachloroethene: how can dual Carbon-Chlorine isotopic measurements help elucidating the underlying reaction mechanism?

NASA Astrophysics Data System (ADS)

Badin, Alice; Buttet, Géraldine; Maillard, Julien; Holliger, Christof; Hunkeler, Daniel

2014-05-01

Chlorinated ethenes (CEs) such as tetrachloroethene (PCE) are common persistent groundwater contaminants. Among clean-up strategies applied to sites affected by such pollution, bioremediation has been considered with a growing interest as it represents a cost-effective, environmental friendly approach. This technique however sometimes leads to an incomplete and slow biodegradation of CEs resulting in an accumulation of toxic metabolites. Understanding the reaction mechanisms underlying anaerobic reductive dechlorination would thus help assessing PCE biodegradation in polluted sites. Stable isotope analysis can provide insight into reaction mechanisms. For chlorinated hydrocarbons, carbon (C) and chlorine (Cl) isotope data (δ13C and δ37Cl) tend to show a linear correlation with a slope (m ≡ ɛC/ɛCl) characteristic of the reaction mechanism [1]. This study hence aims at exploring the potential of a dual C-Cl isotope approach in the determination of the reaction mechanisms involved in PCE reductive dechlorination. C and Cl isotope fractionation were investigated during anaerobic PCE dechlorination by two bacterial consortia containing members of the Sulfurospirillum genus. The specificity in these consortia resides in the fact that they each conduct PCE reductive dechlorination catalysed by one different reductive dehalogenase, i.e. PceADCE which yields trichloroethene (TCE) and cis-dichloroethene (cDCE), and PceATCE which yields TCE only. The bulk C isotope enrichment factors were -3.6±0.3 o for PceATCE and -0.7±0.1o for PceADCE. The bulk Cl isotope enrichment factors were -1.3±0.2 o for PceATCE and -0.9±0.1 o for PceADCE. When applying the dual isotope approach, two m values of 2.7±0.1 and 0.7±0.2 were obtained for the reductive dehalogenases PceATCE and PceADCE, respectively. These results suggest that PCE can be degraded according to two different mechanisms. Furthermore, despite their highly similar protein sequences, each reductive dehalogenase seems to catalyse PCE reductive dechlorination according to a different mechanism. In another study, an m value of 2.5±0.8 was found for PCE anaerobic dechlorination by a bacterial consortium dominated by species closely related to Desulfitobacterium aromaticivorans strain UKTL (consortia A) [2]. This value is indistinguishable from the one found for PceATCE within a 95% confidence interval although the reductive dehalogenase protein sequence of consortia A is distinctly different from the sequences of our two cultures. This suggests that the reaction mechanism is not related to the similarities between reductive dehalogenases. References 1. Abe, Y., et al., Carbon and Chlorine Isotope Fractionation during Aerobic Oxidation and Reductive Dechlorination of Vinyl Chloride and cis-1,2-Dichloroethene. Environmental Science & Technology, 2009. 43(1): p. 101-107. 2. Wiegert, C., et al., Carbon and Chlorine Isotope Fractionation During Microbial Degradation of Tetra- and Trichloroethene. Environmental Science & Technology, 2013. 47(12): p. 6449-6456.

Concentration-dependence of the explosion characteristics of chlorine dioxide gas.

PubMed

Jin, Ri-ya; Hu, Shuang-qi; Zhang, Yin-ghao; Bo, Tao

2009-07-30

The explosion characteristics of chlorine dioxide gas have been studied for the first time in a cylindrical exploder with a shell capacity of 20 L. The experimental results have indicated that the lower concentration limit for the explosive decomposition of chlorine dioxide gas is 9.5% ([ClO(2)]/[air]), whereas there is no corresponding upper concentration limit. Under the experimental conditions, and within the explosion limits, the pressure of explosion increases with increasing concentration of chlorine dioxide gas; the maximum pressure of explosion relative to the initial pressure was measured as 0.024 MPa at 10% ClO(2) and 0.641 MPa at 90% ClO(2). The induction time (the time from the moment of sparking to explosion) has also been found to depend on the concentration of chlorine dioxide gas; thus, at 10% ClO(2) the induction time was 2195 ms, but at 90% ClO(2) the induction time was just 8 ms. The explosion reaction mechanism of ClO(2) is of a degenerate chain-branching type involving the formation of a stable intermediate (Cl(2)O(3)), from which the chain-branching occurs. Chain initiation takes place at the point of ignition and termination takes place at the inner walls of the exploder.

Atmospheric reactivity of alcohols, thiols and fluoroalcohols with chlorine atoms

NASA Astrophysics Data System (ADS)

Garzon Ruiz, Andres

Alcohols, thiols and fluoroalcohols are volatile organic compounds (VOCs) which are emitted to the atmosphere from both natural (vegetation, oceans, volcanoes, etc.) and anthropogenic sources (fuels, solvents, wastewater, incinerators, refrigerants, etc.). These pollutants can be eliminated from the troposphere by deposition on the terrestrial surface, direct photolysis or reaction with different tropospheric oxidants. Reactions of VOCs with tropospheric oxidants are involved in the well-known atmospheric phenomenon of photochemical smog or the production of tropospheric ozone. The oxidation of these VOCs in the troposphere is mainly initiated by reaction with OH radicals during the daytime and with NO radicals at night. However, in recent years, the oxidation by chlorine atoms (Cl) has gained great importance in the study of atmospheric reactions because they may exert some influence in the boundary layer, particularly in marine and coastal environments. In general, Cl atoms are much more reactive species than OH and NO; radicals and therefore low concentrations of Cl may compete with OH and NO3 in hydrocarbon oxidation processes. The main source of tropospheric Cl atoms is believed to be the photolysis of chlorine-containing molecules generated by heterogeneous reactions of sea salt aerosols. It has also been proposed that Cl atoms, produced in the photolysis of Cl2 emitted from industrial processes, may enhance hydrocarbon oxidation rates and ozone production in urban environments. In this work, a kinetic, theoretical and mechanistic study of the reaction of several alcohols, thiols, and fluoroalcohols with Cl atoms has been carried out. Pulsed laser photolysis-fluorescence resonance (PLP-RF) technique was used for the kinetic study as a function of temperature and pressure. An environmental chamber-Fourier transform infrared (FTIR) system was also employed in the kinetic studies. Tropospheric lifetimes of these pollutants were estimated using obtained kinetic data. Products of these reactions were determined by FTIR and derivatization with 2,4-dinitrophenylhydrazine and HPLC analysis. Finally, in order to determine the main reaction pathways a theoretical study at QCISD(T)/6-311G**//MP2(Full)(6-311C** level was performed for each reaction.

BROMIDE-OXIDANT INTERACTIONS AND THM (TRIHALOMETHANE) FORMATION: A LITERATURE REVIEW

EPA Science Inventory

The review focuses on the interactions, not only of bromide and chlorine, but also of bromide and two common oxidation alternatives to chlorine--chlorine dioxide and monochloramine. The data evaluations include discussions of reaction products, potentials for trihalomethane (THM)...

The stability of chlorinated, brominated, and iodinated haloacetamides in drinking water.

PubMed

Ding, Shunke; Chu, Wenhai; Krasner, Stuart W; Yu, Yun; Fang, Chao; Xu, Bin; Gao, Naiyun

2018-06-13

Haloacetamides (HAMs), a group of nitrogenous disinfection byproducts (N-DBPs), can decompose to form corresponding intermediate products and other DBPs. The stability of ten different HAMs, including two chlorinated, five brominated, and three iodinated species was investigated with and without the presence of chlorine, chloramines, and reactive solutes such as quenching agents. The HAM basic hydrolysis and chlorination kinetics were well described by a second-order kinetics model, including first-order in HAM and hydroxide and first-order in HAM and hypochlorite, respectively, whereas the HAM neutral hydrolysis kinetic was first-order in HAM. Furthermore, HAMs decompose instantaneously when exposed to hypochlorite, which was almost two and nine orders of magnitude faster than HAM basic and neutral hydrolysis, respectively. In general, HAM hydrolysis and chlorination rates both increased with increasing pH and the number of halogens substituted on the methyl group. Moreover, chlorinated HAMs are more unstable than their brominated analogs, followed by the iodinated ones, due to the decrease in the electron-withdrawing inductive effect from chlorine to iodine atom. During hydrolysis, HAMs mainly directly decompose into the corresponding haloacetic acids (HAAs) via a nucleophilic reaction between the carbonyl carbon and hydroxide. For HAM chlorination reactions, hypochlorite reacts with HAMs to form the N-chloro-HAMs (N-Cl-HAMs) via Cl + transfer from chlorine to the amide nitrogen. N-Cl-HAMs can further degrade to form HAAs via hypochlorous acid addition. In contrast, the reactions between chloramines and HAMs were found to be insignificant. Additionally, four common quenching agents, including sodium sulfite, sodium thiosulfate, ascorbic acid, and ammonium chloride, were demonstrated to expedite HAM degradation, whereas ammonium chloride was the least influential among the four. Taft linear free energy relationships were established for both HAM hydrolysis and chlorination reactions, based on which the hydrolysis and chlorination rate constants for three monohaloacetamides were estimated. The hydrolysis and chlorination rates of 13 HAMs decreased in the following order: TCAM > BDCAM > DBCAM > TBAM > DCAM > BCAM > DBAM > CIAM > BIAM > DIAM > MCAM > MBAM > MIAM (where C = chloro, B = bromo, I = iodo, T = tri, D = di, M = mono). Lastly, using the HAM kinetic model established in this study, HAM half-lifes in drinking water distribution systems can be predicted on the basis of pH and residual chlorine concentration. Copyright © 2018 Elsevier Ltd. All rights reserved.

ABIOTIC REACTIONS MAY BE THE MOST IMPORTANT MECHANISM IN NATURAL ATTENUATION OF CHLORINATED SOLVENTS

EPA Science Inventory

The EPA Technical Protocol for Evaluating Natural Attenuation of Chlorinated Solvents in Ground Water was developed with the assumption that natural biological reductive dechlorination was the only important mechanism for destruction of chlorinated solvents and their reduction ...

Surey of Alternate Stored Chemical Energy Reactions.

DTIC Science & Technology

1985-12-01

Fr., Report No. CEA-N-1293, 36 p. Pilipovich. D.; Rogers, H. H. and Wilson, R. D., 1972, Chlorine trifluoride oxide. II. Photochemical synthesis...some fluorine and chlorine compounds: Zh. Fiz. Khim., V. 43, No. 2, p. 386-9. Rogers, H. H. and Pilipovich, D., 1973, Oxychlorine trifluoride (Patent...chemical energy reactions has been made for purposes of comparison with the lithium- aluminum /water, lithium/sulfur hexafluoride, and other reaction schemes

Clay-catalyzed reactions of coagulant polymers during water chlorination

USGS Publications Warehouse

Lee, J.-F.; Liao, P.-M.; Lee, C.-K.; Chao, H.-P.; Peng, C.-L.; Chiou, C.T.

2004-01-01

The influence of suspended clay/solid particles on organic-coagulant reactions during water chlorination was investigated by analyses of total product formation potential (TPFP) and disinfection by-product (DBP) distribution as a function of exchanged clay cation, coagulant organic polymer, and reaction time. Montmorillonite clays appeared to act as a catalytic center where the reaction between adsorbed polymer and disinfectant (chlorine) was mediated closely by the exchanged clay cation. The transition-metal cations in clays catalyzed more effectively than other cations the reactions between a coagulant polymer and chlorine, forming a large number of volatile DBPs. The relative catalytic effects of clays/solids followed the order Ti-Mont > Fe-Mont > Cu-Mont > Mn-Mont > Ca-Mont > Na-Mont > quartz > talc. The effects of coagulant polymers on TPFP follow the order nonionic polymer > anionic polymer > cationic polymer. The catalytic role of the clay cation was further confirmed by the observed inhibition in DBP formation when strong chelating agents (o-phenanthroline and ethylenediamine) were added to the clay suspension. Moreover, in the presence of clays, total DBPs increased appreciably when either the reaction time or the amount of the added clay or coagulant polymer increased. For volatile DBPs, the formation of halogenated methanes was usually time-dependent, with chloroform and dichloromethane showing the greatest dependence. ?? 2003 Elsevier Inc. All rights reserved.

REACTION PRODUCTS FROM THE CHLORINATION OF SEAWATER. CHAPTER 34

EPA Science Inventory

Much of the present information on the products formed when seawater is chlorinated is based on observations of laboratory experiments in which chlorine was added to seawater to stimulate conditions of electricity generating plants. Results are reported for a field study at the P...

MERCURY REACTIONS IN THE PRESENCE OF CHLORINE SPECIES: HOMOGENOUS GAS PHASE AND HETEROGENOUS GAS-SOLID PHASE

EPA Science Inventory

The kinetics of mercury chlorination (with HC1) were studied using a flow reactor system with an on-line Hg analyzer and spciation sampling using a set of impingers. Kinetic parameters, such as reaction order (a), activation energy (Eu) and the overall rate constant (k') were es...

[Genotoxicity of drinking water during chlorine and chloramine disinfection and the influence of disinfection conditions using the umu-test].

PubMed

Liu, Qing; Zhang, Li-Ping; Liu, Wen-Jun; Nie, Xue-Biao; Zhang, Su-Xia; Zhang, Shun

2010-01-01

In this study, the effects of disinfectant dosage, reaction time and the ratio of Cl2 to N of disinfectant on genotoxicity of effluent of ozone-biological activated carbon (O3-BAC) during chlorine or chloramine disinfection were investigated using umu-test. It was found that, the genotoxicity of effluent of O3-BAC before disinfection ranged from 20-70 ng/L, and it increased after disinfection by chlorine or chloramines. With the same reaction time(24 h), genotoxicity after chlorination (40-95 ng/L) was higher than that after chloramination (20-40 ng/L) under same initial dosage. For chlorination, with initial dosage increasing from 0 mg/L to 10 mg/L, genotoxicity increased firstly, and got the maximum value at about 0.5-1 mg/L dosage, then decreased and got the minimum value at about 3-5 mg/L dosage, and finally increased again. For chloramination, genotoxicity didn't change that much. With the dosage of 3 mg/L and reaction time increasing from 0 h to 72 h, no matter for chlorine or chloramines disinfection, genotoxicity of effluent of O3-BAC both increased firstly, and got the maximum value at about 2 h, then decreased and got the minimum value at about 18 h, and finally increased again, and genotoxicity after chlorine disinfection (83-120 ng/L) was higher than that after chloramines disinfection (20-62 ng/L) under same reaction time. Further more, effects of the different ratios of Cl2 to N of disinfectant on genotoxicity of effluent of O3-BAC were also studied. Results of this study demonstrate that under test conditions, chloramine disinfection is safer than chlorine disinfection in the aspect of genotoxicity for drinking water, and the changes of genotoxicity are different from those of total HAAs.

The Antarctic Ozone Hole: An Update

NASA Technical Reports Server (NTRS)

Douglass, Anne R.; Newman, Paul A.; Solomon, Susan

2014-01-01

The stratospheric ozone hole, an annual occurrence during austral spring, is caused by heterogeneous conversion of hydrogen chloride and chlorine nitrate to chlorine radicals. These reactions take place of polar stratospheric cloud particles in the cold, isolate Antarctic winter vortex. The chlorine radicals participate in chemical reactions that rapidly deplete ozone when sunlight returns at the end of polar night. International agreements eliminated production of the culprit anthropogenic chlorofluorocarbons in the late 1990s, but due to their long stratospheric lifetime (50-100 years), the ozone hole will continue its annual appearance for years to come.

OZONE PRODUCTION FROM IRRADIATION OF ACETYLENE/CHLORINE MIXTURES IN AIR

EPA Science Inventory

The reaction of chlorine radicals with acetylene in air in the absence of oxides of nitrogen result In the formation of ozone. o ozone is observed when chlorine radicals react with methylacetylene or ethylacetylene under similar conditions. ormyl chloride is observed in all syste...

Determination of Etch Rate Behavior of 4H-SiC Using Chlorine Trifluoride Gas

NASA Astrophysics Data System (ADS)

Miura, Yutaka; Habuka, Hitoshi; Katsumi, Yusuke; Oda, Satoko; Fukai, Yasushi; Fukae, Katsuya; Kato, Tomohisa; Okumura, Hajime; Arai, Kazuo

2007-12-01

The etch rate of single-crystalline 4H-SiC is studied using chlorine trifluoride gas at 673-973 K and atmospheric pressure in a cold wall horizontal reactor. The 4H-SiC etch rate can be higher than 10 μm/min at substrate temperatures higher than 723 K. The etch rate increases with the chlorine trifluoride gas flow rate. The etch rate is calculated by taking into account the transport phenomena in the reactor including the chemical reaction at the substrate surface. The flat etch rate at the higher substrate temperatures is caused mainly by the relationship between the transport rate and the surface chemical reaction rate of chlorine trifluoride gas.

Experimental and Theoretical Studies of Atmosphereic Inorganic Chlorine Chemistry

NASA Technical Reports Server (NTRS)

Sander, Stanley P.; Friedl, Randall R.

1993-01-01

Over the last five years substantial progress has been made in defining the realm of new chlorine chemistry in the polar stratosphere. Application of existing experimental techniques to potentially important chlorine-containing compounds has yielded quantitative kinetic and spectroscopic data as well as qualitative mechanistic insights into the relevant reactions.

EFFECT OF THE DECHLORINATING AGENT, ASCORBIC ACID, ON THE MUTAGENICITY OF CHLORINATED WATER SAMPLES

EPA Science Inventory

XAD resin adsorption has been widely used to concentrate the organic compounds present in chlorinated drinking waters prior to mutagenicity testing. Previous work has shown that mutagenic artifcats can arise due to the reaction of residual chlorine with the resins. Althrough the ...

NON-BIOLOGICAL REACTIONS MAY BE AN IMPORTANT MECHANISM FOR NATURAL ATTENUATION OF CHLORINATED SOLVENTS

EPA Science Inventory

The role of non-biological transformation of chlorinated solvents was not considered in the U.S. EPA Technical Protocol for Evaluating Natural Attenuation of Chlorinated Solvents in Ground Water. This deficiency became very apparent when U.S. EPA conducted a beta test of the Pro...

REACTIONS OF CHLORINE IN DRINKING WATER, WITH HUMIC ACIDS AND 'IN VIVO'

EPA Science Inventory

The use of chlorine as a drinking water disinfectant is known to produce a variety of chlorinated and oxidized derivatives of organic matter present in the source water. Humic substances, which represent the major fraction of the organic matter in natural waters, have been shown ...

Reactivity of chlorine radical with submicron palmitic acid particles: kinetic measurements and products identification

NASA Astrophysics Data System (ADS)

Mendez, M.; Ciuraru, R.; Gosselin, S.; Batut, S.; Visez, N.; Petitprez, D.

2013-06-01

The heterogeneous reaction of Cl. radicals with sub-micron palmitic acid (PA) particles was studied in an aerosol flow tube in the presence or in the absence of O2. Fine particles were generated by homogeneous condensation of PA vapors and introduced in the reactor where chlorine atoms are produced by photolysis of Cl2 using UV lamps surrounding the reactor. The effective reactive uptake coefficient (γ) has been determined from the rate loss of PA measured by GC/MS analysis of reacted particles as a function of the chlorine exposure. In the absence of O2, γ = 14 ± 5 indicates efficient secondary chemistry involving Cl2. GC/MS analyses have shown the formation of monochlorinated and polychlorinated compounds in the oxidized particles. Although, the PA particles are solid, the complete mass can be consumed. In the presence of oxygen, the reaction is still dominated by secondary chemistry but the propagation chain length is smaller than in the absence of O2 which leads to an uptake coefficient γ = 3 ± 1. In the particulate phase, oxocarboxylic acids and dicarboxylic acids are identified by GC/MS. Formation of alcohols and monocarboxylic acids are also suspected. All these results show that solid organic particles could be efficiently oxidized by gas-phase radicals not only on their surface, but also in bulk by mechanisms which are still unclear. Furthermore the identified reaction products are explained by a chemical mechanism showing the pathway of the formation of more functionalized products. They help to understand the aging of primary tropospheric aerosol containing fatty acids.

Reactivity of chlorine radical with submicron palmitic acid particles: kinetic measurements and product identification

NASA Astrophysics Data System (ADS)

Mendez, M.; Ciuraru, R.; Gosselin, S.; Batut, S.; Visez, N.; Petitprez, D.

2013-12-01

The heterogeneous reaction of Cl• radicals with submicron palmitic acid (PA) particles was studied in an aerosol flow tube in the presence or in the absence of O2. Fine particles were generated by homogeneous condensation of PA vapours and introduced into the reactor, where chlorine atoms were produced by photolysis of Cl2 using UV lamps surrounding the reactor. The effective reactive uptake coefficient (γ) has been determined from the rate loss of PA measured by gas chromatography-mass spectrometer (GC/MS) analysis of reacted particles as a function of the chlorine exposure. In the absence of O2, γ = 14 ± 5 indicates efficient secondary chemistry involving Cl2. GC/MS analysis has shown the formation of monochlorinated and polychlorinated compounds in the oxidized particles. Although the PA particles are solid, the complete mass can be consumed. In the presence of oxygen, the reaction is still dominated by secondary chemistry but the propagation chain length is smaller than in the absence of O2, which leads to an uptake coefficient γ = 3 ± 1. In the particulate phase, oxocarboxylic acids and dicarboxylic acids were identified by GC/MS. The formation of alcohols and monocarboxylic acids is also suspected. A reaction pathway for the main products and more functionalized species is proposed. All these results show that solid organic particles could be efficiently oxidized by gas-phase radicals not only on their surface but also in bulk by mechanisms which are still unclear. They help to understand the aging of primary tropospheric aerosol containing fatty acids.

Degradation of DEET and Caffeine under UV/Chlorine and Simulated Sunlight/Chlorine Conditions.

PubMed

Sun, Peizhe; Lee, Wan-Ning; Zhang, Ruochun; Huang, Ching-Hua

2016-12-20

Photoactivation of aqueous chlorine could promote degradation of chlorine-resistant and photochemically stable chemicals accumulated in swimming pools. This study investigated the degradation of two such chemicals, N,N-diethyl-3-methylbenzamide (DEET) and caffeine, by low pressure ultraviolet (UV) light and simulated sunlight (SS) activated free chlorine (FC) in different water matrices. Both DEET and caffeine were rapidly degraded by UV/FC and SS/FC but exhibited different kinetic behaviors. The degradation of DEET followed pseudo-first-order kinetics, whereas the degradation of caffeine accelerated with reaction. Mechanistic study revealed that, under UV/FC, ·OH and Cl· were responsible for degradation of DEET, whereas ClO· related reactive species (ClOrrs), generated by the reaction between FC and ·OH/Cl·, played a major role in addition to ·OH and Cl· in degrading caffeine. Reaction rate constants of DEET and caffeine with the respective radical species were estimated. The imidazole moiety of caffeine was critical for the special reactivity with ClOrrs. Water matrix such as pH had a stronger impact on the UV/FC process than the SS/FC process. In saltwater matrix under UV/FC and SS/FC, the degradation of DEET was significantly inhibited, but the degradation of caffeine was much faster than that in nonsalty solutions. The interaction between Br - and Cl - may play an important role in the degradation of caffeine by UV/FC in saltwater. Reaction product analysis showed similar product patterns by UV/FC and SS/FC and minimal formation of chlorinated intermediates and disinfection byproducts.

Modification of heterogeneous chemistry by complex substrate morphology

DOE Office of Scientific and Technical Information (OSTI.GOV)

Henson, B.F.; Buelow, S.J.; Robinson, J.M.

1998-12-31

This is the final report of a one-year, Laboratory Directed Research and Development (LDRD) project at Los Alamos National Laboratory (LANL). Chemistry in many environmental systems is determined at some stage by heterogeneous reaction with a surface. Typically the surface exists as a dispersion or matrix of particulate matter or pores, and a determination of the heterogeneous chemistry of the system must address the extent to which the complexity of the environmental surface affects the reaction rates. Reactions that are of current interest are the series of chlorine nitrate reactions important in polar ozone depletion. The authors have applied surfacemore » spectroscopic techniques developed at LANL to address the chemistry of chlorine nitrate reactions on porous nitric and sulfuric acid ice surfaces as a model study of the measurement of complex, heterogeneous reaction rates. The result of the study is an experimental determination of the surface coverage of one adsorbed reagent and a mechanism of reactivity based on the dependence of this coverage on temperature and vapor pressure. The resulting mechanism allows the first comprehensive modeling of chlorine nitrate reaction probability data from several laboratories.« less

EFFECT OF HUMIC CONSTITUENTS ON THE TRANSFORMATION OF CHLORINATED PHENOLS AND ANILINES IN THE PRESENCE OF OXIDOREDUCTIVE ENZYMES OR BIRNESSITE. (R823847)

EPA Science Inventory

Chlorinated phenols and anilines are transformed and detoxified in soil
through oxidative coupling reactions mediated by enzymes or metal oxides. The
reactions may be influenced by humic constituents, such as syringaldehyde or
catechol, that originate from lignin d...

ASCORBIC ACID REDUCTION OF ACTIVE CHLORINE PRIOR TO DETERMINING AMES MUTAGENICITY OF CHLORINATED NATURAL ORGANIC MATTER (NOM)

EPA Science Inventory

Many potable water disinfection byproducts (DBPs) that result from the reaction of natural organic matter (NOM) with oxidizing chlorine are known or suspected to be carcinogenic and mutagenic. The Ames assay is routinely used to assess an overall level of mutagenicity for all com...

Method for the synthesis of chlorosilanes

DOEpatents

Wheeler, D.R.; Pollagi, T.P.

1999-08-17

A novel method is described for the synthesis of chlorinated or partially chlorinated organosilanes and organopolysilanes. The chlorination is effected by contacting an organosilanes or organopolysilanes with anhydrous CuCl{sub 2} in a nonpolar alkane solvent, preferably pentane or hexadecane, without the use of a catalyst. Copper metal, which is easily filtered, is a reaction product. The filtrate containing the chlorinated organosilane or organopolysilane can be used directly as a reactant to produce, for example, aminoorganosilanes.

Method for the synthesis of chlorosilanes

DOEpatents

Wheeler, David R.; Pollagi, Timothy P.

1999-01-01

A novel method for the synthesis of chlorinated or partially chlorinated organosilanes and organopolysilanes. The chlorination is effected by contacting an organosilanes or organopolysilanes with anhydrous CuCl.sub.2 in a nonpolar alkane solvent, preferably pentane or hexadecane, without the use of a catalyst. Copper metal, which is easily filtered, is a reaction product. The filtrate containing the chlorinated organosilane or organopolysilane can be used directly as a reactant to produce, for example, aminoorganosilanes.

Biological reduction of chlorinated solvents: Batch-scale geochemical modeling

NASA Astrophysics Data System (ADS)

Kouznetsova, Irina; Mao, Xiaomin; Robinson, Clare; Barry, D. A.; Gerhard, Jason I.; McCarty, Perry L.

2010-09-01

Simulation of biodegradation of chlorinated solvents in dense non-aqueous phase liquid (DNAPL) source zones requires a model that accounts for the complexity of processes involved and that is consistent with available laboratory studies. This paper describes such a comprehensive modeling framework that includes microbially mediated degradation processes, microbial population growth and decay, geochemical reactions, as well as interphase mass transfer processes such as DNAPL dissolution, gas formation and mineral precipitation/dissolution. All these processes can be in equilibrium or kinetically controlled. A batch modeling example was presented where the degradation of trichloroethene (TCE) and its byproducts and concomitant reactions (e.g., electron donor fermentation, sulfate reduction, pH buffering by calcite dissolution) were simulated. Local and global sensitivity analysis techniques were applied to delineate the dominant model parameters and processes. Sensitivity analysis indicated that accurate values for parameters related to dichloroethene (DCE) and vinyl chloride (VC) degradation (i.e., DCE and VC maximum utilization rates, yield due to DCE utilization, decay rate for DCE/VC dechlorinators) are important for prediction of the overall dechlorination time. These parameters influence the maximum growth rate of the DCE and VC dechlorinating microorganisms and, thus, the time required for a small initial population to reach a sufficient concentration to significantly affect the overall rate of dechlorination. Self-inhibition of chlorinated ethenes at high concentrations and natural buffering provided by the sediment were also shown to significantly influence the dechlorination time. Furthermore, the analysis indicated that the rates of the competing, nonchlorinated electron-accepting processes relative to the dechlorination kinetics also affect the overall dechlorination time. Results demonstrated that the model developed is a flexible research tool that is able to provide valuable insight into the fundamental processes and their complex interactions during bioremediation of chlorinated ethenes in DNAPL source zones.

Boron-doped diamond electrooxidation of ethyl paraben: The effect of electrolyte on by-products distribution and mechanisms.

PubMed

Frontistis, Zacharias; Antonopoulou, Maria; Yazirdagi, Melis; Kilinc, Zeynep; Konstantinou, Ioannis; Katsaounis, Alexandros; Mantzavinos, Dionissios

2017-06-15

Ethyl paraben (EP), a representative emerging pollutant of the parabens family, was subject to electrochemical oxidation over a boron-doped diamond (BDD) anode. Experiments were carried out in a single-compartment cell at 10-70 mA cm -2 current density, 200-600 μg L -1 EP concentration, initial solution pH 3-9 and 0.1 M electrolyte concentration. The degradation rate is favored at increased current densities and in the presence of NaCl as the supporting electrolyte, while the pH effect is inconsiderable. For instance, the first order rate constant for the degradation of 200 μg L -1 EP at 30 mA cm -2 was 0.25, 0.1 and 0.07 min -1 with NaCl, Na 2 SO 4 and HClO 4 , respectively. Degradation in secondary treated wastewater was faster than in pure water presumably due to the action of chloride ions present in the effluent. Liquid chromatography time-of-flight mass spectrometry (LC-TOF-MS) was employed to determine major transformation by-products (TBPs). The route of EP degradation with Na 2 SO 4 involves hydroxylation and demethylation reactions, signifying the role of electrogenerated hydroxyl radicals in the process. Twenty one TBPs were identified with NaCl as the electrolyte, including several chlorinated and non-chlorinated dimers and trimers; these findings suggest that indirect oxidation mediated by chlorine radicals and other chlorine active species also takes place. In this view, the role of the supporting electrolyte is crucial since it can influence both reaction kinetics and pathways. Copyright © 2016 Elsevier Ltd. All rights reserved.

Development of a chlorine chemistry module for the Master Chemical Mechanism

NASA Astrophysics Data System (ADS)

Xue, L. K.; Saunders, S. M.; Wang, T.; Gao, R.; Wang, X. F.; Zhang, Q. Z.; Wang, W. X.

2015-06-01

The chlorine atom (Cl·) has a high potential to perturb atmospheric photochemistry by oxidizing volatile organic compounds (VOCs), but the exact role it plays in the polluted troposphere remains unclear. The Master Chemical Mechanism (MCM) is a near explicit mechanism that has been widely applied in the atmospheric chemistry research. While it addresses comprehensively the chemistry initiated by the OH, O3 and NO3 radicals, its representation of the Cl· chemistry is incomplete as it only considers the reactions for alkanes. In this paper, we develop a more comprehensive Cl· chemistry module that can be directly incorporated within the MCM framework. A suite of 199 chemical reactions describes the Cl·-initiated degradation of alkenes, aromatics, aldehydes, ketones, alcohols, and some organic acids and nitrates, along with the inorganic chemistry involving Cl· and its precursors. To demonstrate the potential influence of the new chemistry module, it was incorporated into a MCM box model to evaluate the impacts of nitryl chloride (ClNO2), a product of nocturnal halogen activation by nitrogen oxides (NOx), on the following-day's atmospheric photochemistry. With constraints of recent observations collected at a coastal site in Hong Kong, southern China, the modeling analyses suggest that the Cl· produced from ClNO2 photolysis may substantially enhance the atmospheric oxidative capacity, VOC oxidation, and O3 formation, particularly in the early morning period. The results demonstrate the critical need for photochemical models to include more fully chlorine chemistry in order to better understand the atmospheric photochemistry in polluted environments subject to intense emissions of NOx, VOCs and chlorine-containing constituents.

Development of a chlorine chemistry module for the Master Chemical Mechanism

NASA Astrophysics Data System (ADS)

Xue, L. K.; Saunders, S. M.; Wang, T.; Gao, R.; Wang, X. F.; Zhang, Q. Z.; Wang, W. X.

2015-10-01

The chlorine atom (Cl·) has a high potential to perturb atmospheric photochemistry by oxidizing volatile organic compounds (VOCs), but the exact role it plays in the polluted troposphere remains unclear. The Master Chemical Mechanism (MCM) is a near-explicit mechanism that has been widely applied in the atmospheric chemistry research. While it addresses comprehensively the chemistry initiated by the OH, O3 and NO3 radicals, its representation of the Cl· chemistry is incomplete as it only considers the reactions for alkanes. In this paper, we develop a more comprehensive Cl· chemistry module that can be directly incorporated within the MCM framework. A suite of 205 chemical reactions describes the Cl·-initiated degradation of alkenes, aromatics, alkynes, aldehydes, ketones, alcohols, and some organic acids and nitrates, along with the inorganic chemistry involving Cl· and its precursors. To demonstrate the potential influence of the new chemistry module, it was incorporated into a MCM box model to evaluate the impacts of nitryl chloride (ClNO2), a product of nocturnal halogen activation by nitrogen oxides (NOX), on the following day's atmospheric photochemistry. With constraints of recent observations collected at a coastal site in Hong Kong, southern China, the modeling analyses suggest that the Cl· produced from ClNO2 photolysis may substantially enhance the atmospheric oxidative capacity, VOC oxidation and O3 formation, particularly in the early morning period. The results demonstrate the critical need for photochemical models to include more detailed chlorine chemistry in order to better understand the atmospheric photochemistry in polluted environments subject to intense emissions of NOX, VOCs and chlorine-containing constituents.

Higher modulus compositions incorporating particulate rubber

DOEpatents

Bauman, B.D.; Williams, M.A.; Bagheri, R.

1997-12-02

Rubber particles, to be used as fillers or extenders for various composite polymer systems, are chlorinated by a gas-solid phase reaction with a chlorine-containing gas. A composite polymer containing the chlorinated rubber fillers or extenders exhibits a higher flexural modulus than if prepared using an unchlorinated rubber filler or extender. Chlorination of the rubber particles is carried out by contacting the finely divided rubber particles with a chlorine-containing gas comprising at least about 5 volume percent chlorine. Advantageously, the chlorine can be diluted with air, nitrogen or other essentially inert gases and may contain minor amounts of fluorine. Improved performance is obtained with nitrogen dilution of the chlorine gas over air dilution. Improved polymer composite systems having higher flexural modulus result from the use of the chlorinated rubber particles as fillers instead of unchlorinated rubber particles. 2 figs.

Higher modulus compositions incorporating particulate rubber

DOEpatents

McInnis, E.L.; Scharff, R.P.; Bauman, B.D.; Williams, M.A.

1995-01-17

Rubber particles, to be used as fillers or extenders for various composite polymer systems, are chlorinated by a gas-solid phase reaction with a chlorine-containing gas. A composite polymer containing the chlorinated rubber fillers or extenders exhibits a higher flexural modulus than if prepared using an unchlorinated rubber filler or extender. Chlorination of the rubber particles is carried out by contacting the finely divided rubber particles with a chlorine-containing gas comprising at least about 5 volume percent chlorine. Advantageously, the chlorine can be diluted with air, nitrogen or other essentially inert gases and may contain minor amounts of fluorine. Improved performance is obtained with nitrogen dilution of the chlorine gas over air dilution. Improved polymer composite systems having higher flexural modulus result from the use of the chlorinated rubber particles as fillers instead of unchlorinated rubber particles. 2 figures.

Higher modulus compositions incorporating particulate rubber

DOEpatents

McInnis, E.L.; Bauman, B.D.; Williams, M.A.

1996-04-09

Rubber particles, to be used as fillers or extenders for various composite polymer systems, are chlorinated by a gas-solid phase reaction with a chlorine-containing gas. A composite polymer containing the chlorinated rubber fillers or extenders exhibits a higher flexural modulus than if prepared using an unchlorinated rubber filler or extender. Chlorination of the rubber particles is carried out by contacting the finely divided rubber particles with a chlorine-containing gas comprising at least about 5 volume percent chlorine. Advantageously, the chlorine can be diluted with air, nitrogen or other essentially inert gases and may contain minor amounts of fluorine. Improved performance is obtained with nitrogen dilution of the chlorine gas over air dilution. Improved polymer composite systems having higher flexural modulus result from the use of the chlorinated rubber particles as fillers instead of unchlorinated rubber particles. 2 figs.

Atmospheric origins of perchlorate on Mars and in the Atacama

NASA Astrophysics Data System (ADS)

Catling, D. C.; Claire, M. W.; Zahnle, K. J.; Quinn, R. C.; Clark, B. C.; Hecht, M. H.; Kounaves, S.

2010-01-01

Isotopic studies indicate that natural perchlorate is produced on Earth in arid environments by the oxidation of chlorine species through pathways involving ozone or its photochemical products. With this analogy, we propose that the arid environment on Mars may have given rise to perchlorate through the action of atmospheric oxidants. A variety of hypothetical pathways can be proposed including photochemical reactions, electrostatic discharge, and gas-solid reactions. Because perchlorate-rich deposits in the Atacama desert are closest in abundance to perchlorate measured at NASA's Phoenix Lander site, we made a preliminary study of the means to produce Atacama perchlorate to help shed light on the origin of Martian perchlorate. We investigated gas phase pathways using a 1-D photochemical model. We found that perchlorate can be produced in sufficient quantities to explain the abundance of perchlorate in the Atacama from a proposed gas phase oxidation of chlorine volatiles to perchloric acid. The feasibility of gas phase production for the Atacama provides justification for future investigations of gas phase photochemistry as a possible source for Martian perchlorate.

Citric Acid-Modified Fenton's Reaction for the Oxidation of Chlorinated Ethylenes in Soil Solution Systems

DOE Office of Scientific and Technical Information (OSTI.GOV)

Seol, Yongkoo; Javandel, Iraj

Fenton's reagent, a solution of hydrogen peroxide and ferrous iron catalyst, is used for an in-situ chemical oxidation of organic contaminants. Sulfuric acid is commonly used to create an acidic condition needed for catalytic oxidation. Fenton's reaction often involves pressure buildup and precipitation of reaction products, which can cause safety hazards and diminish efficiency. We selected citric acid, a food-grade substance, as an acidifying agent to evaluate its efficiencies for organic contaminant removal in Fenton's reaction, and examined the impacts of using citric acid on the unwanted reaction products. A series of batch and column experiments were performed with varyingmore » H{sub 2}O{sub 2} concentrations to decompose selected chlorinated ethylenes. Either dissolved iron from soil or iron sulfate salt was added to provide the iron catalyst in the batch tests. Batch experiments revealed that both citric and sulfuric acid systems achieved over 90% contaminant removal rates, and the presence of iron catalyst was essential for effective decontamination. Batch tests with citric acid showed no signs of pressure accumulation and solid precipitations, however the results suggested that an excessive usage of H{sub 2}O{sub 2} relative to iron catalysts (Fe{sup 2+}/H{sub 2}O{sub 2} < 1/330) would result in lowering the efficiency of contaminant removal by iron chelations in the citric acid system. Column tests confirmed that citric acid could provide suitable acidic conditions to achieve higher than 55% contaminant removal rates.« less

Citric acid-modified Fenton's reaction for the oxidation of chlorinated ethylenes in soil solution systems.

PubMed

Seol, Yongkoo; Javandel, Iraj

2008-06-01

Fenton's reagent, a solution of hydrogen peroxide and ferrous iron catalyst, is used for an in situ chemical oxidation of organic contaminants. Sulfuric acid is commonly used to create an acidic condition needed for catalytic oxidation. Fenton's reaction often involves pressure buildup and precipitation of reaction products, which can cause safety hazards and diminish efficiency. We selected citric acid, a food-grade substance, as an acidifying agent to evaluate its efficiencies for organic contaminant removal in Fenton's reaction, and examined the impacts of using citric acid on the unwanted reaction products. A series of batch and column experiments were performed with varying H2O2 concentrations to decompose selected chlorinated ethylenes. Either dissolved iron from soil or iron sulfate salt was added to provide the iron catalyst in the batch tests. Batch experiments revealed that both citric and sulfuric acid systems achieved over 90% contaminant removal rates, and the presence of iron catalyst was essential for effective decontamination. Batch tests with citric acid showed no signs of pressure accumulation and solid precipitations, however the results suggested that an excessive usage of H2O2 relative to iron catalysts (Fe2+/H2O2<1/330) would result in lowering the efficiency of contaminant removal by iron chelation in the citric acid system. Column tests confirmed that citric acid could provide suitable acidic conditions to achieve higher than 55% contaminant removal rates.

Metabolism and mutagenicity of halogenated olefins--a comparison of structure and activity.

PubMed Central

Henschler, D

1977-01-01

Chlorinated ethylenes are metabolized in mammals, as a first step, to epoxides. The fate of these electrophilic intermediates may be reaction with nucleophiles (alkylation), hydrolysis, or intramolecular rearrangement. The latter reaction has been studied in the whole series of chlorinated epoxiethanes. The rearrangement products found were: acyl chlorides (tetrachloro-, trichloro-, and 1,1-dichloroethylenes), or chlorinated aldehydes (1,2-dichloroethylenes, cis- and trans-, vinyl chloride). The metabolities found in vivo are identical with, or further derivatives of these rearrangment products, with one important exception: trichloroethylene. With this compound, in vivo rearrangement yields chloral exclusively. The mechanism of the different rearrangement has been identified as a Lewis acid catalysis. All chlorinated ethylenes have been investigated in a tissue-mediated mutagenicity testing system. The prominent molecular feature of those with mutagenic effects (trichloro-, 1,1-dichloro-, and monochloroethylene) is unsymmetric chlorine substitution which renders the epoxides unstable, whereas symmetric substitution confers relative stability and nonmutagenic property. PMID:348459

Impact of water quality on chlorine demand of corroding copper.

PubMed

Lytle, Darren A; Liggett, Jennifer

2016-04-01

Copper is widely used in drinking water premise plumbing system materials. In buildings such as hospitals, large and complicated plumbing networks make it difficult to maintain good water quality. Sustaining safe disinfectant residuals throughout a building to protect against waterborne pathogens such as Legionella is particularly challenging since copper and other reactive distribution system materials can exert considerable demands. The objective of this work was to evaluate the impact of pH and orthophosphate on the consumption of free chlorine associated with corroding copper pipes over time. A copper test-loop pilot system was used to control test conditions and systematically meet the study objectives. Chlorine consumption trends attributed to abiotic reactions with copper over time were different for each pH condition tested, and the total amount of chlorine consumed over the test runs increased with increasing pH. Orthophosphate eliminated chlorine consumption trends with elapsed time (i.e., chlorine demand was consistent across entire test runs). Orthophosphate also greatly reduced the total amount of chlorine consumed over the test runs. Interestingly, the total amount of chlorine consumed and the consumption rate were not pH dependent when orthophosphate was present. The findings reflect the complex and competing reactions at the copper pipe wall including corrosion, oxidation of Cu(I) minerals and ions, and possible oxidation of Cu(II) minerals, and the change in chlorine species all as a function of pH. The work has practical applications for maintaining chlorine residuals in premise plumbing drinking water systems including large buildings such as hospitals. Published by Elsevier Ltd.

Mass Spectrometry Identification of N-Chlorinated Dipeptides in Drinking Water.

PubMed

Huang, Guang; Jiang, Ping; Li, Xing-Fang

2017-04-04

We report the identification of N-chlorinated dipeptides as chlorination products in drinking water using complementary high-resolution quadrupole time-of-flight (QTOF) and quadrupole ion-trap mass spectrometry techniques. First, three model dipeptides, tyrosylglycine (Tyr-Gly), tyrosylalanine (Tyr-Ala), and phenylalanylglycine (Phe-Gly), reacted with sodium hypochlorite, and these reaction solutions were analyzed by QTOF. N-Cl-Tyr-Gly, N,N-di-Cl-Tyr-Gly, N-Cl-Phe-Gly, N,N-di-Cl-Phe-Gly, N-Cl-Tyr-Ala, and N,N-di-Cl-Tyr-Ala were identified as the major products based on accurate masses, 35 Cl/ 37 Cl isotopic patterns, and MS/MS spectra. These identified N-chlorinated dipeptides were synthesized and found to be stable in water over 10 days except N,N-di-Cl-Phe-Gly. To enable sensitive detection of N-chlorinated dipeptides in authentic water, we developed a high-performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS) method with multiple reaction monitoring (MRM) mode. N-Cl-Tyr-Gly, N,N-di-Cl-Tyr-Gly, N-Cl-Phe-Gly, N-Cl-Tyr-Ala, and N,N-di-Cl-Tyr-Ala along with their corresponding dipeptides were detected in authentic tap water samples. The dipeptides were clearly detected in the raw water, but the N-chlorinated dipeptides were at background levels. These results suggest that the N-chlorinated dipeptides are produced by chlorination. This study has identified N-chlorinated dipeptides as new disinfection byproducts in drinking water. The strategy developed in this study can be used to identify chlorination products of other peptides in drinking water.

Advanced Valve Technology. Volume 2. Materials Compatibility and Liquid Propellant Study

DTIC Science & Technology

1967-11-01

hydrogen fluoride and hydrogen chloride, which are formed by the reaction of chlorine trifluoride with water. Aluminum alloys, 18-8 stainless steels... CHLORINE TRIFLUORIDE (CTF) (ClF3) 1-68 CHLORINE PENTAFLUORIDE 1-72 OXYGEN DIFLUORIDE (OF2) 1-74 PERCHLORYL FLUORIDE (PF) (FC103 or C103F) 1-79...enclosures refer to the Propellant Rating Chart, Page 1-11. 1-67 SPACE STORABLE PROPELLANTS (Continued) OXIDIZERS CHLORINE TRIFLUORIDE (CTF) (CIF 3

Reactive Minerals and Dechlorinating Communities: Mechanisms Governing the Degradation of Chlorinated Ethenes during Back Diffusion from Low Permeability Zones in Aerobic and Anaerobic Environments

NASA Astrophysics Data System (ADS)

Berns, E. C.; Zeng, R.; Singh, H.; Valocchi, A. J.; Sanford, R. A.; Strathmann, T. J.; Schaefer, C. E.; Werth, C. J.

2017-12-01

Low permeability zones (LPZs) comprised of silts and clays, and contaminated with chlorinated ethenes, can act as a long term source of contaminated groundwater by diffusion into adjacent high permeability zones (HPZs). Following initial remediation efforts, chlorinated ethenes that have diffused into LPZs will back diffuse and recontaminate HPZs. Because chlorinated ethenes are known to cause cancer and damage the liver, kidneys, and central nervous system, it is important to understand how they degrade in natural systems and how to model their fate and transport. Previous work has shown that anaerobic hydrogenolysis reactions are facilitated by both dechlorinating microorganisms and reactive minerals. Abiotic dichloro-elimination reactions with reactive minerals can also degrade chlorinated ethenes to acetylene, albeit at slower rates than biotic processes. More recently, studies have explored aerobic abiotic degradation of chlorinated ethenes to formate, glycolate, and carbon dioxide. This study focuses on these biotic and abiotic reactions and their contributions to chlorinated ethene degradation under aerobic and anaerobic conditions at the LPZ/HPZ interface. A two-dimensional flow cell was constructed to model this interface using clay and sand from Pease Air Force Base. The clay was inoculated with a dechlorinating enrichment culture. Tenax adsorbent beads equilibrated with trichloroethylene (TCE) were used as a chlorinated ethene source zone at the base of the clay. TCE and its degradation products diffused from the clay into the sand, where they were removed from the flow cell by groundwater at a rate of 50 mL/day. Volatile compounds were trapped in a sample loop and removed every 48 hours for analysis by GC-FID. Organic and inorganic ions in the effluent were analyzed on the HPLC and IC. The experiment was terminated by freezing the flow cell, and chemical profiles through the flow cell material were created to show the spatial distribution of degradation products. Chemical profiles through the clay were modeled using a 1D diffusion-reaction model, and the contributions of abiotic and biotic processes to TCE degradation were determined. The model and experimental data lend insights into transformation processes that control the fate and transport of chlorinated ethenes at contaminated sites.

The impact of iodinated X-ray contrast agents on formation and toxicity of disinfection by-products in drinking water.

PubMed

Jeong, Clara H; Machek, Edward J; Shakeri, Morteza; Duirk, Stephen E; Ternes, Thomas A; Richardson, Susan D; Wagner, Elizabeth D; Plewa, Michael J

2017-08-01

The presence of iodinated X-ray contrast media (ICM) in source waters is of high concern to public health because of their potential to generate highly toxic disinfection by-products (DBPs). The objective of this study was to determine the impact of ICM in source waters and the type of disinfectant on the overall toxicity of DBP mixtures and to determine which ICM and reaction conditions give rise to toxic by-products. Source waters collected from Akron, OH were treated with five different ICMs, including iopamidol, iopromide, iohexol, diatrizoate and iomeprol, with or without chlorine or chloramine disinfection. The reaction product mixtures were concentrated with XAD resins and the mammalian cell cytotoxicity and genotoxicity of the reaction mixture concentrates was measured. Water containing iopamidol generated an enhanced level of mammalian cell cytotoxicity and genotoxicity after disinfection. While chlorine disinfection with iopamidol resulted in the highest cytotoxicity overall, the relative iopamidol-mediated increase in toxicity was greater when chloramine was used as the disinfectant compared with chlorine. Four other ICMs (iopromide, iohexol, diatrizoate, and iomeprol) expressed some cytotoxicity over the control without any disinfection, and induced higher cytotoxicity when chlorinated. Only iohexol enhanced genotoxicity compared to the chlorinated source water. Copyright © 2017. Published by Elsevier B.V.

The 1988 Arctic Survey, Diurnal Study (Sunrise and Sunset) and Peak Altitude (22 km) Flights for the In Situ Detection of ClO and BrO from the NASA ER-2 Aircraft

NASA Technical Reports Server (NTRS)

Anderson, James G.

1996-01-01

Two critical areas of research were addressed successfully by this research. The first involves NASA ER-2 airborne observations of ClO and BrO radical destruction of ozone within the arctic vortex. The second involves the analysis of diurnal variations in ClO, to test the production and loss rates of ClO that constitutes the test for coupling reactions between the chlorine and nitrogen systems. We discuss results from this research in order.

Impact of water quality on chlorine demand of corroding copper

EPA Pesticide Factsheets

Copper is widely used in drinking water premise plumbing system materials. In buildings such ashospitals, large and complicated plumbing networks make it difficult to maintain good water quality.Sustaining safe disinfectant residuals throughout a building to protect against waterborne pathogenssuch as Legionella is particularly challenging since copper and other reactive distribution system materialscan exert considerable demands. The objective of this work was to evaluate the impact of pH andorthophosphate on the consumption of free chlorine associated with corroding copper pipes over time. Acopper test-loop pilot system was used to control test conditions and systematically meet the studyobjectives. Chlorine consumption trends attributed to abiotic reactions with copper over time weredifferent for each pH condition tested, and the total amount of chlorine consumed over the test runsincreased with increasing pH. Orthophosphate eliminated chlorine consumption trends with elapsedtime (i.e., chlorine demand was consistent across entire test runs). Orthophosphate also greatly reducedthe total amount of chlorine consumed over the test runs. Interestingly, the total amount of chlorineconsumed and the consumption rate were not pH dependent when orthophosphate was present. Thefindings reflect the complex and competing reactions at the copper pipe wall including corrosion,oxidation of Cu(I) minerals and ions, and possible oxidation of Cu(II) minerals, and the change in

Predicting reactivity of model DOM compounds towards chlorine with mediated electrochemical oxidation.

PubMed

de Vera, Glen Andrew; Gernjak, Wolfgang; Radjenovic, Jelena

2017-05-01

Chlorine demand of a water sample depends on the characteristics of dissolved organic matter (DOM). It is an important parameter for water utilities used to assess oxidant and/or disinfectant consumption of source waters during treatment and distribution. In this study, model compounds namely resorcinol, tannic acid, vanillin, cysteine, tyrosine, and tryptophan were used to represent the reactive moieties of complex DOM mixtures. The reactivity of these compounds was evaluated in terms of Cl 2 demand and electron donating capacity (EDC). The EDC was determined by mediated electrochemical oxidation (MEO) which involves the use of 2,2'-azino-bis(3-ethylbenzthiazoline-6-sulfonic acid) (ABTS) as an electron shuttle. The Cl 2 demand of readily oxidizable compounds (resorcinol, tannic acid, vanillin, and cysteine) was found to correlate well with EDC (R 2  = 0.98). The EDC values (mol e - /mol C) of the model compounds are as follows: 1.18 (cysteine) > 0.77 (resorcinol) > 0.59 (vanillin) > 0.52 (tannic acid) > 0.36 (tryptophan) > 0.19 (tyrosine). To determine the effect of pre-oxidation on EDC, ozone was added (0.1 mol O 3 /mol C) into each model compound solution. Ozonation caused a general decrease in EDC (10-40%), chlorine demand (10-30%), and UV absorbance (10-40%), except for tyrosine which showed both increased UV 275 and EDC. Before and after ozonation, 24 h disinfection byproduct (DBP) formation potential tests (Cl 2 residual = 1.5 mg/L) were conducted to evaluate the use of EDC for DBP formation prediction. The results indicate that there was no significant correlation between the EDC of the model compounds and the formation potentials of adsorbable organic chlorine, trichloromethane, and trichloroacetic acid. This suggests that while EDC correlates with Cl 2 demand, chlorine consumption may not directly translate to DBP formation because oxidation reactions may dominate over substitution reactions. Overall, this study provides useful insights on the reactions of ABTS + and HOCl with model DOM compounds, and highlights the potential application of MEO for rapid determination of Cl 2 demand of a water sample. Copyright © 2017 Elsevier Ltd. All rights reserved.

Quasi-Liquid Layer Formation on Ice under Stratospheric Conditions

NASA Technical Reports Server (NTRS)

McNeill, V. Faye; Loerting, Thomas; Trout, Bernhardt L.; Molina, Luisa T.; Molina, Mario J.

2004-01-01

Characterization of the interaction of hydrogen chloride (HCl) with ice is essential to understanding at a molecular level the processes responsible for ozone depletion involving polar stratospheric cloud (PSC) particles. To explain the catalytic role PSC particle surfaces play during chlorine activation, we proposed previously that HCl induces the formation of a disordered region on the ice surface, a quasi-liquid layer (QLL), at stratospheric conditions. The QLL is known to exist in pure ice crystals at temperatures near the melting point, but its existence at stratospheric temperatures (-85 C to -70 C) had not been reported yet. We studied the interaction of HCl with ice under stratospheric conditions using the complementary approach of a) ellipsometry to directly monitor the ice surface, using chemical ionization mass spectrometry (CIMS) to monitor the gas phase species present in the ellipsometry experiments, and b) flow-tube experiments with CIMS detection. Here we show that trace amounts of HCl induce QLL formation at stratospheric temperatures, and that the QLL enhances the chlorine-activation reaction of HCl with chlorine nitrate (ClONO2), and also enhances acetic acid (CH3COOH) adsorption.

N-nitrosodimethylamine (NDMA) formation potential of amine-based water treatment polymers: Effects of in situ chloramination, breakpoint chlorination, and pre-oxidation.

PubMed

Park, Sang Hyuck; Padhye, Lokesh P; Wang, Pei; Cho, Min; Kim, Jae-Hong; Huang, Ching-Hua

2015-01-23

Recent studies show that cationic amine-based water treatment polymers may be important precursors that contribute to formation of the probable human carcinogen N-nitrosodimethylamine (NDMA) during water treatment and disinfection. To better understand how water treatment parameters affect NDMA formation from the polymers, the effects of in situ chloramination, breakpoint chlorination, and pre-oxidation on the NDMA formation from the polymers were investigated. NDMA formation potential (NDMA-FP) as well as dimethylamine (DMA) residual concentration were measured from poly(epichlorohydrin dimethylamine) (polyamine) and poly(diallyldimethylammonium chloride) (polyDADMAC) solutions upon reactions with oxidants including free chlorine, chlorine dioxide, ozone, and monochloramine under different treatment conditions. The results supported that dichloramine (NHCl2) formation was the critical factor affecting NDMA formation from the polymers during in situ chloramination. The highest NDMA formation from the polymers occurred near the breakpoint of chlorination. Polymer chain breakdown and transformation of the released DMA and other intermediates were important factors affecting NDMA formation from the polymers in pre-oxidation followed by post-chloramination. Pre-oxidation generally reduced NDMA-FP of the polymers; however, the treatments involving pre-ozonation increased polyDADMAC's NDMA-FP and DMA release. The strategies for reducing NDMA formation from the polymers may include the avoidance of the conditions favorable to NHCl2 formation and the avoidance of polymer exposure to strong oxidants such as ozone. Copyright © 2014 Elsevier B.V. All rights reserved.

Application of activated carbons from coal and coconut shell for removing free residual chlorine.

PubMed

Ogata, Fumihiko; Tominaga, Hisato; Ueda, Ayaka; Tanaka, Yuko; Iwata, Yuka; Kawasaki, Naohito

2013-01-01

This study investigated the removal of free residual chlorine by activated carbon (AC). ACs were prepared from coal (AC1) and coconut shell (AC2). The specific surface area of AC1 was larger than that of AC2. The removal of free residual chlorine increased with elapsed time and amount of adsorbent. The removal mechanism of free residual chlorine was the dechlorination reaction between hypochlorous acid or hypochlorite ion and AC. Moreover, AC1 was useful in the removal of free residual chlorine in tap water. The optimum condition for the removal of free residual chlorine using a column is space velocity 306 1/h; liner velocity 6.1 m/h.

The maintenance of elevated active chlorine levels in the Antarctic lower stratosphere through HCl null cycles

NASA Astrophysics Data System (ADS)

Müller, Rolf; Grooß, Jens-Uwe; Mannan Zafar, Abdul; Robrecht, Sabine; Lehmann, Ralph

2018-03-01

The Antarctic ozone hole arises from ozone destruction driven by elevated levels of ozone destroying (active) chlorine in Antarctic spring. These elevated levels of active chlorine have to be formed first and then maintained throughout the period of ozone destruction. It is a matter of debate how this maintenance of active chlorine is brought about in Antarctic spring, when the rate of formation of HCl (considered to be the main chlorine deactivation mechanism in Antarctica) is extremely high. Here we show that in the heart of the ozone hole (16-18 km or 85-55 hPa, in the core of the vortex), high levels of active chlorine are maintained by effective chemical cycles (referred to as HCl null cycles hereafter). In these cycles, the formation of HCl is balanced by immediate reactivation, i.e. by immediate reformation of active chlorine. Under these conditions, polar stratospheric clouds sequester HNO3 and thereby cause NO2 concentrations to be low. These HCl null cycles allow active chlorine levels to be maintained in the Antarctic lower stratosphere and thus rapid ozone destruction to occur. For the observed almost complete activation of stratospheric chlorine in the lower stratosphere, the heterogeneous reaction HCl + HOCl is essential; the production of HOCl occurs via HO2 + ClO, with the HO2 resulting from CH2O photolysis. These results are important for assessing the impact of changes of the future stratospheric composition on the recovery of the ozone hole. Our simulations indicate that, in the lower stratosphere, future increased methane concentrations will not lead to enhanced chlorine deactivation (through the reaction CH4 + Cl → HCl + CH3) and that extreme ozone destruction to levels below ≈ 0.1 ppm will occur until mid-century.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rowland, F.S.

This report describes the progress in several projects: gas phase substitution reactions of thermal chlorine atoms with tetramethyl metallo-organic compounds; abstraction reactions by thermal chlorine atoms with tetramethyl metallo-organic compounds; gas phase thermal {sup 38}Cl reactions with M(CH{double_bond}CH{sub 2}){sub n}: non-RRKM decomposition of excited radicals (M = Sn, Si, n = 4; M = Sb, n = 3; M = Hg, n = 2); quantitative product identification for reactions of hydroxyl with {sup 14}CS{sub 2}; and statistical analysis of ground-based measurements of total ozone with Dobson spectrometers. The report also contains a research proposal for work from May, 1991 throughmore » April, 1992.« less

Direct formation of element chlorides from the corresponding element oxides through microwave-assisted carbohydrochlorination reactions.

PubMed

Nordschild, Simon; Auner, Norbert

2008-01-01

A series of technically and economically important element chlorides-such as SiCl4, BCl3, AlCl3, FeCl2, PCl3 and TiCl4-was synthesized through reactions between hydrogen chloride and the corresponding element oxides in the presence of different carbon sources with microwave assistance. This process route was optimized for demonstration purposes for tetrachlorosilane formation and successfully demonstrates the broad applicability of various silicon oxide-containing minerals and materials for carbohydrochlorination. The chlorination reaction occurs at lower temperatures than with conventional heating in a tubular oven, with substantially shorter reaction times and in better yields: quantitatively in the case of tetrachlorosilane, based on the silicon content of the starting material. The experimental procedure is very simple and provides basic information about the suitability of element compounds, especially element oxides, for carbohydrochlorination. According to the general reaction sequence element oxide-->element-->element chloride used in today's technology, this one-step carbohydrochlorination with hydrogen chloride is considerably more efficient, particularly in terms of energy input and reaction times, avoiding the isolation of the pure elements required for chlorination to give the element chlorides with use of the more corrosive and toxic chlorine gas.

Rate constant for the reaction of atomic chlorine with methane

NASA Technical Reports Server (NTRS)

Lin, C. L.; Leu, M. T.; Demore, W. B.

1978-01-01

The rate constant and temperature dependence of the Cl + CH4 reaction have been investigated by the techniques of competitive chlorination of CH4/C2H6 mixtures and by discharge-flow/mass spectroscopy. The objectives were to determine an accurate value for the rate constant for use in stratospheric modeling, and to clarify discrepancies in results previously obtained by different techniques. The results deduced from the competitive chlorination study are in good agreement with the absolute values measured by the mass spectrometric method, and at temperatures above 300 K are in good agreement with measurements by other techniques based on resonance fluorescence detection of atomic chlorine. However, in the 220-300 K region, the competitive experiments indicate lower rate constants than those obtained by resonance fluorescence methods, and do not reproduce the curved Arrhenius plots seen in some of those studies.

A novel microfluidic mixer-based approach for determining inactivation kinetics of Escherichia coli O157:H7 in chlorine solutions.

PubMed

Zhang, Boce; Luo, Yaguang; Zhou, Bin; Wang, Qin; Millner, Patricia D

2015-08-01

Determination of the minimum free chlorine concentration needed to prevent pathogen survival/cross-contamination during produce washing is essential for the development of science-based food safety regulations and practices. Although the trend of chlorine concentration-contact time on pathogen inactivation is generally understood, specific information on chlorine and the kinetics of pathogen inactivation at less than 1.00 s is urgently needed by the produce processing industry. However, conventional approaches to obtain this critical data have been unable to adequately measure very rapid responses. This paper reports our development, fabrication, and test of a novel microfluidic device, and its application to obtain the necessary data on pathogen inactivation by free chlorine in produce wash solution in times as short as 0.10 s. A novel microfluidic mixer with the capability to accurately determine the reaction time and control the chlorine concentration was designed with three inlets for bacterial, chlorine and dechlorinating solutions, and one outlet for effluent collection. The master mold was fabricated on a silicon wafer with microchannels via photopolymerization. Polydimethylsiloxane replicas with patterned microchannels were prototyped via soft lithography. The replicas were further assembled into the micromixer on glass via O2 plasma treatment, and the inlets were connected to a syringe pump for solution delivery. To determine the kinetics of free chlorine on pathogen inactivation, chlorine solutions of varying concentrations were first pumped into the micromixer, together with the addition of bacterial suspension of Escherichia coli O157:H7 through a separate inlet. This was followed by injection of dechlorinating solution to stop the chlorine-pathogen reaction. The effluent was collected and the surviving bacteria cells were enumerated using a modified 'Most Probable Number' method. Free chlorine concentration was determined using a standard colorimetric method. The contact time was experimentally set by adjusting the solution flow rate, and was estimated by computational fluid dynamics modeling. Results showed that 1) pathogen inactivation was significantly affected by free chlorine concentration (P < 0.0001) and subsecond reaction time (P < 0.0001) and their interactions (P < 0.0001); and 2) the current industry practice of using 1.0 mg/L free chlorine will require more than 1.00 s total contact to achieve a 5-log10 reduction in an E. coli O157:H7 population, whereas a 10.0 mg/L free chlorine solution will achieve 5-log10 reduction in as little as 0.25 s. Information obtained from this study will provide critical insight on kinetics of bacterial inactivation for a broad range of sanitizers and produce wash operational conditions, thus facilitating the development and implementation of science-based food safety regulations and practices for improving food safety. Published by Elsevier Ltd.

Kinetic models and pathways of ronidazole degradation by chlorination, UV irradiation and UV/chlorine processes.

PubMed

Qin, Lang; Lin, Yi-Li; Xu, Bin; Hu, Chen-Yan; Tian, Fu-Xiang; Zhang, Tian-Yang; Zhu, Wen-Qian; Huang, He; Gao, Nai-Yun

2014-11-15

Degradation kinetics and pathways of ronidazole (RNZ) by chlorination (Cl2), UV irradiation and combined UV/chlorine processes were investigated in this paper. The degradation kinetics of RNZ chlorination followed a second-order behavior with the rate constants calculated as (2.13 ± 0.15) × 10(2) M(-2) s(-1), (0.82 ± 0.52) × 10(-2) M(-1) s(-1) and (2.06 ± 0.09) × 10(-1) M(-1) s(-1) for the acid-catalyzed reaction, as well as the reactions of RNZ with HOCl and OCl(-), respectively. Although UV irradiation degraded RNZ more effectively than chlorination did, very low quantum yield of RNZ at 254 nm was obtained as 1.02 × 10(-3) mol E(-1). RNZ could be efficiently degraded and mineralized in the UV/chlorine process due to the generation of hydroxyl radicals. The second-order rate constant between RNZ and hydroxyl radical was determined as (2.92 ± 0.05) × 10(9) M(-1) s(-1). The degradation intermediates of RNZ during the three processes were identified with Ultra Performance Liquid Chromatography - Electrospray Ionization - mass spectrometry and the degradation pathways were then proposed. Moreover, the variation of chloropicrin (TCNM) and chloroform (CF) formation after the three processes were further evaluated. Enhanced formation of CF and TCNM precursors during UV/chlorine process deserves extensive attention in drinking water treatment. Copyright © 2014 Elsevier Ltd. All rights reserved.

Use of Nucleic Acid-Based Tools for Monitoring Biostimulation and Bioaugmentation

DTIC Science & Technology

2011-01-01

dechlorination is a promising process for biodegradation of chlorinated solvents. The successful field evaluation and implementation of the reductive...These specialized bacteria use the chlorinated ethenes as electron acceptors and gain energy for growth from the reductive dechlorination reactions...protocol addresses the use of MBTs to quantitatively assess the Dhc population at chlorinated ethene sites and aims at providing guidance to evaluate

Chlorination of oxybenzone: Kinetics, transformation, disinfection byproducts formation, and genotoxicity changes.

PubMed

Zhang, Shujuan; Wang, Xiaomao; Yang, Hongwei; Xie, Yuefeng F

2016-07-01

UV filters are a kind of emerging contaminant, and their transformation behavior in water treatment processes has aroused great concern. In particular, toxic products might be produced during reaction with disinfectants during the disinfection process. As one of the most widely used UV filters, oxybenzone has received significant attention, because its transformation and toxicity changes during chlorine oxidation are a concern. In our study, the reaction between oxybenzone and chlorine followed pseudo-first-order and second-order kinetics. Three transformation products were detected by LC-MS/MS, and the stability of products followed the order of tri-chloro-methoxyphenoyl > di-chlorinated oxybenzone > mono-chlorinated oxybenzone. Disinfection byproducts (DBPs) including chloroform, trichloroacetic acid, dichloroacetic acid and chloral hydrate were quickly formed, and increased at a slower rate until their concentrations remained constant. The maximum DBP/oxybenzone molar yields for the four compounds were 12.02%, 6.28%, 0.90% and 0.23%, respectively. SOS/umu genotoxicity test indicated that genotoxicity was highly elevated after chlorination, and genotoxicity showed a significantly positive correlation with the response of tri-chloro-methoxyphenoyl. Our results indicated that more genotoxic transformation products were produced in spite of the elimination of oxybenzone, posing potential threats to drinking water safety. This study shed light on the formation of DBPs and toxicity changes during the chlorination process of oxybenzone. Copyright © 2016 Elsevier Ltd. All rights reserved.

Modeling and optimization of trihalomethanes formation potential of surface water (a drinking water source) using Box-Behnken design.

PubMed

Singh, Kunwar P; Rai, Premanjali; Pandey, Priyanka; Sinha, Sarita

2012-01-01

The present research aims to investigate the individual and interactive effects of chlorine dose/dissolved organic carbon ratio, pH, temperature, bromide concentration, and reaction time on trihalomethanes (THMs) formation in surface water (a drinking water source) during disinfection by chlorination in a prototype laboratory-scale simulation and to develop a model for the prediction and optimization of THMs levels in chlorinated water for their effective control. A five-factor Box-Behnken experimental design combined with response surface and optimization modeling was used for predicting the THMs levels in chlorinated water. The adequacy of the selected model and statistical significance of the regression coefficients, independent variables, and their interactions were tested by the analysis of variance and t test statistics. The THMs levels predicted by the model were very close to the experimental values (R(2) = 0.95). Optimization modeling predicted maximum (192 μg/l) TMHs formation (highest risk) level in water during chlorination was very close to the experimental value (186.8 ± 1.72 μg/l) determined in laboratory experiments. The pH of water followed by reaction time and temperature were the most significant factors that affect the THMs formation during chlorination. The developed model can be used to determine the optimum characteristics of raw water and chlorination conditions for maintaining the THMs levels within the safe limit.

Vacuum-based surface modification of organic and metallic substrates

NASA Astrophysics Data System (ADS)

Torres, Jessica

Surface physico-chemical properties play an important role in the development and performance of materials in different applications. Consequently, understanding the chemical and physical processes involved during surface modification strategies is of great scientific and technological importance. This dissertation presents results from the surface modification of polymers, organic films and metallic substrates with reactive species, with the intent of simulating important modification processes and elucidating surface property changes of materials under different environments. The reactions of thermally evaporated copper and titanium with halogenated polytetrafluoroethylene (PTFE) and polyvinyl chloride (PVC) are used to contrast the interaction of metals with polymers. Results indicate that reactive metallization is thermodynamically favored when the metal-halogen bond strength is greater than the carbon-halogen bond strength. X-ray post-metallization treatment results in an increase in metal-halide bond formation due to the production of volatile halogen species in the polymer that react with the metallic overlayer. The reactions of atomic oxygen (AO) and atomic chlorine with polyethylene (PE) and self-assembled monolayers (SAMs) films were followed to ascertain the role of radical species during plasma-induced polymer surface modification. The reactions of AO with X-ray modified SAMs are initially the dominated by the incorporation of new oxygen containing functionality at the vacuum/film interface, leading to the production of volatile carbon containing species such as CO2 that erodes the hydrocarbon film. The reaction of atomic chlorine species with hydrocarbon SAMs, reveals that chlorination introduces C-Cl and C-Cl2 functionalities without erosion. A comparison of the reactions of AO and atomic chlorine with PE reveal a maximum incorporation of the corresponding C-O and C-Cl functionalities at the polymer surface. A novel method to prepare phosphorous-containing polymer surfaces through ion implantation of trimethyl phosphine onto PE is presented. Air exposure of the resulting P-implanted PE leads to the surface selective oxidation of phosphorous moieties. P-containing hydrocarbon films are used to model the surface chemical changes of P-containing polymers exposed to AO. Results indicate that oxidized phosphorous species protect the film from AO-induced erosion. The low temperature (<150 K) oxidation of nitrided iron surfaces exposed to oxygen reveal the formation of iron oxynitride (FexNyO z, nitrosonium ions (NO+) as well as nitrite/nitrito and nitrate type species. The production of nitrite/nitrito and nitrate species is taken as evidence for the existence of oxygen insertion chemistry into the iron nitride lattice under these low temperature oxidation conditions. Upon annealing the oxidized iron nitride surface, nitrogen desorbs exclusively as nitric oxide (NO).

Absolute rate constant for the reaction of atomic chlorine with hydrogen peroxide vapor over the temperature range 265-400 K

NASA Technical Reports Server (NTRS)

Michael, J. V.; Whytock, D. A.; Lee, J. H.; Payne, W. A.; Stief, L. J.

1977-01-01

Rate constants for the reaction of atomic chlorine with hydrogen peroxide were measured from 265-400 K using the flash photolysis-resonance fluorescence technique. Analytical techniques were developed to measure H2O2 under reaction conditions. Due to ambiguity in the interpretation of the analytical results, the data combine to give two equally acceptable representations of the temperature dependence. The results are compared to previous work at 298 K and are theoretically discussed in terms of the mechanism of the reaction. Additional experiments on the H + H2O2 reaction at 298 and 359 K are compared with earlier results from this laboratory and give a slightly revised bimolecular rate constant.

Laboratory Studies of Heterogeneous Chemical Processes of Atmospheric Importance

NASA Technical Reports Server (NTRS)

Molina, Mario J.

2004-01-01

The objective of this study is to conduct measurements of chemical kinetics parameters for heterogeneous reactions of importance in the stratosphere and the troposphere. It involves the elucidation of the mechanism of the interaction of HCl vapor with ice surfaces, which is the first step in the heterogeneous chlorine activation processes, as well as the investigation of the atmospheric oxidation mechanism of soot particles emitted by biomass and fossil fuels. The techniques being employed include turbulent flow-chemical ionization mass spectrometry and optical ellipsometry, among others.

State of the art on cyanotoxins in water and their behaviour towards chlorine.

PubMed

Merel, Sylvain; Clément, Michel; Thomas, Olivier

2010-04-01

The occurrence of cyanobacterial blooms is drastically increasing in temperate countries and drinking water resources are threatened. As a result, cyanotoxins should be considered in water treatment to protect human health. This study presents a state of the art on cyanotoxins in water and their behaviour towards chlorination, a common drinking water disinfection process. Chlorination efficiency on cyanotoxins alteration depends on pH, chlorine dose and oxidant nature. Microcystins and cylindrospermopsin are efficiently transformed by chlorine, with respectively 6 and 2 by-products identified. In addition, chlorination of microcystins and cylindrospermopsin is associated with a loss of acute toxicity. Even though they have been less investigated, saxitoxins and nodularins are also altered by chlorine. For these toxins, no by-products have been identified, but the chlorinated mixture does not show acute toxicity. On the contrary, the fact that anatoxin-a has a very slow reaction kinetics suggests that this toxin resists chlorination. Copyright 2009 Elsevier Ltd. All rights reserved.

Oxidation of danofloxacin by free chlorine-kinetic study, structural identification of by-products by LC-MS/MS and potential toxicity of by-products using in silico test.

PubMed

Yassine, Montaha; Rifai, Ahmad; Doumyati, Samah; Trivella, Aurélien; Mazellier, Patrick; Budzinski, Hélène; Al Iskandarani, Mohamad

2017-03-01

In this study, we aimed to investigate the kinetics and the mechanism of reaction of the fluoroquinolone antibacterial danofloxacin (DANO) by free available chlorine (FAC) during water chlorination process. Kinetic study was thus performed at pH 7.2, 20 °C in the presence of an excess of total chlorine. Under these experimental conditions, a second-order reaction rate constant (first-order relative to DANO concentration and first-order relative to FAC concentration) was evaluated to k~1446 M -1  s -1 . Five degradation products were identified at different reaction times. Their structures were investigated by using fragmentations obtained at different CID collision energies in MS/MS experiments. Moreover, the toxicity of the proposed structures was predicted by using T.E.S.T. The results indicated that all by-products may have a developmental toxicity. The oral rat LD 50 concentration was predicted to be lower than that of DANO. Furthermore, two degradation compounds presented a concentration level for fathead minnow LC 50 (96 h) lower than that of DANO and presented toxicity for the marine animals.

Fate of High Priority Pesticides During Drinking Water Treatment

EPA Science Inventory

The fate of organophosphorus (OP) pesticides in the presence of chlorinated oxidants was investigated under drinking water treatment conditions. In the presence of aqueous chlorine, intrinsic rate coefficients were found for the reaction of hypochlorous acid and hypochlorite ion ...

Low Temperature Fluorine Chemistry of Electronegative Elements.

DTIC Science & Technology

1980-07-15

mixtures were prepared in a stainless steel vacuum line well-passivated with chlorine trifluoride (Matheson 98%). In most cases gas mixtures were prepared...niversit% of Tennessee." Knoxville, Tennessee 37916 Matrix Reactions of Fluorine with Chlorine , Bromine, and Iodine. Infrared Detlection of the XF 2, X2F...stainless sieel vacuum line well-passivated with chlorine trifluoride in the formation of these new mixed halogen species. (Matheson. 98.0%). Research

Mechanistic Comparison Between Pd-Catalyzed Ligand Directed C-H Chlorination and C-H Acetoxylation

PubMed Central

Stowers, Kara J.; Sanford, Melanie S.

2009-01-01

This communication describes detailed investigations of the mechanism of the Pd-catalyzed C-H chlorination and acetoxylation of 2-ortho-tolylpyridine. Under the conditions examined, both reactions proceed via rate limiting cyclopalladation. However, substrate and catalyst order as well as Hammett data indicate that the intimate mechanism of cyclopalladation differs significantly between PdCl2-catalyzed chlorination and Pd(OAc)2-catalyzed acetoxylation. PMID:19754074

Chlorinated Phospholipids and Fatty Acids: (Patho)physiological Relevance, Potential Toxicity, and Analysis of Lipid Chlorohydrins

PubMed Central

2016-01-01

Chlorinated phospholipids are formed by the reaction of hypochlorous acid (HOCl), generated by the enzyme myeloperoxidase under inflammatory conditions, and the unsaturated fatty acyl residues or the head group. In the first case the generated chlorohydrins are both proinflammatory and cytotoxic, thus having a significant impact on the structures of biomembranes. The latter case leads to chloramines, the properties of which are by far less well understood. Since HOCl is also widely used as a disinfecting and antibacterial agent in medicinal, industrial, and domestic applications, it may represent an additional source of danger in the case of abuse or mishandling. This review discusses the reaction behavior of in vivo generated HOCl and biomolecules like DNA, proteins, and carbohydrates but will focus on phospholipids. Not only the beneficial and pathological (toxic) effects of chlorinated lipids but also the importance of these chlorinated species is discussed. Some selected cleavage products of (chlorinated) phospholipids and plasmalogens such as lysophospholipids, (chlorinated) free fatty acids and α-chloro fatty aldehydes, which are all well known to massively contribute to inflammatory diseases associated with oxidative stress, will be also discussed. Finally, common analytical methods to study these compounds will be reviewed with focus on mass spectrometric techniques. PMID:28090245

Synthesis of magnesium aluminate spinel by periclase and alumina chlorination

DOE Office of Scientific and Technical Information (OSTI.GOV)

Orosco, Pablo, E-mail: porosco@unsl.edu.ar; Facultad de Química, Bioquímica y Farmacia, Universidad Nacional de San Luis Chacabuco y Pedernera, San Luis; Barbosa, Lucía

2014-11-15

Highlights: • Use of chlorination for the synthesis of magnesium aluminate spinel. • The reagents used were alumina, periclase and chlorine. • Isothermal and non-isothermal assays were performed in air and Cl{sub 2}–N{sub 2} flows. • The chlorination produced magnesium aluminate spinel at 700 °C. • Selectivity of the chlorination reaction to obtain spinel is very high. - Abstract: A pyrometallurgical route for the synthesis of magnesium aluminate spinel by thermal treatment of a mechanical mixture containing 29 wt% MgO (periclase) and 71 wt% Al{sub 2}O{sub 3} (alumina) in chlorine atmosphere was developed and the results were compared with thosemore » obtained by calcining the same mixture of oxides in air atmosphere. Isothermal and non-isothermal assays were performed in an experimental piece of equipment adapted to work in corrosive atmospheres. Both reagents and products were analyzed by differential thermal analysis (DTA), X-ray diffraction (XRD) and X-ray fluorescence (XRF). Thermal treatment in Cl{sub 2} atmosphere of the MgO–Al{sub 2}O{sub 3} mixture produces magnesium aluminate spinel at 700 °C, while in air, magnesium spinel is generated at 930 °C. The synthesis reaction of magnesium aluminate spinel was complete at 800 °C.« less

Examining the interrelationship between DOC, bromide and chlorine dose on DBP formation in drinking water--a case study.

PubMed

Bond, Tom; Huang, Jin; Graham, Nigel J D; Templeton, Michael R

2014-02-01

During drinking water treatment aqueous chlorine and bromine compete to react with natural organic matter (NOM). Among the products of these reactions are potentially harmful halogenated disinfection by-products, notably four trihalomethanes (THM4) and nine haloacetic acids (HAAs). Previous research has concentrated on the role of bromide in chlorination reactions under conditions of a given NOM type and/or concentration. In this study different concentrations of dissolved organic carbon (DOC) from U.K. lowland water were reacted with varying amounts of bromide and chlorine in order to examine the interrelationship between the three reactants in the formation of THM4, dihaloacetic acids (DHAAs) and trihaloacetic acids (THAAs). Results showed that, in general, molar yields of THM4 increased with DOC, bromide and chlorine concentrations, although yields did fluctuate versus chlorine dose. In contrast both DHAA and THAA yields were mainly independent of changes in bromide and chlorine dose at low DOC (1 mg·L(-1)), but increased with chlorine dose at higher DOC concentrations (4 mg·L(-1)). Bromine substitution factors reached maxima of 0.80, 0.67 and 0.65 for the THM4, DHAAs and THAAs, respectively, at the highest bromide/chlorine ratio studied. These results suggest that THM4 formation kinetics depend on both oxidation and halogenation steps, whereas for DHAAs and THAAs oxidation steps are more important. Furthermore, they indicate that high bromide waters may prove more problematic for water utilities with respect to THM4 formation than for THAAs or DHAAs. While mass concentrations of all three groups increased in response to increased bromide incorporation, only the THMs also showed an increase in molar yield. Overall, the formation behaviour of DHAA and THAA was more similar than that of THM4 and THAA. © 2013.

Methyl salicylate: a reactive chemical warfare agent surrogate to detect reaction with hypochlorite.

PubMed

Salter, W Bruce; Owens, Jeffery R; Wander, Joseph D

2011-11-01

Methyl salicylate (MeS) has a rich history as an inert physical simulant for the chemical warfare agents sulfur mustard and soman, where it is used extensively for liquid- and vapor-permeation testing. Here we demonstrate possible utility of MeS as a reactivity simulant for chlorine-based decontaminants. In these experiments MeS was reacted with sodium hypochlorite varying stoichiometry, temperature, reaction time, and pH. No colored oxidation products were observed; however, chlorination of the aromatic ring occurred ortho (methyl 3-chlorosalicylate) and para (methyl 5-chlorosalicylate) to the position bearing the -OH group in both the mono- and disubstituted forms. The monosubstituted para product accumulated initially, and the ortho and 3,5-dichloro products formed over the next several hours. Yields from reactions conducted below pH 11 declined rapidly with decreasing pH. Reactions run at 40 °C produced predominantly para substitution, while those run at 0 °C produced lower yields of ortho- and para-substituted products. Reactions were also carried out on textile substrates of cotton, 50/50 nylon-cotton, and a meta aramid. The textile data broadly reproduced reaction times and stoichiometry observed in the liquid phase, but are complicated by physical and possibly chemical interactions with the fabric. These data indicate that, for hypochlorite-containing neutralizing agents operating at strongly alkaline pH, one can expect MeS to react stoichiometrically with the hypochlorite it encounters. This suggests utility of MeS in lieu of such highly hazardous surrogates as monochloroalkyl sulfides as a simulant for threat scenarios involving the stoichiometric decomposition of sulfur mustard. Specifically, the extent of coverage of the simulant on a fabric by the neutralizing agent can be directly measured. Similar reactivity toward other halogen oxidizing agents is likely but remains to be demonstrated.

Importance of chlorine speciation on de novo formation of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans.

PubMed

Wikström, Evalena; Ryan, Shawn; Touati, Abderrahmane; Telfer, Marnie; Tabor, Dennis; Gullett, Brian K

2003-03-15

The role of chlorine speciation on de novo formation of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDDs/Fs) has been studied thoroughly in an entrained flow reactor during simulated waste combustion. The effects of gas-phase chlorine species such as chlorine (Cl2), hydrogen chloride (HCl), and chlorine radicals (Cl*), as well as ash-bound chlorine, on PCDD/F de novo formation were isolated for investigation. The ash-bound chlorine alone was observed to be a sufficient chlorine source for PCDD/F formation. The addition of HCl to the system did not influence the yields of the PCDDs/Fs nor the degree of chlorination due to its poor chlorinating ability. Addition of 200 ppm of Cl2 to the ash-feed system resulted in increased PCDD/F yields, especially for the octa- and hepta-chlorinated congeners. Altering the reaction temperature to enable the presence of only Cl2 to the system did not change the yields of PCDD/F compared to those when both Cl2/Cl* were present. However, comparison between ash-bound and gas-phase chlorine, the latter at a concentration typical of a realistic combustion process, revealed ash-bound chlorine to be the more important chlorine source for de novo formation of PCDD/F in a full-scale incinerator.

Optimization of chlorine fluxing process for magnesium removal from molten aluminum

NASA Astrophysics Data System (ADS)

Fu, Qian

High-throughput and low operational cost are the keys to a successful industrial process. Much aluminum is now recycled in the form of used beverage cans and this aluminum is of alloys that contain high levels of magnesium. It is common practice to "demag" the metal by injecting chlorine that preferentially reacts with the magnesium. In the conventional chlorine fluxing processes, low reaction efficiency results in excessive reactive gas emissions. In this study, through an experimental investigation of the reaction kinetics involved in this process, a mathematical model is set up for the purpose of process optimization. A feedback controlled chlorine reduction process strategy is suggested for demagging the molten aluminum to the desired magnesium level without significant gas emissions. This strategy also needs the least modification of the existing process facility. The suggested process time will only be slightly longer than conventional methods and chlorine usage and emissions will be reduced. In order to achieve process optimization through novel designs in any fluxing process, a system is necessary for measuring the bubble distribution in liquid metals. An electro-resistivity probe described in the literature has low accuracy and its capability to measure bubble distribution has not yet been fully demonstrated. A capacitance bubble probe was designed for bubble measurements in molten metals. The probe signal was collected and processed digitally. Higher accuracy was obtained by higher discrimination against corrupted signals. A single-size bubble experiment in Belmont metal was designed to reveal the characteristic response of the capacitance probe. This characteristic response fits well with a theoretical model. It is suggested that using a properly designed deconvolution process, the actual bubble size distribution can be calculated. The capacitance probe was used to study some practical bubble generation devices. Preliminary results on bubble distribution generated by a porous plug in Belmont metal showed bubbles much bigger than those in a water model. Preliminary results in molten aluminum showed that the probe was applicable in this harsh environment. An interesting bubble coalescence phenomenon was also observed in both Belmont metal and molten aluminum.

Heterogeneous chemistry on Antarctic polar stratospheric clouds - A microphysical estimate of the extent of chemical processing

NASA Technical Reports Server (NTRS)

Drdla, K.; Turco, R. P.; Elliott, S.

1993-01-01

A detailed model of polar stratospheric clouds (PSCs), which includes nucleation, condensational growth. and sedimentation processes, has been applied to the study of heterogeneous chemical reactions. For the first time, the extent of chemical processing during a polar winter has been estimated for an idealized air parcel in the Antarctic vortex by calculating in detail the rates of heterogeneous reactions on PSC particles. The resulting active chlorine and NO(x) concentrations at first sunrise are analyzed with respect to their influence upon the Antarctic ozone hole using a photochemical model. It is found that the species present at sunrise are primarily influenced by the relative values of the heterogeneous reaction rate constants and the initial gas concentrations. However, the extent of chlorine activation is also influenced by whether N2O5 is removed by reaction with HCl or H2O. The reaction of N2O5 with HCl, which occurs rapidly on type 1 PSCs, activates the chlorine contained in the reservoir species HCl. Hence the presence and surface area of type 1 PSCs early in the winter are crucial in determining ozone depletion.

Thermodynamic and kinetic analysis of the reaction between biological catecholamines and chlorinated methylperoxy radicals

NASA Astrophysics Data System (ADS)

Dimić, Dušan S.; Milenković, Dejan A.; Marković, Jasmina M. Dimitrić; Marković, Zoran S.

2018-05-01

The antiradical potency of catecholamines (dopamine, epinephrine, norepinephrine, L-DOPA), metabolites of dopamine (homovanillic acid, 3-methoxytyramine and 3,4-dihydroxyphenylacetic acid) and catechol towards substituted methylperoxy radicals is investigated. The thermodynamic parameters, together with the kinetic approach, are used to determine the most probable mechanism of action. The natural bond orbital and quantum theory of atoms in molecules are utilised to explain the highest reactivity of trichloromethylperoxy radical. The preferred mechanism is dependent both on the thermodynamic and kinetic parameters . The number of chlorine atoms on radical, the presence of intra-molecular hydrogen bond and number of hydroxy groups attached to the aromatic ring significantly influence the mechanism. The results suggest that sequential proton loss electron transfer (SPLET) is the most probable for reaction with methylperoxy and hydrogen atom transfer (HAT) for reaction with trichloromethylperoxy radicals, with a gradual transition between SPLET and HAT for other two radicals. Due to the significant deprotonation of molecules containing the carboxyl group, the respective anions are also investigated. The HAT and SPLET mechanisms are highly competitive in reaction with MP radical, while the dominant mechanism towards chlorinated radicals is HAT. The reactions in methanol and benzene are also discussed.

Kinetics of membrane damage to high (HNA) and low (LNA) nucleic acid bacterial clusters in drinking water by ozone, chlorine, chlorine dioxide, monochloramine, ferrate(VI), and permanganate.

PubMed

Ramseier, Maaike K; von Gunten, Urs; Freihofer, Pietro; Hammes, Frederik

2011-01-01

Drinking water was treated with ozone, chlorine, chlorine dioxide, monochloramine, ferrate(VI), and permanganate to investigate the kinetics of membrane damage of native drinking water bacterial cells. Membrane damage was measured by flow cytometry using a combination of SYBR Green I and propidium iodide (SGI+PI) staining as indicator for cells with permeabilized membranes and SGI alone to measure total cell concentration. SGI+PI staining revealed that the cells were permeabilized upon relatively low oxidant exposures of all tested oxidants without a detectable lag phase. However, only ozonation resulted in a decrease of the total cell concentrations for the investigated reaction times. Rate constants for the membrane damage reaction varied over seven orders of magnitude in the following order: ozone > chlorine > chlorine dioxide ≈ ferrate > permanganate > chloramine. The rate constants were compared to literature data and were in general smaller than previously measured rate constants. This confirmed that membrane integrity is a conservative and therefore safe parameter for disinfection control. Interestingly, the cell membranes of high nucleic acid (HNA) content bacteria were damaged much faster than those of low nucleic acid (LNA) content bacteria during treatment with chlorine dioxide and permanganate. However, only small differences were observed during treatment with chlorine and chloramine, and no difference was observed for ferrate treatment. Based on the different reactivity of these oxidants it was suggested that HNA and LNA bacterial cell membranes have a different chemical constitution. Copyright © 2010 Elsevier Ltd. All rights reserved.

Formation of Polychlorinated Biphenyls on Secondary Copper Production Fly Ash: Mechanistic Aspects and Correlation to Other Persistent Organic Pollutants

NASA Astrophysics Data System (ADS)

Jiang, Xiaoxu; Liu, Guorui; Wang, Mei; Zheng, Minghui

2015-09-01

Emission of unintentionally formed polychlorinated biphenyls (PCBs) from industrial thermal processes is a global issue. Because the production and use of technical PCB mixtures has been banned, industrial thermal processes have become increasingly important sources of PCBs. Among these processes, secondary copper smelting is an important PCB source in China. In the present study, the potential for fly ash-mediated formation of PCBs in the secondary copper industry, and the mechanisms involved, were studied in laboratory thermochemical experiments. The total PCB concentrations were 37-70 times higher than the initial concentrations. Thermochemical reactions on the fly ash amplified the potential toxic equivalents of PCBs. The formation of PCBs over time and the effect of temperature were investigated. Based on analyses of PCB homologue profiles with different reaction conditions, a chlorination mechanism was proposed for forming PCBs in addition to a de novo synthesis mechanism. The chlorination pathway was supported by close correlations between each pair of adjacent homologue groups. Formation of PCBs and multiple persistent organic pollutants, including polychlorinated dibenzo-p-dioxins, polychlorinated dibenzofurans and polychlorinated naphthalenes, occurred during the tests, indicating that these compounds may share similar formation mechanisms.

Hybrid finite-volume/transported PDF method for the simulation of turbulent reactive flows

NASA Astrophysics Data System (ADS)

Raman, Venkatramanan

A novel computational scheme is formulated for simulating turbulent reactive flows in complex geometries with detailed chemical kinetics. A Probability Density Function (PDF) based method that handles the scalar transport equation is coupled with an existing Finite Volume (FV) Reynolds-Averaged Navier-Stokes (RANS) flow solver. The PDF formulation leads to closed chemical source terms and facilitates the use of detailed chemical mechanisms without approximations. The particle-based PDF scheme is modified to handle complex geometries and grid structures. Grid-independent particle evolution schemes that scale linearly with the problem size are implemented in the Monte-Carlo PDF solver. A novel algorithm, in situ adaptive tabulation (ISAT) is employed to ensure tractability of complex chemistry involving a multitude of species. Several non-reacting test cases are performed to ascertain the efficiency and accuracy of the method. Simulation results from a turbulent jet-diffusion flame case are compared against experimental data. The effect of micromixing model, turbulence model and reaction scheme on flame predictions are discussed extensively. Finally, the method is used to analyze the Dow Chlorination Reactor. Detailed kinetics involving 37 species and 158 reactions as well as a reduced form with 16 species and 21 reactions are used. The effect of inlet configuration on reactor behavior and product distribution is analyzed. Plant-scale reactors exhibit quenching phenomena that cannot be reproduced by conventional simulation methods. The FV-PDF method predicts quenching accurately and provides insight into the dynamics of the reactor near extinction. The accuracy of the fractional time-stepping technique in discussed in the context of apparent multiple-steady states observed in a non-premixed feed configuration of the chlorination reactor.

Chlorine Gas: An Evolving Hazardous Material Threat and Unconventional Weapon

PubMed Central

Jones, Robert; Wills, Brandon; Kang, Christopher

2010-01-01

Chlorine gas represents a hazardous material threat from industrial accidents and as a terrorist weapon. This review will summarize recent events involving chlorine disasters and its use by terrorists, discuss pre-hospital considerations and suggest strategies for the initial management for acute chlorine exposure events. PMID:20823965

Conversion of aryl iodides into aryliodine(III) dichlorides by an oxidative halogenation strategy using 30% aqueous hydrogen peroxide in fluorinated alcohol.

PubMed

Podgorsek, Ajda; Iskra, Jernej

2010-04-20

Oxidative chlorination with HCl/H2O2 in 1,1,1-trifluoroethanol was used to transform aryl iodides into aryliodine(III) dihalides. In this instance 1,1,1-trifluoroethanol is not only the reaction medium, but is also an activator of hydrogen peroxide for the oxidation of hydrochloric acid to molecular chlorine. Aryliodine(III) dichlorides were formed in 72-91% isolated yields in the reaction of aryl iodides with 30% aqueous hydrogen peroxide and hydrochloric acid at ambient temperature. A study of the effect that substituents on the aromatic ring have on the formation and stability of aryliodine(III) dichlorides shows that the transformation is easier to achieve in the presence of the electron-donating groups (i.e. methoxy), but in this case the products rapidly decompose under the reported reaction conditions to form chlorinated arenes. The results suggest that oxidation of hydrogen chloride with hydrogen peroxide is the initial reaction step, while direct oxidation of aryl iodide with hydrogen peroxide is less likely to occur.

Heterogeneous processes: Laboratory, field, and modeling studies

NASA Technical Reports Server (NTRS)

Poole, Lamont R.; Kurylo, Michael J.; Jones, Rod L.; Wahner, Andreas; Calvert, Jack G.; Leu, M.-T.; Fried, A.; Molina, Mario J.; Hampson, Robert F.; Pitts, M. C.

1991-01-01

The efficiencies of chemical families such as ClO(x) and NO(x) for altering the total abundance and distribution of stratospheric ozone are controlled by a partitioning between reactive (active) and nonreactive (reservoir) compounds within each family. Gas phase thermodynamics, photochemistry, and kinetics would dictate, for example, that only about 1 percent of the chlorine resident in the lower stratosphere would be in the form of active Cl or ClO, the remainder existing in the reservoir compounds HCl and ClONO2. The consistency of this picture was recently challenged by the recognition that important chemical transformations take place on polar regions: the Airborne Antarctic Ozone Experiment (AAOE) and the Airborne Arctic Stratospheric Expedition (AASA). Following the discovery of the Antarctic ozone hole, Solomon et al. suggested that the heterogeneous chemical reaction: ClONO2(g)+HCl(s) yields Cl2(g)+HNO3(s) could play a key role in converting chlorine from inactive forms into a species (Cl2) that would rapidly dissociate in sunlight to liberate atomic chlorine and initiate ozone depletion. The symbols (s) and (g) denote solid phase, or adsorbed onto a solid surface, and gas phase, respectively, and represent the approach by which such a reaction is modeled rather than the microscopic details of the reaction. The reaction was expected to be most important at altitudes where PSC's were most prevalent (10 to 25 km), thereby extending the altitude range over which chlorine compounds can efficiently destroy ozone from the 35 to 45 km region (where concentrations of active chlorine are usually highest) to lower altitudes where the ozone concentration is at its peak. This chapter will briefly review the current state of knowledge of heterogeneous processes in the stratosphere, emphasizing those results obtained since the World Meteorological Organization (WMO) conference. Sections are included on laboratory investigations of heterogeneous reactions, the characteristics and climatology of PSC's, stratospheric sulfate aerosols, and evidence of heterogeneous chemical processing.

Chlorine decay and trihalomethane formation following ferrate(VI) preoxidation and chlorination of drinking water.

PubMed

Li, Cong; Luo, Feng; Dong, Feilong; Zhao, Jingguo; Zhang, Tuqiao; He, Guilin; Cizmas, Leslie; Sharma, Virender K

2017-11-01

This paper presents the effect of preoxidation with ferrate(VI) (Fe VI O 4 2- , Fe(VI)) prior to chlorination on chlorine decay and formation of disinfection by-products in filtered raw water from a full-scale drinking water treatment plant. The rate of chlorine decay became significantly faster as the concentration of ferrate(VI) increased. Chlorine degradation followed two first-order decay reactions with rate constants k 1 and k 2 for fast and slow decay, respectively. Kinetic modeling established the relationships between k 1 and k 2 and varying dosages of chlorine and ferrate(VI). When ferrate(VI) was used as a pre-oxidant, the levels of trihalomethanes (trichloromethane (TCM), dichlorobromomethane (DCBM), dibromochloromethane (DBCM), and tribromomethane (TBM)) in water samples decreased as the ferrate(VI) concentration increased. The concentrations of these trihalomethanes followed the order TCM > DCBM ≈ DBCM > TBM. Copyright © 2017 Elsevier Ltd. All rights reserved.

Chlorine isotope effects from isotope ratio mass spectrometry suggest intramolecular C-Cl bond competition in trichloroethene (TCE) reductive dehalogenation.

PubMed

Cretnik, Stefan; Bernstein, Anat; Shouakar-Stash, Orfan; Löffler, Frank; Elsner, Martin

2014-05-20

Chlorinated ethenes are prevalent groundwater contaminants. To better constrain (bio)chemical reaction mechanisms of reductive dechlorination, the position-specificity of reductive trichloroethene (TCE) dehalogenation was investigated. Selective biotransformation reactions (i) of tetrachloroethene (PCE) to TCE in cultures of Desulfitobacterium sp. strain Viet1; and (ii) of TCE to cis-1,2-dichloroethene (cis-DCE) in cultures of Geobacter lovleyi strain SZ were investigated. Compound-average carbon isotope effects were -19.0‰ ± 0.9‰ (PCE) and -12.2‰ ± 1.0‰ (TCE) (95% confidence intervals). Using instrumental advances in chlorine isotope analysis by continuous flow isotope ratio mass spectrometry, compound-average chorine isotope effects were measured for PCE (-5.0‰ ± 0.1‰) and TCE (-3.6‰ ± 0.2‰). In addition, position-specific kinetic chlorine isotope effects were determined from fits of reactant and product isotope ratios. In PCE biodegradation, primary chlorine isotope effects were substantially larger (by -16.3‰ ± 1.4‰ (standard error)) than secondary. In TCE biodegradation, in contrast, the product cis-DCE reflected an average isotope effect of -2.4‰ ± 0.3‰ and the product chloride an isotope effect of -6.5‰ ± 2.5‰, in the original positions of TCE from which the products were formed (95% confidence intervals). A greater difference would be expected for a position-specific reaction (chloride would exclusively reflect a primary isotope effect). These results therefore suggest that both vicinal chlorine substituents of TCE were reactive (intramolecular competition). This finding puts new constraints on mechanistic scenarios and favours either nucleophilic addition by Co(I) or single electron transfer as reductive dehalogenation mechanisms.

The effect of oxidizing water on metallic restorations in the mouth: in vitro reduction behavior of oxidizing water.

PubMed

Nishida, T

1997-03-01

Mouth-rinsing with oxydized water which contains electrolytically generated chlorine is known to hinder dental plaque formation and growth, but it also accelerates the deterioration of metallic restorations in the mouth. The present work consists of an in vitro study to elucidate the electrochemical reactions involved in the reduction of oxydized water on dental alloys through a systematic investigation of the potentiostatic polarization behavior of dental alloy electrodes. The five dental alloys selected for investigation were gold alloy, gold alloy containing platinum, silver-palladium-gold alloy, conventional amalgam and high copper amalgam. The corrosion potentials of all dental alloy electrodes were shown to be more noble in oxydized water than in 0.1N sodium chloride solution. The potential differences between the corrosion potentials were relatively small in the case of amalgam electrodes. The polarization curves for all of the dental alloy electrodes in oxydized water revealed reduction currents of chlorine, hypochlorous acid, dissolved oxygen and oxonium ion. The reduction of chlorine and hypochlorous acid started at a more noble potential than that of dissolved oxygen. The dental alloys studied, except the amalgams, did not dissolve excessively at the corrosion potentials in oxydized water.

Modeling and testing of reactive contaminant transport in drinking water pipes: chlorine response and implications for online contaminant detection.

PubMed

Jeffrey Yang, Y; Goodrich, James A; Clark, Robert M; Li, Sylvana Y

2008-03-01

A modified one-dimensional Danckwerts convection-dispersion-reaction (CDR) model is numerically simulated to explain the observed chlorine residual loss for a "slug" of reactive contaminants instantaneously introduced into a drinking water pipe of assumed no or negligible wall demand. In response to longitudinal dispersion, a contaminant propagates into the bulk phase where it reacts with disinfectants in the water. This process generates a U-shaped pattern of chlorine residual loss in a time-series concentration plot. Numerical modeling indicates that the residual loss curve geometry (i.e., slope, depth, and width) is a function of several variables such as axial Péclet number, reaction rate constants, molar fraction of the fast- and slow-reacting contaminants, and the quasi-steady-state chlorine decay inside the "slug" which serves as a boundary condition of the CDR model. Longitudinal dispersion becomes dominant for less reactive contaminants. Pilot-scale pipe flow experiments for a non-reactive sodium fluoride tracer and the fast-reacting aldicarb, a pesticide, were conducted under turbulent flow conditions (Re=9020 and 25,000). Both the experimental results and the CDR modeling are in agreement showing a close relationship among the aldicarb contaminant "slug", chlorine residual loss and its variations, and a concentration increase of chloride as the final reaction product. Based on these findings, the residual loss curve and its geometry are useful tools to identify the presence of a contaminant "slug" and infer its reactive properties in adaptive contaminant detections.

Transformation of ranitidine during water chlorination and ozonation: Moiety-specific reaction kinetics and elimination efficiency of NDMA formation potential.

PubMed

Jeon, Dahee; Kim, Jisoo; Shin, Jaedon; Hidayat, Zahra Ramadhany; Na, Soyoung; Lee, Yunho

2016-11-15

Ranitidine can produce high yields of N-nitrosodimethylamine (NDMA) upon chloramination and its presence in water resources is a concern for water utilities using chloramine disinfection. This study assessed the efficiency of water chlorination and ozonation in transforming ranitidine and eliminating its NDMA formation potential (NDMA-FP) by determining moiety-specific reaction kinetics, stoichiometric factors, and elimination levels in real water matrices. Despite the fact that chlorine reacts rapidly with the acetamidine and thioether moieties of ranitidine (k>10(8)M(-1)s(-1) at pH 7), the NDMA-FP decreases significantly only when chlorine reacts with the less reactive tertiary amine (k=3×10(3)M(-1)s(-1) at pH 7) or furan moiety (k=81M(-1)s(-1) at pH 7). Ozone reacts rapidly with all four moieties of ranitidine (k=1.5×10(5)-1.6×10(6)M(-1)s(-1) at pH 7) and its reaction with the tertiary amine or furan moiety leads to complete elimination of the NDMA-FP. Treatments of ranitidine-spiked real water samples have shown that ozonation can efficiently deactivate ranitidine in water and wastewater treatment, while chlorination can be efficient for water containing low concentration of ammonia. This result can be applied to the other structurally similar, potent NDMA precursors. Copyright © 2016 Elsevier B.V. All rights reserved.

Tropospheric Halogen Chemistry

NASA Astrophysics Data System (ADS)

von Glasow, R.; Crutzen, P. J.

2003-12-01

Halogens are very reactive chemicals that are known to play an important role in anthropogenic stratospheric ozone depletion chemistry, first recognized by Molina and Rowland (1974). However, they also affect the chemistry of the troposphere. They are of special interest because they are involved in many reaction cycles that can affect the oxidation power of the atmosphere indirectly by influencing the main oxidants O3 and its photolysis product OH and directly, e.g., by reactions of the Cl radical with hydrocarbons (e.g., CH4).Already by the middle of the nineteenth century, Marchand (1852) reported the presence of bromine and iodine in rain and other natural waters. He also mentions the benefits of iodine in drinking water through the prevention of goitres and cretinism. In a prophetic monograph "Air and Rain: The Beginnings of a Chemical Climatology," Smith (1872) describes measurements of chloride in rain water, which he states to originate partly from the oceans by a process that he compares with the bursting of "soap bubbles" which produces "small vehicles" that transfer small spray droplets of seawater to the air. From deviations of the sulfate-to-chloride ratio in coastal rain compared to seawater, Smith concluded that chemical processes occur once the particles are airborne.For almost a century thereafter, however, atmospheric halogens received little attention. One exception was the work by Cauer (1939), who reported that iodine pollution has been significant in Western and Central Europe due to the inefficient burning of seaweed, causing mean gas phase atmospheric concentrations as high as or greater than 0.5 μg m-3. In his classical textbook Air Chemistry and Radioactivity, Junge (1963) devoted less than three pages to halogen gas phase chemistry, discussing chlorine and iodine. As reviewed by Eriksson (1959a, b), the main atmospheric source of halogens is sea salt, derived from the bursting of bubbles of air which are produced by ocean waves and other processes. Early work by Cauer (1951) had shown that Cl/Na and Cl/Mg ratios were lower in air than in seawater, indicating loss of chlorine by "acid displacement" from sea salt by the strong acids, H2SO4 (Eriksson (1959a, b) and HNO3 (Robbins et al., 1959). Already the first measurements of bromine in aerosols by Duce et al. (1963) showed that bromine, like chlorine, was lost from the sea salt particles, whereas iodine was strongly enriched ( Duce et al., 1965). Research since the early 1980s has shown that photochemical processes are actively involved.Interest in the chemistry of atmospheric halogens took a steep upward surge after it was postulated that the release of industrially produced halocarbons, in particular the chlorofluorocarbons (CFCs), CFCl3, and CF2Cl2, could cause severe depletions in stratospheric ozone (Molina and Rowland, 1974) by the reactions involving the CFC photolytic product radicals, Cl and ClO, as catalysts. The first stratospheric measurements of ClO did indeed show its presence in significant quantities in the stratosphere so that by the end of the 1970s USA, Canada, and the Scandinavian countries issued laws against the use of CFC gases as propellants in spray cans. In the mid-1980s the springtime stratospheric ozone hole over Antarctica was discovered by Farman et al. (1985), involving heterogeneous reactions on polar stratospheric clouds that lead to chlorine activation ( Solomon et al., 1986). Ten years later, in 1996, a complete phaseout ofthe production of the CFCs and a number of other chlorine- or bromine-containing chemicals came into effect for all nations in the developed world. In this contribution we will, however, concentrate on the impact of reactive chlorine, bromine, and iodine on tropospheric ozone chemistry.Halogens have the potential to be important in many facets of tropospheric chemistry. A multitude of gas phase reactions and gas-particle interactions occur that include coupling with the sulfur cycle and reactions with hydrocarbons. Loss of ozone by catalytic reactions involving halogen radicals lowers the concentrations of the hydroxyl radical OH and thus the oxidation power of the atmosphere. Figure 1 shows these and other relevant halogen-related processes schematically. The sum of particulate and gaseous halogen concentrations maximize in the marine troposphere. Important for our climate - via feedback with cloud microphysics mainly in the large regions of marine stratocumulus - are links between halogen chemistry and the sulfur cycle. HOBraq and HOClaq can increase the liquid phase oxidation of S(IV) to S(VI), while BrO can decrease the most important in situ source for SO2 in the marine troposphere, namely, the oxidation of DMS to SO2 by reaction with OH by providing an alternate pathway (BrO+DMS) that reduces the yield of SO2 from DMS oxidation. Thus, the presence of bromine and chlorine in the troposphere lowers gas phase SO2 concentrations and thus the formation of new sulfate particles via the reaction sequence SO2+OH→H2SO4. (17K)Figure 1. Schematic depiction of the most important halogen-related processes in the troposphere. High mixing ratios of iodine oxide at a coastal site indicate a potentially significant role of iodine for the destruction of O3 and new particle embryo formation (Alicke et al., 1999; O'Dowd et al., 1998). Almost 20 years earlier, Chameides and Davis (1980) suggested that open ocean iodine chemistry would be initiated by the photolysis of CH3I. This was based on the measurements of Lovelock et al. (1973) and Singh et al. (1979), who found volume mixing ratios of CH3I of 1-5 pmol mol-1 over the ocean.The potentially strong involvement of halogens in tropospheric chemistry was first observed in the Arctic, where strong ozone depletion events were found to coincide with high levels of bromine (Barrie et al., 1988).The first mid-latitude demonstration of reactive halogen chemistry in the troposphere was made downwind of salt pans in the Dead Sea area, where the so far highest atmospheric mixing ratios of BrO were measured (Hebestreit et al., 1999). Volcanoes are sources of halogens as well, mainly in the form of HCl. Biomass burning releases halogens as do industrial processes.So far we have only mentioned chlorine, bromine, and iodine. This is justified because chemistry of fluorine is of no consequence, as very unreactive HF is efficiently formed in the atmosphere, e.g., via the reaction F+H2O→HF+OH. However, several fluorine-containing gases of anthropogenic origin are potentially powerful greenhouse gases, because they absorb strongly in the infrared atmospheric window region near 10 μm. Fully fluorinated gases - such as SF6, CF4, and C2F6 - have atmospheric lifetimes of the order of thousands of years and thus possess very high global warming potential (GWP). Although their abundance in the atmosphere has not yet grown large enough to be of concern for Earth's climate, their production must ultimately be curtailed in the future. The most abundant fully fluorinated gas, CF4, had an atmospheric volume mixing ratio of ˜75 pmol mol-1 in 1995 (Warneck, 1999). Because of their higher concentrations in the atmosphere, about 270 pmol mol-1 and 530 pmol mol-1, respectively, the CFC gases, CFCl3 and CF2Cl2, already exert a significant radiative greenhouse forcing (Ramanathan, 1975) on Earth's climate. For further discussion about atmospheric fluorine, the reader is referred to a thorough review article by Harnisch (1999).Several overview articles have been published on tropospheric halogen chemistry since the early 1980s, starting with Cicerone (1981). Wayne et al. (1995) list in great detail reaction paths, laboratory data, and atmospheric implications of halogen oxides. A good overview on laboratory measurements was also given by de Haan et al. (1999). Reaction cycles involved in tropospheric halogen chemistry and measurements are also thoroughly discussed by Platt (2000) and Platt and Hönninger (2003). Important compilations of laboratory studies that were made to elucidate chemical reaction paths are given by, e.g., DeMore et al. (1997), Sander et al. (2000), and Atkinson et al. (1999, 2000). Emission inventories for chlorine were compiled by Graedel and Keene (1995) and Keene et al. (1999).In Section 4.02.2 of this overview we will first describe the main halogen reaction mechanisms and then discuss, in Section 4.02.3, the springtime surface ozone depletion events in high latitudes that were first observed in the Arctic. Another main part of this chapter is concerned with halogens in the marine boundary layer ( Section 4.02.4). In Section 4.02.5 we describe interactions of halogens with some other elements of atmospheric importance. A very recently discovered environment where halogen chemistry plays a large role are salt lakes ( Section 4.02.6). There the chemistry bears similarity to that of the high-latitude ozone depletion events. This is followed in Section 4.02.7 by a discussion of halogen chemistry in the free troposphere and in Section 4.02.8 by other sources of halogens such as industry and biomass burning.

INVESTIGATION OF TRANSFORMATION PRODUCTS FROM THE CHLORINATION OF ESTROGENIC AND ANDROGENIC COMPOUNDS- Poster

EPA Science Inventory

The objective of this research is to investigate chlorinated by-products of a selected number of steroids representing both estrogens and androgens. Highly controlled reaction conditions were used to ascertain product distribution. Bench-scale studies were conducted to identify...

ENANTIOMERIC COMPOSITION OF CHIRAL HALOACETIC ACID AND HALOACETONITRILE DISINFECTION BYPRODUCTS IN DRINKING WATER

EPA Science Inventory

Haloacetic acids and haloacetonitriles are well-known chlorine disinfection byproducts (DBPs), formed by the reaction of chlorine with natural organic matter. These compounds are of concern to public health because of their possible toxicological properties. Studies to date on th...

Chlorination of UO 2, PuO 2 and rare earth oxides using ZrCl 4 in LiCl-KCl eutectic melt

NASA Astrophysics Data System (ADS)

Sakamura, Yoshiharu; Inoue, Tadashi; Iwai, Takashi; Moriyama, Hirotake

2005-04-01

A new chlorination method using ZrCl 4 in a molten salt bath has been investigated for the pyrometallurgical reprocessing of nuclear fuels. ZrCl 4 has a high reactivity with oxygen but is not corrosive to refractory metals such as steel. Rare earth oxides (La 2O 3, CeO 2, Nd 2O 3 and Y 2O 3) and actinide oxides (UO 2 and PuO 2) were allowed to react with ZrCl 4 in a LiCl-KCl eutectic salt at 773 K to give a metal chloride solution and a precipitate of ZrO 2. An addition of zirconium metal as a reductant was effective in chlorinating the dioxides. When the oxides were in powder form, the reaction was observed to progress rapidly. Cyclic voltammetry provided a convenient way of establishing when the reaction was completed. It was demonstrated that the ZrCl 4 chlorination method, free from corrosive gas, was very simple and useful.

Development of an OClO Slant Column Product for the GOME-2 Sensors

NASA Astrophysics Data System (ADS)

Richter, Andreas; Wittrock, Folkard; Burrows, John P.

2016-04-01

Stratospheric ozone depletion by catalytic reactions involving halogens is one of the most prominent examples of anthropogenic impacts on the atmosphere. In spite of the rapid and successful international action to reduce emissions of CFCs and other ozone depleting substances leading to the Montreal Protocol and its amendments, ozone depletion in polar spring is still observed in both hemispheres on a regular basis. For the coming years, slow ozone recovery is expected but individual years will still see very low ozone columns depending on meteorology and possible interactions with climate change. Monitoring of both ozone and ozone depleting substances in the stratosphere remains a priority to ensure that the predicted reduction in halogen levels and recovery of ozone columns is taking place as predicted. One way to observe stratospheric chlorine activation is by measurements of OClO which can be detected by UV/visible remote sensing from the ground and from satellite. While the link between OClO levels and chlorine activation is complicated by the fact that a) OClO is not directly involved in ozone depletion but is produced by reaction of BrO and ClO and b) is rapidly photolysed at daylight, the long existing data series from both ground-based and satellite observations makes it an interesting tracer of chlorine activation. The GOME-2 instruments on the MetOp series of satellites are nadir viewing UV/vis spectrometers having the spectral coverage and resolution needed for Differential Optical Absorption Spectroscopy retrievals of OClO. With their combined lifetime of more than 15 years, they can provide a long-term data set. However, previous attempts to create an OClO product for GOME-2 suffered from large scatter in the OClO data and time-dependent offsets. Here we present an improved OClO slant column retrieval for the two instruments GOME2-A and GOME2-B. The data is shown to be of similar quality as for earlier instruments such as SCIAMACHY, and is consistent between the instruments. The time series from the two instruments nicely reproduces the large interannual variability in chlorine activation in both hemispheres. Validation with ground-based DOAS zenith-sky observations in Ny-Ålesund shows very good agreement in NH spring. Some baseline drift remains in the GOME2-A data which could be further reduced by application of an offset correction.

Reaction of diazepam and related benzodiazepines with chlorine. Kinetics, transformation products and in-silico toxicological assessment.

PubMed

Carpinteiro, Inmaculada; Rodil, Rosario; Quintana, José Benito; Cela, Rafael

2017-09-01

In this work, the reaction of four benzodiazepines (diazepam, oxazepam, nordazepam and temazepam) during water chlorination was studied by means of liquid chromatography-quadrupole-time of flight-mass spectrometry (LC-QTOF-MS). For those compounds that showed a significant degradation, i.e. diazepam, oxazepam and nordazepam, parameters affecting to the reaction kinetics (pH, chlorine and bromide level) were studied in detail and transformation products were tentatively identified. The oxidation reactions followed pseudofirst-order kinetics with rate constants in the range of 1.8-42.5 M -1  s -1 , 0.13-1.16 M -1  s -1 and 0.04-20.4 M -1  s -1 corresponding to half-life values in the range of 1.9-146 min, 1.8-87 h and 2.5-637 h for oxazepam, nordazepam and diazepam, respectively, depending of the levels of studied parameters. Chlorine and pH affected significantly the reaction kinetics, where an increase of the pH resulted into a decrease of the reaction rate, whereas higher chlorine dosages led to faster kinetics, as expected in this case. The transformation of the studied benzodiazepines occurs mainly at the 1,4-diazepine 7-membered-ring, resulting in ring opening to form benzophenone derivatives or the formation of a 6-membered pyrimidine ring, leading to quinazoline derivatives. The formation of these by-products was also tested in real surface water samples observing kinetics of oxazepam degradation slower in river than in creek water, while the degradation of the two other benzodiazepines occurred only in the simpler sample (creek water). Finally, the acute and chronical toxicity and mutagenicity of precursors and transformation products were estimated using quantitative structure-activity relationship (QSAR) software tools: Ecological Structure Activity Relationships (ECOSAR) and Toxicity Estimation Software Tool (TEST), finding that some transformation products could be more toxic/mutagenic than the precursor drug, but additional test would be needed to confirm this fact. Copyright © 2017 Elsevier Ltd. All rights reserved.

Temperature sensitivity indicates that chlorination of organic matter in forest soil is primarily biotic.

PubMed

Bastviken, David; Svensson, Teresia; Karlsson, Susanne; Sandén, Per; Oberg, Gunilla

2009-05-15

Old assumptions that chloride is inert and that most chlorinated organic matter in soils is anthropogenic have been challenged by findings of naturally formed organochlorines. Such natural chlorination has been recognized for several decades, but there are still very few measurements of chlorination rates or estimates of the quantitative importance of terrestrial chlorine transformations. While much is known about the formation of specific compounds, bulk chlorination remains poorly understood in terms of mechanisms and effects of environmental factors. We quantified bulk chlorination rates in coniferous forest soil using 36Cl-chloride in tracer experiments at different temperatures and with and without molecular oxygen (O2). Chlorination was enhanced by the presence of O2 and had a temperature optimum at 20 degrees C. Minimum rates were found at high temperatures (50 degrees C) or under anoxic conditions. The results indicate (1) that most of the chlorination between 4 and 40 degrees C was biotic and driven by O2 dependent enzymes, and (2) that there is also slower background chlorination occurring under anoxic conditions at 20 degrees C and under oxic conditions at 50 degrees C. Hence, while oxic and biotic chlorination clearly dominated, chlorination by other processes including possible abiotic reactions was also detected.

Severe Adverse Reactions Following Ketoconazole, Fluconazole, and Environmental Exposures: A Case Report.

PubMed

Lieberman, Allan; Curtis, Luke

2018-04-18

In this case report, we describe a 66-year-old man who developed multiple adverse reactions beginning at age 56 after exposure to several azole antifungal drugs including ketoconazole and fluconazole. He also had a history of more than 40 years exposure to chemicals including pesticides, wood preservatives, fertilizers, and welding chemicals. His reactions involved dehydration (requiring several liters of intravenous fluids in less than an hour to alleviate this condition), angioedema, nausea, tinnitus, hypotension, and difficulty breathing. His acute adverse reactions were triggered by a wide range of chemicals including gasoline, diesel fuel, pesticides, chlorine, topical isopropyl alcohol, and paper mill emissions. His acute reactions were also triggered by a wide range of foods such as bananas, apples, milk, white potatoes, and processed sweets. A number of mechanisms could be responsible for his increased sensitivity to chemicals following exposure to fluconazole/ketoconazole, including inhibition of P450 and other detoxification enzymes, acetaldehyde buildup, and neurogenic sensitization.

Chlorination and chloramination of bisphenol A, bisphenol F, and bisphenol A diglycidyl ether in drinking water.

PubMed

Lane, Rachael F; Adams, Craig D; Randtke, Stephen J; Carter, Ray E

2015-08-01

Bisphenol A (BPA), bisphenol F (BPF), and bisphenol A diglycidyl ether (BADGE) are common components of epoxy coatings used in food packaging and in drinking water distribution systems. Thus, leachates from the epoxy may be exposed to the disinfectants free chlorine (Cl2/HOCl/OCl(-)) and monochloramine (MCA, NH2Cl). Bisphenols are known endocrine disrupting chemicals (EDC) with estrogenic activity. Chlorination by-products have the potential to have reduced or enhanced estrogenic qualities, and are, therefore, of interest. In this work, chlorination reactions for bisphenols and BADGE were explored (via LC/MS/MS) and kinetic modeling (using a pseudo-first order approach) was conducted to predict the fate of these compounds in drinking water. The half-lives of BPA and BPF with 1 mg/L of free chlorine ranged from 3 to 35 min over the pH range from 6 to 11 and the temperature range of 10-25 °C. Half-lives for reactions of BPA and BPF with a nominal MCA concentration of 3.5 mg/L as Cl2 were from 1 to 10 days and were greater at higher pH and lower temperature. Formation of chlorinated bisphenol A by-products was observed during the kinetic studies. BADGE was found unreactive with either oxidant. Copyright © 2015. Published by Elsevier Ltd.

Chlorine in solid fuels fired in pulverized fuel boilers sources, forms, reactions, and consequences: a literature review

DOE Office of Scientific and Technical Information (OSTI.GOV)

David A. Tillman; Dao Duong; Bruce Miller

2009-07-15

Chlorine is a significant source of corrosion and deposition, both from coal and from biomass, and in PF boilers. This investigation was designed to highlight the potential for corrosion risks associated with once-through units and advanced cycles. The research took the form of a detailed literature investigation to evaluate chlorine in solid fuels: coals of various ranks and origins, biomass fuels of a variety of types, petroleum cokes, and blends of the above. The investigation focused upon an extensive literature review of documents dating back to 1991. The focus is strictly corrosion and deposition. To address the deposition and corrosionmore » issues, this review evaluates the following considerations: concentrations of chlorine in available solid fuels including various coals and biomass fuels, forms of chlorine in those fuels, and reactions - including reactivities - of chlorine in such fuels. The assessment includes consideration of alkali metals and alkali earth elements as they react with, and to, the chlorine and other elements (e.g., sulfur) in the fuel and in the gaseous products of combustion. The assessment also includes other factors of combustion: for example, combustion conditions including excess O{sub 2} and combustion temperatures. It also considers analyses conducted at all levels: theoretical calculations, bench scale laboratory data and experiments, pilot plant experiments, and full scale plant experience. Case studies and plant surveys form a significant consideration in this review. The result of this investigation focuses upon the concentrations of chlorine acceptable in coals burned exclusively, in coals burned with biomass, and in biomass cofired with coal. Values are posited based upon type of fuel and combustion technology. Values are also posited based upon both first principles and field experience. 86 refs., 8 figs., 7 tabs.« less

Reactions of chlorine nitrate with HCl and H2O. [ozone controlling chemistry in stratosphere

NASA Technical Reports Server (NTRS)

Hatakeyama, Shiro; Leu, Ming-Taun

1986-01-01

The kinetics of the reactions of chlorine nitrate with HCl and H2O are characterized using a static photolysis/Fourier transform infrared spectrophotometer apparatus. For the homogeneous gas-phase reaction with HCl, an upper limit for the rate constant of less than 8.4 x 10 to the -21st, and for the reaction with H2O, a limit of less than 3.4 x 10 to the -21st cu cm/molecule per s, were obtained at 296 + or - 2 K. The yield of HNO3 is almost unity in both cases, and no synergistic effect is noted between HCl and H2O. The kinetic behavior of the reaction with H2O is well described by simple first-order kinetics, while the behavior of the reaction with HCl is described in terms of the Langmuir adsorption isotherm.

FIGAERO ToF CIMS measurements of chlorine photochemical activation by nitryl chloride chemistry at a semi-rural site in Beijing

NASA Astrophysics Data System (ADS)

Le Breton, Michael; Hallquist, Åsa M.; Kant Pathak, Ravi; Simpson, David; Wang, Yujue; Zheng, Jing; Yang, Yudong; Shang, Dongjie; Wang, Haichao; Lu, Keding; Guo, Song; Hu, Min; Hallquist, Mattias

2017-04-01

Severe pollution events across China pose a major threat to air quality and climate through the direct emission of pollutants, but also via the production of photochemically induced secondary pollutants. Nitryl chloride (ClNO2), produced from heterogeneous reactions of dinitrogen pentoxide (N2O5) and aerosols containing chloride, is photolysed rapidly in sunlight and activates chlorine. Subsequent daytime oxidation via the chlorine atom can proceed orders of magnitude faster than that of the hydroxyl radical and therefore significantly perturb radical budgets and concentrations of ozone and secondary pollutants. Knowledge of the formation pathways, abundance and fate of these secondary pollutants, which can depend on ClNO2 abundance, is not fully understood but is necessary to support abatement strategies which will efficiently account for both primary and secondary pollutants. A Time of Flight Chemical Ionisation Mass Spectrometer (ToF CIMS) utilising the Filter Inlet for Gases and AEROsols (FIGAERO) was deployed in Changping, Beijing, during June and July, 2016 as part of an intercollaborative project to assess the photochemical smog in China. Concentrations of ClNO2 regularly exceeded 500 ppt throughout the campaign and reached a maximum concentration of 2.8 ppb, whereas relatively low N2O5 concentrations were observed, indicating a rapid heterogeneous production of ClNO2. Correlation of particulate chloride and carbon monoxide during the campaign suggests an anthropogenic chlorine source, also supported by high daytime Cl2 concentrations. Observations of ClNO2 desorptions using the FIGAERO suggest a possible unaccounted particulate reservoir of active chlorine in highly polluted regions. The persistence of ClNO2 several hours passed sunrise significantly increases the atomic chlorine production rate throughout the day further perturbing standard daytime oxidation processes. Simultaneous ToF CIMS measurements of Cl2, ClNO2, HCl, HOCl, OClO and ClONO2 were implemented into steady state calculations using the Master Chemical Mechanism (MCM) to assess how the daytime activation of chlorine competes with OH as a dominant oxidant in this heavily polluted region. The reactions of atomic chlorine with VOCs are traced and assessed via the gas and particle phase measurements of chlorinated VOCs and supporting Proton Transfer Reaction Mass Spectrometer (PTR MS) VOC measurements. This provides the first high frequency measurements of unique tracers for chlorine atom chemistry, several of which are represented in the MCM, in both the gas and particle phase and enable the detailed assessment of their diurnal variation and importance for photochemical smog formation.

Transformation of Organophosphorus Pesticides in the Presence of Aqueous Chlorine: Kinetics, Pathways, and Structure-Activity Relationships

EPA Science Inventory

The fate of organophosphorus (OP) pesticides in the presence of aqueous chlorine was investigated under simulated drinking water treatment conditions. Intrinsic rate coefficients were found for the reaction of hypochlorous acid (kHOCl,OP) and hypochlorite ion (kOCl,OP) for eight...

Long term impact of anthropogenic emissions of halogenated hydrocarbons on stratospheric ozone level

NASA Technical Reports Server (NTRS)

1977-01-01

Reaction kinetics are studied for stratospheric chlorine atoms, OH initiated degradation of carbon-chlorine compounds, the chemical decomposition of stratospheric HCl and ClONO2. A photochemical study is made of the decomposition of O3 over the wavelength range 2935 to 3165 deg A.

Formation of N-nitrosodimethylamine (NDMA) from reaction of monochloramine: a new disinfection by-product.

PubMed

Choi, Junghoon; Valentine, Richard L

2002-02-01

Studies have been conducted specifically to investigate the hypothesis that N-nitrosodimethylamine (NDMA) can be produced by reactions involving monochloramine. Experiments were conducted using dimethylamine (DMA) as a model precursor. NDMA was formed from the reaction between DMA and monochloramine indicating that it should be considered a potential disinfection by-product. The formation of NDMA increased with increased monochloramine concentration and showed maximum in yield when DMA was varied at fixed monochloramine concentrations. The mass spectra of the NDMA formed from DMA and 15N isotope labeled monochloramine (15NH2Cl) showed that the source of one of the nitrogen atoms in the nitroso group in NDMA was from monochloramine. Addition of 0.05 and 0.5 mM of preformed monochloramine to a secondarily treated wastewater at pH 7.2 also resulted in the formation of 3.6 and 111 ng/L of NDMA, respectively, showing that this is indeed an environmentally relevant NDMA formation pathway. The proposed NDMA formation mechanism consists of (i) the formation of 1,1-dimethylhydrazine (UDMH) intermediate from the reaction of DMA with monochloramine followed by, (ii) the oxidation of UDMH by monochloramine to NDMA, and (iii) the reversible chlorine transfer reaction between monochloramine and DMA which is parallel to (i). We conclude that reactions involving monochloramine in addition to classical nitrosation reactions are potentially important pathways for NDMA formation.

Potential for formation of disinfection by-products from storage of chlorinated surface water in the Basalt aquifer near Fallon, Nevada

USGS Publications Warehouse

Fram, Miranda S.; Maurer, Douglas K.; Lico, Michael S.

2005-01-01

Increased pumpage from a basalt aquifer near Fallon, Nevada, has caused its water levels to decline and has induced changes in the quality of water pumped from the basalt. The aquifer is the sole source of water for municipal supply to the city of Fallon, the Naval Air Station Fallon, and the Fallon Paiute-Shoshone Tribe. These changes may be mitigated by storage of surface water in the basalt for subsequent use. Because chlorination of the surface water may be required for storage, the U.S. Geological Survey, in cooperation with the Fallon Paiute-Shoshone Tribe, made laboratory tests using laboratory carbon-organic-free water, surface-water, ground-water, and basaltic-rock samples to determine the potential for formation of disinfection by-products. Experiments with water samples only (no rock and no chlorine) indicated no change in dissolved-organic-carbon (DOC) concentrations over a 20-day reaction period; whereas, all experiments using rock, water, and no chlorine indicated an increase in DOC concentrations. The greatest increase in DOC concentrations for all three water samples occurred in experiments with the rock samples from outcrops on Rattlesnake Hill. Experiments with water only and chlorine yielded a total trihalomethane (THM) concentration of 97.4 ?g/L for the ground-water sample and 347 ?g/L for the surface-water sample. Experiments with mixtures of water, rocks, and chlorine indicated that reactions with the rock consumed chlorine and released significant amounts of organic carbon from the rock, increasing the DOC concentration in the water. The organic carbon in the rocks likely is associated with the secondary clay minerals that line vesicles and fractures in the rocks. THM concentrations were greatest, from 335 to 909 ?g/L, for surface water equilibrated with rock samples from Rattlesnake Hill. However, the concentration of chlorine required to produce these high THM concentrations ranged from 18 to 84 mg/L. The results of the experiments suggest that the amount of organic carbon released from the rocks during successive cycles of recharge, storage, and recovery of chlorinated surface water may be relatively small. The chlorine demand of the rocks is so large that all of the free chlorine in the entire volume of recharged water likely would be consumed by only a very small volume of the aquifer surrounding an injection well, or beneath an infiltration bed. The majority of the volume of the aquifer filled by the stored water likely would never come in contact with free chlorine, and the increases in concentration of DOC observed in these experiments likely would occur in a very small volume of the stored water. For this reason, increases in concentration of THMs for the entire volume of water stored also likely would be considerably less than those measured in these experiments. To test this hypothesis, additional laboratory experiments using varying levels of chlorination, varying lengths of reaction periods, and repeated cycles of chlorination would be useful. A field experiment made at a small scale in an isolated part of the basalt aquifer would aid in the design of an operational system.

Reductive Outer-Sphere Single Electron Transfer Is an Exception Rather than the Rule in Natural and Engineered Chlorinated Ethene Dehalogenation.

PubMed

Heckel, Benjamin; Cretnik, Stefan; Kliegman, Sarah; Shouakar-Stash, Orfan; McNeill, Kristopher; Elsner, Martin

2017-09-05

Chlorinated ethenes (CEs) such as perchloroethylene, trichloroethylene and dichloroethylene are notorious groundwater contaminants. Although reductive dehalogenation is key to their environmental and engineered degradation, underlying reaction mechanisms remain elusive. Outer-sphere reductive single electron transfer (OS-SET) has been proposed for such different processes as Vitamin B 12 -dependent biodegradation and zerovalent metal-mediated dehalogenation. Compound-specific isotope effect ( 13 C/ 12 C, 37 Cl/ 35 Cl) analysis offers a new opportunity to test these hypotheses. Defined OS-SET model reactants (CO 2 radical anions, S 2- -doped graphene oxide in water) caused strong carbon (ε C = -7.9‰ to -11.9‰), but negligible chlorine isotope effects (ε Cl = -0.12‰ to 0.04‰) in CEs. Greater chlorine isotope effects were observed in CHCl 3 (ε C = -7.7‰, ε Cl = -2.6‰), and in CEs when the exergonicity of C-Cl bond cleavage was reduced in an organic solvent (reaction with arene radical anions in glyme). Together, this points to dissociative OS-SET (SET to a σ* orbital concerted with C-Cl breakage) in alkanes compared to stepwise OS-SET (SET to a π* orbital followed by C-Cl cleavage) in ethenes. The nonexistent chlorine isotope effects of chlorinated ethenes in all aqueous OS-SET experiments contrast strongly with pronounced Cl isotope fractionation in all natural and engineered reductive dehalogenations reported to date suggesting that OS-SET is an exception rather than the rule in environmental transformations of chlorinated ethenes.

Effects of Chlorine Promoted Oxidation on Arsenic Release from Sulfide Minerals

NASA Astrophysics Data System (ADS)

West, N.; Schreiber, M.; Gotkowitz, M.

2007-12-01

High arsenic concentrations (>100 ppb) have been measured in wells completed in the Ordovician St. Peter sandstone aquifer of eastern Wisconsin. The primary source of arsenic is As-bearing sulfide minerals within the aquifer. Periodic disinfection of wells by chlorination may facilitate arsenic release to groundwater by increasing the rate of sulfide mineral oxidation. During typical well disinfection procedures, aquifer solids exposed along uncased portions of wells remain in direct contact with chlorine disinfection solutions for up to twenty-four hours. Due to the redox sensitivity of arsenic mobility in groundwater, it is important to evaluate the effect of repeatedly adding oxidizers to an arsenic impacted aquifer system. This study focuses on abiotic processes that mobilize arsenic from the solid phase during controlled exposure to chlorinated solutions. Two St. Peter samples with As concentrations of 21 and 674 ppm were selected for the experiments. Before reaction, the aquifer mineralogy is characterized using scanning electron microscopy (SEM) and electron microprobe analysis (EMPA). The samples are then reacted with solutions of 60 mg/L free chlorine, 1200 mg/L free chlorine, or nanopure water (control) at pH 7.0 and pH 8.5. These parameters represent typical solution chemistries present within the wells after disinfection. Solutions are sampled periodically during the experiments and analyzed for As, Fe, other trace metals such as Co, Mo, Cr, and Ni, and sulfate. Analysis of the post-reaction solids using SEM, EMPA, laser ablation ICP-MS and Raman techniques are used to document the changes in mineralogy due to chlorination and to document which solid phases contain As.

Genotoxic properties of haloacetonitriles: drinking water by-products of chlorine disinfection

DOE Office of Scientific and Technical Information (OSTI.GOV)

Daniel, F.B.; Schenck, K.M.; Mattox, J.K.

Chlorinated and brominated haloacetonitriles (HAN), known drinking water contaminants which form during chlorine disinfection, were investigated for genotoxic activity. The HAN produced DNA strand breaks in cultured human lymphoblastic (CCRF-CEM) cells, bound to the nucleophilic trapping agent 4-(p-nitrobenzyl)pyridine and formed a covalent bond to polyadenylic acid in a cell-free reaction system. Thus, we have demonstrated that these chemicals are genotoxic, which would indicate a potential for carcinogenic activity and for human health hazard.

Launch Safety, Toxicity, and Environmental Effects of the High Performance Oxidizer ClF(5)

DTIC Science & Technology

1994-03-31

Pentafluoride," J. Phys. Chem. 74, 1183 (1970). 7. J. A. Blauer, H. G. McMath, F. C. Jaye, and V. S, Engleman, " Decomposition Kinetics of Chlorine Trifluoride ...similar. A greater concern is propellant release in the stratosphere. Fluorine atoms lead to catalytic decomposition of 03 at rates similar to chlorine ...Propulsion Meeting - Publication 550, 3, 447 (1990). 4. R. F. Sawyer, E. T. McMullen, and P. Purgalis, "The Reaction of Hydrazine and Chlorine Pentafluoride

Dechlorination of TCE with palladized iron

DOEpatents

Fernando, Quintus; Muftikian, Rosy; Korte, Nic

1997-01-01

The present invention relates to various methods, such as an above-ground method and an in-ground method, of using a palladized iron bimetallic system for the dechlorination of chlorinated organic compounds from effluents containing the same. The use of palladized iron bimetallic system results in the dechlorination of the chlorinated organic compound into environmentally safe reaction products. The present invention also provides kits, devices, and other instruments that use the above-mentioned palladized iron bimetallic system for the dechlorination of chlorinated organic compounds.

Dechlorination of TCE with palladized iron

DOEpatents

Fernando, Quintus; Muftikian, Rosy; Korte, Nic

1998-01-01

The present invention relates to various methods, such as an above-ground method and an in-ground method, of using a palladized iron bimetallic system for the dechlorination of chlorinated organic compounds from effluents containing the same. The use of palladized iron bimetallic system results in the dechlorination of the chlorinated organic compound into environmentally safe reaction products. The present invention also provides kits, devices, and other instruments that use the above-mentioned palladized iron bimetallic system for the dechlorination of chlorinated organic compounds.

Dechlorination of TCE with palladized iron

DOEpatents

Fernando, Q.; Muftikian, R.; Korte, N.

1998-06-02

The present invention relates to various methods, such as an above-ground method and an in-ground method, of using a palladized iron bimetallic system for the dechlorination of chlorinated organic compounds from effluents containing the same. The use of palladized iron bimetallic system results in the dechlorination of the chlorinated organic compound into environmentally safe reaction products. The present invention also provides kits, devices, and other instruments that use the above-mentioned palladized iron bimetallic system for the dechlorination of chlorinated organic compounds. 10 figs.

Dechlorination of TCE with palladized iron

DOEpatents

Fernando, Q.; Muftikian, R.; Korte, N.

1997-03-18

The present invention relates to various methods, such as an above-ground method and an in-ground method, of using a palladized iron bimetallic system for the dechlorination of chlorinated organic compounds from effluents containing the same. The use of palladized iron bimetallic system results in the dechlorination of the chlorinated organic compound into environmentally safe reaction products. The present invention also provides kits, devices, and other instruments that use the above-mentioned palladized iron bimetallic system for the dechlorination of chlorinated organic compounds. 10 figs.

Occurrence of by-products of strong oxidants reacting with drinking water contaminants--scope of the problem.

PubMed Central

Rice, R G; Gomez-Taylor, M

1986-01-01

This paper describes results of a detailed literature review of the organic and inorganic by-products that have been identified as being formed in aqueous solution with four of the strong oxidizing/disinfecting agents commonly employed in drinking water treatment. These agents are: chlorine, chlorine dioxide, chloramine, and ozone. Significant findings include the production of similar nonchlorinated organic oxidation products from chlorine, chlorine dioxide, and ozone. In addition, all three chlorinous oxidants/disinfectants can produce chlorinated by-products under certain conditions. The presence of chloronitrile compounds in drinking waters is indicated to arise from reactions of chlorine or chloramine to amine/amide functions in amino acids or proteinaceous materials, followed by dehydrohalogenation. These nitriles could hydrolyze to produce the corresponding chloroacetic acids. It is concluded that to minimize the presence of oxidation by-products in drinking waters, the concentrations of oxidizable organic/inorganic impurities should be lowered before any oxidizing agent is added. PMID:3545807

Evidence for strong, widespread chlorine radical chemistry associated with pollution outflow from continental Asia

PubMed Central

Baker, Angela K.; Sauvage, Carina; Thorenz, Ute R.; van Velthoven, Peter; Oram, David E.; Zahn, Andreas; Brenninkmeijer, Carl A. M.; Williams, Jonathan

2016-01-01

The chlorine radical is a potent atmospheric oxidant, capable of perturbing tropospheric oxidative cycles normally controlled by the hydroxyl radical. Significantly faster reaction rates allow chlorine radicals to expedite oxidation of hydrocarbons, including methane, and in polluted environments, to enhance ozone production. Here we present evidence, from the CARIBIC airborne dataset, for extensive chlorine radical chemistry associated with Asian pollution outflow, from airborne observations made over the Malaysian Peninsula in winter. This region is known for persistent convection that regularly delivers surface air to higher altitudes and serves as a major transport pathway into the stratosphere. Oxidant ratios inferred from hydrocarbon relationships show that chlorine radicals were regionally more important than hydroxyl radicals for alkane oxidation and were also important for methane and alkene oxidation (>10%). Our observations reveal pollution-related chlorine chemistry that is both widespread and recurrent, and has implications for tropospheric oxidizing capacity, stratospheric composition and ozone chemistry. PMID:27845366

PPCP degradation by chlorine-UV processes in ammoniacal water: new reaction insights, kinetic modeling and DBP formation.

PubMed

Zhang, Ruochun; Meng, Tan; Huang, Ching-Hua; Ben, Weiwei; Yao, Hong; Liu, Ruini; Sun, Peizhe

2018-06-15

The combination of chlorine and UV (i.e. chlorine-UV process) has been attracting more attentions in recent years due to its ready incorporation into existing water treatment facilities to remove PPCPs. However, limited information is available on the impact of total ammonia nitrogen (TAN). This study investigated two model PPCPs, N,N-diethyl-3-toluamide (DEET) and caffeine (CAF), in the two stages of chlorine-UV process (i.e. chlorination and UV/chlor(am)ine) to elucidate the impact of TAN. During chlorination, the degradation of DEET and CAF was positively correlated with the overall consumption of total chlorine by TAN. Reactive nitrogen intermediates, including HNO/NO- and ONOOH/ONOO-, along with OH were identified as major contributors to the removal of DEET and CAF. During UV irradiation, DEET and CAF were degraded under UV/chlorine or UV/NH2Cl conditions. OH and Cl were the major reactive species to degrade DEET and CAF under UV/NH2Cl conditions, whereas OCl played a major role for degrading CAF under UV/chlorine conditions. Numerical models were developed to predict the removal of DEET and CAF under chlorination-UV process. Chlorinated disinfection byproducts were detected. Overall, this study presented kinetic features and mechanistic insights on the degradation of PPCPs under chlorine-UV process in ammoniacal water.

Tested Demonstrations.

ERIC Educational Resources Information Center

Gilbert, George L., Ed.

1983-01-01

Free radical chlorination of methane is used in organic chemistry to introduce free radical/chain reactions. In spite of its common occurrence, demonstrations of the reaction are uncommon. Therefore, such a demonstration is provided, including background information, preparation of reactants/reaction vessel, introduction of reactants, irradiation,…

Biodegradation of Chlorinated Solvents: Reactions near DNAPL and Enzyme Function

DOE Office of Scientific and Technical Information (OSTI.GOV)

McCarty, P. L.; Spormann, Alfred M.; Criddle, Craig, S.

Chlorinated solvents are among the most widespread groundwater contaminants in the country, contamination which is also among the most difficult and expensive for remediation. These solvents are biodegradable in the absence of oxygen, but this biodegradation requires both a food source for the organisms (electron donor) and the presence of chlorinated solvent biodegrading organisms. These two requirements are present naturally at some contamination sites, leading to natural attenuation of the solvents. If one or both requirements are absent, then engineered bioremediation either through addition of an external electron donor or through bioaugmentation with appropriate microorganisms, or both, may be usedmore » for site remediation. The most difficult case for cleanup is when a large residual of undissolved chlorinated solvents are present, residing as dense -non-aqueous-phase- liquid ( DNAPL). A major focus of this study was on the potential for biodegradation of the solvents when pre sent as DNAPL where concentrations are very high and potential for toxicity to microorganisms exist. Another focus was on a better understanding of the biological mechanisms involved in chlorinated solvent biodegradation . These studies were directed towards the chlorinated solvents, trichloroethene (TCE), tetrachloroethene or perchloroethene (PCE), and carbon tetrachloride (CT). The potential for biodegradation of TCE and PCE DNAPL was clearly demonstrated in this research. From column soil studies and batch studies we found there to be a clear advantage in focusing efforts at bioremediation near the DNAPL. Here, chlorinated solvent concentrations are the highest, both because of more favorable reaction kinetics and because such high solvent concentrations are toxic to microorganisms, such as methanogens, which compete with dehalogenators for the electron donor. Additionally, biodegradation near a PCE DNAPL results in an enhanced dissolution rate for the chlorinated solvent, by factors of three to five times, leading to a more rapid clean-up of the DNAPL zone. The most favored electron donor to add is one which partitions well with the chlorinated solvent or can be concentrated near it. Unfortunately, an ideal electron donor, such as vegetable oil, is difficult to introduce and mix with DNAPL in the ground, doing this properly remains an engineering challenge. Numerical model studies have indicated that several factors may significantly influence the rate and extent of enhancement, including the inhibitory effects of PCE and cDCE, the level of ED concentration, DNAPL configuration, and competition for ED. Such factors need to be considered when contemplating engineered DNAPL bioremediation. Pseudomonas stuzeri KC is an organism that transforms CT to carbon dioxide and chloride without the formation of the hazardous intermediate, chloroform. This is accomplished by production and secretion of a molecule called PDTC. This study was direct ed towards determining how PDTC works. Cu (II) at a ratio of 1:1 Cu to PDTC was found to result in the most rapid CT transformation, confirming that the PDTC-Cu complex is both a reactant and a catalyst in CT transformation. CT degradation requires that the PDTC be in a reduced form, which is generated by contact with cell components. Fe(II) inhibits CT transformation by PDTC. Studies indicated that this inhibition is enhanced by some compound or factor in the supernatant with molecular weight greater than 10,000 Da. We have made progress in determining what this factor might be, but have not yet been able to identify it. In related studies, we found that CT transformation by another organism, Shewanella oneidensis MR1, also involves an excreted factor, but this factor is different from PDTC and results in chloroform transformation as an intermediate. Our studies have indicated that this factor is similar to vitamin K2, and we have also confirmed that vitamin K2 does transform C T into chloroform.« less

Transformation of methylparaben during water chlorination: Effects of bromide and dissolved organic matter on reaction kinetics and transformation pathways.

PubMed

Yoom, Hoonsik; Shin, Jaedon; Ra, Jiwoon; Son, Heejong; Ryu, Dongchoon; Kim, Changwon; Lee, Yunho

2018-09-01

The reaction kinetics, products, and pathways of methylparaben (MeP) during water chlorination with and without bromide (Br - ) were investigated to better understand the fate of parabens in chlorinated waters. During the chlorination of MeP-spiked waters without Br - , MeP was transformed into mono-Cl-MeP and di-Cl-MeP with apparent second-order rate constants (k app ) of 64M -1 s -1 and 243M -1 s -1 at pH7, respectively, while further chlorination of di-Cl-MeP was relatively slower (k app =1.3M -1 s -1 at pH7). With increasing Br - concentration, brominated MePs, such as mono-Br-MeP, Br-Cl-MeP, and di-Br-MeP, became major transformation products. The di-halogenated MePs (di-Cl-MeP, Br,Cl-MeP, and di-Br-MeP) showed relatively low reactivity to chlorine at pH7 (k app =1.3-4.6M -1 s -1 ) and bromine (k app =32-71M -1 s -1 ), which explains the observed high stability of di-halogenated MePs in chlorinated waters. With increasing pH from 7 to 8.5, the transformation of di-halogenated MePs was further slowed due to the decreasing reactivity of di-MePs to chlorine. The formation of the di-halogenated MePs and their further transformation become considerably faster at Br - concentrations higher than 0.5μM (40μg/L). Nonetheless, the accelerating effect of Br - diminishes in the presence of dissolved organic matter (DOM) extract (Suwannee River humic acid (SRHA)) due to a more rapid consumption of bromine by DOM than chlorine. The effect of Br - on the fate of MeP was less in the tested real water matrices, possibly due to a more rapid bromine consumption by the real water DOM compared to SRHA. A kinetic model was developed based on the determined species-specific second-order rate constants for chlorination/bromination of MeP and its chlorinated and brominated MePs and the transformation pathway information, which could reasonably simulate the transformation of MePs during the chlorination of water in the presence of Br - and selected DOM. Copyright © 2017 Elsevier B.V. All rights reserved.

Desulfurizing Coal By Chlorinolysis and Hydrogenation

NASA Technical Reports Server (NTRS)

Kalvinskas, J. J.; Rohatgi, N. K.

1983-01-01

85 percent of organic and pyritic sulfur in coal removed by combination of chlorinolysis and hydrogeneration. Coal is fed to hydrogenator after chlorination. Coal flows against hydrogen current increasing mixing and reducing hydrogen consumption. Excess hydrogen is recovered from gaseous reaction products. Product coal contained 62.5 percent less total sulfur than same coal after chlorination.

LP/LIF STUDY OF THE FORMATION AND CONSUMPTION OF MERCURY (I) CHLORIDE: KINETICS OF MERCURY CHLORINATION

EPA Science Inventory

The laser photolysis/laser induced flourescence (LP/LIF) technique has been applied to studies of gas-phase mercury (Hg) chlorination. Mercury (I) chloride (HgCl) has been detected via LIF at 272 nm from reactions of elemental Hg and Cl atoms generated from the 193 nm photolysis ...

Economical Treatment of Dredged Material to Facilitate Beneficial Use

DTIC Science & Technology

2014-08-01

Mifflin DM stabilization results . ............................................................................................. 54 ERDC/EL TR-14-11 vii...deficits resulting from chemical reactions taking place in reduced sediments during disposal. Direct injection of chemical oxidants into the...usually the meta- and para-chlorines on the biphenyl structure. Aerobic conditions usually degrade the resulting lightly chlorinated PCBs with the

Stratospheric Ozone Reactive Chemicals Generated by Space Launches Worldwide.

DTIC Science & Technology

1994-11-01

I ODCs). Their carbon - chlorine bond is severed in the stratosphere by solar photolysis or reaction. Once the carbon-chlorine bond is broken, the...include the Russian Proton and Energia , and the Chinese Long March series. Roughly half (seven per year) of the Ariane 4 launches use two solid strap-ons

Synthesis, structural investigations on organotin(IV) chlorin-e6 complexes, their effect on sea urchin embryonic development and induced apoptosis.

PubMed

Pellerito, Claudia; D'Agati, Paolo; Fiore, Tiziana; Mansueto, Caterina; Mansueto, Valentina; Stocco, Giancarlo; Nagy, László; Pellerito, Lorenzo

2005-06-01

Four new organotin(IV) chlorin derivatives, [chlorin=chlorin-e(6)=21H,23H-porphine-2-propanoic acid, 18-carboxy-20-(carboxymethyl)-8-ethenyl-13-ethyl-2,3-di-hydro-3,7,12,17-tetramethyl-(2S-trans)-], with formula (R(2)Sn)(3)(chlorin)(2).2H(2)O (R=Me, n-Bu) and (R(3)Sn)(3)chlorin.2H(2)O (R=Me, Ph) have been synthesized. The solid state and solution phase structures have been investigated by FT-IR, (119)Sn Mössbauer, (1)H and (13)C NMR spectroscopy. In the solid state, (R(2)Sn)(3)(chlorin)(2).2H(2)O complexes contain six coordinated Sn(IV), in a skew trapezoidal environment by forming trans-R(2)SnO(4) polymeric units. As far as (R(3)Sn)(3)chlorin.2H(2)O complexes are concerned, Sn(IV) is five coordinated in a polymeric (oligomeric) trigonal bipyramidal environment and eq-R(3)SnO(2) units, in the solid state. In saturated solutions, a polymeric structure comparable to the solid phase, with carboxylate groups of the ligand behaving in monoanionic bidentate fashion bridging Sn(IV) atoms, was detected for the (Me(3)Sn)(3)chlorin.2H(2)O complex, while in more diluted ones a tetrahedral configuration for the trimethyltin(IV) moieties was observed. Cytotoxic activity of the novel organotin(IV) chlorin was investigated in order to assay the effect on sea urchin embryonic development. The results obtained demonstrated that (n-Bu(2)Sn)(3)(chlorin)(2).2H(2)O and (Ph(3)Sn)(3)chlorin.2H(2)O exerted the antimitotic effect on the early stages of sea urchin development. In addition, the cytotoxic effect exerted by (n-Bu(2)Sn)(3)(chlorin)(2).2H(2)O appeared with necrosis of the blastomeres, which were clearly destroyed. After treatment with (Ph(3)Sn)(3)chlorin.2H(2)O, a programmed cell death was triggered, as shown by light microscope observations through morphological assays. The apoptotic events in 2-cell stage embryos revealed: (i) DNA fragmentation, with the TUNEL reaction (terminal deoxynucleotidyl transferase-mediated dUTP nick end labelling); (ii) phosphatidylserine translocation in the membrane, with Annexin-V assay and (iii) cytoplasm blebbing, with the TUNEL reaction. The results demonstrated that the novel compound (Ph(3)Sn)(3)chlorin.2H(2)O was the most toxic derivative, by exerting antimitotic effect very early and by triggering apoptosis in the 2-cell stage of sea urchin embryonic development.

Ion-enhanced chemical etching of ZrO2 in a chlorine discharge

NASA Astrophysics Data System (ADS)

Sha, Lin; Cho, Byeong-Ok; Chang, Jane P.

2002-09-01

Chlorine plasma is found to chemically etch ZrO2 thin films in an electron cyclotron resonance reactor, and the etch rate scaled linearly with the square root of ion energy at high ion energies with a threshold energy between 12-20 eV. The etching rate decreased monotonically with increasing chamber pressures, which corresponds to reduced electron temperatures. Optical emission spectroscopy and quadrupole mass spectrometry were used to identify the reaction etching products. No Zr, O, or ZrCl were detected as etching products, but highly chlorinated zirconium compounds (ZrCl2, ZrCl3, and ZrCl4) and ClO were found to be the dominant etching products. ZrCl3 was the dominant etching products at low ion energies, while ZrCl4 became dominant at higher ion energies. This is consistent with greater momentum transfer and enhanced surface chlorination, as determined by x-ray photoelectron spectroscopy, at increased ion energies. Several ion-enhanced chemical reactions are proposed to contribute to the ZrO2 etching. copyright 2002 American Vacuum Society.

Elucidating the Higher Stability of Vanadium (V) Cations in Mixed Acid Based Redox Flow Battery Electrolytes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Vijayakumar, M.; Wang, Wei; Nie, Zimin

2013-11-01

The Vanadium (V) cation structures in mixed acid based electrolyte solution were analysed by density functional theory (DFT) based computational modelling and 51V and 35Cl Nuclear Magnetic Resonance (NMR) spectroscopy. The Vanadium (V) cation exists as di-nuclear [V2O3Cl2.6H2O]2+ compound at higher vanadium concentrations (≥1.75M). In particular, at high temperatures (>295K) this di-nuclear compound undergoes ligand exchange process with nearby solvent chlorine molecule and forms chlorine bonded [V2O3Cl2.6H2O]2+ compound. This chlorine bonded [V2O3Cl2.6H2O]2+ compound might be resistant to the de-protonation reaction which is the initial step in the precipitation reaction in Vanadium based electrolyte solutions. The combined theoretical and experimental approachmore » reveals that formation of chlorine bonded [V2O3Cl2.6H2O]2+ compound might be central to the observed higher thermal stability of mixed acid based Vanadium (V) electrolyte solutions.« less

Method of introducing additive into a reaction gas flow

DOE Office of Scientific and Technical Information (OSTI.GOV)

Michelfelder, S.; Chughtai, M.Y.

1984-04-03

A method of continuously introducing additive, which is conveyed by gaseous and/or liquid carriers, into a turbulent reaction gas flow in the combustion chamber of a steam generator having dry ash withdrawal for selective removal, in a dry manner, of environmentally harmful gaseous noxious materials, such as sulfur, chlorine, and chlorine compounds, which are contained in a hot reaction gas flow which results after a complete or incomplete flame combustion of solid, liquid, or gaseous fuels. Depending upon the additive introduced, heat is stored and/or used for decomposition reactions. The additive, is first introduced at one or more input locations,more » due to locally different pressure conditions in the combustion chamber, into one or more recirculation flows which are within the system and are closed. The additive is subsequently withdrawn from these recirculation flows and is introduced into the reaction gas flow.« less

More rapid polar ozone depletion through the reaction of HOCl with HCl on polar stratospheric clouds

NASA Technical Reports Server (NTRS)

Prather, Michael J.

1992-01-01

The direct reaction of HOCl with HCl is shown here to play a critical part in polar ozone loss. Observations of high levels of OClO and ClO in the springtime Antarctic stratosphere confirm that most of the available chlorine is in the form of ClO(x). But current photochemical models have difficulty converting HCl to ClO(x) rapidly enough in early spring to account fully for the observations. Here, a chemical model is used to show that the direct reaction of HOCl with HCl provides the missing mechanism. As alternative sources of nitrogen-containing oxidants have been converted in the late autumn to inactive HNO3 by known reactions on the sulfate layer aerosols, the reaction of HOCl with HCl on polar stratospheric clouds becomes the most important pathway for releasing that stratospheric chlorine which goes into polar night as HCl.

Formation of brominated disinfection byproducts during Chloramination of drinking water: new polar species and overall kinetics.

PubMed

Zhai, Hongyan; Zhang, Xiangru; Zhu, Xiaohu; Liu, Jiaqi; Ji, Min

2014-01-01

The formation of brominated disinfection byproducts (Br-DBPs), which are generally significantly more cytotoxic and genotoxic than their chlorinated analogues, in chloramination has not been fully examined. In this work, the formation of new polar Br-DBPs in simulated drinking waters was examined using state-of-the-art ultraperformance liquid chromatography/electrospray ionization-triple quadrupole mass spectrometry. As many as 29 aliphatic, aromatic, or nitrogenous polar Br-DBPs were detected in chloramination, and five of them (including 2,4,6-tribromoresorcinol, 2,6-dibromo-4-nitrophenol, 2,2,4-tribromo-5-hydroxy-4-cyclopentene-1,3-dione, 2,2,4-dibromochloro-5-hydroxy-4-cyclopentene-1,3-dione, and 2,2,4-bromodichloro-5-hydroxy-4-cyclopentene-1,3-dione) were tentatively identified. Unlike chlorination, chloramination favored the formation of aromatic and nitrogenous polar Br-DBPs and was mild enough to allow polar intermediate Br-DBPs to accumulate. To further explore the formation mechanism of Br-DBPs in chloramination, a quantitative empirical model involving 33 major reactions was developed to describe the overall kinetics. According to the modeling results, bromochloramine and monobromamine were the major species responsible for 54.2-58.1% and 41.7-45.7%, respectively, of the formed Br-DBPs, while hypobromous acid accounted for only 0.2% of the formed Br-DBPs; direct reactions between monochloramine and natural organic matter accounted for the majority of the formed chlorinated DBPs (93.7-95.1%); hypochlorous acid and hypobromous acid in the chloramination were at ng/L or subng/L levels, which were not enough to cause polar intermediate Br-DBPs to decompose.

Thermal reactive hazards of HMX with contaminants.

PubMed

Peng, Deng-Jr; Chang, Cheng-Ming; Chiu, Miin

2004-10-18

In the past, many unexpected runaway accidents occurred in manufacturing processes, involving volatile chemical and explosive storage and transportation. Incompatible product reactions of high explosives must be carefully considered using loss prevention strategies for thermal hazards risk analysis. High explosive reactions vary via environmental changes, contact materials, or process situations, such as onset temperature and shifts in reaction type when high explosives are in contact with contaminants. Therefore, the manufacture and handling of high explosives require the utmost in safety and loss prevention. HMX (cyclotetramethyene tetranitramine) is one kind of high explosive widely used around the world which is stable with high detonation strength properties. In this study, the influences of contaminants on HMX are investigated. The studied contaminants include ferrous chloride tetrahydrate, ferric chloride hexahydrate, acetone solution, acetic acid, and nitric acid. DSC thermal curves and incompatible reaction kinetic evaluations were preformed using iron, chlorine and acid. Organic acetone solution has lesser effects on HMX. Hopefully, this study will lead to improved thermal hazards risk analysis and reduce accidents.

Transformation of Flame Retardant Tetrabromobisphenol A by Aqueous Chlorine and the Effect of Humic Acid.

PubMed

Gao, Yuan; Pang, Su-Yan; Jiang, Jin; Ma, Jun; Zhou, Yang; Li, Juan; Wang, Li-Hong; Lu, Xue-Ting; Yuan, Li-Peng

2016-09-06

In this work, it was found that the most widely used brominated flame retardant tetrabromobisphenol A (TBrBPA) could be transformed by free chlorine over a wide pH range from 5 to 10 with apparent second-order rate constants from 138 to 3210 M(-1)·s(-1). A total of eight products, including one quinone-like compound (i.e., 2,6-dibromoquinone), two dimers, and several simple halogenated phenols (e.g., 4-(2-hydroxyisopropyl)-2,6-dibromophenol, 2,6-dibromohydroquinone, and 2,4,6-tribromophenol), were detected by high-performance liquid chromatography tandem mass spectrometry (HPLC-MS/MS) using a novel precursor ion scan (PIS) approach. A tentative reaction pathway was proposed: chlorine initially oxidized TBrBPA leading to the formation of a phenoxy radical, and then this primary radical and its secondary intermediates (e.g., 2,6-dibromo-4-isopropylphenol carbocation) formed via beta-scission subsequently underwent substitution, dimerization, and oxidation reactions. Humic acid (HA) considerably inhibited the degradation rates of TBrBPA by chlorine even accounting for oxidant consumption. A similar inhibitory effect of HA was also observed in permanganate and ferrate oxidation. This inhibitory effect was possibly attributed to the fact that HA competitively reacted with the phenoxy radical of TBrBPA and reversed it back to parent TBrBPA. This study confirms that chlorine can transform phenolic compounds (e.g., TBrBPA) via electron transfer rather than the well-documented electrophilic substitution, which also have implications on the formation pathway of halo-benzoquinones during chlorine disinfection. These findings can improve the understanding of chlorine chemistry in water and wastewater treatment.

Cl app: android-based application program for monitoring the residue chlorine in water

NASA Astrophysics Data System (ADS)

Intaravanne, Yuttana; Sumriddetchkajorn, Sarun; Porntheeraphat, Supanit; Chaitavon, Kosom; Vuttivong, Sirajit

2015-07-01

A farmer usually uses a cheap chemical material called chlorine to destroy the cell structure of unwanted organisms and remove some plant effluents in a baby shrimp farm. A color changing of the reaction between chlorine and chemical indicator is used to monitor the residue chlorine in water before releasing a baby shrimp into a pond. To get rid of the error in color reading, our previous works showed how a smartphone can be functioned as a color reader for estimating the chlorine concentration in water. In this paper, we show the improvement of interior configuration of our prototype and the distribution to several baby shrimp farms. In the future, we plan to make it available worldwide through the online market as well as to develop more application programs for monitoring other chemical substances.

Proteomic Adaptations to Starvation Prepare Escherichia coli for Disinfection Tolerance

PubMed Central

Du, Zhe; Nandakumar, Renu; Nickerson, Kenneth; Li, Xu

2015-01-01

Despite the low nutrient level and constant presence of secondary disinfectants, bacterial re-growth still occurs in drinking water distribution systems. The molecular mechanisms that starved bacteria use to survive low-level chlorine-based disinfectants are not well understood. The objective of this study is to investigate these molecular mechanisms at the protein level that prepare starved cells for disinfection tolerance. Two commonly used secondary disinfectants chlorine and monochloramine, both at 1 mg/L, were used in this study. The proteomes of normal and starved Escherichia coli (K12 MG1655) cells were studied using quantitative proteomics. Over 60-min disinfection, starved cells showed significantly higher disinfection tolerance than normal cells based on the inactivation curves for both chlorine and monochloramine. Proteomic analyses suggest that starvation may prepare cells for the oxidative stress that chlorine-based disinfection will cause by affecting glutathione metabolism. In addition, proteins involved in stress regulation and stress responses were among the ones up-regulated under both starvation and chlorine/monochloramine disinfection. By comparing the fold changes under different conditions, it is suggested that starvation prepares E. coli for disinfection tolerance by increasing the expression of enzymes that can help cells survive chlorine/monochloramine disinfection. Protein co-expression analyses show that proteins in glycolysis and pentose phosphate pathway that were up-regulated under starvation are also involved in disinfection tolerance. Finally, the production and detoxification of methylglyoxal may be involved in the chlorine-based disinfection and cell defense mechanisms. PMID:25463932

Proteomic adaptations to starvation prepare Escherichia coli for disinfection tolerance.

PubMed

Du, Zhe; Nandakumar, Renu; Nickerson, Kenneth W; Li, Xu

2015-02-01

Despite the low nutrient level and constant presence of secondary disinfectants, bacterial re-growth still occurs in drinking water distribution systems. The molecular mechanisms that starved bacteria use to survive low-level chlorine-based disinfectants are not well understood. The objective of this study is to investigate these molecular mechanisms at the protein level that prepare starved cells for disinfection tolerance. Two commonly used secondary disinfectants chlorine and monochloramine, both at 1 mg/L, were used in this study. The proteomes of normal and starved Escherichia coli (K12 MG1655) cells were studied using quantitative proteomics. Over 60-min disinfection, starved cells showed significantly higher disinfection tolerance than normal cells based on the inactivation curves for both chlorine and monochloramine. Proteomic analyses suggest that starvation may prepare cells for the oxidative stress that chlorine-based disinfection will cause by affecting glutathione metabolism. In addition, proteins involved in stress regulation and stress responses were among the ones up-regulated under both starvation and chlorine/monochloramine disinfection. By comparing the fold changes under different conditions, it is suggested that starvation prepares E. coli for disinfection tolerance by increasing the expression of enzymes that can help cells survive chlorine/monochloramine disinfection. Protein co-expression analyses show that proteins in glycolysis and pentose phosphate pathway that were up-regulated under starvation are also involved in disinfection tolerance. Finally, the production and detoxification of methylglyoxal may be involved in the chlorine-based disinfection and cell defense mechanisms. Copyright © 2014 Elsevier Ltd. All rights reserved.

Chlorine fate and transport in drinking water distribution systems: Results from experimental and modeling studies

NASA Astrophysics Data System (ADS)

Clark, Robert M.

2011-12-01

It has become generally accepted that water quality can deteriorate in a distribution system through microbiological and chemical reactions in the bulk phase and/or at the pipe wall. The most serious aspect of water quality deterioration in a network is the loss of the disinfectant residual that can weaken the barrier against microbial contamination. Studies have suggested that one factor contributing to the loss of disinfectant residuals is the reaction between bulk phase disinfectants and pipe wall material. Free chlorine loss in corroded metal and PVC pipes, subject to changes in velocity, was assessed during an experiment conducted under controlled conditions in a specially constructed pipe loop located at the US Environmental Protection Agency's (EPA's) Test and Evaluation (T&E) Facility in Cincinnati, Ohio (USA). These studies demonstrated that in older unlined metal pipes, the loss of chlorine residual increases with velocity but that wall demand in PVC was negligible.

Chlorination of alumina in kaolinitic clay

NASA Astrophysics Data System (ADS)

Grob, B.; Richarz, W.

1984-09-01

The chlorination of alumina in kaolinitic clay with Cl2 and CO gas mixtures was studied gravimetrically. The effects of the calcination method and of NaCl addition on the reactivity of the clay were examined. Fast reaction rates were achieved only with samples previously exposed to a sulfating treatment. Optimum conditions, with maximum yield and selectivity to A1C13 and minimum SiO2 conversion, were found between 770 and 970 K. At higher temperatures the SiCl4 formed poisons the reactive alumina surface by selective chemisorption with a marked decrease of the reaction rate.

Analysis of the thermal reaction products of para polyphenylene by combined gas chromatography-mass spectrometry

NASA Technical Reports Server (NTRS)

Fewell, L. L.

1976-01-01

Analysis of the volatiles and sublimate produced when para-polyphenylene is pyrolyzed to constant weight under vacuum in the temperature range from 380 to 1000 C indicates that the polymer undergoes thermal degradation in two stages. The first stage involved dehydrohalogenation, which is essentially a curing reaction that produces crosslinking between polyphenylene chains resulting from the loss of chlorine from the polymer in the form of hydrogen chloride. The second stage of the thermal degradation is dehydrogenation because hydrogen is the major volatile species. Increasing amounts of polycyclic aromatic hydrocarbons (phenanthrene and 9, 10 benzphenanthrene) in the sublimate, concomitant with increasing C/H ratios of the polymeric residue with pyrolysis temperature, is consistent with the buildup of polynuclear structures in the polymer matrix.

Modeling the formation of TOCl, TOBr and TOI during chlor(am)ination of drinking water.

PubMed

Zhu, Xiaohu; Zhang, Xiangru

2016-06-01

The use of chlorine and chloramines in drinking water disinfection may produce innumerable halogenated disinfection byproducts (DBPs). Because of the impossibility of measuring the concentration and evaluating the toxicity of each individual halogenated DBP in a water sample, total organic halogen (TOX) as a collective parameter and a toxicity indicator for all the halogenated DBPs has been gaining popularity in recent years. TOX can be divided into total organic chlorine (TOCl), total organic bromine (TOBr), and total organic iodine (TOI). Previously, the authors' group studied the formation kinetics of TOCl and TOBr in chlor(am)ination using two models. In this study, we further explored the formation kinetics of TOI as well as TOCl and TOBr during chlor(am)ination by carefully selecting a series of iodine-related reactions and incorporating them into the two kinetic models. The models well predicted the levels of TOCl, TOBr, TOI, and total chlorine residual during chlorination and chloramination of simulated raw waters. According to the modeling results, 57.1-73.6% of the total generated iodinated DBPs in chlorination was converted to their chlorinated and brominated analogues by the substitution with hypochlorous acid and hypobromous acid; while in chloramination, with the presence of excessive monochloramine, the formed hypoiodous acid might react with monochloramine to form an iodine-substituted intermediate (proposed as chloroiodamine), which was responsible for 41.4-49.8% of the total generated iodinated DBPs, and meantime 51.9-52.6% of the total generated iodinated DBPs underwent deiodination via the base-catalyzed hydrolysis. The models were successfully applied in determining the lag time between the dosages of chlorine and ammonia, a challenging issue in chlorine-chloramine sequential treatment. This study provided important insights into kinetic reactions that control the formation of overall halogenated DBPs in chlor(am)ination. Copyright © 2016 Elsevier Ltd. All rights reserved.

A GC-MS method for the detection of toluene and ethylbenzene in volatile substance abuse.

PubMed

El-Haj, B M; Al-Amri, A M; Hassan, M H; Bin-Khadem, R K; Al-Hadi, A A

2000-09-01

The interference of some substances with the gas chromatography-flame ionization detection and gas chromatography-Fourier transform infrared detection of toluene and ethylbenzene in volatile substance abuse poses problems. A gas chromatography-mass spectrometry (GC-MS) method that will overcome such interference has been developed for the detection of toluene and/or ethylbenzene in the headspace of preparations and products containing these substances and in the headspace of blood samples in the cases of volatile substance abuse. The method is based on converting toluene to benzoic acid via the formation of benzotrichloride. The latter compound was obtained upon the reaction of toluene with chlorine gas under direct sunlight conditions. In the presence of water, benzotrichloride was converted to benzoic acid. Ethylbenzene was converted to benzoic acid and two phenylethanols via the formation of side chain chloro-substituted phenylethanes followed by reaction with water. The chloro-substituted phenylethanes were obtained by the reaction of ethylbenzene with chlorine under direct sunlight conditions. The benzoic acid resulting from toluene and/or ethylbenzene and the two phenylethanols resulting from ethylbenzene were detected by GC-MS as their trimethylsilyl (TMS) derivatives. For the method to be viable for the detection of volatile substance abuse, the chlorination reactions were effected in the gaseous state.

Oxidative degradation of pentachlorophenol by permanganate for ISCO application.

PubMed

Matta, Roger; Chiron, Serge

2018-03-01

Potassium permanganate (KMnO 4 ) has been an effective technology for the in situ chemical oxidation (ISCO) of many organic compounds including chlorinated alkanes and alkenes, but it has rarely been applied for oxidizing aromatic organochlorines. This study confirms the ability of permanganate to oxidize an aromatic chlorinated compound, pentachlorophenol (PCP), in an efficient manner at neutral pH. The rate of the reaction between KMnO 4 and PCP was calculated and the results indicated that the reaction between PCP and permanganate is relatively fast with a second-order rate constant k″ ∼ 30 M -1  s -1 . Besides the kinetic aspect, the authors identified the main reaction by-products, and proposed a possible reaction mechanism scheme. The general pathway shows the formation of chlorinated intermediates, and ultimately, the complete mineralization to chloride, water, and CO 2 confirmed by total organic carbon and chloride measurement in solution. Flow-through column experiments, consisting of flushing a PCP-contaminated sandy or natural soil with oxidant, showed the good ability of permanganate to eliminate the pollutant. After 24 h of treatment, 77% and 56% of PCP abatement were obtained for sandy and natural soil, respectively. These findings show the high potential of permanganate for the in situ remediation of aromatic organochlorine contaminated soils.

Oxidation of fluoroquinolone antibiotics and structurally related amines by chlorine dioxide: Reaction kinetics, product and pathway evaluation.

PubMed

Wang, Pei; He, Yi-Liang; Huang, Ching-Hua

2010-12-01

Fluoroquinolones (FQs) are a group of widely prescribed antibiotics and have been frequently detected in the aquatic environment. The reaction kinetics and transformation of seven FQs (ciprofloxacin (CIP), enrofloxacin (ENR), norfloxacin (NOR), ofloxacin (OFL), lomefloxacin (LOM), pipemidic acid (PIP) and flumequine (FLU)) and three structurally related amines (1-phenylpiperazine (PP), N-phenylmorpholine (PM) and 4-phenylpiperidine (PD)) toward chlorine dioxide (ClO(2)) were investigated to elucidate the behavior of FQs during ClO(2) disinfection processes. The reaction kinetics are highly pH-dependent, can be well described by a second-order kinetic model incorporating speciation of FQs, and follow the trend of OFL > ENR > CIP ∼ NOR ∼ LOM > > PIP in reactivity. Comparison among FQs and related amines and product characterization indicate that FQs' piperazine ring is the primary reactive center toward ClO(2). ClO(2) likely attacks FQ's piperazinyl N4 atom followed by concerted fragmentation involving piperazinyl N1 atom, leading to dealkylation, hydroxylation and intramolecular ring closure at the piperazine moiety. While FQs with tertiary N4 react faster with ClO(2) than FQs with secondary N4, the overall reactivity of the piperazine moiety also depends strongly on the quinolone ring through electronic effects. The reaction rate constants obtained in clean water matrix can be used to model the decay of CIP by ClO(2) in surface water samples, but overestimate the decay in wastewater samples. Overall, transformation of FQs, particularly for those with tertiary N4 amines, could be expected under typical ClO(2) disinfection conditions. However, the transformation may not eliminate antibacterial activity because of little destruction at the quinolone ring. Copyright © 2010 Elsevier Ltd. All rights reserved.

Chlorine inactivation of Tubifex tubifex in drinking water and the synergistic effect of sequential inactivation with UV irradiation and chlorine.

PubMed

Nie, Xiao-Bao; Li, Zhi-Hong; Long, Yuan-Nan; He, Pan-Pan; Xu, Chao

2017-06-01

The inactivation of Tubifex tubifex is important to prevent contamination of drinking water. Chlorine is a widely-used disinfectant and the key factor in the inactivation of T. tubifex. This study investigated the inactivation kinetics of chlorine on T. tubifex and the synergistic effect of the sequential use of chlorine and UV irradiation. The experimental results indicated that the Ct (concentration × time reaction ) concept could be used to evaluate the inactivation kinetics of T. tubifex with chlorine, thus allowing for the use of a simpler Ct approach for the assessment of T. tubifex chlorine inactivation requirements. The inactivation kinetics of T. tubifex by chlorine was found to be well-fitted to a delayed pseudo first-order Chick-Watson expression. Sequential experiments revealed that UV irradiation and chlorine worked synergistically to effectively inactivate T. tubifex as a result of the decreased activation energy, E a , induced by primary UV irradiation. Furthermore, the inactivation effectiveness of T. tubifex by chlorine was found to be affected by several drinking water quality parameters including pH, turbidity, and chemical oxygen demand with potassium permanganate (COD Mn ) concentration. High pH exhibited pronounced inactivation effectiveness and the decrease in turbidity and COD Mn concentrations contributed to the inactivation of T. tubifex. Copyright © 2017 Elsevier Ltd. All rights reserved.

Cold Incineration of Chlorophenols in Aqueous Solution by Advanced Electrochemical Process Electro-Fenton. Effect of Number and Position of Chlorine Atoms on the Degradation Kinetics

NASA Astrophysics Data System (ADS)

Oturan, Nihal; Panizza, Marco; Oturan, Mehmet A.

2009-09-01

This study reports the kinetics of the degradation of several chlorophenols (CPs), such as monochlorophenols (2-chlorophenol and 4-chlorophenol), dichlorophenols (2,4-dichlorophenol and 2,6- dichlorophenol), trichlorophenols (2,3,5- trichlorophenol and 2,4,5-trichlorophenol), 2,3,5,6-tetrachlorophenol, and pentachlorophenol, by the electro-Fenton process using a carbon felt cathode and a Pt anode. The effect of number and the position of the chlorine atoms in the aromatic ring on the oxidative degradation rate was evaluated and discussed. The oxidation reaction of all the CPs with hydroxyl radicals evidenced a pseudo-first-order kinetics and the rate constant decreased with increasing the number of chlorine atoms. The absolute rate constant of second-order reaction kinetics between CPs and •OH was determined by the competition kinetics method in the range of (3.56-7.75) × 109 M-1 s-1 and follows the same sequence of the apparent rate constants. The mineralization of several CPs and of a mixture of all CPs under study was monitored by the total organic carbon (TOC) removal and the chlorine release during mineralization was followed by ion chromatography. Our results demonstrated that more chlorinated phenols are more difficult to mineralize; however for all the tested CPs, almost quantitative release of chloride ions was obtained after 6 h of treatment.

The gas fluxing of aluminum: Mathematical modeling and experimental investigations

NASA Astrophysics Data System (ADS)

Fjeld, Autumn Marie

Chlorine fluxing is an essential purification step in aluminum refining in which impurities such as Ca, Na, Li, and Mg are removed by bubbling a mixture of chlorine and argon gas through molten aluminum. The gas is injected into the fluxing vessel through a rotating shaft and impeller which simultaneously agitates the melt, while breaking up and dispersing gas bubbles through the liquid phase. The efficiency of impurity removal and control of toxic chlorine and chloride emissions are dependent upon the extent of gas dispersion or mixing, residence time of the bubbles, and surface area of the bubbles. Clearly the gas injection and distribution within the liquid metal cannot be directly observed and such operations are often poorly controlled and not well understood. Problems arise when the injection gas, i.e. chlorine, is not completely consumed by reaction with impurities and the excess is reported as emissions of chlorides such as toxic HCl. The intention is to improve the technology to eliminate this waste (saving on the energy entailed in the chlorine production and reducing pollution) by better dispersion of the injected gas throughout the metal. Previous experimental investigations using a capacitance probe, capable of immersion in liquid aluminum for several hours, have been carried out to detect bubbles in an industrial fluxing unit at the Alcoa Technical Center. Bubble frequency data have shown the bubbles to be fairly well dispersed in the areas of the fluxing unit, decreasing in observed bubble frequency with increasing distance from the impeller (source of gas injection). To gain further insight and add to our experimental findings, two computational models have been developed to simulate the complex two-phase fluid dynamics of a rotary gas injection system. The results of these two modeling approaches are presented and analyzed and compared to experimental bubble measurements gathered using the capacitance probe. Bubble size distributions and residence times from the discrete phase model were incorporated in an external demagging reaction model to predict chlorine utilization efficiency. This simplified model included several assumptions regarding the kinetics and reaction path, however the model showed reasonable agreement to prior experimental magnesium removal data and provides valuable information related to the interplay of reaction progress in a fluxing unit and the fluid dynamics, in terms of bubble size, trajectory and resulting bubble residence time.

Dehalogenation of aromatics by nucleophilic aromatic substitution.

PubMed

Sadowsky, Daniel; McNeill, Kristopher; Cramer, Christopher J

2014-09-16

Nucleophilic aromatic substitution has been implicated as a mechanism for both the biotic and abiotic hydrodehalogenation of aromatics. Two mechanisms for the aqueous dehalogenation of aromatics involving nucleophilic aromatic substitution with hydride as a nucleophile are investigated using a validated density functional and continuum solvation protocol. For chlorinated and brominated aromatics, nucleophilic addition ortho to carbon-halogen bonds via an anionic intermediate is predicted to be the preferred mechanism in the majority of cases, while concerted substitution is predicted to be preferred for most fluorinated aromatics. Nucleophilic aromatic substitution reactions with the hydroxide and hydrosulfide anions as nucleophiles are also investigated and compared.

Effect of temperature and pH on dehalogenation of total organic chlorine, bromine and iodine in drinking water.

PubMed

Abusallout, Ibrahim; Rahman, Shamimur; Hua, Guanghui

2017-11-01

Disinfection byproduct (DBP) concentrations in drinking water distribution systems and indoor water uses depend on competitive formation and degradation reactions. This study investigated the dehalogenation kinetics of total organic chlorine (TOCl), bromine (TOBr) and iodine (TOI) produced by fulvic acid under different pH and temperature conditions, and total organic halogen (TOX) variations in a treated drinking water under simulated distribution system and heating scenarios. TOX dehalogenation rates were generally in the order of TOI ≅ TOCl(NH 2 Cl) > TOBr > TOCl(Cl 2 ). The half-lives of different groups of TOX compounds formed by fulvic acid varied between 27 and 139 days during incubation at 20 °C and 0.98-2.17 days during heating at 55 °C. Base-catalyzed reactions played a major role in TOX degradation as evidenced by enhanced dehalogenation under high pH conditions. The results of heating of a treated water in the presence of residuals showed that TOX concentrations of chlorinated samples increased rapidly when chlorine residuals were present and then gradually decreased after chlorine residuals were exhausted. The final TOX concentrations of chlorinated samples after heating showed moderate decreases with increasing ambient water ages. Chloraminated samples with different ambient water ages exhibited similar final TOX concentrations during simulated distribution system and heating experiments. This study reinforces the importance of understanding DBP variations in indoor water uses as wells as in distribution systems to provide more accurate DBP information for exposure assessment and regulatory determination. Published by Elsevier Ltd.

Chlorination of humic materials: Byproduct formation and chemical interpretations

USGS Publications Warehouse

Reckhow, D.A.; Singer, P.C.; Malcolm, R.L.

1990-01-01

Ten aquatic humic and fulvic acids were isolated and studied with respect to their reaction with chlorine. Yields of TOX, chloroform, trichloroacetic acid, dichloroacetic acid, dichloroacetonitrile, and 1,1,1-trichloropropanone were measured at pH 7 and 12. Humic acids produced higher concentrations than their corresponding fulvic acids of all byproducts except 1,1,1-trichloropropanone. Chlorine consumption and byproduct formation were related to fundamental chemical characteristics of the humic materials. A statistical model was proposed for activated aromatic content based on 13C NMR and base titration data. The values estimated from this model were found to be well correlated with chlorine consumption. Specific byproduct formation was related to UV absorbance, nitrogen content, or the activated aromatic content. ?? 1990 American Chemical Society.

Quantitative structure-activity relationships (QSARs) for the transformation of organic micropollutants during oxidative water treatment.

PubMed

Lee, Yunho; von Gunten, Urs

2012-12-01

Various oxidants such as chlorine, chlorine dioxide, ferrate(VI), ozone, and hydroxyl radicals can be applied for eliminating organic micropollutant by oxidative transformation during water treatment in systems such as drinking water, wastewater, and water reuse. Over the last decades, many second-order rate constants (k) have been determined for the reaction of these oxidants with model compounds and micropollutants. Good correlations (quantitative structure-activity relationships or QSARs) are often found between the k-values for an oxidation reaction of closely related compounds (i.e. having a common organic functional group) and substituent descriptor variables such as Hammett or Taft sigma constants. In this study, we developed QSARs for the oxidation of organic and some inorganic compounds and organic micropollutants transformation during oxidative water treatment. A number of 18 QSARs were developed based on overall 412 k-values for the reaction of chlorine, chlorine dioxide, ferrate, and ozone with organic compounds containing electron-rich moieties such as phenols, anilines, olefins, and amines. On average, 303 out of 412 (74%) k-values were predicted by these QSARs within a factor of 1/3-3 compared to the measured values. For HO(·) reactions, some principles and estimation methods of k-values (e.g. the Group Contribution Method) are discussed. The developed QSARs and the Group Contribution Method could be used to predict the k-values for various emerging organic micropollutants. As a demonstration, 39 out of 45 (87%) predicted k-values were found within a factor 1/3-3 compared to the measured values for the selected emerging micropollutants. Finally, it is discussed how the uncertainty in the predicted k-values using the QSARs affects the accuracy of prediction for micropollutant elimination during oxidative water treatment. Copyright © 2012 Elsevier Ltd. All rights reserved.

[Formation mechanism and chemical safety of nonintentional chemical substances present in chlorinated drinking water and wastewater].

PubMed

Onodera, Sukeo

2010-09-01

This paper reviews the formation mechanism and chemical safety of nonintentional chemical substances (NICS) present in chlorine-treated water containing organic contaminants. Undesirable compounds, i.e., NICS, may be formed under certain conditions when chlorine reacts with organic matter. The rate and extent of chlorine consumption with organics are strongly dependent on their chemical structures, particularly whether double bonds or sulfur and nitrogen atoms occur in the molecules. Organothiophosphorus pesticides (P=S type) are easily oxidized to their phosphorus compounds (P=O type) in chlorinated water containing HOCl as little as 0.5 mg/l, resulting in an increase in cholinesterase-inhibitory activity. Chlorination of phenols in water also produces a series of highly chlorinated compounds, including chlorophenols, chloroquinones, chlorinated carboxylic acids, and polychlorinated phenoxyphenols (PCPPs). In some of these chloroquinones, 2,6-dichloroalkylsemiquinones exhibit a strong mutagenic response as do positive controls used in the Ames test. 2-phenoxyphenols in these PCPPs are particularly interesting, as they are present in the chlorine-treated phenol solution and they are also precursors (predioxins) of the highly toxic chlorinated dioxins. Polynuclear aromatic hydrocarbons (PAHs) were found to undergo chemical changes due to hypochlorite reactions to give chloro-substituted PAHs, oxygenated (quinones) and hydroxylated (phenols) compounds, but they exhibit a lower mutagenic response. In addition, field work was performed in river water and drinking water to obtain information on chemical distribution and their safety, and the results are compared with those obtained in the model chlorination experiments.

Modeling the impact of chlorine emissions from coal combustion and prescribed waste incineration on tropospheric ozone formation in China

NASA Astrophysics Data System (ADS)

Liu, Yiming; Fan, Qi; Chen, Xiaoyang; Zhao, Jun; Ling, Zhenhao; Hong, Yingying; Li, Weibiao; Chen, Xunlai; Wang, Mingjie; Wei, Xiaolin

2018-02-01

Chlorine radicals can enhance atmospheric oxidation, which potentially increases tropospheric ozone concentration. However, few studies have been done to quantify the impact of chlorine emissions on ozone formation in China due to the lack of a chlorine emission inventory used in air quality models with sufficient resolution. In this study, the Anthropogenic Chlorine Emissions Inventory for China (ACEIC) was developed for the first time, including emissions of hydrogen chloride (HCl) and molecular chlorine (Cl2) from coal combustion and prescribed waste incineration (waste incineration plant). The HCl and Cl2 emissions from coal combustion in China in 2012 were estimated to be 232.9 and 9.4 Gg, respectively, while HCl emission from prescribed waste incineration was estimated to be 2.9 Gg. Spatially the highest emissions of HCl and Cl2 were found in the North China Plain, the Yangtze River Delta, and the Sichuan Basin. Air quality model simulations with the Community Multiscale Air Quality (CMAQ) modeling system were performed for November 2011, and the modeling results derived with and without chlorine emissions were compared. The magnitude of the simulated HCl, Cl2 and ClNO2 agreed reasonably with the observation when anthropogenic chlorine emissions were included in the model. The inclusion of the ACEIC increased the concentration of fine particulate Cl-, leading to enhanced heterogeneous reactions between Cl- and N2O5, which resulted in the higher production of ClNO2. Photolysis of ClNO2 and Cl2 in the morning and the reaction of HCl with OH in the afternoon produced chlorine radicals which accelerated tropospheric oxidation. When anthropogenic chlorine emissions were included in the model, the monthly mean concentrations of fine particulate Cl-, daily maximum 1 h ClNO2, and Cl radicals were estimated to increase by up to about 2.0 µg m-3, 773 pptv, and 1.5 × 103 molecule cm-3 in China, respectively. Meanwhile, the monthly mean daily maximum 8 h O3 concentration was found to increase by up to 2.0 ppbv (4.1 %), while the monthly mean NOx concentration decreased by up to 0.5 ppbv (6.1 %). The anthropogenic chlorine emissions potentially increased the 1 h O3 concentration by up to 7.7 ppbv in China. This study highlights the need for the inclusion of anthropogenic chlorine emission in air quality modeling and demonstrated its importance in tropospheric ozone formation.

Molten Salt Electrolysis of MgCl2 in a Cell with Rapid Chlorine Removal Feature

NASA Astrophysics Data System (ADS)

Demirci, Gökhan; Karakaya, İshak

An experimental electrolytic magnesium production cell was designed to remove chlorine gas from the electrolyte rapidly and demonstrate the beneficial effects of reduced chlorine dissolution into the molten salt electrolyte. The back reaction that is the main cause of current losses in electrolytic magnesium production was reduced as a result of effective separation of electrode products and decreased contact time of chlorine gas with the electrolyte. Moreover, smaller inter electrode distances employed and lower chlorine gas present on the anode surface made it possible to work at low cell voltages. Electrolytic cell was tested at different current densities. Energy consumption of 7.0 kWh kg-1 Mg that is slightly above the theoretical minimum, 6.2 kWh kg-1 Mg, at 0.68 Acm-2 anodic current density was achieved for a MgCl2/NaCl/KCl electrolyte.

Organochlorine compounds and the biogeochemical cycle of chlorine in soils: A review

NASA Astrophysics Data System (ADS)

Vodyanitskii, Yu. N.; Makarov, M. I.

2017-09-01

Chloride ions in soil may interact with soil organic matter and form organochlorine compounds in situ. The biotic chlorination of soil organic substances takes places under aerobic conditions with participation of H2O2 forming from peroxidases released by soil microorganisms (in particular, by microscopic fungi). The abiotic chlorination results also from the redox reactions with the participation of Fe3+/Fe2+ system, but it develops several times slower. Chlorination of soil organic substances is favored by Cl- coming to soil both from natural (salinized soil-forming rocks and groundwater, sea salt) and anthropogenic sources of chlorides, i.e., spills of saline water at oil production, road deicing chemicals, mineral fertilizers, etc. The study of the biogeochemical chlorine cycle should take into account the presence of organochlorine compounds in soils, in addition to transformation and migration of chloride ions.

Chemical Loss of Ozone in the Arctic Polar Vortex in the Winter of 1991-1992

NASA Technical Reports Server (NTRS)

Salawitch, R. J.; Wofsy, S. C.; Gottlieb, E. W.; Lait, L. R.; Newman, P. A.; Schoeberl, M. R.; Strahan, S. E.; Loewenstein, M.; Podolske, J. R.; Chan, K. R.;

JPRS Report, Science & Technology USSR: Chemistry.

DTIC Science & Technology

1991-07-26

difluoride, bromine trifluoride , or chlorine trifluoride all had oxygen contents not exceeding 3 x 10ŗ percent by weight. Laser ultramicroscopy...concentration values. Using chlorine trifluoride was found to result in strong scat- tering of radiation on particles of submicronic size. Figures 2...Catalysts and Catalytic Combustion Reactions. VII. A Study of the Change in the Nature of Contacts Between Primary Particles in Aluminum Hydroxides

Dechlorination of TCE with palladized iron

DOEpatents

Fernando, Q.; Muftikian, R.; Korte, N.

1997-04-01

The present invention relates to various methods, such as an above-ground method and an in-ground method, of using a palladized iron bimetallic system for the dechlorination of chlorinated organic compounds from various effluents or contaminated soil containing the same. The use of palladized iron bimetallic system results in the dechlorination of the chlorinated organic compound into environmentally safe reaction products. 10 figs.

Dechlorination of TCE with palladized iron

DOEpatents

Fernando, Quintus; Muftikian, Rosy; Korte, Nic

1997-01-01

The present invention relates to various methods, such as an above-ground method and an in-ground method, of using a palladized iron bimetallic system for the dechlorination of chlorinated organic compounds from various effluents or contaminated soil containing the same. The use of palladized iron bimetallic system results in the dechlorination of the chlorinated organic compound into environmentally safe reaction products.

Molecular emission in laser-induced breakdown spectroscopy: An investigation of its suitability for chlorine quantification on Mars

NASA Astrophysics Data System (ADS)

Vogt, D. S.; Rammelkamp, K.; Schröder, S.; Hübers, H. W.

2018-03-01

The intensity of the molecular CaCl emission in LIBS spectra is examined in order to evaluate its suitability for the detection of chlorine in a Martian environment. Various mixtures resembling Martian targets with varying Cl content are investigated under simulated Martian conditions. The reactions leading to the formation of CaCl are modeled based on reaction kinetics and are used to fit the measured CaCl band intensities. MgCl bands are also investigated as potential alternatives to CaCl, but no MgCl bands can be identified in samples containing both Mg and Cl. The study confirms that CaCl is well suited for the indirect detection of chlorine, but finds a strong dependence on the concentrations of Ca and Cl in the sample. Spectra from samples with a high chlorine concentration can have low-intensity CaCl emission due to a deficiency of Ca. A qualitative estimate of the sample composition is possible based on the ratio of the band intensity of CaCl to the intensity of Ca emission lines. Time-resolved measurements show that the CaCl concentration in the plasma is highest after about 1 μs.

Variations in Stratospheric Inorganic Chlorine Between 1991 and 2006

NASA Technical Reports Server (NTRS)

Lary, D. J.; Waugh, D. W.; Douglass, A. R.; Stolarski, R. S.; Newman, P. A.; Mussa, H.

2007-01-01

So how quickly will the ozone hole recover? This depends on how quickly the chlorine content (Cl2) of the atmosphere will decline. The ozone hole forms over the Antarctic each southern spring (September and October). The extremely small ozone amounts in the ozone hole are there because of chemical reactions of ozone with chlorine. This chlorine originates largely from industrially produced chlorofluorocarbon (CFC) compounds. An international agreement, the Montreal Protocol, is drastically reducing the amount of chlorine-containing compounds that we are releasing into the atmosphere. To be able to attribute changes in stratospheric ozone to changes in chlorine we need to know the distribution of atmospheric chlorine. However, due to a lack of continuous observations of all the key chlorine gases, producing a continuous time series of stratospheric chlorine has not been achieved to date. We have for the first time devised a technique to make a 17-year time series for stratospheric chlorine that uses the long time series of HCl observations made from several space borne instruments and a neural network. The neural networks allow us to both inter-calibrate the various HCl instruments and to infer the total amount of atmospheric chlorine from HCl. These new estimates of Cl, provide a much needed critical test for current global models that currently predict significant differences in both Cl(sub y) and ozone recovery. These models exhibit differences in their projection of the recovery time and our chlorine content time series will help separate the good from the bad in these projections.

Factorial analysis of the trihalomethane formation in the reaction of colloidal, hydrophobic, and transphilic fractions of DOM with free chlorine.

PubMed

Platikanov, Stefan; Tauler, Roma; Rodrigues, Pedro M S M; Antunes, Maria Cristina G; Pereira, Dilson; Esteves da Silva, Joaquim C G

2010-09-01

This study focuses on the factors that affect trihalomethane (THMs) formation when dissolved organic matter (DOM) fractions (colloidal, hydrophobic, and transphilic fractions) in aqueous solutions were disinfected with chlorine. DOM fractions were isolated and fractionated from filtered lake water and were characterized by elemental analysis. The investigation involved a screening Placket-Burman factorial analysis design of five factors (DOM concentration, chlorine dose, temperature, pH, and bromide concentration) and a Box-Behnken design for a detailed assessment of the three most important factor effects (DOM concentration, chlorine dose, and temperature). The results showed that colloidal fraction has a relatively low contribution to THM formation; transphilic fraction was responsible for about 50% of the chloroform generation, and the hydrophobic fraction was the most important to the brominated THM formation. When colloidal and hydrophobic fraction solutions were disinfected, the most significant factors were the following: higher DOM fraction concentration led to higher THM concentration, an increase of pH corresponded to higher concentration levels of chloroform and reduced bromoform, higher levels of chlorine dose and temperature produced a rise in the total THM formation, especially of the chlorinated THMs; higher bromide concentration generates higher concentrations of brominated THMs. Moreover, linear models were implemented and response surface plots were obtained for the four THM concentrations and their total sum in the disinfection solution as a function of the DOM concentration, chlorine dose, and temperature. Overall, results indicated that THM formation models were very complex due to individual factor effects and significant interactions among the factors. In order to reduce the concentration of THMs in drinking water, DOM concentrations must be reduced in the water prior to the disinfection. Fractionation of DOM, together with an elemental analysis of the fractions, is important issue in the revealing of the quality and quantity characteristics of DOM. Systematic study composed from DOM fraction investigation and factorial analysis of the responsible parameters in the THM formation reaction can, after an evaluation of the adjustment of the models with the reality, serves well for the evaluation of the spatial and temporal variability in the THM formation in dependence of DOM. However, taking into consideration the natural complexity of DOM, different operations and a strict control of them (like coagulation/flocculation and filtration) has to be used to quantitatively remove DOM from the raw water. Assuming that this study represents a local case study, similar experiments can be easily applied and will supply with relevant information every local water treatment plant meeting problems with THM formation. The coagulation/flocculation and the filtration stages are the main mechanisms to remove DOM, particularly the colloidal DOM fraction. With the objective to minimize THMs generation, different unit operation designed to quantitatively remove DOM from water must be optimized.

Full Kinetics from First Principles of the Chlorine Evolution Reaction over a RuO2 (110) Model Electrode.

PubMed

Exner, Kai S; Anton, Josef; Jacob, Timo; Over, Herbert

2016-06-20

Current progress in modern electrocatalysis research is spurred by theory, frequently based on ab initio thermodynamics, where the stable reaction intermediates at the electrode surface are identified, while the actual energy barriers are ignored. This approach is popular in that a simple tool is available for searching for promising electrode materials. However, thermodynamics alone may be misleading to assess the catalytic activity of an electrochemical reaction as we exemplify with the chlorine evolution reaction (CER) over a RuO2 (110) model electrode. The full procedure is introduced, starting from the stable reaction intermediates, computing the energy barriers, and finally performing microkinetic simulations, all performed under the influence of the solvent and the electrode potential. Full kinetics from first-principles allows the rate-determining step in the CER to be identified and the experimentally observed change in the Tafel slope to be explained. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Different removal behaviours of multiple trace antibiotics in municipal wastewater chlorination.

PubMed

Li, Bing; Zhang, Tong

2013-06-01

The chlorination behaviours of 12 antibiotics belonging to six classes at environmentally relevant concentrations were systematically examined under typical conditions relevant to municipal wastewater chlorination. Cefotaxime, cefalexin, ampicillin and tetracycline were completely removed under all three initial free chlorine dosages (5 mg/L, 10 mg/L, and 15 mg/L). The removal efficiencies of sulphamethoxazole, sulphadiazine, roxithromycin, anhydro-erythromycin, ofloxacin, and trimethoprim were closely correlated to the residual free chlorine concentration, and no further significant mass removal was observed after the residual free chlorine concentration decreased to less than ≈ 0.75 mg/L. Ammonia plays a critical role during chlorination because of its competition with antibiotics for free chlorine to form combined chlorine, which reacts slowly with these antibiotics. Except for norfloxacin and ciprofloxacin, the removal behaviours of the 10 other target antibiotics under ammonia nitrogen concentrations ranging from 2 to 15 mg/L were characterised by a rapid initial removal rate upon contact with free chlorine during the first 5 s-1 min (depending on the specific antibiotic and ammonia nitrogen concentration) and then a much slower removal rate. Free chlorine was responsible for the reaction with antibiotics during the rapid stage (first 5 s-1 min), whereas combined chlorine reacted with antibiotics in the subsequent slow stage. Combined chlorine can remove norfloxacin and ciprofloxacin at a relatively faster rate. The presence of suspended solids at 30 mg/L slightly decreased the antibiotic removal rate. The kinetic rate constants decreased by 2.1-13.9%, while the half-lives increased by 2.0-15.0% compared to those of a 0 mg/L suspended solid for the target antibiotics. Copyright © 2013 Elsevier Ltd. All rights reserved.

Re-engineering an artificial sweetener: transforming sucralose residuals in water via advanced oxidation.

PubMed

Keen, Olya S; Linden, Karl G

2013-07-02

Sucralose is an artificial sweetener persistently present in wastewater treatment plant effluents and aquatic environments impacted by human activity. It has a potential to accumulate in the water cycle due to its resistance to common water and wastewater treatment processes. This study examined UV/H2O2 advanced oxidation and found that hydroxyl substitution of the chlorine atoms on the sucralose molecule can form a carbohydrate consisting of fructose and sugar alcohol, very similar to environmentally benign sucrose. The second-order reaction rate constant for loss of parent molecule via reaction with hydroxyl radical was determined to be (1.56 ± 0.03)·10(9) M(-1)s(-1). The degradation pathway involves substitution of a single chlorine by a hydroxyl group, with cyclic moiety being a preferential site for initial dechlorination. Further reaction leads to full dechlorination of the molecule, presumably via hydroxyl group substitution as well. No direct photolysis by UV wavelengths above 200 nm was observed. Because of its photostability when exposed to UV wavelengths ≥200 nm, known stability with ozone, limits of quantification by mass spectrometry close to or below environmental concentrations (<5 μg/L) without preconcentration, and otherwise stable nature, sucralose can be used as an in situ hydroxyl radical probe for UV-based and ozone-based AOP processes. As a compound safe for human consumption, sucralose makes a suitable full scale hydroxyl radical probe fit even for drinking water treatment plant applications. Its main drawback as a probe is lack of UV detection and as a result a need for mass spectrometry analysis.

Breathing spiral waves in the chlorine dioxide-iodine-malonic acid reaction-diffusion system.

PubMed

Berenstein, Igal; Muñuzuri, Alberto P; Yang, Lingfa; Dolnik, Milos; Zhabotinsky, Anatol M; Epstein, Irving R

2008-08-01

Breathing spiral waves are observed in the oscillatory chlorine dioxide-iodine-malonic acid reaction-diffusion system. The breathing develops within established patterns of multiple spiral waves after the concentration of polyvinyl alcohol in the feeding chamber of a continuously fed, unstirred reactor is increased. The breathing period is determined by the period of bulk oscillations in the feeding chamber. Similar behavior is obtained in the Lengyel-Epstein model of this system, where small amplitude parametric forcing of spiral waves near the spiral wave frequency leads to the formation of breathing spiral waves in which the period of breathing is equal to the period of forcing.

High temperature electrolytic recovery of oxygen from gaseous effluents from the carbo-chlorination of lunar anorthite and the hydrogenation of ilmenite: A theoretical study

NASA Technical Reports Server (NTRS)

Erstfield, T. E.; Williams, R. J.

1979-01-01

A thermodynamic analysis discusses the compositions of gaseous effluents from the reaction of carbon and chlorine and of hydrogen with lunar anorthite and ilmenite, respectively. The computations consider the effects of the indigenous volatiles on the solid/gas reactions and on the composition of the effluent gases. A theoretical parameterization of the high temperature electrolysis of such gases is given for several types of solid ceramic electrolytes, and the effect of oxygen removal on the effluents is computed. Potential chemical interactions between the gases and the ceramic electrolytes are analyzed and discussed.

The photochemistry and kinetics of chlorine compounds important to stratospheric mid-latitude ozone destruction

NASA Astrophysics Data System (ADS)

Goldfarb, Leah

1997-09-01

The catalytic destruction of stratospheric ozone via chlorinated species was first proposed in the 1970's. Since that time a decline in column ozone abundance in the polar regions as well as at mid-latitudes has been observed. Much of this reduction has been attributed to the increases in anthropogenic chlorine compounds such as CFCs. This study summarizes experimental results obtained using pulsed-photolysis resonance fluorescence and pulsed- photolysis long-path absorption methods to study processes important to chlorine-catalyzed ozone destruction: the quantum yields of the products in the dissociation of ClONO2 and the reactions of free radicals with ClONO2 and ClO. The quantum yields for the production of O, Cl and ClO from ClONO2 were studied at specific laser wavelengths (193, 222, 248, and 308 nm). Cl and ClO yields were comparable at nearly all the wavelengths, expect for 193 nm, where the O atom yield was appreciable. The yields at 308 nm (a wavelength available in the stratosphere) were 0.64 ± 0.17 for Cl, 0.37 ± 0.18 for ClO and <0.05 for O. The rate coefficients of O and Cl atoms with ClONO2 were measured over a wide range of temperatures, and the NO3 product yield for the former reaction, previously unreported, was determined to be ~1. The kinetics of the reaction of O atoms with ClO were measured using a new experimental system built specifically to investigate such radical-radical reactions. A slight negative temperature dependence (E/B = -90 ± 30) was observed over the temperature range (227-363 K). From the measured Arrhenius equation the rate constant at 240 K is 4.1 × 10-11 cm3molecule-1s-1 which is in excellent agreement (l.4% greater) with the currently recommended value. This observation is significant, since this reaction is the rate limiting the dominate chlorine catalytic cycle that destroys O3 near 40 km. To analyze the implications of the kinetic and photochemical information from this work, a box model was constructed. The vertical profile of ozone concentrations and loss rates calculated by this simple model compare well with atmospheric measurements and calculations.

Extraction of titanium from low-iron nitrided Malaysian ilmenite by chlorination

NASA Astrophysics Data System (ADS)

Ibrahim, Najwa; Ahmadi, Eltefat; Rahman, Shaik Abdul; Fauzi, M. N. Ahmad; Rezan, Sheikh Abdul

2017-01-01

In this paper, production of TiCl4 from low-iron nitrided ilmenite samples at relatively low temperature using chlorine gas generated from the reaction between KMnO4 and HCl has been investigated. The effects of chlorination soaking time, potassium permanganate (KMnO4) to hydrochloric acid (HCl) molar ratio and aluminium powder catalyst in chlorine gas generation on titanium extraction from nitrided Malaysian ilmenite were examined. The low-iron nitrided Malaysian ilmenite contained titanium oxycarbonitride (TiOxCyNz) after carbothermal reduction and nitridation with subsequent leaching. Chlorination process was performed at 500°C for 30 - 60 minutes. Statistical analysis of the data was done by Design of Experiment (DOE) to identify the significant variables and their interactions. The results achieved in this study showed that the highest extent of chlorination was about 98.34% at 500°C for 60 minutes. The lowest extent of chlorination was about 68.51% obtained in KMnO4 to HCl molar ratio of 2.0 and 0.35 g of aluminium powder. The chlorinated titanium oxycarbonitride powders and TiCl4 solutions were analyzed by X-ray diffraction (XRD) and inductively coupled plasma-optical emission spectroscopy (ICP-OES), respectively. The purpose of this study was to explore the relationship between the processing parameters on extracting titanium via pyrometallurgical technique.

Bromate formation from the oxidation of bromide in the UV/chlorine process with low pressure and medium pressure UV lamps.

PubMed

Fang, Jingyun; Zhao, Quan; Fan, Chihhao; Shang, Chii; Fu, Yun; Zhang, Xiangru

2017-09-01

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.

Ionic Fluorine Chemistry.

DTIC Science & Technology

SOLID ROCKET OXIDIZERS, *LIQUID ROCKET OXIDIZERS, CHLORATES, FLUORIDES, ACETONES, CHLORINE COMPOUNDS, NITROSO COMPOUNDS, *HALOGEN COMPOUNDS, ADDITION REACTIONS, CESIUM COMPOUNDS, CHLORIDES, COMPLEX COMPOUNDS

Mixing of gaseous reactants in chemical generation of atomic iodine for COIL: two-dimensional study

NASA Astrophysics Data System (ADS)

Jirasek, Vit; Spalek, Otomar; Kodymova, Jarmila; Censky, Miroslav

2003-11-01

Two-dimensional CFD model was applied for the study of mixing and reaction between gaseous chlorine dioxide and nitrogen monoxide diluted with nitrogen during atomic iodine generation. The influence of molecular diffusion on the production of atomic chlorine as a precursor of atomic iodine was predominantly studied. The results were compared with one-dimensional modeling of the system.

Annual Report to Congress, Fiscal Year 1997. A Report by The Council of the Strategic Environmental Research and Development Program

DTIC Science & Technology

1998-03-01

Discovery of Novel Enzymatic Reactions and Determination of Biodegradation Mechanisms and Pathways. b. Phytoremediation of Explosives Contaminated...Groundwater using Wetlands and Aquatic Plants. c. Phytoremediation of Munitions Contaminated Soils. d. Enhanced TNT Biodegradation Through Genetic Manipulation...Microbial Communities Active in the Enhanced Aerobic Treatment of Chlorinated Ethenes. c. Phytoremediation of Shallow Chlorinated Solvent Plumes

Reaction of bromine and chlorine with phenolic compounds and natural organic matter extracts--Electrophilic aromatic substitution and oxidation.

PubMed

Criquet, Justine; Rodriguez, Eva M; Allard, Sebastien; Wellauer, Sven; Salhi, Elisabeth; Joll, Cynthia A; von Gunten, Urs

2015-11-15

Phenolic compounds are known structural moieties of natural organic matter (NOM), and their reactivity is a key parameter for understanding the reactivity of NOM and the disinfection by-product formation during oxidative water treatment. In this study, species-specific and/or apparent second order rate constants and mechanisms for the reactions of bromine and chlorine have been determined for various phenolic compounds (phenol, resorcinol, catechol, hydroquinone, phloroglucinol, bisphenol A, p-hydroxybenzoic acid, gallic acid, hesperetin and tannic acid) and flavone. The reactivity of bromine with phenolic compounds is very high, with apparent second order rate constants at pH 7 in the range of 10(4) to 10(7) M(-1) s(-1). The highest value was recorded for the reaction between HOBr and the fully deprotonated resorcinol (k = 2.1 × 10(9) M(-1) s(-1)). The reactivity of phenolic compounds is enhanced by the activating character of the phenolic substituents, e.g. further hydroxyl groups. With the data set from this study, the ratio between the species-specific rate constants for the reactions of chlorine versus bromine with phenolic compounds was confirmed to be about 3000. Phenolic compounds react with bromine or chlorine either by oxidation (electron transfer, ET) or electrophilic aromatic substitution (EAS) processes. The dominant process mainly depends on the relative position of the hydroxyl substituents and the possibility of quinone formation. While phenol, p-hydroxybenzoic acid and bisphenol A undergo EAS, hydroquinone, catechol, gallic acid and tannic acid, with hydroxyl substituents in ortho or para positions, react with bromine by ET leading to quantitative formation of the corresponding quinones. Some compounds (e.g. phloroglucinol) show both partial oxidation and partial electrophilic aromatic substitution and the ratio observed for the pathways depends on the pH. For the reaction of six NOM extracts with bromine, electrophilic aromatic substitution accounted for only 20% of the reaction, and for one NOM extract (Pony Lake fulvic acid) it accounted for <10%. This shows that for natural organic matter samples, oxidation (ET) is far more important than bromine incorporation (EAS). Copyright © 2015 Elsevier Ltd. All rights reserved.

Understanding the insight into the mechanisms and dynamics of the Cl-initiated oxidation of (CH3)3CC(O)X and the subsequent reactions in the presence of NO and O2 (X = F, Cl, and Br).

PubMed

Bai, Feng-Yang; Lv, Shuang; Ma, Yuan; Liu, Chun-Yu; He, Chun-Fang; Pan, Xiu-Mei

2017-03-01

In this work, the density functional and high-level ab initio theories are adopted to investigate the mechanisms and kinetics of reaction of (CH 3 ) 3 CC(O)X (X = F, Cl, and Br) with atomic chlorine. Rate coefficients for the reactions of chlorine atom with (CH 3 ) 3 CC(O)F (k 1 ), (CH 3 ) 3 CC(O)Cl (k 2 ), and (CH 3 ) 3 CC(O)Br (k 3 ) are calculated using canonical variational transition state theory coupled with small curvature tunneling method over a wide range of temperatures from 250 to 1000 K. The dynamic calculations are performed by the variational transition state theory with the interpolated single-point energies method at the CCSD(T)/aug-cc-pVDZ//B3LYP/6-311++G(d,p) level of theory. Computed rate constant is in good line with the available experimental value. The rate constants for the title reactions are in this order: k 1

Mass spectrometric measurement of hydrogen isotope fractionation for the reactions of chloromethane with OH and Cl

NASA Astrophysics Data System (ADS)

Keppler, Frank; Bahlmann, Enno; Greule, Markus; Schöler, Heinz Friedrich; Wittmer, Julian; Zetzsch, Cornelius

2018-05-01

Chloromethane (CH3Cl) is an important provider of chlorine to the stratosphere but detailed knowledge of its budget is missing. Stable isotope analysis is a potentially powerful tool to constrain CH3Cl flux estimates. The largest degree of isotope fractionation is expected to occur for deuterium in CH3Cl in the hydrogen abstraction reactions with its main sink reactant tropospheric OH and its minor sink reactant Cl atoms. We determined the isotope fractionation by stable hydrogen isotope analysis of the fraction of CH3Cl remaining after reaction with hydroxyl and chlorine radicals in a 3.5 m3 Teflon smog chamber at 293 ± 1 K. We measured the stable hydrogen isotope values of the unreacted CH3Cl using compound-specific thermal conversion isotope ratio mass spectrometry. The isotope fractionations of CH3Cl for the reactions with hydroxyl and chlorine radicals were found to be -264±45 and -280±11 ‰, respectively. For comparison, we performed similar experiments using methane (CH4) as the target compound with OH and obtained a fractionation constant of -205±6 ‰ which is in good agreement with values previously reported. The observed large kinetic isotope effects are helpful when employing isotopic analyses of CH3Cl in the atmosphere to improve our knowledge of its atmospheric budget.

Induction of Escherichia coli into a VBNC state through chlorination/chloramination and differences in characteristics of the bacterium between states.

PubMed

Chen, Sheng; Li, Xi; Wang, Yahong; Zeng, Jie; Ye, Chengsong; Li, Xianping; Guo, Lizheng; Zhang, Shenghua; Yu, Xin

2018-05-30

Many pathogens can enter into a viable but nonculturable (VBNC) state in response to harsh environmental stresses. Bacteria in this state can retain certain features of viable cells, such as cellular integrity, metabolic activity, or virulence and may present health risks associated with drinking water. In this study, we investigated the ability of chlorination and chloramination, which are widely used methods to disinfect drinking water, to induce Escherichia coli into a VBNC state. After treatment with chlorine and chloramine at concentrations of 1, 2, 3, and 4 mg/L, the counts of culturable E. coli cells decreased from 10 6  CFU/mL to 0 CFU/mL at 5-60 min post treatment. Meanwhile, viable cell counts were still approximately 10 3 -10 5  cells/mL. These viable E. coli cells may be induced into a VBNC state by chlorination and chloramination. Scanning electron microscopy and laser confocal microscopy showed that some bacteria maintained cellular integrity, but the average length of VBNC cells was less than that of culturable cells. Respiratory activity of VBNC cells decreased approximately 50% relative to that of culturable cells. We also used heavy water (D 2 O) combined with Raman microspectroscopy to show that E. coli in a VBNC state retained metabolic activity involving water (e.g. condensation reactions) at the single-cell level. Furthermore, soxR, gadA, and katG genes remained highly expressed, suggesting that VBNC cells were physiologically active. Finally, resuscitation of VBNC cells induced by chlorine in Luria-Bertani (LB) broth was identified by calculating the generation time. Results of this study will facilitate a better understanding of the health risks associated with VBNC bacteria and the development of more effective strategies for drinking water disinfection. Copyright © 2018. Published by Elsevier Ltd.

Two-step chlorination: A new approach to disinfection of a primary sewage effluent.

PubMed

Li, Yu; Yang, Mengting; Zhang, Xiangru; Jiang, Jingyi; Liu, Jiaqi; Yau, Cie Fu; Graham, Nigel J D; Li, Xiaoyan

2017-01-01

Sewage disinfection aims at inactivating pathogenic microorganisms and preventing the transmission of waterborne diseases. Chlorination is extensively applied for disinfecting sewage effluents. The objective of achieving a disinfection goal and reducing disinfectant consumption and operational costs remains a challenge in sewage treatment. In this study, we have demonstrated that, for the same chlorine dosage, a two-step addition of chlorine (two-step chlorination) was significantly more efficient in disinfecting a primary sewage effluent than a one-step addition of chlorine (one-step chlorination), and shown how the two-step chlorination was optimized with respect to time interval and dosage ratio. Two-step chlorination of the sewage effluent attained its highest disinfection efficiency at a time interval of 19 s and a dosage ratio of 5:1. Compared to one-step chlorination, two-step chlorination enhanced the disinfection efficiency by up to 0.81- or even 1.02-log for two different chlorine doses and contact times. An empirical relationship involving disinfection efficiency, time interval and dosage ratio was obtained by best fitting. Mechanisms (including a higher overall Ct value, an intensive synergistic effect, and a shorter recovery time) were proposed for the higher disinfection efficiency of two-step chlorination in the sewage effluent disinfection. Annual chlorine consumption costs in one-step and two-step chlorination of the primary sewage effluent were estimated. Compared to one-step chlorination, two-step chlorination reduced the cost by up to 16.7%. Copyright © 2016 Elsevier Ltd. All rights reserved.

Impacts of the January 2005 solar particle events on middle atmospheric chlorine species

NASA Astrophysics Data System (ADS)

Winkler, Holger; Sinnhuber, Miriam; Notholt, Justus; Maik Wissing, Jan; Kallenrode, May-Britt; Santee, Michelle

It is well established that solar particle events (SPEs) are sources of significant chemical dis-turbances in the Earth's polar atmosphere. The observed SPE effects on nitrogen, hydrogen and oxygen compounds have been investigated in some detail in recent years, and they can be reproduced by atmospheric models using basic parametrizations for NOx and HOx produc-tion as a funtion of the particle impact ionisation. However, there are considerable differences between model predictions and measurements concerning several other trace gases including chlorine species. Two major SPEs occurred on January 17, and January 20, 2005. The latter had an exceptionally hard energy spectrum which caused maximum particle impact ionization at stratospheric altitudes. The Microwave Limb Sounder (MLS) instrument on-board the Aura satellite has measured a short-term decrease of HCl in the northern polar region corresponding to January 2005 SPEs. The peak HCl depletion is ˜300 ppt at 35-40 km. This is comparable to the depletion of messopheric HCl observed by the HALOE instrument during the July 2000 SPE. We will present simulation results of the University of Bremen Ion Chemistry (UBIC) model for the SPEs in January 2005 focusing on chlorine species. The simulations indicate that the observed short-term decrease of middle atmospheric HCl is due to a conversion into active chlorine species such as Cl, ClO and HOCl. The magnitude of the observed HCl loss can only be reproduced if reactions of negative chlorine species and the production of O(1 D) from the reaction N(2 D) + O2 are taken into account. The model results will be compared to MLS/Aura data of HCl, HOCl and ClO. Additionally, the impacts of the observed chlorine activation, e.g. on ozone, will be assessed.

[Formation process of nitrogenous disinfection byproduct trichloronitromethane in drinking water and its influencing factors].

PubMed

Ding, Chun-Sheng; Zou, Bang-Wen; Miao, Jia; Fu, Yang-Ping; Shen, Jia-Chen

2013-08-01

A novel method is described in this paper, which uses methyl tertiary butyl ether (MTBE) as extractant and 1,2-dibromopropane as internal standard for the determination of nitrogenous disinfection byproduct trichloronitromethane (TCNM) by gas chromatography mass spectrometry (GC-MS). The formation process of TCNM and its influencing factors were evaluated with methylamine as the precursor during chlorination. The results indicated that the TCNM amount produced under alkaline condition was higher than those produced under the neutral and acidic conditions, and the TCNM amount increased with the increase of pH value. It was found that the TCNM amount increased with the increase of chlorine addition when the chlorine dosage was in the range of 2-8 mmol x L(-1). However, the TCNM amount was reduced when the chlorine dosage was enhanced from 8 mmol x L(-1) to 12 mmol x L(-1), under which conditions the concentration of free chlorine was higher and methylamine was turned into nitriles and aldehydes through other reactions. It was also found that the TCNM amount increased with the increase of methylamine addition when the methylamine dosage was in the range of 0.5-4 mmol x L(-1). Temperature was another important factor that affected the TCNM formation from methylamine especially in the range of 10-30 degrees C and the higher the temperature, the more the TCNM amount produced. The formation process of TCNM from methylamine by chlorination was in accordance with the mechanism of an electrophilic reaction, in which HClO and ClO(-) could be used as the electrophilic reagents to attack methylamine and then to form TCNM.

Four groups of new aromatic halogenated disinfection byproducts: effect of bromide concentration on their formation and speciation in chlorinated drinking water.

PubMed

Pan, Yang; Zhang, Xiangru

2013-02-05

Bromide is naturally present in source waters worldwide. Chlorination of drinking water can generate a variety of chlorinated and brominated disinfection byproducts (DBPs). Although substantial efforts have been made to examine the effect of bromide concentration on the formation and speciation of halogenated DBPs, almost all previous studies have focused on trihalomethanes and haloacetic acids. Given that about 50% of total organic halogen formed in chlorination remains unknown, it is still unclear how bromide concentration affects the formation and speciation of the new/unknown halogenated DBPs. In this study, chlorinated drinking water samples with different bromide concentrations were prepared, and a novel approach-precursor ion scan using ultra performance liquid chromatography/electrospray ionization-triple quadrupole mass spectrometry-was adopted for the detection and identification of polar halogenated DBPs in these water samples. With this approach, 11 new putative aromatic halogenated DBPs were identified, and they were classified into four groups: dihalo-4-hydroxybenzaldehydes, dihalo-4-hydroxybenzoic acids, dihalo-salicylic acids, and trihalo-phenols. A mechanism for the formation of the four groups of new aromatic halogenated DBPs was proposed. It was found that increasing the bromide concentration shifted the entire polar halogenated DBPs as well as the four groups of new DBPs from being less brominated to being more brominated; these new aromatic halogenated DBPs might be important intermediate DBPs formed in drinking water chlorination. Moreover, the speciation of the four groups of new DBPs was modeled: the speciation patterns of the four groups of new DBPs well matched those determined from the model equations, and the reactivity differences between HOBr and HOCl in reactions forming the four groups of new DBPs were larger than those in reactions forming trihalomethanes and haloacetic acids.

Modeling bromide effects on yields and speciation of dihaloacetonitriles formed in chlorinated drinking water.

PubMed

Roccaro, Paolo; Chang, Hyun-shik; Vagliasindi, Federico G A; Korshin, Gregory V

2013-10-15

This study examined effects of bromide on yields and speciation of dihaloacetonitrile (DHAN) species that included dichloro-, bromochloro- and dibromoacetonitriles generated in chlorinated water. Experimental data obtained using two water sources, varying concentrations and characters of Natural Organic Matter (NOM), bromide concentrations, reaction times, chlorine doses, temperatures and pHs were interpreted using a semi-phenomenological model that assumed the presence of three kinetically distinct sites in NOM (denoted as sites S1, S2 and S3) and the occurrence of sequential incorporation of bromine and chlorine into them. One site was found to react very fast with the chlorine and bromine but its contribution in the DHAN generation was very low. The site with the highest contribution to the yield of DHAN (>70%) has the lowest reaction rates. The model introduced dimensionless coefficients (denoted as φ1(DHAN), φ2(DHAN) and φ3(DHAN)) applicable to the initial DHAN generation sites and their monochlorinated and monobrominated products, respectively. These parameters were used to quantify the kinetic preference to bromine incorporation over that of chlorine. Values of these coefficients optimized for DHAN formation were indicative of the strongly preferential incorporation of bromine into the engaged NOM sites. The same set of φ(i)(DHAN) coefficients could be used to model the speciation of DHAN released from their kinetically different precursors. The dimensionless speciation coefficients φ(i)(DHAN) were determined to be site specific and dependent on the NOM content and character as well as pH. The presented model of DHAN formation and speciation can help quantify in more detail the generation of DHAN and provide more insight necessary for further assessment of their potential health effects. Copyright © 2013 Elsevier Ltd. All rights reserved.

Chlorine hazard evaluation for the zinc-chlorine electric vehicle battery. Final technical report

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zalosh, R.G.; Bajpai, S.N.; Short, T.P.

1980-04-01

An evaluation of the hazards associated with conceivable accidental chlorine releases from zinc-chlorine electric vehicle batteries is presented. Since commercial batteries are not yet available, this hazard assessment is based both on theoretical chlorine dispersion models and small-scale and large-scale spill tests with chlorine hydrate. Six spill tests involving chlorine hydrate indicate that the danger zone in which chlorine vapor concentrations intermittently exceed 100 ppM extends at least 23 m directly downwind of a spill onto a warm road surface. Chlorine concentration data from the hydrate spill tests compare favorably with calculations based on a quasi-steady area source dispersion modelmore » and empirical estimates of the hydrate decomposition rate. The theoretical dispersion model has been combined with assumed hydrate spill probabilities and current motor vehicle accident statistics in order to project expected chlorine-induced fatality rates. These calculations indicate that expected chlorine fatality rates are several times higher in a city with a warm and calm climate than in a colder and windier city. Calculated chlorine-induced fatality rate projections for various climates are presented as a function of hydrate spill probability in order to illustrate the degree of vehicle/battery crashworthiness required to maintain chlorine-induced fatality rates below current vehicle fatility rates due to fires and asphyxiations.« less

Use of multiple regression models to evaluate the formation of halonitromethane via chlorination/chloramination of water from Tai Lake and the Qiantang River, China.

PubMed

Hong, Huachang; Qian, Lingya; Xiong, Yujing; Xiao, Zhuoqun; Lin, Hongjun; Yu, Haiying

2015-01-01

The deterioration of water quality, especially organic pollution in Tai Lake and the Qiantang River, have recently received attention in China. The objectives of this study were to evaluate the formation of halonitromethanes (HNMs) using multiple regression models for chlorination and chloramination and to identify the key factors that influence the formation of HNMs in Tai Lake and the Qiantang River. The results showed that the total formation of HNMs (T-HNMs) during chlorination and chloramination could be described using the following models: (1) [Formula: see text] =(10)(5.267)(DON)(6.645)(Br(-))(0.737)(DOC)(-)(5.537)(Cl2)(0.333)(t)(0.165) (R(2)=0.974, p<0.01, n=33), and (2) T-HNMNH2Cl=(10)(-)(2.481)(Cl2)(0.451)(NO2(-))(0.382)(Br(-))(0.630)(t)(0.640)(Temp)(0.581) (R(2)=0.961, p<0.05, n=33), respectively. The key factors that influenced the T-HNM yields during chlorination were dissolved organic nitrogen (DON), bromide and dissolved organic carbon (DOC). The nitrite and bromide concentrations and the reaction time mainly affected the T-HNM yields during chloramination. Additional analysis indicated that the bromine incorporation factors (BIFs) for trihalogenated HNMs generally decreased as the chlorine/chloramine dose, temperature and reaction time decreased and increased as the bromide concentration increased. Copyright © 2014 Elsevier Ltd. All rights reserved.

Formation and fate of alkyl nitrates from chlorine-initiated oxidation of alkanes

NASA Astrophysics Data System (ADS)

Wang, D. S.; Hildebrandt Ruiz, L.

2017-12-01

Alkanes are a main source of anthropogenic volatile organic compounds (VOCs). Studies suggest that large alkanes, despite having high carbon mass, often do not significantly contribute to secondary organic aerosol (SOA) formation due to their low reactivity towards hydroxyl radicals. Chlorine radicals react much more quickly with alkanes; for example, the reaction of Cl with n-decane is about 50 times faster than the reaction of OH with n-decane. High reactive chlorine concentrations have been reported within continental regions as well as near coastal regions. The rapid oxidation of alkanes by chlorine radicals can therefore be a potentially significant, and overlooked source of alkylperoxy radicals and SOA formation. We present results from environmental chamber experiments on chlorine-initiated oxidation of C8, C10, and C12 linear and branched alkanes. Experiments were conducted under high NOx conditions to simulate highly polluted industrial environments. Formation of multigenerational gas-phase oxidation products were monitored using a High-Resolution Time-of-Flight Chemical Ionization Mass Spectrometer (CIMS). High SOA formation was observed using an Aerosol Chemical Speciation Monitor (ACSM). Aerosol volatility was determined using a thermodenuder and a kinetic aerosol evaporation model. Particle-phase composition was investigated using a Filter Inlet for Gases and AEROsols (FIGAERO) coupled to the CIMS, where dimer and oligomer formation were observed. Results from this study can be used to more accurately represent the fate of anthropogenic alkanes and SOA loadings in the atmosphere.

Efficient interfacial charge transfer through plasmon sensitized Ag@Bi2O3 hierarchical photoanodes for photoelectrocatalytic degradation of chlorinated phenols.

PubMed

Eswar, Neerugatti KrishnaRao; Adhikari, Sangeeta; Ramamurthy, Praveen C; Madras, Giridhar

2018-01-31

The present work demonstrates an extremely proficient and robust study of efficient interfacial charge transfer through plasmonic Ag decorated Bi 2 O 3 hierarchical photoanodes for the photoelectrochemical treatment of chlorinated phenols. Unique 2D flake-like Bi 2 O 3 hierarchical nanostructures were grown onto a fluorine-doped tin oxide (FTO) substrate by a simple chemical bath deposition method using triethanolamine as complexing agent. The formation of Bi 2 O 3 on FTO was governed by the decomposition of a nucleated bismuth-hydroxyl complex (Bi 2 O 1-x (OH) x ) and modification to the electrode was carried out by the deposition of Ag via a chemical reduction method using hydrazine hydrate. Both the fabricated electrodes were well characterized for their photo- and electro-optical properties. Efficient charge separation was observed due to the surface plasmon resonance phenomenon of silver nanoparticles with the favorable intrinsic properties of Bi 2 O 3 under application of a small electric bias of 1 V preventing the recombination of charge carriers and thereby increasing the rate of photoelectrocatalytic degradation of the chlorinated phenols. PEC degradation using the Ag@Bi 2 O 3 photoelectrode followed the trend 4-CP < 2,4-DCP < 2,4,6-TCP < P-CP due to efficient attack at the chlorinated positions by reactive oxygen species with increasing chlorine substitution and also due to the absence of an expected chain reaction of the generated chlorine radicals (Cl˙) during the PEC reaction. The PEC activity of Ag@Bi 2 O 3 was 1.5 times higher than a Bi 2 O 3 nanoflake electrode for 4-CP over 2 h. The fabricated Ag@Bi 2 O 3 proved to be an efficient photoelectrode with synergistic solar-induced photoactivity. A detailed mechanistic study in the presence of scavengers suggests degradation by produced hydroxyl radical species. Thus, physical insights into the degradation of chlorinated phenols were obtained.

Evidence for Perchlorates and the Origin of Chlorinated Hydrocarbons Detected by SAM at the Rocknest Aeolian Deposit in Gale Crater

NASA Technical Reports Server (NTRS)

Glavin, Daniel P.; Freissinet, Caroline; Miller, Kristen E.; Eigenbrode, Jennifer L.; Brunner, Anna E.; Buch, Arnaud; Sutter, Brad; Archer, P. Douglas, Jr.; Atreya, Sushil K.; Brinckerhoff, William B.;

Process for removing thorium and recovering vanadium from titanium chlorinator waste

DOEpatents

Olsen, Richard S.; Banks, John T.

1996-01-01

A process for removal of thorium from titanium chlorinator waste comprising: (a) leaching an anhydrous titanium chlorinator waste in water or dilute hydrochloric acid solution and filtering to separate insoluble minerals and coke fractions from soluble metal chlorides; (b) beneficiating the insoluble fractions from step (a) on shaking tables to recover recyclable or otherwise useful TiO.sub.2 minerals and coke; and (c) treating filtrate from step (a) with reagents to precipitate and remove thorium by filtration along with acid metals of Ti, Zr, Nb, and Ta by the addition of the filtrate (a), a base and a precipitant to a boiling slurry of reaction products (d); treating filtrate from step (c) with reagents to precipitate and recover an iron vanadate product by the addition of the filtrate (c), a base and an oxidizing agent to a boiling slurry of reaction products; and (e) treating filtrate from step (d) to remove any remaining cations except Na by addition of Na.sub.2 CO.sub.3 and boiling.

Free Radical Chemistry of Disinfection Byproducts. 3. Degradation Mechanisms of Chloronitromethane, Bromonitromethane and Dichloronitromethane

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bruce J. Mincher; Stephen P. Mezyk; William J. Cooper

2010-01-01

Halonitromethanes (HNMs) are byproducts formed through ozonation and chlorine/ chloramine disinfection processes in drinking waters that contain dissolved organic matter and bromide ions. These species occur at low concentration, but have been determined to have high cytotoxicity and mutagenicity and therefore may represent a human health hazard. In this study, we have investigated the chemistry involved in the mineralization of HNMs to non-hazardous inorganic products through the application of advanced oxidation and reduction processes. We have combined measured absolute reaction rate constants for the reactions of chloronitromethane, bromonitromethane and dichloronitromethane with the hydroxyl radical and the hydrated electron with amore » kinetic computer model in an attempt to elucidate the reaction pathways of these HNMs. The results are compared to measurements of stable products resulting from steady-state 60Co y-irradiations of the same compounds. The model predicted the decomposition of the parent compounds and ingrowth of chloride and bromide ions with excellent accuracy, but the prediction of the total nitrate ion concentration was slightly in error, reflecting the complexity of nitrogen oxide species reactions in irradiated solution.« less

Tropospheric Trace Gas Interactions with Aerosols

NASA Technical Reports Server (NTRS)

Penner, Joyce E.; Maddrea, George L., Jr. (Technical Monitor)

2002-01-01

Tropospheric aerosols are of considerable environmental importance. They modify the radiative budget of Earth by scattering and absorbing radiation, and by providing nuclei for cloud formation. Additionally, they provide surfaces for heterogeneous and multiphase reactions that affect tropospheric chemistry. For example, Dentener and Crutzen (1993) showed that reactions of N2O5 and NO3 with sulfate aerosols may significantly alter the tropospheric concentrations of NO(x), O3, and OH by converting NOx to HNO3 which is rapidly removed by precipitation. Zhang et al. (1994) assumed these same reactions would occur on dust aerosols and showed that dust outbreaks may reduce NO(x) levels by up to 50%. Dentener et al. (1996) studied the possible effect of reactions on dust on sulfate, nitrate, and O3 concentration. Heterogeneous and multiphase reactions on aerosols may also perturb the sulfur cycle the chlorine cycle and the bromine cycle. Because these reactions can release free chlorine and free bromine they might lead to the destruction of ozone in the marine boundary layer that may be important to include in models of tropospheric chemistry. The goal of our proposed work is to examine the role of heterogeneous and multiphase reactions in the tropospheric cycles of reactive nitrogen and sulfur.

Metabolism of halogenated ethylenes.

PubMed Central

Leibman, K C; Ortiz, E

1977-01-01

The metabolism of the chlorinated ethylenes may be explained by the formation of chloroethylene epoxides as the first intermediate products. The evidence indicates that these epoxides rearrange with migration of chlorine to form chloroacetaldehydes and chloroacetyl chlorides. Thus, monochloroacetic acid, chloral hydrate, and trichloroacetic acid have been found in reaction mixtures of 1,1-dichloroethylene, trichloroethylene, and tetrachloroethylene, respectively, with rat liver microsomal systems. Rearrangements of the chloroethylene, and glycols formed from the epoxides by hydration may also take place, but would appear, at least in the case of 1,1-dichloroethylene, to be quantitatively less important. The literature on the metabolism of chlorinated ethylenes and its relationship to their toxicity is reviewed. PMID:612463

Abatement of chlorinated compounds in groundwater contaminated by HCH wastes using ISCO with alkali activated persulfate.

PubMed

Santos, A; Fernandez, J; Rodriguez, S; Dominguez, C M; Lominchar, M A; Lorenzo, D; Romero, A

2018-02-15

In this work, in situ chemical oxidation (ISCO) with alkali activated persulfate has been tested for the elimination of HCH isomers and other chlorinated compounds in groundwater from Sabiñanigo (Sardas landfill), which was contaminated by solid and liquid wastes illegally dumped in the area by a company producing lindane. Due to the site lithology and the type of pollutants found in groundwater (HCHs and chlorobenzenes) alkali (NaOH) activated persulfate (PS) was selected as oxidant. The influence of variables such as PS concentration (42-200mM) and NaOH:PS molar ratio (2:1 to 4:1) on chlorinated compound abatement has been studied and a kinetic model to predict the composition of all chlorinated organic compounds (COCs) in the aqueous phase with time was obtained. It was found that a fast initial hydrodechlorination reaction took place in which HCH isomers reacted to trichlorobenzenes (mainly 1,2,4 TCB) at pH≥12. Mono-, di-, tri and tetrachlorobenzenes remaining were oxidized without producing aromatic intermediates. At the condition tested a first order kinetic model for COCs and PS concentration was obtained. Zero order alkali concentration was obtained while pH was being kept at 12 for the whole reaction time. Copyright © 2017 Elsevier B.V. All rights reserved.

Physical chemistry of the H2SO4/HNO3/H2O system - Implications for polar stratospheric clouds

NASA Technical Reports Server (NTRS)

Molina, M. J.; Zhang, R.; Wooldridge, P. J.; Mcmahon, J. R.; Kim, J. E.; Chang, H. Y.; Beyer, K. D.

1993-01-01

Polar stratospheric clouds (PSCs) play a key role in stratospheric ozone depletion. Surface-catalyzed reactions on PSC particles generate chlorine compounds that photolyze readily to yield chlorine radicals, which in turn destroy ozone very efficiently. The most prevalent PSCs form at temperatures several degrees above the ice frost point and are believed to consist of HNO3 hydrates; however, their formation mechanism is unclear. Results of laboratory experiments are presented which indicate that the background stratospheric H2SO4/H2O aerosols provide an essential link in this mechanism: These liquid aerosols absorb significant amounts of HNO3 vapor, leading most likely to the crystallization of nitric acid trihydrate (NAT). The frozen particles then grow to form PSCs by condensation of additional amounts of HNO3 and H2O vapor. Furthermore, reaction probability measurements reveal that the chlorine radical precursors are formed readily at polar stratospheric temperatures not just on NAT and ice crystals, but also on liquid H2SO4 solutions and on solid H2SO4 hydrates. These results imply that the chlorine activation efficiency of the aerosol particles increases rapidly as the temperature approaches the ice frost point regardless of the phase or composition of the particles.

Influence of the order of reagent addition on NDMA formation during chloramination.

PubMed

Schreiber, I Marie; Mitch, William A

2005-05-15

The formation of the potent carcinogen, N-nitrosodimethylamine (NDMA), during chlorine disinfection has caused significant concern among drinking water and wastewater recycling utilities practicing intentional or unintentional chloramination. Previous research modeled NDMA formation as arising from a reaction between monochloramine and organic nitrogen precursors, such as dimethylamine, via an unsymmetrical dimethylhydrazine (UDMH) intermediate. Contrary to the importance of monochloramine indicated by previous studies, hypochlorite formed an order of magnitude more NDMA than monochloramine when applied to a secondary municipal wastewater effluent containing excess ammonia. Experiments involving variation of the order that each reagent (i.e., hypochlorite, ammonium chloride, and dimethylamine) was added to solution suggest two factors that may be more important for NDMA formation than the presence of monochloramine: (i) the chlorination state of organic nitrogen precursors and (ii) the partial formation of dichloramine. Although dichloramine formation was most influenced by the pH conditions under which inorganic chloramine formation was performed, mixing effects related to the order of reagent addition may be important at full-scale plants. Chloramination strategies are suggested that may reduce NDMA formation by nearly an order of magnitude.

Chlorination of low-band-gap polymers: Toward high-performance polymer solar cells

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mo, Daize; Wang, Huan; Chen, Hui

Here, halogenation is an effective way to tune the energy levels of organic semiconducting materials. To date, fluorination of organic semiconducting materials to fabricate polymer solar cells (PSCs) has been used far more than chlorination; however, fluorine exchange reactions suffer from low yields and the resulting fluorinated polymer always comes with higher price, which will greatly hinder their commercial applications. Herein, we designed and synthesized a series of chlorinated donor-acceptor (D-A) type polymers, in which benzo[1,2-b:4,5- b]dithiophene and chlorinated benzothiadiazole units are connected by thiophene π-bridges with an asymmetric alkyl chain. These chlorinated polymers showed deep highest occupied molecular orbitalmore » energy levels, which promoted the efficiency of their corresponding PSCs by increasing the device open circuit voltage. The asymmetric alkyl chain on the thiophene moieties gave the final polymer sufficient solubility for solution processing and strong π-π stacking in films allowed for high mobility. Although the introduction of a large chlorine atom increased the torsion angle of the polymer backbone, the chlorinated polymers maintained high crystallinity and a favorable backbone orientation in the blended films. These factors contributed to respectable device performances from thick-film devices, which showed PCEs as high as 9.11% for a 250 nm-thick active layer. These results demonstrate that chlorination is a promising method to fine tune the energy levels of conjugated polymers, and chlorinated benzothiadiazole may be a versatile building block in materials for efficient solar energy conversion.« less

Chlorination of low-band-gap polymers: Toward high-performance polymer solar cells

DOE PAGES

Mo, Daize; Wang, Huan; Chen, Hui; ...

2017-03-08

Here, halogenation is an effective way to tune the energy levels of organic semiconducting materials. To date, fluorination of organic semiconducting materials to fabricate polymer solar cells (PSCs) has been used far more than chlorination; however, fluorine exchange reactions suffer from low yields and the resulting fluorinated polymer always comes with higher price, which will greatly hinder their commercial applications. Herein, we designed and synthesized a series of chlorinated donor-acceptor (D-A) type polymers, in which benzo[1,2-b:4,5- b]dithiophene and chlorinated benzothiadiazole units are connected by thiophene π-bridges with an asymmetric alkyl chain. These chlorinated polymers showed deep highest occupied molecular orbitalmore » energy levels, which promoted the efficiency of their corresponding PSCs by increasing the device open circuit voltage. The asymmetric alkyl chain on the thiophene moieties gave the final polymer sufficient solubility for solution processing and strong π-π stacking in films allowed for high mobility. Although the introduction of a large chlorine atom increased the torsion angle of the polymer backbone, the chlorinated polymers maintained high crystallinity and a favorable backbone orientation in the blended films. These factors contributed to respectable device performances from thick-film devices, which showed PCEs as high as 9.11% for a 250 nm-thick active layer. These results demonstrate that chlorination is a promising method to fine tune the energy levels of conjugated polymers, and chlorinated benzothiadiazole may be a versatile building block in materials for efficient solar energy conversion.« less

Cold plasma processing of local planetary ores for oxygen and metallurgically important metals

NASA Technical Reports Server (NTRS)

Lynch, D. C.; Bullard, D.; Ortega, R.

1990-01-01

The utilization of a cold plasma in chlorination processing is described. Essential equipment and instruments were received, the experimental apparatus assembled and tested, and preliminary experiments conducted. The results of the latter lend support to the original hypothesis: a cold plasma can both significantly enhance and bias chemical reactions. In two separate experiments, a cold plasma was used to reduce TiCl4 vapor and chlorinate ilmenite. The latter, reacted in an argon-chlorine plasma, yielded oxygen. The former experiment reveals that chlorine can be recovered as HCl vapor from metal chlorides in a hydrogen plasma. Furthermore, the success of the hydrogen experiments has lead to an analysis of the feasibility of direct hydrogen reduction of metal oxides in a cold plasma. That process would produce water vapor and numerous metal by-products.

Gasification Characteristics and Kinetics of Coke with Chlorine Addition

NASA Astrophysics Data System (ADS)

Wang, Cui; Zhang, Jianliang; Jiao, Kexin; Liu, Zhengjian; Chou, Kuochih

2017-10-01

The gasification process of metallurgical coke with 0, 1.122, 3.190, and 7.132 wt pct chlorine was investigated through thermogravimetric method from ambient temperature to 1593 K (1320 °C) in purified CO2 atmosphere. The variations in the temperature parameters that T i decreases gradually with increasing chlorine, T f and T max first decrease and then increase, but both in a downward trend indicated that the coke gasification process was catalyzed by the chlorine addition. Then the kinetic model of the chlorine-containing coke gasification was obtained through the advanced determination of the average apparent activation energy, the optimal reaction model, and the pre-exponential factor. The average apparent activation energies were 182.962, 118.525, 139.632, and 111.953 kJ/mol, respectively, which were in the same decreasing trend with the temperature parameters analyzed by the thermogravimetric method. It was also demonstrated that the coke gasification process was catalyzed by chlorine. The optimal kinetic model to describe the gasification process of chlorine-containing coke was the Šesták Berggren model using Málek's method, and the pre-exponential factors were 6.688 × 105, 2.786 × 103, 1.782 × 104, and 1.324 × 103 min-1, respectively. The predictions of chlorine-containing coke gasification from the Šesták Berggren model were well fitted with the experimental data.

Research in Chemical Kinetics: Progress Report, January 1, 1978 to September 30, 1978

DOE R&D Accomplishments Database

Rowland, F. S.

1978-01-01

Research was conducted on the following topics: stratospheric chemistry of chlorinated molecules, atmospheric chemistry of methane, atmospheric chemistry of cosmogenic tritium, reactions of energetic and thermal radioactive atoms, methylene chemistry, and laboratory simulation of chemical reactions in Jupiter atmosphere. (DLC)

Kinetic Model for the Radical Degradation of Tri-Halonitromethane Disinfection Byproducts in Water

DOE Office of Scientific and Technical Information (OSTI.GOV)

Stephen P. Mezyk; Bruce J. Mincher; William J. Cooper

The halonitromethanes (HNMs) are byproducts of the ozonation and chlorine/chloramine treatment of drinking waters. Although typically occurring at low concentrations HNMs have high cytotoxicity and mutagenicity, and may therefore represent a significant human health hazard. In this study, we have investigated the radical based mineralization of fully-halogenated HNMs in water using the congeners bromodichloronitromethane and chlorodibromonitromethane. We have combined absolute reaction rate constants for their reactions with the hydroxyl radical and the hydrated electron as measured by electron pulse radiolysis and analytical measurements of stable product concentrations obtained by 60Co steady-state radiolysis with a kinetic computer model that includes watermore » radiolysis reactions and halide/nitrogen oxide radical chemistry to fully elucidate the reaction pathways of these HNMs. These results are compared to our previous similar study of the fully chlorinated HNM chloropicrin. The full optimized computer model, suitable for predicting the behavior of this class of compounds in irradiated drinking water is provided.« less

Tetrachlorinated Polycyclic Aromatic Dicarboximides: New Electron-Poor Π-Scaffolds and NIR Emitters by Palladium-Catalyzed Annulation Reaction.

PubMed

Mahl, Magnus; Shoyama, Kazutaka; Rühe, Jessica; Grande, Vincenzo; Würthner, Frank

2018-04-24

Herein we report a palladium-catalyzed annulation reaction consisting of a Suzuki-Miyaura cross-coupling and a C-H arylation cascade for the synthesis of tetrachlorinated polycyclic aromatic dicarboximides (PADIs). This convergent synthetic route afforded a broad series of hitherto unknown electron-deficient PADIs under optimized reaction conditions by coupling of a dibromo-tetrachloro-perylene dicarboximide with different polycyclic aromatic hydrocarbon (PAH) boronic acid pinacol esters in up to 89% yields. The new PADI compounds show broad absorption in the visible range and some of them emit in the near-infrared (NIR) region. Cyclic and square wave voltammetric studies revealed that these tetrachlorinated PADIs are more electron-deficient than a non-chlorinated reference compound and they possess lower lying frontier orbitals. Thus, the newly synthesized electron-poor PADIs are potential n-type semiconductors. Moreover, these chlorinated PADIs are interesting building blocks for the construction of large π-extended arrays by metal-mediated coupling reactions. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Thermal Synthesis of Perchlorinated Oligosilanes: A Fresh Look at an Old Reaction.

PubMed

Neumeyer, Felix; Schweizer, Julia I; Meyer, Lioba; Sturm, Alexander G; Nadj, Andor; Holthausen, Max C; Auner, Norbert

2017-09-07

A combined experimental and theoretical study of the high-temperature reaction of SiCl 4 and elemental silicon is presented. The nature and reactivity of the product formed upon rapid cooling of the gaseous reaction mixture is investigated by comparison with the defined model compounds cyclo-Si 5 Cl 10 , n-Si 5 Cl 12 and n-Si 4 Cl 10 . A DFT assessment provides mechanistic insight into the oligosilane formation. Experimental 29 Si NMR investigations, supported by quantum-chemical 29 Si NMR calculations, consistently show that the reaction product is composed of discrete molecular perchlorinated oligosilanes. Low-temperature chlorination is an unexpectedly selective means for the transformation of cyclosilanes to acyclic species by endocyclic Si-Si bond cleavage, and we provide a mechanistic rationalization for this observation. In contrast to the raw material, the product obtained after low-temperature chlorination represents an efficient source of neo-Si 5 Cl 12 or the amine-stabilized disilene EtMe 2 N⋅SiCl 2 Si(SiCl 3 ) 2 through reaction with aliphatic amines. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Reactions of silicon-based ceramics in mixed oxidation chlorination environments

NASA Technical Reports Server (NTRS)

Marra, John E.; Kreidler, Eric R.; Jacobson, Nathan S.; Fox, Dennis S.

1988-01-01

The reaction of silicon-based ceramics with 2 percent Cl2/Ar and 1 percent Cl2/1 percent to 20 percent O2/Ar at 950 C was studied with thermogravimetric analysis and high-pressure mass spectrometry. Pure Si, SiO2, several types of SiC, and Si3N4 were examined. The primary corrosion products were SiCl4(g) and SiO2(s) with smaller amounts of volatile silicon oxychlorides. The reactions appear to occur by chlorine penetration of the SiO2 layer, and gas-phase diffusion of the silicon chlorides away from the sample appears to be rate limiting. Pure SiO2 shows very little reaction with Cl2, SiC with excess Si is more reactive than the other materials with Cl2, whereas SiC with excess carbon is more reactive than the other materials with Cl2/O2. Si3N4 shows very little reaction with Cl2. These differences are explained on the basis of thermodynamic and microstructural factors.

Hydrogen Abstraction by Chlorine Atom from Small Organic Molecules Containing Amino Acid Functionalities: An Assessment of Theoretical Procedures

NASA Astrophysics Data System (ADS)

Taylor, Mark S.; Ivanic, Sandra A.; Wood, Geoffrey P. F.; Easton, Christopher J.; Bacskay, George B.; Radom, Leo

2009-07-01

A high-level quantum chemistry investigation has been carried out for the abstraction by chlorine atom of hydrogen from methane and five monosubstituted methanes, chosen to reflect the chemical functionalities contained in amino acids and peptides. A modified W1' procedure is used to calculate benchmark barriers and reaction energies for the six reactions. The reactions demonstrate a broad range of barrier heights and reaction energies, which can be rationalized using curve-crossing and molecular orbital theory models. In addition, the performance of a range of computationally less demanding electronic structure methods is assessed for calculating the energy profiles for the six reactions. It is found that the G3X(MP2)-RAD procedure compares best with the W1' benchmark, demonstrating a mean absolute deviation (MAD) from W1' of 2.1 kJ mol-1. The more economical RMP2/G3XLarge and UB2-PLYP/G3XLarge methods are also shown to perform well, with MADs from W1' of 2.9 and 3.0 kJ mol-1, respectively.

Changes in Dissolved Organic Matter Composition and Disinfection Byproduct Precursors in Advanced Drinking Water Treatment Processes.

PubMed

Phungsai, Phanwatt; Kurisu, Futoshi; Kasuga, Ikuro; Furumai, Hiroaki

2018-03-20

Molecular changes in dissolved organic matter (DOM) from treatment processes at two drinking water treatment plants in Japan were investigated using unknown screening analysis by Orbitrap mass spectrometry. DOM formulas with carbon, hydrogen and oxygen (CHO-DOM) were the most abundant class in water samples, and over half of them were commonly found at both plants. Among the treatment processes, ozonation induced the most drastic changes to DOM. Mass peak intensities of less saturated CHO-DOM (positive (oxygen subtracted double bond equivalent per carbon (DBE-O)/C)) decreased by ozonation, while more saturated oxidation byproducts (negative (DBE-O)/C) increased and new oxidation byproducts (OBPs) were detected. By Kendrick mass analysis, ozone reactions preferred less saturated CHO-DOM in the same alkylation families and produced more saturated alkylation families of OBPs. Following ozonation, biological activated carbon filtration effectively removed <300 Da CHO-DOM, including OBPs. Following chlorination, over 50 chlorinated formulas of disinfection byproducts (DBPs) were found in chlorinated water samples where at least half were unknown. Putative precursors of these DBPs were determined based on electrophilic substitutions and addition reactions. Ozonation demonstrated better decomposition of addition reaction-type precursors than electrophilic substitution-type precursors; over half of both precursor types decreased during biological activated carbon filtration.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Habermehl, Scott D.

Described methods are useful for depositing a silicon carbide film including Alpha-SiC at low temperatures (e.g., below about 1400.degree. C.), and resulting multi-layer structures and devices. A method includes introducing a chlorinated hydrocarbon gas and a chlorosilicon gas into a reaction chamber, and reacting the chlorinated hydrocarbon gas with the chlorosilicon gas at a temperature of less than about 1400.degree. C. to grow the silicon carbide film. The silicon carbide film so-formed includes Alpha-SiC.

A study on the reaction between chlorine trifluoride gas and glass-like carbon

NASA Astrophysics Data System (ADS)

Saito, Yoji; Nishizawa, Takashi; Hamaguchi, Maki

2005-02-01

The reaction between glass-like carbon (GC) and chlorine trifluoride (ClF 3) gas was investigated with weight measurements, surface analysis, and gas desorption measurements, where the ClF 3 gas is used for the in situ cleaning of tubes in silicon-related fabrication equipment. From Auger electron spectroscopy and X-ray photoelectron spectroscopy measurements, a carbon mono-fluoride, -(CF) n-, film near the surface of GC is considered to be grown onto the GC surface above 400 °C by the chemical reaction with ClF 3, and this thickness of the fluoride film depends on the temperature. The grown fluoride film desorbs by annealing in a vacuum up to 600 °C. Although GC is apparently etched by ClF 3 over 600 °C, the etch rate of GC is much lower than that of SiC and quartz.

Rapid Hydrogen and Oxygen Atom Transfer by a High-Valent Nickel-Oxygen Species.

PubMed

Corona, Teresa; Draksharapu, Apparao; Padamati, Sandeep K; Gamba, Ilaria; Martin-Diaconescu, Vlad; Acuña-Parés, Ferran; Browne, Wesley R; Company, Anna

2016-10-05

Terminal high-valent metal-oxygen species are key reaction intermediates in the catalytic cycle of both enzymes (e.g., oxygenases) and synthetic oxidation catalysts. While tremendous efforts have been directed toward the characterization of the biologically relevant terminal manganese-oxygen and iron-oxygen species, the corresponding analogues based on late-transition metals such as cobalt, nickel or copper are relatively scarce. This scarcity is in part related to the "Oxo Wall" concept, which predicts that late transition metals cannot support a terminal oxido ligand in a tetragonal environment. Here, the nickel(II) complex (1) of the tetradentate macrocyclic ligand bearing a 2,6-pyridinedicarboxamidate unit is shown to be an effective catalyst in the chlorination and oxidation of C-H bonds with sodium hypochlorite as terminal oxidant in the presence of acetic acid (AcOH). Insight into the active species responsible for the observed reactivity was gained through the study of the reaction of 1 with ClO - at low temperature by UV-vis absorption, resonance Raman, EPR, ESI-MS, and XAS analyses. DFT calculations aided the assignment of the trapped chromophoric species (3) as a nickel-hypochlorite species. Despite the fact that the formal oxidation state of the nickel in 3 is +4, experimental and computational analysis indicate that 3 is best formulated as a Ni III complex with one unpaired electron delocalized in the ligands surrounding the metal center. Most remarkably, 3 reacts rapidly with a range of substrates including those with strong aliphatic C-H bonds, indicating the direct involvement of 3 in the oxidation/chlorination reactions observed in the 1/ClO - /AcOH catalytic system.

A novel method for the synthesis of zirconia powder

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bohe, A.E.; Pasquevich, D.M.

A novel method for the synthesis of zirconia powder is presented in this paper. The formation of fine particles of zirconia takes place when metallic zirconium and hematite are heated in the presence of gaseous chlorine. The overall process, which can be described by the following reaction: 3 Zr(s) + 2 Fe{sub 2}O{sub 3}(s) {r_arrow} 3 ZrO{sub 2}(s) + 4 Fe(s), occurs by a mass-transport mechanism through the vapor phase between 723 and 1223 K. The vapor-mass transport among the solid species takes place by means of zirconium and iron chlorides. The fundamentals of synthesis are discussed on the basismore » of a detailed thermodynamic analysis of reactions involved in the process, as well as by a characterization of the solid phases formed at various temperatures at XRD and SEM examinations.« less

Infrared identification of the σ-complex of Cl-C6H6 in the reaction of chlorine atom and benzene in solid para-hydrogen.

PubMed

Bahou, Mohammed; Witek, Henryk; Lee, Yuan-Pern

2013-02-21

The reaction of a chlorine atom with benzene (C6H6) is important in organic chemistry, especially in site-selective chlorination reactions, but its product has been a subject of debate for five decades. Previous experimental and theoretical studies provide no concrete conclusion on whether the product is a π- or σ-form of the Cl-C6H6 complex. We took advantage of the diminished cage effect of para-hydrogen (p-H2) to produce Cl in situ to react with C6H6 (or C6D6) upon photolysis of a Cl2/C6H6 (or C6D6)/p-H2 matrix at 3.2 K. The infrared spectrum, showing intense lines at 1430.5, 833.6, 719.8, 617.0, and 577.4 cm(−1), and several weaker ones for Cl-C6H6, and the deuterium shifts of observed new lines unambiguously indicate that the product is a 6-chlorocyclohexadienyl radical, i.e., the σ-complex of Cl-C6H6. Observation of the σ-complex rather than the π-complex indicates that the σ-complex is more stable in solid p-H2 at 3.2 K. The spectral information is crucial for further investigations of the Cl + C6H6 reaction either in the gaseous or solution phase.

Atmospheric degradation mechanisms of hydrogen containing chlorofluorocarbons (HCFC) and fluorocarbons (HFC)

NASA Technical Reports Server (NTRS)

Zellner, Reinhard

1990-01-01

The current knowledge of atmospheric degradation of hydrogen containing chlorofluorocarbons (HCFC 22 (CHClF2), HCFC 123 (CHCl2CF3), HCFC 124 (CHClFCF3), HCFC 141b (CFCl2CH3), HCFC 142b (CF2ClCH3)) and fluorocarbons (HFC 125 (CHF2CF3), HFC 134a (CH2FCF3), HFC 152a (CHF2CH3)) is assessed. Except for the initiation reaction by OH radicals, there are virtually no experimental data available concerning the subsequent oxidative breakdown of these molecules. However, from an analogy to the degradation mechanisms of simple alkanes, some useful guidelines as to the expected intermediates and final products can be derived. A noteable exception from this analogy, however, appears for the oxi-radicals. Here, halogen substitution induces new reaction types (C-Cl and C-C bond ruptures) which are unknown to the unsubstituted analogues and which modify the nature of the expected carbonyl products. Based on an evaluation of these processes using estimated bond strength data, the following simplified rules with regards to the chlorine content of the HCFC's may be deduced: (1) HCFC's containing one chlorine atom such as 22 and 142b seem to release their chlorine content essentially instantaneous with the initial attack on the parent by OH radicals, and for HCFC 124, such release is apparently prevented; (2) HCFC's such as 123 and 141b with two chlorine atoms are expected to release only one of these instantaneously; and the second chlorine atom may be stored in potentially long-lived carbonyl compounds such as CF3CClO or CClFO.

Observations of denitrification and dehydration in the winter polar stratospheres

NASA Technical Reports Server (NTRS)

Fahey, D. W.; Kelly, K. K.; Kawa, S. R.; Tuck, A. F.; Loewenstein, M.

1990-01-01

It is argued that denitrification of the Arctic stratosphere can be explained by the selective growth and sedimentation of aerosol particles rich in nitric acid. Because reactive nitrogen species moderate the destruction of ozone by chlorine-catalyzed reactions by sequestering chlorine in reservoir species such as ClONO2, the possibility of the removal of reactive nitrogen without dehydration should be allowed for in attempts to model ozone depletion in the Arctic. Indeed, denitrification along with elevated concentrations of reactive chlorine observed in 1989 indicate that the Arctic was chemically primed for ozone destruction without an extended period of temperatures below the frost point, as is characteristic of the Antarctic.

Use of Field-Scale Phytotechnology for Chlorinated Solvents, Metals, Explosives and Propellants, and Pesticides

EPA Pesticide Factsheets

For this document, the US EPA collected information about 79 field-scale phytotechnology projects conducted throughout the US and Canada that involved treatment of soil and groundwater contaminated with chlorinated solvents, metals, explosives and...

RELATIONSHIPS BETWEEN LABORATORY AND PILOT-SCALE COMBUSTION OF SOME CHLORINATED HYDROCARBONS

EPA Science Inventory

Factors governing the occurence of trace amounts of residual organic substance emmissions (ROSEs) in full-scale incierators are not fully understood. Pilot-scale spray combustion expereiments involving some liquid chlorinated hydrocarbons (CHCs) and their dilute mixtures with hy...

Dechlorination of short chain chlorinated paraffins by nanoscale zero-valent iron.

PubMed

Zhang, Zhi-Yong; Lu, Mang; Zhang, Zhong-Zhi; Xiao, Meng; Zhang, Min

2012-12-01

In this study, nanoscale zero-valent iron (NZVI) particles were synthesized and used for the reductive dehalogenation of short chain chlorinated paraffins (SCCPs) in the laboratory. The results show that the dechlorination rate of chlorinated n-decane (CP(10)) by NZVI increased with decreased solution pH. Increasing the loading of NZVI enhanced the dechlorination rate of CP(10). With an increase in temperature, the degradation rate increased. The reduction of CP(10) by NZVI was accelerated with increasing the concentration of humic acid up to 15 mg/L but then was inhibited. The dechlorination of CP(10) within the initial 18 h followed pseudo-first order rate model. The formation of intermediate products indicates a stepwise dechlorination pathway of SCCPs by NZVI. The carbon chain length and chlorination degree of SCCPs have a polynominal impact on dechlorination reactions. Copyright © 2012 Elsevier B.V. All rights reserved.

Kinetic Analysis of Haloacetonitrile Stability in Drinking Waters.

PubMed

Yu, Yun; Reckhow, David A

2015-09-15

Haloacetonitriles (HANs) are an important class of drinking water disinfection byproducts (DBPs) that are reactive and can undergo considerable transformation on time scales relevant to system distribution (i.e., from a few hours to a week or more). The stability of seven mono-, di-, and trihaloacetonitriles was examined under a variety of conditions including different pH levels and disinfectant doses that are typical of drinking water distribution systems. Results indicated that hydroxide, hypochlorite, and their protonated forms could react with HANs via nucleophilic attack on the nitrile carbon, forming the corresponding haloacetamides (HAMs) and haloacetic acids (HAAs) as major reaction intermediates and end products. Other stable intermediate products, such as the N-chloro-haloacetamides (N-chloro-HAMs), may form during the course of HAN chlorination. A scheme of pathways for the HAN reactions was proposed, and the rate constants for individual reactions were estimated. Under slightly basic conditions, hydroxide and hypochlorite are primary reactants and their associated second-order reaction rate constants were estimated to be 6 to 9 orders of magnitude higher than those of their protonated conjugates (i.e., neutral water and hypochlorous acid), which are much weaker but more predominant nucleophiles at neutral and acidic pHs. Developed using the estimated reaction rate constants, the linear free energy relationships (LFERs) summarized the nucleophilic nature of HAN reactions and demonstrated an activating effect of the electron withdrawing halogens on nitrile reactivity, leading to decreasing HAN stability with increasing degree of halogenation of the substituents, while subsequent shift from chlorine to bromine atoms has a contrary stabilizing effect on HANs. The chemical kinetic model together with the reaction rate constants that were determined in this work can be used for quantitative predictions of HAN concentrations depending on pH and free chlorine contact times (CTs), which can be applied as an informative tool by drinking water treatment and system management engineers to better control these emerging nitrogenous DBPs, and can also be significant in making regulatory decisions.

Factors affecting THMs, HAAs and HNMs formation of Jin Lan Reservoir water exposed to chlorine and monochloramine.

PubMed

Hong, Huachang; Xiong, Yujing; Ruan, Mengyong; Liao, Fanglei; Lin, Hongjun; Liang, Yan

2013-02-01

The formations of THMs, HAAs, and HNMs from chlorination and chloramination of water from Jinlan Reservoir were investigated in this study. Results showed that monochloramine rather than chlorine generally resulted in lower concentration of DBPs, and the DBPs formation varied greatly as the treatment conditions changed. Specifically, the yields of THMs, HAAs and HNMs all increased with the high bromide level and high disinfectant dose both during chlorination and chloramination. The longer reaction time had a positive effect on the formation of THMs, HAAs and HNMs during chlorination and HNMs during chloramination. However, no time effect was observed on the formation of THMs and HAAs during chloramination. An increase in pH enhanced the levels of THMs and HNMs upon chlorination but reduced levels of HNMs upon chloramination. As for the THMs in chloramination and HAAs in chlorination and chloramination, no obvious pH effect was observed. The elevated temperature significantly increased the yields of THMs during chlorination and HNMs during chloramination, but has no effect on THMs and HAAs yields during chloramination. In the same temperature range, the formation of HAAs and HNMs in chlorination showed a first increasing and then a decreasing trend. In chloramination study, addition of nitrite markedly increased the formation of HNMs but had little impact on the formation of THMs and HAAs. While in chlorination study, the presence of high nitrite levels significantly reduced the yields of THMs, HAAs and HNMs. Range analysis revealed that the bromide and disinfectant levels were the major factors affecting THMs, HAAs and HNMs formation, in both chlorination and chloramination. Finally, comparisons of the speciation of mono-halogenated, di-halogenated, tri-halogenated HAAs and HNMs between chlorination and monochloramination were also conducted, and factors influencing the speciation pattern were identified. Copyright © 2012 Elsevier B.V. All rights reserved.

Transformation mechanism of benzophenone-4 in free chlorine promoted chlorination disinfection.

PubMed

Xiao, Ming; Wei, Dongbin; Yin, Junxia; Wei, Guohua; Du, Yuguo

2013-10-15

The UV-filter BP-4 (2-hydroxy-4-methoxybenzophenone-5-sulfonic acid) has been frequently observed in the environment, showing high potentials to invade drinking water, swimming water, or wastewater reclamation treatment systems. With the help of high performance liquid chromatography-high resolution mass spectrometry and nuclear magnetic resonance spectroscopy, 10 new products from free chlorine-promoted BP-4 disinfection have been disclosed and their possible transformation routes have been investigated. The first route is chlorine substitution of BP-4 and its transformation products, forming mono-, di-, and tri-chlorinated BP-4 analogs. The second is Baeyer-Villiger-Type oxidation, converting diphenyl ketone to phenyl ester derivatives. The third is ester hydrolysis, generating corresponding phenolic and benzoic products. The fourth is decarboxylation, replacing the carboxyl group by chloride in the benzoic-type intermediate. The fifth is desulfonation, degrading the sulfonic group through an alternative chlorine substitution on the benzene ring. Orthogonal experiments have been established to investigate the species transformed from BP-4 at different pH values and free available chlorine (FAC) dosages. The reaction pathways are strongly dependent on pH conditions, while an excessive amount of FAC eliminates BP-4 to the smaller molecules. The initial transformation of BP-4 in chlorination system follows pseudo-first-order kinetics, and its half-lives ranged from 7.48 s to 1.26 × 10(2) s. More importantly, we have observed that the FAC-treated BP-4 aqueous solution might increase the genotoxic potentials due to the generation of chlorinated disinfection by-products. Copyright © 2013 Elsevier Ltd. All rights reserved.

IR spectroscopic study of Pt-containing zeolites in the hydrodechlorination reaction of C 2 chlorinated hydrocarbons

NASA Astrophysics Data System (ADS)

Hannus, I.; Kropok, Zs.; Halász, J.

2007-05-01

Some of the chlorinated organic compounds are widely used commercially, because of their advantageous chemical/physical properties or having toxicity for pestiferous living substances. However, emitted into the atmosphere they are responsible for diminishing the ozone layer in the stratosphere. Therefore, a lot of effort is devoted in finding proper solutions to decompose these chemicals in environmentally friendly ways. Platinum on different carriers play very important role in catalytic hydrodechlorination of these compounds. We have found that Pt-containing Y-FAU zeolite is an active catalyst in the hydrodechlorination of trichloroethene. IR spectroscopic experiments showed that the final products are ethane and HCl, and the hydrogen/reactant ratio exerts large influence on the rate of the hydrodechlorination reaction.

Effect of nitric oxide on photochemical ozone formation in mixtures of air with molecular chlorine and with trichlorofluoromethane

NASA Technical Reports Server (NTRS)

Bittker, D. A.; Wong, E. L.

1978-01-01

Ozone formation in a reaction chamber at room temperature and atmospheric pressure were studied for the photolysis of mixtures of NO with either Cl2 or CFCl3 in air. Both Cl2 + NO and CFCl3 + NO in air strongly inhibited O3 formation during the entire 3 to 4 hour reaction. A chemical mechanism that explains the results was presented. An important part of this mechanism was the formation and destruction of chlorine nitrate. Computations were performed with this same mechanism for CFCl3-NO-air mixtures at stratospheric temperatures, pressures, and concentrations. Results showed large reductions in steady-state O3 concentrations in these mixtures as compared with pure air.

Regression equations for disinfection by-products for the Mississippi, Ohio and Missouri rivers

USGS Publications Warehouse

Rathbun, R.E.

1996-01-01

Trihalomethane and nonpurgeable total organic-halide formation potentials were determined for the chlorination of water samples from the Mississippi, Ohio and Missouri Rivers. Samples were collected during the summer and fall of 1991 and the spring of 1992 at twelve locations on the Mississippi from New Orleans to Minneapolis, and on the Ohio and Missouri 1.6 km upstream from their confluences with the Mississippi. Formation potentials were determined as a function of pH, initial free-chlorine concentration, and reaction time. Multiple linear regression analysis of the data indicated that pH, reaction time, and the dissolved organic carbon concentration and/or the ultraviolet absorbance of the water were the most significant variables. The initial free-chlorine concentration had less significance and bromide concentration had little or no significance. Analysis of combinations of the dissolved organic carbon concentration and the ultraviolet absorbance indicated that use of the ultraviolet absorbance alone provided the best prediction of the experimental data. Regression coefficients for the variables were generally comparable to coefficients previously presented in the literature for waters from other parts of the United States.

Bromine incorporation into five DBP classes upon chlorination of water with extremely low SUVA values.

PubMed

Hong, Huachang; Yan, Xiaoqing; Song, Xuhui; Qin, Yanyan; Sun, Hongjie; Lin, Hongjun; Chen, Jianrong; Liang, Yan

2017-07-15

The main objective of this study was to assess the effects of disinfection conditions on bromine incorporation into disinfection by-products (DBPs) during chlorination of water with low specific UV absorbance (SUVA). Five classes of DBPs were included: trihalomethanes (THMs), dihaloacetic acids (di-HAAs), trihaloacetic acids (tri-HAAs), dihaloacetonitriles (DHANs) and trihalonitromethanes (THNMs). Results showed that the bromine utilization in DBPs formation was positive related with reaction time, pH and temperature. On the other hand, the bromine substitution factors (BSFs) of DBPs were generally increased with pH (except tri-HAAs) and bromide concentration, but decreased with the reaction time, temperature and chlorine dose. Moreover, the BSFs values varied with DBP classes with the ranking being as following: THNMs≫DHANs≫tri-HAAs>THM≈di-HAAs. These results were mostly similar with the references, yet the pH effect on BSFs as well as the rank of BSFs for different DBP classes may differ with the specific UV absorbance of organic matter. Copyright © 2017 Elsevier B.V. All rights reserved.

8-Chloroadenine: a novel product formed from hypochlorous acid-induced damage to calf thymus DNA.

PubMed

Matthew Whiteman Andrew Jenner Barry Halliwell

1999-01-01

Hypochlorous acid (HOCl) is formed by the action of the enzyme myeloperoxidase on hydrogen peroxide and chloride ions. It has been shown to be highly bactericidal and cytotoxic by a variety of mechanisms, one of which, may be the modification of DNA. Previously we have demonstrated by GC-MS analysis that exposure of calf thymus DNA to HOCl causes extensive pyrimidine modification, including 5-chlorocytosine formation. Using GC-MS analysis, we now demonstrate the formation of an additional chlorinated base product, 8-Cl adenine. The addition of 50 μM HOCl was sufficient to produce a significant increase in this product. The reaction of HOCl with adenine in calf thymus DNA was shown to be rapid with the reaction complete after 1 min. pH-dependence studies suggest HOCl rather than its conjugate base (OCl-) to be responsible for 8-Cl adenine formation. Other commercially available chlorinated base products, 6-Cl guanine or 2-Cl adenine were not detected. Therefore, 8-Cl adenine might prove a useful biomarker for studying the role of reactive chlorine species (RCS) during inflammatory processes.

Evaluation of lead recovery efficiency from waste CRT funnel glass by chlorinating volatilization process.

PubMed

Erzat, Aris; Zhang, Fu-Shen

2014-01-01

The current study was carried out to develop a novel process, namely chloride volatilization procedure for lead recovery from waste cathode ray tube (CRT) funnel glass. In the recovery system, the glass powder was first compressed into cylindrical pellet homogeneously with chlorinating agents, and then subjected to thermal treatment for solid-phase reaction. In this case, lead could be easily released from the silicon oxide network of the glass and it was recovered in the form of PbCl₂. It was found that CaCl2 was the most effective chlorinating agent, and the optimum operation temperature, holding time and system pressure were 1000 °C, 2 h, 600 ± 50 Pa, respectively. The evaporated PbCl₂could be easily recovered by a cooling device. The evaporation ratio of lead from waste CRT was 99.1% and the purity of the recovered PbCl₂product was 97.0%. The reaction routes and lead recovery mechanisms of the process were identified. This study provides an efficient and practical process for waste CRT funnel glass detoxification and recycling.

Health Effects from Swimming Training in Chlorinated Pools and the Corresponding Metabolic Stress Pathways

PubMed Central

Li, Jiang-Hua; Wang, Zhi-Hui; Zhu, Xiao-Juan; Deng, Zhao-Hui; Cai, Can-Xin; Qiu, Li-Qiang; Chen, Wei; Lin, Ya-Jun

2015-01-01

Chlorination is the most popular method for disinfecting swimming pool water; however, although pathogens are being killed, many toxic compounds, called disinfection by-products (DBPs), are formed. Numerous epidemiological publications have associated the chlorination of pools with dysfunctions of the respiratory system and with some other diseases. However, the findings concerning these associations are not always consistent and have not been confirmed by toxicological studies. Therefore, the health effects from swimming in chlorinated pools and the corresponding stress reactions in organisms are unclear. In this study, we show that although the growth and behaviors of experimental rats were not affected, their health, training effects and metabolic profiles were significantly affected by a 12-week swimming training program in chlorinated water identical to that of public pools. Interestingly, the eyes and skin are the organs that are more directly affected than the lungs by the irritants in chlorinated water; instead of chlorination, training intensity, training frequency and choking on water may be the primary factors for lung damage induced by swimming. Among the five major organs (the heart, liver, spleen, lungs and kidneys), the liver is the most likely target of DBPs. Through metabolomics analysis, the corresponding metabolic stress pathways and a defensive system focusing on taurine were presented, based on which the corresponding countermeasures can be developed for swimming athletes and for others who spend a lot of time in chlorinated swimming pools. PMID:25742134

FLUORINATION PROCESS

DOEpatents

McMillan, T.S.

1957-10-29

A process for the fluorination of uranium metal is described. It is known that uranium will react with liquid chlorine trifluoride but the reaction proceeds at a slow rate. However, a mixture of a halogen trifluoride together with hydrogen fluoride reacts with uranium at a significantly faster rate than does a halogen trifluoride alone. Bromine trifluoride is suitable for use in the process, but chlorine trifluoride is preferred. Particularly suitable is a mixture of ClF/sub 3/ and HF having a mole ratio (moles

Technical Compliance Guide for Clean Air Act Section 112(r) Risk Management Plan Program

DTIC Science & Technology

1996-06-01

hydrochloric acid , and nitric acid are expected to exist in reportable quantities at Army installations. Chlorine is expected to be the most widely...to form hypochlorous acid and hypochlorites... if excess chlorine is added to the process, the reaction will continue with ammonia or other... Hydrochloric Acid . Hydrochloric acid is commonly used in many industrial and laboratory type oI CAAA-90, Section 112(r), RMP Checklist applications. It is

The Antarctic ozone hole

NASA Technical Reports Server (NTRS)

Stolarski, Richard S.

1988-01-01

Processes that may be responsible for the thinning in the ozone layer above the South Pole are described. The chlorine catalytic cycle which destroys ozone is described, as are the major types of reactions that are believed to interfere with this cycle by forming chlorine reservoirs. The suspected contributions of polar stratospheric clouds to these processes are examined. Finally, the possibility that the ozone hole may be due more to a shift in atmospheric dynamics than to chemical destruction is addressed.

Formation of organic chloramines during chlor(am)ination and UV/chlor(am)ination of algae organic matter in drinking water.

PubMed

Zhang, Tian-Yang; Lin, Yi-Li; Xu, Bin; Cheng, Tuo; Xia, Sheng-Ji; Chu, Wen-Hai; Gao, Nai-Yun

2016-10-15

Surface water are frequently subjected to problems of algal blooms and release of algae organic matter (AOM) from the algae cells, which cause many water quality issues. This study investigated the formation of organic chloramines and nitrogenous disinfection by-products (N-DBPs) during chlor(am)ination and UV/chlor(am)ination of AOM in drinking water. AOM caused higher organic chloramine formation than humic acid and fulvic acid during chlor(am)ination. The formation of organic chloramines increased first and then decreased with the increase of free chlorine dosage, but kept increasing with the increase of NH2Cl dosage. During AOM chlorination, the formation of organic chloramines kept decreasing as the reaction time went by, and the maximum organic chloramine proportion (79.1%) in total chlorine occurred at 8 h. However, during AOM chloramination, the formation of organic chloramines increased first, decreased in the following and then increased again as the reaction time went by, and the maximum organic chloramine proportion (22.1%) in total chlorine occurred at 24 h. UV irradiation pretreatment did not effectively influence organic chloramine formation during AOM chlor(am)ination, but accelerated the degradation of organic chloramines during chloramination. Besides, UV pretreatment enhanced the formation of N-DBPs during the subsequent chlor(am)ination of AOM, especially dichloroacetonitrile. Copyright © 2016 Elsevier Ltd. All rights reserved.

Sol-gel analogous aminolysis-ammonolysis of chlorosilanes to chlorine-free Si/(C)/N-materials.

PubMed

Wiltzsch, Conny; Wagler, Jörg; Roewer, Gerhard; Kroke, Edwin

2009-07-28

Large amounts of chlorosilanes, especially SiCl4 and CH3SiCl3, are produced as side-products of the industrial fabrication of solar or electronic grade silicon and the Müller-Rochow process. It was a goal of the present study to transform these compounds into useful chlorine-free precursors for Si/(C)/N ceramics via a sol-gel analogous liquid processing route. Chlorine substitution of the chlorosilanes (mixtures) with diethylamine did not yield chlorine-free products, complete reactions are only possible with lithium diethylamide. However, aminolyses with n-propylamine were successful. Transamination with ammonia was not possible with diethylaminosilanes but was with n-propylaminosilanes in various solvents. This result was attributed to steric reasons and polar interactions of the N-H groups. Colourless solid or liquid polysilazanes were obtained, depending on the silane (mixture) and the solvent. Transamination reactions of CH3Si(NH-n-Pr)3 in chloroform reproducibly yielded a cage-like oligosilazane of the composition (CH3)9Si9(NH)12N. Single crystal X-ray structure analysis revealed a seven-cyclic cluster containing four six- and three ten-membered silazane rings. This unique silazane cage as well as the other aminosilanes and the silazanes were comprehensively characterised using multi-nuclear solid state and solution NMR, elemental analyses and thermal gravimetry (TGA).

Analytical and biological characterization of halogenated gemfibrozil produced through chlorination of wastewater.

PubMed

Bulloch, Daryl N; Lavado, Ramon; Forsgren, Kristy L; Beni, Szabolcs; Schlenk, Daniel; Larive, Cynthia K

2012-05-15

The cholesterol-lowering pharmaceutical gemfibrozil is a relevant environmental contaminant because of its frequency of detection in U.S. wastewaters at concentrations which have been shown to disrupt endocrine function in aquatic species. The treatment of gemfibrozil solutions with sodium hypochlorite yielded a 4'-chlorinated gemfibrozil analog (chlorogemfibrozil). In the presence of bromide ion, as is often encountered in municipal wastewater, hypobromous acid generated through a halogen exchange reaction produced an additional 4'-brominated gemfibrozil product (bromogemfibrozil). Standards of chloro- and bromogemfibrozil were synthesized, isolated and characterized using mass spectrometry and NMR spectroscopy. Mass spectrometry was used to follow the in situ halogenation reaction of gemfibrozil in deionized water and wastewater matrices, and to measure levels of gemfibrozil (254 ± 20 ng/L), chlorogemfibrozil (166 ± 121 ng/L), and bromogemfibrozil (50 ± 11 ng/L) in advanced primary wastewater treatment effluent treated by chlorination. Chlorogemfibrozil demonstrated a significant (p < 0.05) reduction in the levels of 11-ketotestosterone at 55.1 μg/L and bromogemfibrozil demonstrated a significant (p < 0.05) reduction in the levels of testosterone at 58.8 μg/L in vivo in Japanese medaka in a 21 day exposure. These results indicated that aqueous exposure to halogenated degradates of gemfibrozil enhanced the antiandrogenicity of the parent compound in a model fish species, demonstrating that chlorination may increase the toxicity of pharmaceutically active compounds in surface water.

Antifouling strategies and corrosion control in cooling circuits.

PubMed

Cristiani, P; Perboni, G

2014-06-01

Biofouling and corrosion phenomena dramatically reduce the functionality of industrial cooling circuits, especially in marine environments. This study underlines the effectiveness of a low level chlorination treatment of seawater to prevent biological fouling and biocorrosion. Reported examples emphasize the reaction of chlorine with bromide, ammonia and organic compounds in seawater and the effectiveness of a treatment performed in such a way to guarantee a residual concentration lower than 3μM at the outlet of the condensers. In a brief review of antifouling strategies, alternatives to chlorination and the monitoring approach able to optimize the treatments are also reported. An integrated, on-line system based on electrochemical probes (Biox system and a linear polarization resistance probe) demonstrated to be sufficient to monitor in real time: corrosion, biofilm growth and chemical treatments based on chlorine or alternative oxidant products (chlorine dioxide, etc.). A careful electrochemical monitoring and the optimized treatments help the plant operators of industrial cooling circuits prevent the decay of the equipment performance, allowing at the same time the control of the halogenated by-products formation. Copyright © 2014 Elsevier B.V. All rights reserved.

Long-term persistence of a single Legionella pneumophila strain possessing the mip gene in a municipal shower despite repeated cycles of chlorination.

PubMed

Cooper, I R; White, J; Mahenthiralingam, E; Hanlon, G W

2008-10-01

The ability of Legionella pneumophila to colonise domestic water systems is a primary cause of outbreaks of Legionnaire's disease in humans. World Health Organization guidelines recommend that drinking water is chlorinated to between 0.2 and 1mg/L [Chlorine in drinking-water. Guidelines for drinking-water quality, 2nd edn. Geneva: World Health Organization; 1996], but L. pneumophila is repeatedly isolated from chlorinated water systems, indicating that this treatment is not effective at preventing colonisation. Current UK guidelines recommend a one-off treatment of 20-50mg/L of free chlorine to remove the bacteria. In this study we report on the persistence of L. pneumophila serogroup 1 in a domestic shower system despite repeated cycles of chlorination at 50mg/L for 1h exposure time, over the course of two and a half years. Persisting isolates were subjected to in-vitro phenotypic analyses and polymerase chain reaction analysis for the toxin-encoding mip gene. Random amplified polymorphic DNA typing was also performed to determine whether the isolates recovered on different occasions were the same strain. We found that seven isolates of L. pneumophila recovered over a two-and-a-half year period are the same genetically defined strain, indicating that the bacteria can persist despite repeated cycles of chlorination after each successive isolation.

Chlorination of 2-phenoxypropanoic acid with NCP in aqueous acetic acid: using a novel ortho-para relationship and the para/meta ratio of substituent effects for mechanism elucidation.

PubMed

Segurado, Manuel A P; Reis, João Carlos R; de Oliveira, Jaime D Gomes; Kabilan, Senthamaraikannan; Shanthi, Manohar

2007-07-06

Rate constants were measured for the oxidative chlorodehydrogenation of (R,S)-2-phenoxypropanoic acid and nine ortho-, ten para- and five meta-substituted derivatives using (R,S)-1-chloro-3-methyl-2,6-diphenylpiperidin-4-one (NCP) as chlorinating agent. The kinetics was run in 50% (v/v) aqueous acetic acid acidified with perchloric acid under pseudo-first-order conditions with respect to NCP at temperature intervals of 5 K between 298 and 318 K, except at the highest temperature for the meta derivatives. The dependence of rate constants on temperature was analyzed in terms of the isokinetic relationship (IKR). For the 20 reactions studied at five different temperatures, the isokinetic temperature was estimated to be 382 K, which suggests the preferential involvement of water molecules in the rate-determining step. The dependence of rate constants on meta and para substitution was analyzed using the tetralinear extension of the Hammett equation. The parameter lambda for the para/meta ratio of polar substituent effects was estimated to be 0.926, and its electrostatic modeling suggests the formation of an activated complex bearing an electric charge near the oxygen atom belonging to the phenoxy group. A new approach is introduced for examining the effect of ortho substituents on reaction rates. Using IKR-determined values of activation enthalpies for a set of nine pairs of substrates with a given substituent, a linear correlation is found between activation enthalpies of ortho and para derivatives. The correlation is interpreted in terms of the selectivity of the reactant toward para- or ortho-monosubstituted substrates, the slope of which being related to the ortho effect. This slope is thought to be approximated by the ratio of polar substituent effects from ortho and para positions in benzene derivatives. Using the electrostatic theory of through-space interactions and a dipole length of 0.153 nm, this ratio was calculated at various positions of a charged reaction center along the benzene C1-C4 axis, being about 2.5 near the ring and decreasing steeply with increasing distance until reaching a minimum value of -0.565 at 1.3 nm beyond the aromatic ring. Activation enthalpies and entropies were estimated for substrates bearing the isoselective substituent in either ortho and para positions, being demonstrated that they are much different from the values for the parent substrate. The electrophilic attack on the phenolic oxygen atom by the protonated chlorinating agent is proposed as the rate-determining step, this step being followed by the fast rearrangement of the intermediate thus formed, leading to products containing chlorine in the aromatic ring.

Selective methane chlorination to methyl chloride by zeolite Y-based catalysts

NASA Astrophysics Data System (ADS)

Joo, Hyeonho; Kim, Daeho; Lim, Kwang Soo; Choi, Yong Nam; Na, Kyungsu

2018-03-01

The CH4 chlorination over Y zeolites was investigated to produce CH3Cl in a high yield. Three different catalytic systems based on Y zeolite were tested for enhancement of CH4 conversion and CH3Cl selectivity: (i) HY zeolites in H+-form having various Si/Al ratios, (ii) Pt/HY zeolites supporting Pt metal nanoparticles, (iii) Pt/NaY zeolites in Na+-form supporting Pt metal nanoparticles. The reaction was carried out using the gas mixture of CH4 and Cl2 with the respective flow rates of 15 and 10 mL min-1 at 300-350 °C using a fixed-bed reactor under a continuous gas flow condition (gas hourly space velocity = 3000 mL g-1 h-1). Above the reaction temperature of 300 °C, the CH4 chlorination is spontaneous even in the absence of catalyst, achieving 23.6% of CH4 conversion with 73.4% of CH3Cl selectivity. Under sufficient supplement of thermal energy, Cl2 molecules can be dissociated to two chlorine radicals, which triggered the C-H bond activation of CH4 molecule and thereby various chlorinated methane products (i.e., CH3Cl, CH2Cl2, CHCl3, CCl4) could be produced. When the catalysts were used under the same reaction condition, enhancement in the CH4 conversion was observed. The Pt-free HY zeolite series with varied Si/Al ratios gave around 27% of CH4 conversion, but there was a slight decrease in CH3Cl selectivity with about 64%. Despite the difference in acidity of HY zeolites having different Si/Al ratios, no prominent effect of the Si/Al ratios on the catalytic performance was observed. This suggests that the catalytic contribution of HY zeolites under the present reaction condition is not strong enough to overcome the spontaneous CH4 chlorination. When the Pt/HY zeolite catalysts were used, the CH4 conversion reached further up to 30% but the CH3Cl selectivity decreased to 60%. Such an enhancement of CH4 conversion could be attributed to the strong catalytic activity of HY and Pt/HY zeolite catalysts. However, both catalysts induced the radical cleavage of Cl2 more favorably, which ultimately decreased the CH3Cl selectivity. Such trade-off relationship between CH4 conversion and CH3Cl selectivity can be slightly broken by using Pt/NaY zeolite catalyst that is known to possess Frustrated Lewis Pairs (FLP) that are very useful for ionic cleavage of H2 to H+ and H-. Similarly, in the present work, Pt/NaY(FLP) catalysts enhanced the CH4 conversion while keeping the CH3Cl selectivity as compared to the Pt/HY zeolite catalysts.

Delta 37Cl and Characterisation of Petroleum-gas Reservoirs

NASA Astrophysics Data System (ADS)

Woulé Ebongué, V.; Jendrzejewski, N.; Walgenwitz, F.; Pineau, F.; Javoy, M.

2003-04-01

The geochemical characterisation of formation waters from oil/gas fields is used to detect fluid-flow barriers in reservoirs and to reconstruct the system dynamic. During the progression of the reservoir filling, the aquifer waters are pushed by hydrocarbons toward the reservoir bottom and their compositions evolve due to several parameters such as water-rock interactions, mixing with oil-associated waters, physical processes etc. The chemical and isotopic evolution of these waters is recorded in irreducible waters that have been progressively "fossilised" in the oil/gas column. Residual salts precipitated from these waters were recovered. Chloride being the most important dissolved anion in these waters and not involved in diagenetic reactions, its investigation should give insights into the different transport or mixing processes taking place in the sedimentary basin and point out to the formation waters origins. The first aim of our study was to test the Cl-RSA technique (Chlorine Residual Salts Analysis) based on the well-established Sr-RSA technique. The main studied area is a turbiditic sandstone reservoir located in the Lower Congo basin in Angola. Present-day aquifer waters, irreducible waters from sandstone and shale layers as well as drilling mud and salt dome samples were analysed. Formation waters (aquifer and irreducible trapped in shale) show an overall increase of chlorinity with depth. Their δ37Cl values range from -1.11 ppm to +2.30 ppm ± 0.05 ppm/ SMOC. Most Cl-RSA data as well as the δ37Cl obtained on a set of water samples (from different aquifers in the same area) are lower than -0.13 ppm with lower δ37Cl values at shallower depths. In a δ37Cl versus chlorinity diagram, they are distributed along a large range of chlorinity: 21 to 139 g/l, in two distinct groups. (1) Irreducible waters from one of the wells display a positive correlation between chlorinity and the δ37Cl values. (2) In contrary, the majority of δ37Cl measured on aquifers and on residual salts from a second well are anti-correlated with chlorinity. The preliminary determinations of δ37Cl values of sandstone irreducible waters seem to match the values obtained on irreducible waters trapped in the shale porosity. δ37Cl values and chlorinities are used to identify the contributions of physico-chemical processes such as ion filtration, diffusion or mixing. The chronology of the events and their relative importance are discussed.

Laboratory Studies of Heterogeneous Chemical Processes of Atmospheric Importance

NASA Technical Reports Server (NTRS)

Molina, Mario J.

2003-01-01

The objective of this study is to conduct measurements of chemical kinetics parameters for heterogeneous reactions of importance in the stratosphere and the troposphere. It involves the elucidation of the mechanism of the interaction of HC1 vapor with ice surfaces, which is the first step in the heterogeneous chlorine activation processes, as well as the investigation of the atmospheric oxidation mechanism of soot particles emitted by biomass and fossil fuels. The techniques being employed include turbulent flow- chemical ionization mass spectrometry and optical ellipsometry, among others. The next section summarizes our research activities during the first year of the project, and the section that follows consists of the statement of work for the second year.

Evaluation of disinfection by-product formation potential (DBPFP) during chlorination of two algae species--Blue-green Microcystis aeruginosa and diatom Cyclotella meneghiniana.

PubMed

Liao, Xiaobin; Liu, Jinjin; Yang, Mingli; Ma, Hongfang; Yuan, Baoling; Huang, Ching-Hua

2015-11-01

Microcystis aeruginosa (blue-green alga) commonly blooms in summer and Cyclotella meneghiniana (diatom) outbreaks in fall in the reservoirs that serve as drinking water sources in Southeast China. Herein, an evaluation of disinfection by-product formation potential (DBPFP) from them during chlorination should be conducted. Five DBPs including trichloromethane (TCM), trichloronitromethane (TCNM), dichloroacetonitrile (DCAN), 1,1-dichloropropanone (1,1-DCP) and 1,1,1-trichloropropanone (1,1,1-TCP) were monitored. The formation potential of TCM and TCNM was enhanced with the increase of reaction time and chlorine dosage, whereas that of DCAN, 1,1-DCP and 1,1,1-TCP increased first and then fell with continuing reaction time. M. aeruginosa showed higher DBPFP than C. meneghiniana, the yield of DBPs varied with components of algal cells. The DBPFP order from components of M. aeruginosa was cell suspension (CS) ≈ intracellular organic matter (IOM) > extracellular organic matter (EOM) > cell debris (CD), which indicated that IOM was the main DBP precursors for M. aeruginosa. The yields of DBPs from components of C. meneghiniana were in the order of CS>IOM≈ CD ≈ EOM, suggesting that three components made similar contributions to the total DBP formation. The amount of IOM with higher DBPFP leaked from both algae species increased with the chlorine dosage, indicating that chlorine dosage should be considered carefully in the treatment of eutrophic water for less destroying of the cell integrity. Though fluorescence substances contained in both algae species varied significantly, the soluble microbial products (SMPs) and aromatic protein-like substances were the main cellular components that contributed to DBP formation for both algae. Copyright © 2015 Elsevier B.V. All rights reserved.

Atmospheric Production of Perchlorate on Earth and Mars

NASA Astrophysics Data System (ADS)

Claire, M.; Catling, D. C.; Zahnle, K. J.

2009-12-01

Natural production and preservation of perchlorate on Earth occurs only in arid environments. Isotopic evidence suggests a strong role for atmospheric oxidation of chlorine species via pathways including ozone or its photochemical derivatives. As the Martian atmosphere is both oxidizing and drier than the driest places on Earth, we propose an atmospheric origin for the Martian perchlorates measured by NASA's Phoenix Lander. A variety of hypothetical formation pathways can be proposed including atmospheric photochemical reactions, electrostatic discharge, and gas-solid reactions. Here, we investigate gas phase formation pathways using a 1-D photochemical model (Catling et al. 2009, accepted by JGR). Because perchlorate-rich deposits in the Atacama desert are closest in abundance to perchlorate measured at NASA's Phoenix Lander site, we start with a study of the means to produce Atacama perchlorate. We found that perchlorate can be produced in sufficient quantities to explain the abundance of perchlorate in the Atacama from a proposed gas phase oxidation of chlorine volatiles to perchloric acid. These results are sensitive to estimated reaction rates for ClO3 species. The feasibility of gas phase production for the Atacama provides justification for further investigations of gas phase photochemistry as a possible source for Martian perchlorate. In addition to the Atacama results, we will present a preliminary study incorporating chlorine chemistry into an existing Martian photochemical model (Zahnle et al. JGR 2008).

Predicting gaseous reaction rates of short chain chlorinated paraffins with ·OH: overcoming the difficulty in experimental determination.

PubMed

Li, Chao; Xie, Hong-Bin; Chen, Jingwen; Yang, Xianhai; Zhang, Yifei; Qiao, Xianliang

2014-12-02

Short chain chlorinated paraffins (SCCPs) are under evaluation for inclusion in the Stockholm Convention on persistent organic pollutants. However, information on their reaction rate constants with gaseous ·OH (kOH) is unavailable, limiting the evaluation of their persistence in the atmosphere. Experimental determination of kOH is confined by the unavailability of authentic chemical standards for some SCCP congeners. In this study, we evaluated and selected density functional theory (DFT) methods to predict kOH of SCCPs, by comparing the experimental kOH values of six polychlorinated alkanes (PCAs) with those calculated by the different theoretical methods. We found that the M06-2X/6-311+G(3df,2pd)//B3LYP/6-311 +G(d,p) method is time-effective and can be used to predict kOH of PCAs. Moreover, based on the calculated kOH of nine SCCPs and available experimental kOH values of 22 PCAs with low carbon chain, a quantitative structure-activity relationship (QSAR) model was developed. The molecular structural characteristics determining the ·OH reaction rate were discussed. logkOH was found to negatively correlate with the percentage of chlorine substitutions (Cl%). The DFT calculation method and the QSAR model are important alternatives to the conventional experimental determination of kOH for SCCPs, and are prospective in predicting their persistence in the atmosphere.

Chlorine activation indoors and outdoors via surface-mediated reactions of nitrogen oxides with hydrogen chloride

PubMed Central

Raff, Jonathan D.; Njegic, Bosiljka; Chang, Wayne L.; Gordon, Mark S.; Dabdub, Donald; Gerber, R. Benny; Finlayson-Pitts, Barbara J.

2009-01-01

Gaseous HCl generated from a variety of sources is ubiquitous in both outdoor and indoor air. Oxides of nitrogen (NOy) are also globally distributed, because NO formed in combustion processes is oxidized to NO2, HNO3, N2O5 and a variety of other nitrogen oxides during transport. Deposition of HCl and NOy onto surfaces is commonly regarded as providing permanent removal mechanisms. However, we show here a new surface-mediated coupling of nitrogen oxide and halogen activation cycles in which uptake of gaseous NO2 or N2O5 on solid substrates generates adsorbed intermediates that react with HCl to generate gaseous nitrosyl chloride (ClNO) and nitryl chloride (ClNO2), respectively. These are potentially harmful gases that photolyze to form highly reactive chlorine atoms. The reactions are shown both experimentally and theoretically to be enhanced by water, a surprising result given the availability of competing hydrolysis reaction pathways. Airshed modeling incorporating HCl generated from sea salt shows that in coastal urban regions, this heterogeneous chemistry increases surface-level ozone, a criteria air pollutant, greenhouse gas and source of atmospheric oxidants. In addition, it may contribute to recently measured high levels of ClNO2 in the polluted coastal marine boundary layer. This work also suggests the potential for chlorine atom chemistry to occur indoors where significant concentrations of oxides of nitrogen and HCl coexist. PMID:19620710

Novel pathways for elimination of chlorine atoms from growing Si(100) surfaces in CVD reactors

NASA Astrophysics Data System (ADS)

Kunioshi, Nílson; Hagino, Sho; Fuwa, Akio; Yamaguchi, Katsunori

2018-05-01

Reactions leading to elimination of chlorine atoms from growing Si(100) surfaces were simulated using clusters of silicon atoms of different sizes and shapes, and at the UB3LYP/6-31 g(d,p) level of theory. The reactions of type SiCl2(s) + 2 H2(g), where (s) indicates an adsorbed species at the surface and (g) a gas-phase species, were found to proceed in two steps: SiCl2(s) + H2(g) → SiHCl(s) + HCl(g) and SiHCl(s) + H2(g) → SiH2(s) + HCl(g), each having activation energies around 55 kcal/mol, a value which is comparable to experimental values published in the literature. In addition, the results suggested that H-passivation of Si(100) surfaces support reactions leading to canonical epitaxial growth, providing a plausible explanation for the convenience of passivating the surfaces prior to silicon deposition. The reactions analyzed here can therefore be seen as important steps in the mechanism of epitaxial growth of Si(100) surfaces.

Contrast Between 1992 and 1997 High Latitude Spring Haloe Observations of Lower Stratospheric HCl

NASA Technical Reports Server (NTRS)

Douglass, A. R.; Kawa, S. R.

1998-01-01

HCl measurements from HALOE in the northern hemisphere during mid-May 1997 revealed vortex fragments in which the chlorine reservoir partitioning was strongly pushed toward HCl (approx. 90% HCl, approx. 10% ClONO2), similar to partitioning previously observed in the Antarctic vortex region. In contrast, observations of ClONO2 and HCl in the northern polar spring, 1992, and in other years, show these species established the balance typical for gas phase photochemical reactions in this region (approx. 60% HCl, approx. 40% ClONO2). Annually, chlorine reservoirs in the winter lower stratosphere polar vortex are converted to chlorine radicals via heterogeneous reactions on particle surfaces at very cold temperatures (less than about 200 K). As temperatures warm in spring, the heterogeneous processes become insignificant compared with gas phase reactions, and the chlorine reservoirs are reformed. Measurements through the northern winter/spring in 1992 show rapid formation of ClONO2, followed by steady loss of ClONO2 and increasing HCl. Although ClONO2 measurements are not available for 1997, the HCl increase in 1997 is observed to be much more rapid and the eventual HCl mixing ratio is about 50% greater than that of 1992. The observations are examined through comparison with the Goddard three-dimensional chemistry and transport model. This model utilizes winds and temperatures from the Goddard Earth Observing System Data Assimilation System and a complete integration scheme for stratospheric photochemistry. Analysis of the evolution of HCl and ClONO2 shows that the observed difference in the overall rate of HCl formation is explained by the sensitivity of the gas-phase chemistry to the ozone mixing ratio and the temperature. The results show that the model accurately simulates HCl and ClONO2 evolution during these two winters. Model validity is further supported by comparisons with O3 and reactive nitrogen species NO and NO2. This analysis provides a sensitive test of the lower stratospheric chlorine photochemistry, particularly because the analysis considers constituent evolution at a time when the HCl and ClONO2 are far from a photochemical stationary state.

The behavior of SiC and Si3N4 ceramics in mixed oxidation/chlorination environments

NASA Technical Reports Server (NTRS)

Marra, John E.; Kreidler, Eric R.; Jacobson, Nathan S.; Fox, Dennis S.

1989-01-01

The behavior of silicon-based ceramics in mixed oxidation/chlorination environments was studied. High pressure mass spectrometry was used to quantitatively identify the reaction products. The quantitative identification of the corrosion products was coupled with thermogravimetric analysis and thermodynamic equilibrium calculations run under similar conditions in order to deduce the mechanism of corrosion. Variations in the behavior of the different silicon-based materials are discussed. Direct evidence of the existence of silicon oxychloride compounds is presented.

METHOD FOR PRODUCING THORIUM TETRACHLORIDE

DOEpatents

Mason, E.A.; Cobb, C.M.

1960-03-15

A process for producing thorium tetrachloride from thorium concentrate comprises reacting thorium concentrates with a carbonaceous reducing agent in excess of 0.05 part by weight per part of thoriferous concentrate at a temperature in excess of 1300 deg C, cooling and comminuting the mass, chlorinating the resulting comminuting mass by suspending in a gaseous chlorinating agent in a fluidized reactor at a temperatare maintained between about l85 deg C and 770 deg C, and removing the resulting solid ThCl/sub 4/ from the reaction zone.

An assessment of potential degradation products in the gas-phase reactions of alternative fluorocarbons in the troposphere

NASA Technical Reports Server (NTRS)

Niki, Hiromi

1990-01-01

Tropospheric chemical transformations of alternative hydrofluorocarbons (HCF's) and hydrochlorofluorocarbons (HCFC's) are governed by hydroxyl radical initiated oxidation processes, which are likely to be analogous to those known for alkanes and chloroalkanes. A schematic diagram is used to illustrate plausible reaction mechanisms for their atmospheric degradation, where R, R', and R'' denote the F- and/or Cl-substituted alkyl groups derived from HCF's and HCFC's subsequent th the initial H atom abstraction by HO radicals. At present, virtually no kinetic data exist for the majority of these reactions, particularly for those involving RO. Potential degradation intermediates and final products include a large variety of fluorine- and/or chlorine-containing carbonyls, acids, peroxy acids, alcohols, hydrogen peroxides, nitrates and peroxy nitrates, as summarized in the attached table. Probably atmospheric lifetimes of these compounds were also estimated. For some carbonyl and nitrate products shown in this table, there seem to be no significant gas-phase removal mechanisms. Further chemical kinetics and photochemical data are needed to quantitatively assess the atmospheric fate of HCF's and HCFC's, and of the degradation products postulated in this report.

Kinetics of the oxidation of cylindrospermopsin and anatoxin-a with chlorine, monochloramine and permanganate.

PubMed

Rodríguez, Eva; Sordo, Ana; Metcalf, James S; Acero, Juan L

2007-05-01

Cyanobacteria produce toxins that may contaminate drinking water sources. Among others, the presence of the alkaloid toxins cylindrospermopsin (CYN) and anatoxin-a (ANTX) constitutes a considerable threat to human health due to the acute and chronic toxicity of these compounds. In the present study, not previously reported second-order rate constants for the reactions of CYN and ANTX with chlorine and monochloramine and of CYN with potassium permanganate were determined and the influence of pH and temperature was established for the most reactive cases. It was found that the reactivity of CYN with chlorine presents a maximum at pH 7 (rate constant of 1265 M(-1)s(-1)). However, the oxidation of CYN with chloramine and permanganate are rather slow processes, with rate constants <1 M(-1)s(-1). The first chlorination product of CYN was found to be 5-chloro-CYN (5-Cl-CYN), which reacts with chlorine 10-20 times slower than the parent compound. The reactivity of ANTX with chlorine and chloramines is also very low (k<1M(-1)s(-1)). The elimination of CYN and ANTX in surface water was also investigated. A chlorine dose of 1.5 mg l(-1) was enough to oxidize CYN almost completely. However, 3 mg l(-1) of chlorine was able to remove only 8% of ANTX, leading to a total formation of trihalomethanes (TTHM) at a concentration of 150 microg l(-1). Therefore, chlorination is a feasible option for CYN degradation during oxidation and disinfection processes but not for ANTX removal. The permanganate dose required for CYN oxidation is very high and not applicable in waterworks.

Revisiting Antarctic Ozone Depletion

NASA Astrophysics Data System (ADS)

Grooß, Jens-Uwe; Tritscher, Ines; Müller, Rolf

2015-04-01

Antarctic ozone depletion is known for almost three decades and it has been well settled that it is caused by chlorine catalysed ozone depletion inside the polar vortex. However, there are still some details, which need to be clarified. In particular, there is a current debate on the relative importance of liquid aerosol and crystalline NAT and ice particles for chlorine activation. Particles have a threefold impact on polar chlorine chemistry, temporary removal of HNO3 from the gas-phase (uptake), permanent removal of HNO3 from the atmosphere (denitrification), and chlorine activation through heterogeneous reactions. We have performed simulations with the Chemical Lagrangian Model of the Stratosphere (CLaMS) employing a recently developed algorithm for saturation-dependent NAT nucleation for the Antarctic winters 2011 and 2012. The simulation results are compared with different satellite observations. With the help of these simulations, we investigate the role of the different processes responsible for chlorine activation and ozone depletion. Especially the sensitivity with respect to the particle type has been investigated. If temperatures are artificially forced to only allow cold binary liquid aerosol, the simulation still shows significant chlorine activation and ozone depletion. The results of the 3-D Chemical Transport Model CLaMS simulations differ from purely Lagrangian longtime trajectory box model simulations which indicates the importance of mixing processes.

Reaction of β-blockers and β-agonist pharmaceuticals with aqueous chlorine. Investigation of kinetics and by-products by liquid chromatography quadrupole time-of-flight mass spectrometry.

PubMed

Quintana, José Benito; Rodil, Rosario; Cela, Rafael

2012-06-01

The degradation of two β-blockers (atenolol and propranolol) and one β-receptor agonist (salbutamol) during water chlorination was investigated by liquid chromatography-mass spectrometry (LC-MS). An accurate-mass quadrupole time-of-flight system (QTOF) was used to follow the time course of the pharmaceuticals and also used in the identification of the by-products. The degradation kinetics of these drugs was investigated at different concentrations of chlorine, bromide and sample pH by means of a Box-Behnken experimental design. Depending on these factors, dissipation half-lives varied in the ranges 68-145 h for atenolol, 1.3-33 min for salbutamol and 42-8362 min for propranolol. Normally, an increase in chlorine dosage and pH resulted in faster degradation of these pharmaceuticals. Moreover, the presence of bromide in water samples also resulted in a faster transformation of atenolol at low chlorine doses. The use of an accurate-mass high-resolution LC-QTOF-MS system permitted the identification of a total of 14 by-products. The transformation pathway of β-blockers/agonists consisted mainly of halogenations, hydroxylations and dealkylations. Also, many of these by-products are stable, depending on the chlorination operational parameters employed.

A combined ToF-SIMS and XPS study for the elucidation of the role of water in the performances of a Post-Plasma Process using LaMnO3+δ as catalyst in the total oxidation of trichloroethylene

NASA Astrophysics Data System (ADS)

Nuns, N.; Beaurain, A.; Dinh, M. T. Nguyen; Vandenbroucke, A.; De Geyter, N.; Morent, R.; Leys, C.; Giraudon, J.-M.; Lamonier, J.-F.

2014-11-01

LaMnO3+δ which is an environment-friendly and inexpensive material has been previously used as catalyst in Post-Plasma Catalysis (PPC) in the total oxidation of trichloroethylene (TCE) which is a solvent widely used in dry cleaning and degreasing processes. It has been shown that the process efficiency increases in moist air (RH = 18%).The issue we want to address herein is the effect of water on the location of chlorine at the surface of the catalyst as chlorine is able to alter the catalyst structure, activity and stability. Therefore, a combined Time of Flight-Secondary Ion Mass Spectrometry (ToF-SIMS) and X-ray Photoelectron Spectroscopy (XPS) study has been carried out on the fresh LaMnO3+δ catalyst (LM) and used catalysts after performing PPC with TCE diluted in dry synthetic air (LM0) or with industrial air containing water (LM18; 18 stands for the Relative Humidity) and CO2 (about 560 ppmv) at a temperature of 150 °C. XPS and ToF-SIMS results both show the presence of chlorine on the tested catalysts whose amount increases by exposure of the catalyst to the reactive mixture in dry synthetic air. XPS results reveal that chlorine is present as both chloride ion and covalent chlorine on LM0 while organic chlorinated residues are absent on LM18 catalyst. ToF-SIMS study indicates that lanthanum excess as oxide(hydroxide) partially covering the perovskite mainly transforms into LaOCl and to a minor extent into LaCl3. Extent of Mn chlorination seems to be favored over LM0 having a higher MnClx±/MnOCl± ionic ratio compared to LM18. Furthermore ToF-SIMS clearly identifies C1 chlorinated organic ions, mainly CH2Cl+ and CHCl2-, on LM0 which may contribute to the XPS Cl organic component. From the combined ToF-SIMS and XPS results it is found that water delays the surface degradation extent of the perovskite into related (oxy)(hydroxy)chlorinated inorganic phases by less molecular chlorine and related chlorine species on the catalyst surface. A reaction scheme of Cl removal over LaMnO3+δ emphasing the role of water is given taking into account the detection of ToF-SIMS ions representative of the successive Mn intermediate states. As a consequence water allows tuning the degradation pathways of the main intermediate of the reaction, dichloroacetyl chloride (DCAC), which decomposes to give phosgene, HCCl3 and CCl4 by a successive Cl incorporation over (oxy)(hydroxy)chorinated perovskite or/and Mn species while COx species are likely formed over the perovskite.

Synthesis of SYEP Plasticizer

DTIC Science & Technology

1975-10-01

Decomposition of fluorodinitroethanol 15 — i<’*<<>mmtmmmmmmt^mm aoceie^s wW ** ^.^ -cUo. t^«t»-, « U.t a „«til reaction temperature U the...by formaldehyde make difficult to study this reaction quantitatively. Eplchlorohydrin homologues containing better leaving groups than chlorine ...dealt with study of reaction variables with emphasis of Im- proving the yield of l,3-blB(fluorodinltroethoxy)isopropanol, the key-inter- mediate, from

A benign synthesis of alane by the composition-controlled mechanochemical reaction of sodium hydride and aluminum chloride

DOE PAGES

Hlova, Ihor; Goldston, Jennifer F.; Gupta, Shalabh; ...

2017-05-30

Solid-state mechanochemical synthesis of alane (AlH 3) starting from sodium hydride (NaH) and aluminum chloride (AlCl 3) has been achieved at room temperature. The transformation pathway of this solid-state reaction was controlled by a stepwise addition of AlCl 3 to the initial reaction mixture that contained sodium hydride in excess of stoichiometric amount. As in the case of previously investigated LiH–AlCl 3 system, complete selectivity was achieved whereby formation of unwanted elemental aluminum was fully suppressed, and AlH 3 was obtained in quantitative yield. Reaction progress during each step was investigated by means of solid-state NMR and powder X-ray diffraction,more » which revealed that the overall reaction proceeds through a series of intermediate alanates that may be partially chlorinated. The NaH–AlCl 3 system presents some subtle differences compared to LiH–AlCl 3 system particularly with respect to optimal concentrations needed during one of the reaction stages. Based on the results, we postulate that high local concentrations of NaH may stabilize chlorine-containing derivatives and prevent decomposition into elemental aluminum with hydrogen evolution. As a result, complete conversion with quantitative yield of alane was confirmed by both SSNMR and hydrogen desorption analysis.« less

A benign synthesis of alane by the composition-controlled mechanochemical reaction of sodium hydride and aluminum chloride

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hlova, Ihor; Goldston, Jennifer F.; Gupta, Shalabh

Solid-state mechanochemical synthesis of alane (AlH 3) starting from sodium hydride (NaH) and aluminum chloride (AlCl 3) has been achieved at room temperature. The transformation pathway of this solid-state reaction was controlled by a stepwise addition of AlCl 3 to the initial reaction mixture that contained sodium hydride in excess of stoichiometric amount. As in the case of previously investigated LiH–AlCl 3 system, complete selectivity was achieved whereby formation of unwanted elemental aluminum was fully suppressed, and AlH 3 was obtained in quantitative yield. Reaction progress during each step was investigated by means of solid-state NMR and powder X-ray diffraction,more » which revealed that the overall reaction proceeds through a series of intermediate alanates that may be partially chlorinated. The NaH–AlCl 3 system presents some subtle differences compared to LiH–AlCl 3 system particularly with respect to optimal concentrations needed during one of the reaction stages. Based on the results, we postulate that high local concentrations of NaH may stabilize chlorine-containing derivatives and prevent decomposition into elemental aluminum with hydrogen evolution. As a result, complete conversion with quantitative yield of alane was confirmed by both SSNMR and hydrogen desorption analysis.« less

Determination of the thermal stability of perfluoropolyalkyl ethers by tensimetry

NASA Technical Reports Server (NTRS)

Helmick, Larry A.; Jones, William R., Jr.

1992-01-01

The thermal decomposition temperatures of several perfluoropolyalkyl ether fluids were determined with a computerized tensimeter. In general, the decomposition temperatures of the commercial fluids were all similar and significantly higher than those for noncommercial fluids. Correlation of the decomposition temperatures with the molecular structures of the primary components of the commercial fluids revealed that the stability of the fluids was not affected by carbon chain length, branching, or adjacent difluoroformal groups. Instead, stability was limited by the presence of small quantities of thermally unstable material and/or chlorine-containing material arising from the use of chlorine containing solvents during synthesis. Finally, correlation of decomposition temperatures with molecular weights for two fluids supports a chain cleavage reaction mechanism for one and an unzipping reaction mechanism for the other.

Microbial community response to chlorine conversion in a chloraminated drinking water distribution system.

PubMed

Wang, Hong; Proctor, Caitlin R; Edwards, Marc A; Pryor, Marsha; Santo Domingo, Jorge W; Ryu, Hodon; Camper, Anne K; Olson, Andrew; Pruden, Amy

2014-09-16

Temporary conversion to chlorine (i.e., "chlorine burn") is a common approach to controlling nitrification in chloraminated drinking water distribution systems, yet its effectiveness and mode(s) of action are not fully understood. This study characterized occurrence of nitrifying populations before, during and after a chlorine burn at 46 sites in a chloraminated distribution system with varying pipe materials and levels of observed nitrification. Quantitative polymerase chain reaction analysis of gene markers present in nitrifying populations indicated higher frequency of detection of ammonia oxidizing bacteria (AOB) (72% of samples) relative to ammonia oxidizing archaea (AOA) (28% of samples). Nitrospira nitrite oxidizing bacteria (NOB) were detected at 45% of samples, while presence of Nitrobacter NOB could not be confirmed at any of the samples. During the chlorine burn, the numbers of AOA, AOB, and Nitrospira greatly reduced (i.e., 0.8-2.4 log). However, rapid and continued regrowth of AOB and Nitrospira were observed along with nitrite production in the bulk water within four months after the chlorine burn, and nitrification outbreaks appeared to worsen 6-12 months later, even after adopting a twice annual burn program. Although high throughput sequencing of 16S rRNA genes revealed a distinct community shift and higher diversity index during the chlorine burn, it steadily returned towards a condition more similar to pre-burn than burn stage. Significant factors associated with nitrifier and microbial community composition included water age and sampling location type, but not pipe material. Overall, these results indicate that there is limited long-term effect of chlorine burns on nitrifying populations and the broader microbial community.

The dependence of chlorine decay and DBP formation kinetics on pipe flow properties in drinking water distribution.

PubMed

Zhao, Yingying; Yang, Y Jeffrey; Shao, Yu; Neal, Jill; Zhang, Tuqiao

2018-04-27

Simultaneous chlorine decay and disinfection byproduct (DBP) formation have been discussed extensively because of their regulatory and operational significance. This study further examines chemical reaction variability in the water quality changes under various hydrodynamic conditions in drinking water distribution. The variations of kinetic constant for overall chlorine decay (k E ) and trihalomethane (THM) formation were determined under stagnant to turbulent flows using three devices of different wall demand and two types of natural organic matters (NOM) in water. The results from the comparative experiments and modeling analyses show the relative importance of wall demand (k w ), DBP-forming chlorine decay (k D ), and other bulk demand (k b ' ) for pipe flows of Re = 0-52500. It is found that chlorine reactivity of virgin NOM is the overriding factor. Secondly, for tap water NOM of lower reactivity, pipe flow properties (Re or u) can significantly affect k E , the THM yield (T), formation potential (Y), and the time to reach the maximum THM concentration (t max ) through their influence on kinetic ratio k D (k b ' +k w ). These observations, corroborating with turbidity variations during experiments, cannot be explained alone by chlorine dispersion to and from the pipe wall. Mass exchanges through deposition and scale detachment, most likely being flow-dependent, may have contributed to the overall chlorine decay and DBP formation rates. Thus for the simultaneous occurrence of chlorine decay and DBP formation, model considerations of NOM reactivity, pipe types (wall demand), flow hydraulics, and their interactions are essential. Copyright © 2018 Elsevier Ltd. All rights reserved.

Tetrakis-amido high flux membranes

DOEpatents

McCray, S.B.

1989-10-24

Composite RO membranes of a microporous polymeric support and a polyamide reaction product of a tetrakis-aminomethyl compound and a polyacylhalide are disclosed, said membranes exhibiting high flux and good chlorine resistance.

Tetrakis-amido high flux membranes

DOEpatents

McCray, Scott B.

1989-01-01

Composite RO membranes of a microporous polymeric support and a polyamide reaction product of a tetrakis-aminomethyl compound and a polyacylhalide are disclosed, said membranes exhibiting high flux and good chlorine resistance.

Wastewater injection, aquifer biogeochemical reactions, and resultant groundwater N fluxes to coastal waters: Kā'anapali, Maui, Hawai'i.

PubMed

Fackrell, Joseph K; Glenn, Craig R; Popp, Brian N; Whittier, Robert B; Dulai, Henrietta

2016-09-15

We utilize N and C species concentration data along with δ(15)N values of NO3(-) and δ(13)C values of dissolved inorganic C to evaluate the stoichiometry of biogeochemical reactions (mineralization, nitrification, anammox, and denitrification) occurring within a subsurface wastewater plume that originates as treated wastewater injection and enters the coastal waters of Maui as submarine groundwater discharge. Additionally, we compare wastewater effluent time-series data, injection rates, and treatment history with submarine spring discharge time-series data. We find that heterotrophic denitrification is the primary mechanism of N loss within the groundwater plume and that chlorination for pathogen disinfection suppresses microbial activity in the aquifer responsible for N loss, resulting in increased coastal ocean N loading. Replacement of chlorination with UV disinfection may restore biogeochemical reactions responsible for N loss within the aquifer and return N-attenuating conditions in the effluent plume, reducing N loading to coastal waters. Copyright © 2016 Elsevier Ltd. All rights reserved.

Structural characterization of aquatic humic material. 2. Phenolic content and its relationship to chlorination mechanism in an isolated aquatic fulvi acid

USGS Publications Warehouse

Norwood, D.L.; Christman, R.F.; Hatcher, P.G.

1987-01-01

The complementary techniques of solid-state 13G nuclear magnetic resonance spectroscopy and chemical degradation were utilized to examine the lignin/phenolic substructure of an isolated aquatic fulvic acid capable of producing upon aqueous chlorination a number of organohalides typically found in municipal drinking water. Results indicate that while phenolic moieties are present in the fulvic acid, they account for only a minor fraction of the total carbon. A sequential chemical degradation experiment utilizing aqueous chlorine and CuO demonstrated that the lignin/phenolic substructure was attacked by the chlorine. It is concluded that while phenolic ring rupture mechanisms appear to be important in organohalide generation, other aqueous chlorination mechanisms involving aliphatic and other types of aromatic structures should also be considered. ?? 1987 American Chemical Society.

Modeling the interaction of ozone with chloroform and bromoform under conditions close to stratospheric

NASA Astrophysics Data System (ADS)

Strokova, N. E.; Yagodovskaya, T. V.; Savilov, S. V.; Lukhovitskaya, E. E.; Vasil'ev, E. S.; Morozov, I. I.; Lunin, V. V.

2013-02-01

The reactions of ozone with chloroform and bromoform are studied using a flow gas discharge vacuum unit under conditions close to stratospheric (temperature range, 77-250 K; pressure, 10-3-0.1 Torr in the presence of nitrate ice). It is shown that the reaction with bromoform begins at 160 K; the reaction with chloroform, at 190 K. The reaction products are chlorine and bromine oxides of different composition, identified by low-temperature FTIR spectroscopy. The presence of nitrate ice raises the temperature of reaction onset to 210 K.

The OH-initiated atmospheric chemical reactions of polyfluorinated dibenzofurans and polychlorinated dibenzofurans: A comparative theoretical study.

PubMed

Zeng, Xiaolan; Chen, Jing; Qu, Ruijuan; Pan, Xiaoxue; Wang, Zunyao

2017-02-01

The atmospheric chemical reactions of some polyfluorinated dibenzofurans (PFDFs) and polychlorinated dibenzofurans (PCDFs), initiated by OH radical, were investigated by performing theoretical calculations using density functional theory (DFT) and B3LYP/6-311++G(2df,p) method. The obtained results indicate that OH addition reactions of PFDFs and PCDFs occurring at C 1∼4 and C A sites are thermodynamic spontaneous changes and the branching ratio of the PF(C)DF-OH adducts is decided primarily by kinetic factor. The OH addition reactions of PFDFs taking place at fluorinated C 1∼4 positions are kinetically comparable with those occurring at nonfluorinated C 1∼4 positions, while OH addition reactions of PCDFs occurring at chlorinated C 1∼4 sites are negligible. The total rate constants of the addition reactions of PFDFs or PCDFs become smaller with consecutive fluorination or chlorination, and substituting at C 1 position has more adverse effects than substitution at other sites. The succedent O 2 addition reactions of PF(C)DF-OH adducts are thermodynamic nonspontaneous processes under the atmospheric conditions, and have high Gibbs free energies of activation (Δ r G ≠ ). The substituted dibenzofuranols are the primary oxidation products for PCDFs under the atmospheric conditions. However, other oxidative products may also be available for PFDFs besides substituted dibenzofuranols. Copyright © 2016 Elsevier Ltd. All rights reserved.

Effect of halogenated impurities on lifetime of organic light emitting diode

NASA Astrophysics Data System (ADS)

Yamawaki, Hayato; Suzuki, Kunihiko; Kubota, Tomohiro; Watabe, Takeyoshi; Ishigaki, Ayumi; Nakamura, Rina; Inoue, Hideko; Nakashima, Harue; Horikoshi, Nozomi; Nowatari, Hiromi; Kataishi, Riho; Hamada, Toshiki; Sasaki, Toshiki; Suzuki, Tsunenori; Seo, Satoshi

2016-09-01

We investigated a correlation between lifetime and the halogen element concentration in an organic light-emitting diode (OLED) and conducted experiments and simulations to discuss degradation mechanisms due to the halogen. OELD is generally formed of high-purity materials. Since the synthesis of high-purity materials takes time and cost, quantitative understanding of the kind, amount, and influence of impurities in OLED devices is expected. The results of combustion ion chromatography show that, if the chlorine concentration in the host material is more than several parts per million, the lifetime of the device is drastically reduced. The chlorine element, which is derived from the chlorinated by-product of the host material, is found to be transferred from the chloride to other materials (e.g., an emissive dopant) according to the results of LC-MS analysis. In addition, the electron transport layer including such impurities is also found to adversely affect the lifetime. The results of TOF-SIMS analysis suggest that the dissociated chlorine element diffuse to the light-emitting layer side when the device is driven. The results of simulations (Gaussian 09) and electrochemical analyses (cyclic voltammetry and electrolysis) reveal that the halogen element is easy to dissociate from halide by excitation or reduction. The halogen element can repeat reactions with the peripheral materials by excitation or reduction and cause damages, e.g., generate radicals or further reaction products due to the radicals. The results of simulation suggest that, such compounds have low energy level and become quenchers.

Control of mineral scale deposition in cooling systems using secondary-treated municipal wastewater.

PubMed

Li, Heng; Hsieh, Ming-Kai; Chien, Shih-Hsiang; Monnell, Jason D; Dzombak, David A; Vidic, Radisav D

2011-01-01

Secondary-treated municipal wastewater (MWW) is a promising alternative to freshwater as power plant cooling system makeup water, especially in arid regions. A prominent challenge for the successful use of MWW for cooling is potentially severe mineral deposition (scaling) on pipe surfaces. In this study, theoretical, laboratory, and field work was conducted to evaluate the mineral deposition potential of MWW and its deposition control strategies under conditions relevant to power plant cooling systems. Polymaleic acid (PMA) was found to effectively reduce scale formation when the makeup water was concentrated four times in a recirculating cooling system. It was the most effective deposition inhibitor of those studied when applied at 10 mg/L dosing level in a synthetic MWW. However, the deposition inhibition by PMA was compromised by free chlorine added for biogrowth control. Ammonia present in the wastewater suppressed the reaction of the free chlorine with PMA through the formation of chloramines. Monochloramine, an alternative to free chlorine, was found to be less reactive with PMA than free chlorine. In pilot tests, scaling control was more challenging due to the occurrence of biofouling even with effective control of suspended bacteria. Phosphorous-based corrosion inhibitors are not appropriate due to their significant loss through precipitation reactions with calcium. Chemical equilibrium modeling helped with interpretation of mineral precipitation behavior but must be used with caution for recirculating cooling systems, especially with use of MWW, where kinetic limitations and complex water chemistries often prevail. Copyright © 2010 Elsevier Ltd. All rights reserved.

Type of disinfectant in drinking water and patterns of mortality in Massachusetts.

PubMed Central

Zierler, S; Danley, R A; Feingold, L

1986-01-01

Chlorination has been the major strategy for disinfection of drinking water in the United States. Concern about the potential health effects of the reaction by-products of chlorine has prompted use of alternative strategies. One such method is chloramination, a treatment process that does not appear to have carcinogenic by-products, but may have less potent biocidal activity than chlorination. We examined the patterns of mortality of residents in Massachusetts who died between 1969 and 1983 and lived in communities using drinking water that was disinfected either by chlorine or chloramine. Comparison of type of disinfectant among 51,645 cases of deaths due to selected cancer sites and 214,988 controls who died from cardiovascular, cerebrovascular, or pulmonary disease, or from lymphatic cancer showed small variation in the patterns of mortality. Bladder cancer was moderately associated with residence at death in a chlorinated community (mortality odds ratio = 1.7, 95% confidence interval = 1.3-2.2) in a logistic regression analysis using controls who died from lymphatic cancer. A slight excess of deaths from pneumonia and influenza was observed in communities whose residents drank chloraminated water compared to residents from chlorinated communities, as well as to all Massachusetts residents (standardized mortality ratio = 118, 95% confidence interval = 116-120 for chloraminated communities, and standardized mortality ratio = 98, 95% confidence interval = 95-100 for chlorinated communities). These results are intended to be preliminary and crude descriptions of the relationship under study.(ABSTRACT TRUNCATED AT 250 WORDS) PMID:3816730

Potential sources of artifacts and backgrounds generated by the sample preparation of the SAM experiment aboard the Curiosity Rover on Mars

NASA Astrophysics Data System (ADS)

Buch, Arnaud; Belmahdi, Imene; Szopa, Cyril; Freissinet, Caroline; Glavin, Daniel P.; Eigenbrode, Jennifer; Summons, Roger; Miller, Kristen; Coll, Patrice; cabane, Michel; Navarro-Gonzalez, Rafael; Stern, Jennifer; Coscia, David; Teinturier, Samuel; Bonnet, Jean-Yves; Dequaire, Tristan; Mahaffy, Paul; MSL Science Team

2016-10-01

Sample Analysis at Mars (SAM) is one of the instruments of the MSL mission. Three analytical devices are onboard SAM: the Tunable Laser Spectrometer (TLS), the Gas Chromatography (GC) and the Mass Spectrometer (MS). To adapt the nature of a sample to the analytical devices used on SAM, a sample preparation and gas processing system is implemented with (a) a pyrolysis system, (b) wet chemistry: MTBSTFA and TMAH (c) the hydrocarbon trap (silica beads, Tenax® TA and Carbosieve G) which is employed to concentrate volatiles released from the sample prior to GC-MS analysis [1].Volatile compounds and abundant chlorinated hydrocarbons have been detected with SAM when analyzing samples collected in several sites explored by Curiosity rover. Some volatile compounds (chlorinated and non-chlorinated) come from the degradation of the MTBSTFA under high temperature or by the reaction of Martian oxychlorine compounds (present in the samples) with terrestrial carbon coming from the derivatization agent (MTBSTFA) used in SAM [2,3]. But other chlorinated compounds do not follow this pathway. For example, Chlorobenzene has been detected by SAM but it cannot be formed by the reaction of MTBSTFA and perchlorates. Then, two other reaction pathways for chlorobenzene were therefore proposed: (1) reactions between the volatile thermal degradation products of perchlorates (e.g. O2, Cl2 and HCl) and Tenax® and (2) the interaction of perchlorates (T>200°C) with organic material from Mars's soil such as benzenecarboxylates. However, even if major part of the chlorobenzene detected has been identified as Martian origin [4] it is important to list all the potential byproducts able to be released from the Tenax®.Thus, this study inventory all the possible compounds which are originated from Tenax®, MTBSTFA and their interaction with perchlorate.References: [1] Buch, A. et al. (2009) J chrom. A, 43, 143-151. [2] Glavin, D., A. et al. (2013), LPSC. [3] Eigenbrode, J. et al. (2013), LPSC. [4] Freissinet, C. et al., JGR (2015)

CCl 4 chemistry on the reduced selvedge of a α-Fe 2O 3(0 0 0 1) surface: a scanning tunneling microscopy study

NASA Astrophysics Data System (ADS)

Rim, Kwang Taeg; Fitts, Jeffrey P.; Müller, Thomas; Adib, Kaveh; Camillone, Nicholas; Osgood, Richard M.; Joyce, S. A.; Flynn, George W.

2003-09-01

Scanning tunneling microscopy (STM) and low energy electron diffraction (LEED) were used to study the degradation of CCl 4 on the reduced selvedge of a natural single crystal α-Fe 2O 3(0 0 0 1) surface in ultrahigh vacuum. Before exposure to CCl 4, STM images indicate that approximately 85% of the reduced surface exhibits a Fe 3O 4(1 1 1) 2 × 2 termination, while the remaining 15% is terminated by 1 × 1 and superstructure phases. Images obtained after room temperature dosing with CCl 4 and subsequent flashing to 600 K reveal that chlorine atoms are adsorbed only on surface regions with the Fe 3O 4(1 1 1) 2 × 2 termination, not on 1 × 1 and superstructure regions. Chlorine atoms from dissociative adsorption of CCl 4 are observed to occupy two distinct positions located atop lattice protrusions and in threefold oxygen vacancy sites. However, in companion chemical labeling experiments, chlorine atoms provided by room temperature, dissociative Cl 2 adsorption on this surface are found to occupy sites atop lattice protrusions exclusively. The clear dissimilarity in STM feature shape and brightness at the two distinct chlorine adsorption sites arising from CCl 4 dissociation as well as the results of the Cl 2 chemical labeling experiments are best explained via reactions on a Fe 3O 4(1 1 1) 2 × 2 selvedge terminated by a 1/4 monolayer of tetrahedrally coordinated iron atoms. On this surface, adsorption atop an iron atom occurs for both the CCl 4 and Cl 2 dissociative reactions. A second adsorption site, assigned as binding to second layer iron atoms left exposed following surface oxygen atom abstraction resulting in the formation of phosgene (COCl 2), only appears in the case of reaction with CCl 4. The reaction mechanism and active site requirements for CCl 4 degradation on iron oxide surfaces are discussed in light of this evidence and in the context of our previously reported results from Auger electron spectroscopy (AES), LEED, temperature-programmed desorption (TPD), and X-ray photoelectron spectroscopy studies.

Integrated hydraulic and organophosphate pesticide injection simulations for enhancing event detection in water distribution systems.

PubMed

Schwartz, Rafi; Lahav, Ori; Ostfeld, Avi

2014-10-15

As a complementary step towards solving the general event detection problem of water distribution systems, injection of the organophosphate pesticides, chlorpyrifos (CP) and parathion (PA), were simulated at various locations within example networks and hydraulic parameters were calculated over 24-h duration. The uniqueness of this study is that the chemical reactions and byproducts of the contaminants' oxidation were also simulated, as well as other indicative water quality parameters such as alkalinity, acidity, pH and the total concentration of free chlorine species. The information on the change in water quality parameters induced by the contaminant injection may facilitate on-line detection of an actual event involving this specific substance and pave the way to development of a generic methodology for detecting events involving introduction of pesticides into water distribution systems. Simulation of the contaminant injection was performed at several nodes within two different networks. For each injection, concentrations of the relevant contaminants' mother and daughter species, free chlorine species and water quality parameters, were simulated at nodes downstream of the injection location. The results indicate that injection of these substances can be detected at certain conditions by a very rapid drop in Cl2, functioning as the indicative parameter, as well as a drop in alkalinity concentration and a small decrease in pH, both functioning as supporting parameters, whose usage may reduce false positive alarms. Copyright © 2014 Elsevier Ltd. All rights reserved.

Lagrangian photochemical modeling studies of the 1987 Antarctic spring vortex. II - Seasonal trends in ozone

NASA Technical Reports Server (NTRS)

Austin, J.; Jones, R. L.; Mckenna, D. S.; Buckland, A. T.; Anderson, J. G.; Fahey, D. W.; Farmer, C. B.; Heidt, L. E.; Proffitt, M. H.; Vedder, J. F.

1989-01-01

A photochemical model consisting of 40 species and 107 reactions is integrated along 80-day air parcel trajectories calculated in the lower stratosphere for the springtime Antarctic. For the trajectory starting at 58 deg S, which may be regarded as outside the circumpolar vortex, only a small change in O3 occurs in the model. In contrast, for the air parcel starting in the vortex at 74 deg S, the O3 concentration is reduced by 93 percent during the 80 days from the beginning of August to late October. The model results for several species are compared with measurements from the Airborne Antarctic Ozone Experiment and, in general, good agreement is obtained. In the model, the dentrification of the air parcels in polar stratospheric clouds increases the amount of chlorine present in active form. Heterogeneous reactions maintain high active chlorine which destroys O3 via the formation of the ClO dimer. Results of calculations with reduced concentrations of inorganic chlorine show considerably reduced O3 destruction rates and compare favorably with the behavior of total O3 since the late 1970s. The remaining major uncertainties in the photochemical aspects of the Antarctic ozone hole are highlighted.

Sulfide chemiluminescence detection

DOEpatents

Spurlin, Stanford R.; Yeung, Edward S.

1985-01-01

A method of chemiluminescently determining a sulfide which is either hydrogen sulfide or methyl mercaptan by reacting the sulfide with chlorine dioxide at low pressure and under conditions which allow a longer reaction time in emission of a single photon for every two sulfide containing species, and thereafter, chemiluminescently detecting and determining the sulfide. The invention also relates not only to the detection method, but the novel chemical reaction and a specifically designed chemiluminescence detection cell for the reaction.

The Properties of Fluorine, Oxygen Bifluoride, and Chlorine Trifluoride

DTIC Science & Technology

1949-09-06

they should be of forg€;d steel. Welded joints are excellent provided the welds are slag -free. Cast iron or any ether material containing silica cannot...400°C brilliant light Manganese powder form; 500°C formation of fluoride with glowing Zinc Cadmium powder form; heating glowing and flashing...reaction upon heating Magnesium at first, no reaction; explosive reaction Aluminum after ignition with carbon Zinc TV „ 1X11 Lead Cupfier L

Atmospheric pressure ionization of chlorinated ethanes in ion mobility spectrometry and mass spectrometry

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ewing, Robert G.; Atkinson, David A.; Benson, Michael T.

2015-05-16

This study investigates the APCI mechanisms associated with chlorinated ethanes in an attempt to define conditions under which unique pseudo-molecular adducts, in addition to chloride ion, can be produced for analytical measurements using IMS and MS. The ionization chemistry of chlorinated compounds typically leads to the detection of only the halide ions. Using molecular modeling, which provides insights into the ion formation and relative binding energies, predictions for the formation of pseudo-molecular adducts are postulated. Predicted structures of the chloride ion with multiple hydrogens on the ethane backbone was supported by the observation of specific pseudo-molecular adducts in IMS andmore » MS spectra. With the proper instrumental conditions, such as short reaction times and low temp.« less

Arctic chlorine activation and ozone depletion: Comparison of chemistry transport models with satellite observations.

NASA Astrophysics Data System (ADS)

Grooß, J.-U.; Wegner, T.; Müller, R.; Chipperfield, M. P.; Feng, W.; Santee, M. L.

2009-04-01

The accurate simulation of Arctic stratospheric ozone depletion has been an issue for two decades. However, there are still notable quantitative discrepancies between the models and observations. We show results from the SLIMCAT and CLaMS 3D chemistry-transport models that differ in some aspects of simulated chlorine activation and descent in the polar vortex. Consequently, the estimates of accumulated ozone depletion in the polar vortex for these two models in cold Arctic winters still largely disagree. As shown recently by Santee et al. (JGR, 2008) using MLS and ACE data, the extent of chlorine activation for the cold Arctic winter of 2004/2005 within the basic SLIMCAT model is overestimated with the likely consequence of too much simulated ozone depletion. In contrast, the CLaMS simulation for the same winter shows too little chlorine activation compared to observations, and therefore likely too little loss. For SLIMCAT the version used by Santee et al. has been updated to replace the equilibrium treatment of NAT PSCs with a Lagrangian microphysical scheme. This leads to smaller regions of NAT particles and less denitrification, in better agreement with observations. The impact of this on the modeled extent of chlorine activation will be discussed. For CLaMS we have changed the parameterization of heterogeneous reactions on liquid aerosols from Carslaw et al. to that of Shi et al. (2001), with which chlorine activation on liquid aerosol becomes more efficient. In turn, the simulated chlorine activation agrees better with the observations. The impact of these model changes on chlorine activation and ozone loss will be assessed and remaining model-observation discrepancies will be discussed in terms of different model formulations. We will also show the impact of recent lab measurements of Cl2O2 absorption cross sections by von Hobe et al. (2009) on the simulated ozone depletion. References: von Hobe, M., F. Stroh, H. Beckers, T. Benter, and H. Willner, The UV/Vis absorption spectrum of matrix isolated dichlorine peroxide, ClOOCl, Phys. Chem. Chem. Phys. , doi:10.1039/B814373K, 2009. Santee M. L., I. A. MacKenzie, G. L. Manney, M. P. Chipperfield, P. F. Bernath, K. A. Walker, C. D. Boone, L. Froidevaux, N. J. Livesey, J. W. Waters, A study of stratospheric chlorine partitioning based on new satellite measurements and modeling, J. Geophys. Res., 113, D12307, doi:10.1029/2007JD009057, 2008. Shi, Q., J. Jayne, C. Kolb, D. Worsnop, and P. Davidovits, Kinetic model for reaction of ClONO2 with H2O and HCl and HOCl with HCl in sulfuric acid solutions, J. Geophys. Res., 106, 24259-24274, 2001.

Infrared identification of the {sigma}-complex of Cl-C{sub 6}H{sub 6} in the reaction of chlorine atom and benzene in solid para-hydrogen

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bahou, Mohammed; Witek, Henryk; Lee, Yuan-Pern

2013-02-21

The reaction of a chlorine atom with benzene (C{sub 6}H{sub 6}) is important in organic chemistry, especially in site-selective chlorination reactions, but its product has been a subject of debate for five decades. Previous experimental and theoretical studies provide no concrete conclusion on whether the product is a {pi}- or {sigma}-form of the Cl-C{sub 6}H{sub 6} complex. We took advantage of the diminished cage effect of para-hydrogen (p-H{sub 2}) to produce Cl in situ to react with C{sub 6}H{sub 6} (or C{sub 6}D{sub 6}) upon photolysis of a Cl{sub 2}/C{sub 6}H{sub 6} (or C{sub 6}D{sub 6})/p-H{sub 2} matrix at 3.2more » K. The infrared spectrum, showing intense lines at 1430.5, 833.6, 719.8, 617.0, and 577.4 cm{sup -1}, and several weaker ones for Cl-C{sub 6}H{sub 6}, and the deuterium shifts of observed new lines unambiguously indicate that the product is a 6-chlorocyclohexadienyl radical, i.e., the {sigma}-complex of Cl-C{sub 6}H{sub 6}. Observation of the {sigma}-complex rather than the {pi}-complex indicates that the {sigma}-complex is more stable in solid p-H{sub 2} at 3.2 K. The spectral information is crucial for further investigations of the Cl + C{sub 6}H{sub 6} reaction either in the gaseous or solution phase.« less

Microsomal oxidation of tribromoethylene and reactions of tribromoethylene oxide.

PubMed

Yoshioka, Tadao; Krauser, Joel A; Guengerich, F Peter

2002-11-01

Halogenated olefins are of interest because of their widespread use in industry and their potential toxicity to humans. Epoxides are among the enzymatic oxidation products and have been studied in regard to their toxicity. Most of the attention has been given to chlorinated epoxides, and we have previously studied the reactions of the mono-, di-, tri-, and tetrachloroethylene oxides. To further test some hypotheses concerning the reactivity of these compounds, we prepared tribromoethylene (TBE) oxide and compared it to trichloroethylene (TCE) oxide and other chlorinated epoxides. TBE oxide reacted with H(2)O about 3 times faster than did TCE oxide. Several hydrolysis products of TBE oxide were the same as formed from TCE oxide, i.e., glyoxylic acid, CO, and HCO(2)H. Br(2)CHCO(2)H was formed from TBE oxide; the yield was higher than for Cl(2)CHCO(2)H formed in the hydrolysis of TCE oxide. The yield of tribromoacetaldehyde was < 0.4% in aqueous buffer (pH 7.4). In rat liver microsomal incubations containing TBE and NADPH, Br(2)CHCO(2)H was a major product, and tribromoacetaldehyde was a minor product. These results are consistent with schemes previously developed for halogenated epoxides, with migration of bromine being more favorable than for chlorine. Reaction of TBE oxide with lysine yielded relatively more N-dihaloacetyllysine and less N-formyllysine than in the case of TCE oxide. This same pattern was observed in the products of the reaction of TBE oxide with the lysine residues in bovine serum albumin. We conclude that the proposed scheme of hydrolysis of halogenated epoxides follows the expected halide order and that this can be used to rationalize patterns of hydrolysis and reactivity of other halogenated epoxides.

Manufacture of Oxygen-Containing Chlorinated Cyclic Compound

DOEpatents

McBee, E.T.; Newcomer, J.S.

1950-08-15

This patent discloses a method for making chloranil, or tetrachloroquinone, which comprises heating tetrachlorohydroxy-benzoic acid with SbF{sub 5}, hydrolyzing the reaction product to produce tetrachlorohydroquinone and oxidizing the tetrachlorohydroquinone to chloranil.

Preparation of B-trichloroborazine

NASA Technical Reports Server (NTRS)

Riccitiello, Salvatore R.; Hsu, Ming-Ta S.; Chen, Timothy S.

1987-01-01

The present invention relates to a method of preparing B-trichloroborazine. Generally, the method includes the combination of gaseous boron trichloride in an anhydrous aprotic organic solvent followed by addition of excess gaseous ammonia at ambient temperature or below. The reaction mixture is heated to about 100 to 140 C followed by cooling, removal of the solid ammonium chloride at ambient temperature, distillation of the solvent under vacuum if necessary at a temperature of up to about 112 C, and recovery of the B-trichloroborazine. Solvents include toluene, benzene, xylene, chlorinated hydrocarbons, chlorinated aromatic compounds, or mixtures thereof. Toluene is a preferred solvent. The process provides a convenient synthesis of a material which often decomposes on standing. B-trichloroborazine is useful in a number of chemical reactions, and particularly in the formation of high temperature inorganic polymers and polymer precursors.

Relationship of dietary iodide and drinking water disinfectants to thyroid function in experimental animals.

PubMed Central

Revis, N W; McCauley, P; Holdsworth, G

1986-01-01

The importance of dietary iodide on the reported hypothyroid effect of drinking water disinfectants on thyroid function was investigated. Previous studies have also showed differences in the relative sensitivity of pigeons and rabbits to chlorinated water. Pigeons and rabbits were exposed for 3 months to diets containing high (950 ppb) or low (300 ppb) levels of iodide and to drinking water containing two levels of chlorine. Results showed that the high-iodide diet prevented the hypothyroid effect observed in pigeons given the low-iodide diet and chlorinated drinking water. Similar trends were observed in rabbits exposed to the same treatment; however, significant hypothyroid effects were not observed in this animal model. The factor associated with the observed effect of dietary iodide on the chlorine-induced change in thyroid function is unknown, as is the relative sensitivity of rabbits and pigeons to the effect of chlorine. Several factors may explain the importance of dietary iodide and the relative sensitivity of these species. For example, the iodine formed by the known reaction of chlorine with iodide could result in a decrease in the plasma level of iodide because of the relative absorption rates of iodide and iodine in the intestinal tract, and the various types and concentrations of chloroorganics (metabolites) formed in the diet following the exposure of various dietary constituents to chlorine could affect the thyroid function. The former factor was investigated in the present studies. Results do not confirm a consistent, significant reduction in the plasma level of iodide in rabbits and pigeons exposed to chlorinated water and the low-iodide diet. The latter factor is being investigated. PMID:3816728

Oxidation of sulfamethoxazole (SMX) by chlorine, ozone and permanganate--a comparative study.

PubMed

Gao, Shanshan; Zhao, Zhiwei; Xu, Yongpeng; Tian, Jiayu; Qi, Hong; Lin, Wei; Cui, Fuyi

2014-06-15

Sulfamethoxazole (SMX), a typical sulfonamide antibiotic, has been widely detected in secondary wastewater effluents and surface waters. In this work we investigated the oxidative degradation of SMX by commonly used oxidants of chlorine, ozone and permanganate. Chlorine and ozone were shown to be more effective for the removal of SMX (0.05-5.0mg/L), as compared with permanganate. Higher pH enhanced the oxidation of SMX by ozone and permanganate, but decreased the removal by chlorine. Moreover, the ozonation of SMX was significantly influenced by the presence of humic acid (HA), which exhibited negligible influence on the oxidation by chlorine and permanganate. Fairly lower mineralization of SMX occurred during the oxidation reactions, with the highest dissolved organic carbon (DOC) removal of 13% (for ozone). By using LC-MS/MS, 7, 5 and 5 oxidation products were identified for chlorine, ozone and permanganate and possible transformation pathways were proposed. It was shown that different oxidants shared some common pathways, such as the cleavage of SN bond, the hydroxylation of the benzene ring, etc. On the other hand, each of the oxidants also exhibited exclusive degradation mechanisms, leading to the formation of different transformation products (TPs). This work may provide useful information for the selection of oxidants in water treatment processes. Copyright © 2014 Elsevier B.V. All rights reserved.

Field determination of PCB in transformer oil. Volume 2. Clor-N-Oil PCB screening test. Final report

DOE Office of Scientific and Technical Information (OSTI.GOV)

Fisher, D.J.; Rouse, T.O.; Lynn, T.

1984-10-01

The requirements for handling and disposing of transformer minerals oils containing more than 50 ppM PCB are, by federal regulation, different from those for oils containing lower concentrations. A rapid and simple test to distinguish between samples containing more than or less than this concentration would simplify proper control of transformer oils. This report describes the development of a small disposable test kit that can be used on-site to screen the chlorine content of transformer oils. The kit consists of two soft plastic tubes in which thin walled glass ampules containing premeasured amounts of reagents are broken. The reaction sequencemore » in the kits converts the chlorine in PCB to chloride ion. The color of the liquid in the kit after the last step is blue to purple if the chloride content due to the initial chlorine concentration of the oil is less than 20 ppM. If the chlorine content of the oil is below 20 ppM, the PCB content must be below 50 ppM. The liquid is colorless if the chlorine content is greater than 20 ppM. In this latter case, it is necessary to determine by gas chromatography whether the PCB content is actually greater than 50 ppM or if there is some other source of chlorine in the oil.« less

As(III) oxidation by active chlorine and subsequent removal of As(V) by Al13 polymer coagulation using a novel dual function reagent.

PubMed

Hu, Chengzhi; Liu, Huijuan; Chen, Guixia; Jefferson, William A; Qu, Jiuhui

2012-06-19

An electrochemically prepared water treatment reagent containing a high concentration of Al(13) polymer and active chlorine (PACC) showed promising potential for the removal of As(III) due to the combined function of oxidation and coagulation. The results indicated that PACC was effective for As(III) removal through oxidation by the active chlorine and subsequent removal of As(V) by coagulation with the Al(13) polymer. The As(III) was oxidized to As(V) by active chlorine in PACC, with a stoichiometric rate of 0.99 mg Cl(2)/mg As(III). The Al(13) polymer was the most active Al species responsible for As(V) removal in PACC. To meet As drinking water standards the stoichiometric weight ratio of Cl(2)/Al within PACC was 0.09 for the treatment of As(III). Considering the process of As(III) oxidation and As(V) coagulation together, the optimal pH conditions for the removal of As by PACC was within the neutral range, which facilitated the reaction of As(III) with active chlorine and favored the formation of Al hydroxide flocs. The presence of humic acid reduced the As(III) removal efficiency of PACC due to its negative influence on subsequent As(V) coagulation, and disinfection byproduct yields were very low in the presence of insufficient or stoichiometric active chlorine.

Enzymatic Halogenation and Dehalogenation Reactions: Pervasive and Mechanistically Diverse.

PubMed

Agarwal, Vinayak; Miles, Zachary D; Winter, Jaclyn M; Eustáquio, Alessandra S; El Gamal, Abrahim A; Moore, Bradley S

2017-04-26

Naturally produced halogenated compounds are ubiquitous across all domains of life where they perform a multitude of biological functions and adopt a diversity of chemical structures. Accordingly, a diverse collection of enzyme catalysts to install and remove halogens from organic scaffolds has evolved in nature. Accounting for the different chemical properties of the four halogen atoms (fluorine, chlorine, bromine, and iodine) and the diversity and chemical reactivity of their organic substrates, enzymes performing biosynthetic and degradative halogenation chemistry utilize numerous mechanistic strategies involving oxidation, reduction, and substitution. Biosynthetic halogenation reactions range from simple aromatic substitutions to stereoselective C-H functionalizations on remote carbon centers and can initiate the formation of simple to complex ring structures. Dehalogenating enzymes, on the other hand, are best known for removing halogen atoms from man-made organohalogens, yet also function naturally, albeit rarely, in metabolic pathways. This review details the scope and mechanism of nature's halogenation and dehalogenation enzymatic strategies, highlights gaps in our understanding, and posits where new advances in the field might arise in the near future.

Surface Characterization of Mesoporous CoOx/SBA-15 Catalyst upon 1,2-Dichloropropane Oxidation.

PubMed

Finocchio, Elisabetta; Gonzalez-Prior, Jonatan; Gutierrez-Ortiz, Jose Ignacio; Lopez-Fonseca, Ruben; Busca, Guido; de Rivas, Beatriz

2018-05-29

The active combustion catalyst that is based on 30 wt % cobalt oxide on mesoporous SBA-15 has been tested in 1,2-dichloropropane oxidation and is characterized by means of FT-IR (Fourier transform infrared spectroscopy) and ammonia-TPD (temperature-programmed desorption). In this work, we report the spectroscopic evidence for the role of surface acidity in chloroalkane conversion. Both Lewis acidity and weakly acidic silanol groups from SBA support are involved in the adsorption and initial conversion steps. Moreover, total oxidation reaction results in the formation of new Bronsted acidic sites, which are likely associated with the generation of HCl at high temperature and its adsorption at the catalyst surface. Highly dispersed Co oxide on the mesoporous support and Co-chloride or oxychloride particles, together with the presence of several families of acidic sites originated from the conditioning effect of reaction products may explain the good activity of this catalyst in the oxidation of Chlorinated Volatile Organic Compounds.

UV/chlorine as an advanced oxidation process for the degradation of benzalkonium chloride: Synergistic effect, transformation products and toxicity evaluation.

PubMed

Huang, Nan; Wang, Ting; Wang, Wen-Long; Wu, Qian-Yuan; Li, Ang; Hu, Hong-Ying

2017-05-01

Benzalkonium chlorides (BACs), as typical cationic surfactants and biocides widely applied in household and industrial products, have been frequently detected as micropollutants in many aquatic environments. In this study, the combination of UV irradiation and chlorine (UV/chlorine), a newly interested advanced oxidation process, was used to degrade dodecylbenzyldimethylammonium chloride (DDBAC). UV/chlorine showed synergistic effects on DDBAC degradation comparing to UV irradiation or chlorination alone. Radical quenching experiments indicated that degradation of DDBAC by UV/chlorine involved both UV photolysis and radical species oxidation, which accounted for 48.4% and 51.6%, respectively. Chlorine dosage and pH are essential parameters affecting the treatment efficiency of UV/chlorine. The pseudo first order rate constant (k obs, DDBAC ) increased from 0.046 min -1 to 0.123 min -1 in response to chlorine dosage at 0-150 mg/L, and the degradation percentage of DDBAC within 12 min decreased from 81.4% to 56.6% at pH 3.6-9.5. Five main intermediates were identified and semi-quantified using HPLC-MS/MS and a possible degradation pathway was proposed. The degradation mechanisms of DDBAC by UV/chlorine included cleavage of the benzyl-nitrogen bond and hydrogen abstraction of the alkyl chain. Trichloromethane (TCM), chloral hydrate (CH), trichloropropanone (TCP), dichloropropanone (DCP) and dichloroacetonitrile (DCAN) were detected using GC-ECD. The formation of chlorinated products increased rapidly initially, then decreased (TCM, TCP, DCP and DCAN) or remained stable (CH) with extended treatment. The actual formation of TCM peaked at 30 min (50.3 μg/L), while other chlorinated products did not exceed 10 μg/L throughout the process. Based on the luminescent bacterial assay, DDBAC solution underwent almost complete detoxification subjected to UV/chlorine treatment for 120 min, which is more effective than UV irradiation or chlorination alone. Copyright © 2017 Elsevier Ltd. All rights reserved.

Degradation of lipid regulators by the UV/chlorine process: Radical mechanisms, chlorine oxide radical (ClO•)-mediated transformation pathways and toxicity changes.

PubMed

Kong, Xiujuan; Wu, Zihao; Ren, Ziran; Guo, Kaiheng; Hou, Shaodong; Hua, Zhechao; Li, Xuchun; Fang, Jingyun

2018-06-15

Degradation of three lipid regulators, i.e., gemfibrozil, bezafibrate and clofibric acid, by a UV/chlorine treatment was systematically investigated. The chlorine oxide radical (ClO • ) played an important role in the degradation of gemfibrozil and bezafibrate with second-order rate constants of 4.2 (±0.3) × 10 8  M -1  s -1 and 3.6 (±0.1) × 10 7  M -1  s -1 , respectively, whereas UV photolysis and the hydroxyl radical (HO • ) mainly contributed to the degradation of clofibric acid. The first-order rate constants (k') for the degradation of gemfibrozil and bezafibrate increased linearly with increasing chlorine dosage, primarily due to the linear increase in the ClO • concentration. The k' values for gemfibrozil, bezafibrate, and clofibric acid degradation decreased with increasing pH from 5.0 to 8.4; however, the contribution of the reactive chlorine species (RCS) increased. Degradation of gemfibrozil and bezafibrate was enhanced in the presence of Br - , whereas it was inhibited in the presence of natural organic matter (NOM). The presence of ammonia at a chlorine: ammonia molar ratio of 1:1 resulted in decreases in the k' values for gemfibrozil and bezafibrate of 69.7% and 7%, respectively, but led to an increase in that for clofibric acid of 61.8%. Degradation of gemfibrozil by ClO • was initiated by hydroxylation and chlorine substitution on the benzene ring. Then, subsequent hydroxylation, bond cleavage and chlorination reactions led to the formation of more stable products. Three chlorinated intermediates were identified during ClO • oxidation process. Formation of the chlorinated disinfection by-products chloral hydrate and 1,1,1-trichloropropanone was enhanced relative to that of other by-products. The acute toxicity of gemfibrozil to Vibrio fischeri increased significantly when subjected to direct UV photolysis, whereas it decreased when oxidized by ClO • . This study is the first to report the transformation pathway of a micropollutant by ClO • . Copyright © 2018 Elsevier Ltd. All rights reserved.

A COMPREHENSIVE ANALYSIS OF CHLORINE TRANSPORT AND FATE FOLLOWING A LARGE ENVIRONMENTAL RELEASE

DOE Office of Scientific and Technical Information (OSTI.GOV)

Buckley, R.; Hunter, C.; Werth, D.

2011-05-10

A train derailment occurred in Graniteville, South Carolina during the early morning of January 6, 2005, and resulted in the release of a large amount of cryogenic pressurized liquid chlorine to the environment in a short time period. A comprehensive evaluation of the transport and fate of the released chlorine was performed, accounting for dilution, diffusion, transport and deposition into the local environment. This involved the characterization of a three-phased chlorine release, a detailed determination of local atmospheric mechanisms acting on the released chlorine, the establishment of atmospheric-hydrological physical exchange mechanisms, and aquatic dilution and mixing. This presentation will providemore » an overview of the models used in determining the total air-to-water mass transfer estimated to have occurred as a result of the roughly 60 tons of chlorine released into the atmosphere from the train derailment. The assumptions used in the modeling effort will be addressed, along with a comparison with available observational data to validate the model results. Overall, model-estimated chlorine concentrations in the airborne plume compare well with human and animal exposure data collected in the days after the derailment.« less

Nocturnal chlorine radical reservoir species at noon during CalNex-LA 2010

NASA Astrophysics Data System (ADS)

Mielke, L. H.; Griffith, S. M.; Hansen, R. F.; Dusanter, S.; Stevens, P. S.; Flynn, J. H.; Grossberg, N.; Lefer, B. L.; Veres, P. R.; Roberts, J. M.; Gilman, J. B.; Kuster, W. C.; Young, C. J.; Washenfelder, R. A.; Cochran, A. K.; Osthoff, H. D.

2011-12-01

While the role of the hydroxyl radical (OH) in the oxidation of volatile organic compounds (VOCs) is relatively well understood and recognized, less attention has been paid to Cl as an oxidant even though Cl is more reactive towards VOCs than OH. In the troposphere, mixing ratios of chlorine atoms are quite low (103 - 105 atoms cm-3), making them difficult to quantify directly in the atmosphere. The presence of chlorine atoms has been inferred only indirectly using hydrocarbon ratios, but this approach works well only in very remote environments. In polluted coastal urban areas such as Los Angeles, modeling studies have indicated that Cl radical initiated chemistry can have a significant impact on ozone formation. Here, chlorine atoms are produced by reaction of OH with hydrochloric acid and by photolysis of photolabile chlorine containing species, such as the nocturnally formed nitryl chloride (ClNO2) and molecular chlorine (Cl2). In this presentation, measurements of ClNO2 and Cl2 mixing ratios using chemical ionization mass spectrometry (CIMS) at the Calnex-LA campaign ground site between May 15, and June 15, 2010 are presented with a focus on their daytime abundances and photolysis to produce Cl atoms. Photolysis of ClNO2 in the morning (7 am to 10 am) produced Cl atoms at a median rate of 6.1×105 atoms cm-3 s-1. Daytime ClNO2 was observed with a median mixing ratio of 14 parts-per-trillion by volume (pptv). Assuming a steady state between ClNO2 photolysis and its formation via the reaction of Cl atom with NO2, we calculate a median Cl atom concentration of up to 1×105 atoms cm-3, approximately 3% of that of OH, which was quantified by laser induced fluorescence. Implications of Cl on the oxidation of VOCs in the Los Angeles area will be discussed. For example, methane is oxidized by Cl at a relative rate of up to half that of OH under the conditions outlined above.

Absolute rate of the reaction of C l(2P) with methane from 200-500 K

NASA Technical Reports Server (NTRS)

Whytock, D. A.; Lee, J. H.; Michael, J. V.; Payne, W. A.; Stief, L. J.

1976-01-01

Rate constants for the reaction of atomic chlorine with methane have been measured from 200-500K using the flash photolysis-resonance fluorescence technique. When the results from fourteen equally spaced experimental determinations are plotted in Arrhenius form a definite curvature is noted. The results are compared to previous work and are theoretically discussed.

Reaction of tetracycline with biologically relevant chloramines

NASA Astrophysics Data System (ADS)

Benavides, J.; Barrias, P.; Piro, N.; Arenas, A.; Orrego, A.; Pino, E.; Villegas, L.; Dorta, E.; Aspée, A.; López-Alarcón, C.

2017-05-01

Helicobacter pylori (H. pylori) infection triggers inflammatory processes with the consequent production of hypochlorous acid (HOCl), monochloramine (NH2Cl), and protein-derived chloramines. As the therapy for eradicating H. pylori is partially based on the use of tetracycline, we studied the kinetic of its consumption elicited by HOCl, NH2Cl, N-chloro-n-butylamine (NHCl-But, used as a lysine-derived chloramine model), and lysozyme-derived chloramines. In the micromolar concentration range, tetracycline reacted rapidly with HOCl, generating in the first few seconds intermediates of short half-life. In contrast, a slow tetracycline consumption was observed in the presence of high NH2Cl and NHCl-But concentrations (millimolar range). Similar chlorinated products of tetracycline were identified by mass spectrometry, in the presence of HOCl and NH2Cl. These results evidenced that tautomers of tetracycline are pivotal intermediates in all reactions. In spite of the low reactivity of chloramines towards tetracycline, it is evident that, in the concentration range where they are produced in a H. pylori infection (millimolar range), the reactions lead to oxidation and/or chlorination of tetracycline. This kind of reactions, which were also observed triggered by lysozyme-derived chloramines, could limit the efficiency of the tetracycline-based therapy.

Sulfide chemiluminescence detection

DOEpatents

Spurlin, S.R.; Yeung, E.S.

1985-11-26

A method is described for chemiluminescently determining a sulfide which is either hydrogen sulfide or methyl mercaptan by reacting the sulfide with chlorine dioxide at low pressure and under conditions which allow a longer reaction time in emission of a single photon for every two sulfide containing species, and thereafter, chemiluminescently detecting and determining the sulfide. The invention also relates not only to the detection method, but the novel chemical reaction and a specifically designed chemiluminescence detection cell for the reaction. 4 figs.

Apparatus for use in sulfide chemiluminescence detection

DOEpatents

Spurlin, Stanford R.; Yeung, Edward S.

1987-01-01

A method of chemiluminescently determining a sulfide which is either hydrogen sulfide or methyl mercaptan by reacting the sulfide with chlorine dioxide at low pressure and under conditions which allow a longer reaction time in emission of a single photon for every two sulfide containing species, and thereafter, chemiluminescently detecting and determining the sulfide. The invention also relates not only to the detection method, but the novel chemical reaction and a specifically designed chemiluminescence detection cell for the reaction.

Sulfate aerosols and polar stratospheric cloud formation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tolbert, M.A.

Before the discovery of the Antarctic ozone hole, it was generally assumed that gas-phase chemical reactions controlled the abundance of stratospheric ozone. However, the massive springtime ozone losses over Antarctica first reported by Farman et al in 1985 could not be explained on the basis of gas-phase chemistry alone. In 1986, Solomon et al suggested that chemical reactions occurring on the surfaces of polar stratospheric clouds (PSCs) could be important for the observed ozone losses. Since that time, an explosion of laboratory, field, and theoretical research in heterogeneous atmospheric chemistry has occurred. Recent work has indicated that the most importantmore » heterogeneous reaction on PSCs is ClONO[sub 2] + HCl [yields] Cl[sub 2] + HNO[sub 3]. This reaction converts inert chlorine into photochemically active Cl[sub 2]. Photolysis of Cl[sub 2] then leads to chlorine radicals capable of destroying ozone through very efficient catalytic chain reactions. New observations during the second Airborne Arctic Stratospheric Expedition found stoichiometric loss of ClONO[sub 2] and HCl in air processed by PSCs in accordance with reaction 1. Attention is turning toward understanding what kinds of aerosols form in the stratospheric, their formation mechanism, surface area, and specific chemical reactivity. Some of the latest findings, which underline the importance of aerosols, were presented at a recent National Aeronautics and Space Administration workshop in Boulder, Colorado.« less

Degradation kinetics of organic chloramines and formation of disinfection by-products during chlorination of creatinine.

PubMed

Zhang, Tianyang; Xu, Bin; Wang, Anqi; Cui, Changzheng

2018-03-01

Organic chloramines can interfere with the measurement of effective combined chlorine in chlorinated water and are potential intermediate products of highly toxic disinfection by-products (DBPs). In order to know more about the degradation and transformation of organic chloramines, a typical organic chloramine precursor creatinine was selected for investigation and a corresponding individual organic chloramine chlorocreatinine was prepared in this study. The preparation condition of chlorocreatinine by chlorination was established as chlorine/creatinine = 1 M/M, reaction time = 2 h and pH = 7.0. Then the degradation kinetics of chlorocreatinine during further chlorination was studied, and a second-order rate constant of 1.16 (±0.14) M -1 s -1 was obtained at pH 7.0. Solution pH significantly influenced the degradation rate, and the elementary rate constants of chlorocreatinine with HOCl+H + , HOCl, OCl - and chlorocreatinine - with OCl - were calculated as 2.43 (±1.55) × 10 4  M -2  s -1 , 1.05 (±0.09) M -1 s -1 , 2.86 (±0.30) M -1 s -1 and 3.09 (±0.24) M -1 s -1 , respectively. Besides, it was found that chlorocreatinine could be further converted into several C-DBPs (chloroform and trichloroacetone) and N-DBPs (dichloroacetonitrile (DCAN) and trichloronitromethane (TCNM)) during chlorination. The total yield of DBPs increased obviously with increasing pH, especially for TCNM. In addition, the presence of humic acid in creatinine solution could increase the formation of DCAN obviously during chlorination. Based on the UPLC-Q-TOF-MS analysis, the conversion pathways of chlorocreatinine were proposed. Several kinds of intermediate products were also identified as organic chloramines and some of them could even exist stably during the further chlorination. Copyright © 2017 Elsevier Ltd. All rights reserved.

Photochemical modeling of the Antarctic stratosphere: Observational constraints from the airborne Antarctic ozone experiment and implications for ozone behavior

NASA Technical Reports Server (NTRS)

Rodriguez, Jose M.; Sze, Nien-Dak; Ko, Malcolm K. W.

1988-01-01

The rapid decrease in O3 column densities observed during Antarctic spring has been attributed to several chemical mechanisms involving nitrogen, bromine, or chlorine species, to dynamical mechanisms, or to a combination of the above. Chlorine-related theories, in particular, predict greatly elevated concentrations of ClO and OClO and suppressed abundances of NO2 below 22 km. The heterogeneous reactions and phase transitions proposed by these theories could also impact the concentrations of HCl, ClNO3 and HNO3 in this region. Observations of the above species have been carried out from the ground by the National Ozone Expedition (NOZE-I, 1986, and NOZE-II, 1987), and from aircrafts by the Airborne Antarctic Ozone Experiment (AAOE) during the austral spring of 1987. Observations of aerosol concentrations, size distribution and backscattering ratio from AAOE, and of aerosol extinction coefficients from the SAM-II satellite can also be used to deduce the altitude and temporal behavior of surfaces which catalyze heterogeneous mechanisms. All these observations provide important constraints on the photochemical processes suggested for the spring Antarctic stratosphere. Results are presented for the concentrations and time development of key trace gases in the Antarctic stratosphere, utilizing the AER photochemical model. This model includes complete gas-phase photochemistry, as well as heterogeneous reactions. Heterogeneous chemistry is parameterized in terms of surface concentrations of aerosols, collision frequencies between gas molecules and aerosol surfaces, concentrations of HCl/H2O in the frozen particles, and probability of reaction per collision (gamma). Values of gamma are taken from the latest laboratory measurements. The heterogeneous chemistry and phase transitions are assumed to occur between 12 and 22 km. The behavior of trace species at higher altitudes is calculated by the AER 2-D model without heterogeneous chemistry. Calculations are performed for solar illumination conditions typical of 60, 70, and 80 S, from July 15 to October 31.

[Detection of astrovirus RNA from sewage works, seawater and native oysters samples in Chiba City, Japan using reverse transcription-polymerase chain reaction].

PubMed

Yokoi, H; Kitahashi, T; Tanaka, T; Utagawa, E

2001-04-01

Through a year from April, 1999 to March, 2000, 20 samples, which consisted of raw sewage (2), chlorine-treated sewage (2), seawater (10) and naturally grown oysters (6), were collected monthly both from the sewage works at Mihama-ku, Chiba City and at a yacht harbor in Chiba City Bay, Japan. Astrovirus RNA were detected by reverse transcription-polymerase chain reaction (RT-PCR) and was typed by direct sequencing. Astrovirus positive products were detected from 9 samples (raw sewage; 1/2, chlorine-treated sewage; 2/2, seawater; 5/10 and oysters; 1/6) collected in April, 1999. In May, positive products were detected from 4 samples (raw sewage; 2/2 and seawater; 2/10). In June, only 1 positive product was detected from raw sewage. The number of positive samples showed a tendency to decrease and no positive products were detected from samples collected in July, 1999 to January, 2000. After that period, positive products were again detected from 3 samples (raw sewage; 1/2, chlorine-treated sewage; 2/2) collected in February, 2000. In March, the number of positive samples showed the peak and positive products were detected from 12 samples (raw sewage; 2/2, chlorine-treated sewage; 2/2, seawater; 7/10 and oysters: 1/6). Astrovirus positive products detected in April, May, June, July, 1999 and February, 2000 were classified into type 1 or 2 by sequencing, whereas in March, 2000 were type 1, 2, 3, 6 and 7.

Collisional quenching dynamics and reactivity of highly vibrationally excited molecules

NASA Astrophysics Data System (ADS)

Liu, Qingnan

Highly excited molecules are of great importance in many areas of chemistry including photochemistry. The dynamics of highly excited molecules are affected by the intermolecular and intramolecular energy flow between many different kinds of motions. This thesis reports investigations of the collisional quenching and reactivity of highly excited molecules aimed at understanding the dynamics of highly excited molecules. There are several important questions that are addressed. How do molecules behave in collisions with a bath gas? How do the energy distributions evolve in time? How is the energy partitioned for both the donor and bath molecules after collisions? How do molecule structure, molecule state density and intermolecular potential play the role during collisional energy transfer? To answer these questions, collisional quenching dynamics and reactivity of highly vibrationally excited azabenzene molecules have been studied using high resolution transient IR absorption spectroscopy. The first study shows that the alkylated pyridine molecules that have been excited with Evib˜38,800 cm-1 impart less rotational and translational energy to CO2 than pyridine does. Comparison between the alkylated donors shows that the strong collisions are reduced for donors with longer alkyl chains by lowering the average energy per mode but longer alkyl chain have increased flexibility and higher state densities that enhance energy loss via strong collisions. In the second study, the role of hydrogen bonding interactions is explored in collision of vibrationally excited pyridines with H2O. Substantial difference in the rotational energy of H 2O is correlated with the structure of the global energy minimum. A torque-inducing mechanism is proposed that involves directed movement of H 2O between sigma and pi-hydrogen bonding interactions with the pyridine donors. In the third study the dynamics of strong and weak collisions for highly vibrationally excited methylated pyridine molecules with HOD are reported. Lower limits to the overall collision rate are directly determined from experimental measurements and compared to Lennard-Jones models which underestimate the collision rate for highly vibrationally excited azabenzenes with HOD. The fourth study explores reactive collisions of highly vibrationally excited pyridine molecules. D-atom abstraction reactions of highly vibrationally excited pyridine-d5 molecules and chlorine radical show a rate enhancement of ˜90 relative to the reaction of room temperature pyridine-d5 with chlorine radical. A single quantum of C-D stretching vibration is observed to be used for the vibrational driven reaction. Reactions of 2-picoline-d3 with chlorine radical do not show a similar enhancement. For this case, the fast rotation of --CD3 group in highly vibrationally excited 2-picoline-d3 inhibits the D-atom abstraction.

Effects of thermal treatment on halogenated disinfection by-products in drinking water.

PubMed

Wu, W W; Benjamin, M M; Korshin, G V

2001-10-01

The influence of heating or boiling on the formation and behavior of disinfection by-products (DBPs) was investigated in DBP-spiked reagent water, municipal tap water, and synthetic water containing chlorinated aquatic humic substances. Thermal cleavage of larger halogenated species leads to both formation of smaller chlorinated molecules (including THMs and HAAs) and dechlorination of organics. In parallel with their formation from larger molecules, THMs can be volatilized, and this latter process dominates the change in their concentration when water is boiled. HAAs are not volatile, but they can be destroyed by chemical reactions at elevated temperatures, with the net effect being loss of trihalogenated HAAs and either formation or loss of less chlorinated HAAs. Although other identifiable DBPs can be generated at slightly elevated temperatures, in most cases their concentrations decline dramatically when the solution is heated.

The reaction of chlorobenzene with plasma of H2O, CO2 and CH4 obtained by an alternating-current plasma torch with a vortex stabilization

NASA Astrophysics Data System (ADS)

Surov, A. V.; Subbotin, D. I.; Obraztsov, N. V.; Popov, S. D.; Popov, V. E.; Litvyakova, A. I.; Pavlov, A. V.; Serba, E. O.; Spodobin, V. A.; Nakonechny, Gh V.

2018-01-01

This paper presents the three-phase ac plasma torch with a vortex stabilization of the arc, and two inputs of plasma environments: the electrode zone and the arc zone. Shielding gas (carbon dioxide) is supplied in the electrode zone and steam, methane and vapor of chlorobenzene are fed in the arc zone. By means of it the life time of electrodes is increased significantly. Chlorobenzene is selected, as it is the simplest aromatic chlorine-containing substance. The chemical process flows in two pathways: the formation of synthesis gas and the formation of soot. The gaseous chlorine-containing compound was only hydrogen chloride, yield of soot was 0.98% by weight of the raw materials, and the chlorine content was 2.08 wt% by the soot.

Transformation of aminopyrine in the presence of free available chlorine: Kinetics, products, and reaction pathways.

PubMed

Cai, Mei-Quan; Feng, Li; Zhang, Li-Qiu

2017-03-01

Aminopyrine (AMP) has been frequently detected in the aquatic environment. In this study, the transformation mechanism of AMP by free available chlorine (FAC) oxidation was investigated. The results showed that FAC reacted with AMP rapidly, and a 74% elimination was achieved for 1.30 μM AMP after 2 min at 14.08 μM FAC dose. AMP chlorination was strongly pH-dependent, and its reaction included second- and third-order kinetic processes. Three active FAC species, including chlorine monoxide (Cl 2 O), molecular chlorine (Cl 2 ), and hypochlorous acid (HOCl), were observed to contribute to AMP degradation. The intrinsic rate constants of each FAC species with neutral (AMP 0 ) and cation (AMP + ) species were obtained by kinetic fitting. Cl 2 O exhibited the highest reactivity with AMP 0 (k AMP0, Cl2O  = (4.33 ± 1.4) × 10 9  M -1 s -1 ). In addition, Cl 2 showed high reactivity (10 6 -10 7  M -1 s -1 ) in the presence of chloride, compared with HOCl (k AMP+, HOCl  = (5.73 ± 0.23) × 10 2  M -1 s -1 , k AMP0, HOCl  = (9.68 ± 0.96) × 10 2  M -1 s -1 ). At pH 6.15 and 14.08 μM FAC dose without chloride addition, the contribution of Cl 2 O reached to the maximum (33.3%), but in the whole pH range, HOCl was the main contributor (>66.6%) for AMP degradation. The significance of Cl 2 was noticeable in water containing chloride. Moreover, 11 transformation products were identified, and the main transformation pathways included pyrazole ring breakage, hydroxylation, dehydrogenation, and halogenation. Copyright © 2016 Elsevier Ltd. All rights reserved.

Phosphazene Polymers Containing Carborane

NASA Technical Reports Server (NTRS)

Fewell, L. L.; Parker, J. A.; Basi, R. J.

1986-01-01

Addition of carborane increases thermal stability. Carborane-substituted polyphosphazenes prepared by thermal polymerization of phenylcarbonyl-pentachlorocyclotriphosphazene followed by reaction with sodium trifluoroethoxide to replace remaining chlorine atoms with trifluoroethoxy groups. Improved polymers offer high char yields and resistance to hydrolysis.

Apparatus for use in sulfide chemiluminescence detection

DOEpatents

Spurlin, S.R.; Yeung, E.S.

1987-01-06

A method is described for chemiluminescently determining a sulfide which is either hydrogen sulfide or methyl mercaptan by reacting the sulfide with chlorine dioxide at low pressure and under conditions which allow a longer reaction time in emission of a single photon for every two sulfide containing species, and thereafter, chemiluminescently detecting and determining the sulfide. The invention also relates not only to the detection method, but the novel chemical reaction and a specifically designed chemiluminescence detection cell for the reaction. 4 figs.

Method of generating chemiluminescent light

DOEpatents

Spurlin, S.R.; Yeung, E.S.

1986-03-11

A method of chemiluminescently determining a sulfide which is either hydrogen sulfide or methyl mercaptan by reacting the sulfide with chlorine dioxide at low pressure and under conditions which allow a longer reaction time in emission of a single photon for every two sulfide containing species, and thereafter, chemiluminescently detecting and determining the sulfide. The invention also relates not only to the detection method, but the novel chemical reaction that generates chemiluminescent light and a specifically designed chemiluminescence detection cell for the reaction. 4 figs.

Method of generating chemiluminescent light

DOEpatents

Spurlin, Stanford R.; Yeung, Edward S.

1986-01-01

A method of chemiluminescently determining a sulfide which is either hydrogen sulfide or methyl mercaptan by reacting the sulfide with chlorine dioxide at low pressure and under conditions which allow a longer reaction time in emission of a single photon for every two sulfide containing species, and thereafter, chemiluminescently detecting and determining the sulfide. The invention also relates not only to the detection method, but the novel chemical reaction that generates chemiluminescent light and a specifically designed chemiluminescence detection cell for the reaction.

Zircon Carburation Studies as Intermediate Stage in the Zirconium Fabrication; ESTUDIOS ENCAMINADOS A LA CARBURACTION DEL CIRON COMO ETAPA INTERMEDIA EN LA OBTENCION DE CIRCONIO

DOE Office of Scientific and Technical Information (OSTI.GOV)

Huertas, V.A.; Gonzalez, L.S.; Lopez, M.

1963-01-01

Zirconium carbide and carbonitride mixtures were obtained by Kroll's method. Reaction products were identified by micrography and x-ray diffraction analysis. The optimum graphite content in the initial charge for the carburization reaction was studied. Zirconium, silicon, and carbon content in the final product was controlled as a function of current in the furnace and reaction time. Further chlorination of the final product was performed successfully. (auth)

4-Hydroxylated metabolites of the antiestrogens tamoxifen and toremifene are metabolized to unusually stable quinone methides.

PubMed

Fan, P W; Zhang, F; Bolton, J L

2000-01-01

Tamoxifen is widely prescribed for the treatment of hormone-dependent breast cancer, and it has recently been approved by the Food and Drug Administration for the chemoprevention of this disease. However, long-term usage of tamoxifen has been linked to increased risk of developing endometrial cancer in women. One of the suggested pathways leading to the potential toxicity of tamoxifen involves its oxidative metabolism to 4-hydroxytamoxifen, which may be further oxidized to an electrophilic quinone methide. The resulting quinone methide has the potential to alkylate DNA and may initiate the carcinogenic process. To further probe the chemical reactivity and toxicity of such an electrophilic species, we have prepared the 4-hydroxytamoxifen quinone methide chemically and enzymatically, examined its reactivity under physiological conditions, and quantified its reactivity with GSH. Interestingly, this quinone methide is unusually stable; its half-life under physiological conditions is approximately 3 h, and its half-life in the presence of GSH is approximately 4 min. The reaction between 4-hydroxytamoxifen quinone methide and GSH appears to be a reversible process because the quinone methide GSH conjugates slowly decompose over time, regenerating the quinone methide as indicated by LC/MS/MS data. The tamoxifen GSH conjugates were detected in microsomal incubations with 4-hydroxytamoxifen; however, none were observed in breast cancer cell lines (MCF-7) perhaps because very little quinone methides is formed. Toremifene, which is a chlorinated analogue of tamoxifen, undergoes similar oxidative metabolism to give 4-hydroxytoremifene, which is further oxidized to the corresponding quinone methide. The toremifene quinone methide has a half-life of approximately 1 h under physiological conditions, and its rate of reaction in the presence of excess GSH is approximately 6 min. More detailed analyses have indicated that the 4-hydroxytoremifene quinone methide reacts with two molecules of GSH and loses chlorine to give the corresponding di-GSH conjugates. The reaction mechanism likely involves an episulfonium ion intermediate which may contribute to the potential cytotoxic effects of toremifene. Similar to what was observed with 4-hydroxytamoxifen, 4-hydroxytoremifene was metabolized to di-GSH conjugates in microsomal incubations at about 3 times the rate of 4-hydroxytamoxifen, although no conjugates were detected with MCF-7 cells. Finally, these data suggest that quinone methide formation may not make a significant contribution to the cytotoxic and genotoxic effects of tamoxifen and toremifene.

Determination of the thermal stability of perfluoroalkylethers

NASA Technical Reports Server (NTRS)

Helmick, Larry S.; Jones, William R., Jr.

1990-01-01

The thermal decomposition temperatures of several commercial and custom synthesized perfluoroalkylether fluids were determined with a computerized tensimeter. In general, the decomposition temperatures of the commercial fluids were all similar and significantly higher than those for custom synthesized fluids. Correlation of the decomposition temperatures with the molecular structures of the primary components of the commercial fluids revealed that the stability of the fluids is not affected by intrinsic factors such as carbon chain length, branching, or cumulated difluoroformal groups. Instead, correlation with extrinsic factors revealed that the stability may be limited by the presence of small quantities of thermally unstable material and/or chlorine-containing material arising from the use of chlorine-containing solvents during synthesis. Finally, correlation of decomposition temperatures with molecular weights for Demnum and Krytox fluids supports a chain cleavage reaction mechanism for Demnum fluids and an unzipping reaction mechanism for Krytox fluids.

Heterogeneous interactions of chlorine nitrate, hydrogen chloride, and nitric acid with sulfuric acid surfaces at stratospheric temperatures

NASA Technical Reports Server (NTRS)

Tolbert, Margaret A.; Rossi, Michel J.; Golden, David M.

1988-01-01

The heterogeneous interactions of ClONO2, HCl, and HNO3 with sulfuric acid surfaces were studied using a Knudsen cell flow reactor. The surfaces studied, chosen to simulate global stratospheric particulate, were composed of 65-75 percent H2SO4 solutions at temperatures in the range -63 to -43 C. Heterogeneous loss, but not reaction, of HNO3 and HCl occurred on these surfaces; the measured sticking coefficients are reported. Chlorine nitrate reacted on the cold sulfuric acid surfaces, producing gas-phase HOCl and condensed HNO3. CLONO2 also reacted with HCl dissolved in the 65-percent H2SO4 solution at -63 C, forming gaseous Cl2. In all cases studied, the sticking and/or reaction coefficients were much larger for the 65-percent H2SO4 solution at -63 C than for the 75-percent solution at -43 C.

Enantioselective decarboxylative chlorination of β-ketocarboxylic acids

PubMed Central

Shibatomi, Kazutaka; Kitahara, Kazumasa; Sasaki, Nozomi; Kawasaki, Yohei; Fujisawa, Ikuhide; Iwasa, Seiji

2017-01-01

Stereoselective halogenation is a highly useful organic transformation for multistep syntheses because the resulting chiral organohalides can serve as precursors for various medicinally relevant derivatives. Even though decarboxylative halogenation of aliphatic carboxylic acids is a useful and fundamental synthetic method for the preparation of a variety of organohalides, an enantioselective version of this reaction has not been reported. Here we report a highly enantioselective decarboxylative chlorination of β-ketocarboxylic acids to obtain α-chloroketones under mild organocatalytic conditions. The present method is also applicable for the enantioselective synthesis of tertiary α-chloroketones. The conversions of the resulting α-chloroketones into α-aminoketones and α-thio-substituted ketones via SN2 reactions at the tertiary carbon centres are also demonstrated. These results constitute an efficient approach for the synthesis of chiral organohalides and are expected to enhance the availability of enantiomerically enriched chiral compounds with heteroatom-substituted chiral stereogenic centres. PMID:28580951

Enantioselective decarboxylative chlorination of β-ketocarboxylic acids

NASA Astrophysics Data System (ADS)

Shibatomi, Kazutaka; Kitahara, Kazumasa; Sasaki, Nozomi; Kawasaki, Yohei; Fujisawa, Ikuhide; Iwasa, Seiji

2017-06-01

Stereoselective halogenation is a highly useful organic transformation for multistep syntheses because the resulting chiral organohalides can serve as precursors for various medicinally relevant derivatives. Even though decarboxylative halogenation of aliphatic carboxylic acids is a useful and fundamental synthetic method for the preparation of a variety of organohalides, an enantioselective version of this reaction has not been reported. Here we report a highly enantioselective decarboxylative chlorination of β-ketocarboxylic acids to obtain α-chloroketones under mild organocatalytic conditions. The present method is also applicable for the enantioselective synthesis of tertiary α-chloroketones. The conversions of the resulting α-chloroketones into α-aminoketones and α-thio-substituted ketones via SN2 reactions at the tertiary carbon centres are also demonstrated. These results constitute an efficient approach for the synthesis of chiral organohalides and are expected to enhance the availability of enantiomerically enriched chiral compounds with heteroatom-substituted chiral stereogenic centres.

Effect of nitrite on the formation of halonitromethanes during chlorination of organic matter from different origin

NASA Astrophysics Data System (ADS)

Hong, Huachang; Qian, Lingya; Xiao, Zhuoqun; Zhang, Jianqing; Chen, Jianrong; Lin, Hongjun; Yu, Haiying; Shen, Liguo; Liang, Yan

2015-12-01

Occurrence of halonitromethanes (HNMs) in drinking water has been a public concern due to the potential risks to human health. Though quite a lot of work has been carried out to understand the formation of HNMs, the relationship between HNMs formation and the nitrite remains unclear. In this study, the effects of nitrite on the formation of HNMs during chlorination of organic matter from different origin were assessed. Organic matter (OM) derived from phoenix tree (fallen leaves: FLOM; green leaves: GLOM) and Microcystis aeruginosa (intracellular organic matter: IOM) were used to mimic the allochthonous and autochthonous organic matter in surface water, respectively. Results showed that HNMs yields were significantly enhanced with the addition of nitrite, and the highest enhancement was observed for FLOM, successively followed by GLOM and IOM, suggesting that the contribution of nitrite to HNMs formation was positively related with SUVA (an indicator for aromaticity) of OM. Therefore, the nitrite contamination should be strictly controlled for the source water dominated by allochthonous OM, which may significantly reduce the formation of HNMs during chlorination. Moreover, given a certain nitrite level, the higher pH resulted in higher stimulation of HNM formation, yet the chlorine dose (always added in excess resulting in residual reactive chlorine), reaction time and temperature did not show obvious influence.

DFT application for chlorin derivatives photosensitizer drugs modeling

NASA Astrophysics Data System (ADS)

Machado, Neila; Carvalho, B. G.; Téllez Soto, C. A.; Martin, A. A.; Favero, P. P.

2018-04-01

Photodynamic therapy is an alternative form of cancer treatment that meets the desire for a less aggressive approach to the body. It is based on the interaction between a photosensitizer, activating light, and molecular oxygen. This interaction results in a cascade of reactions that leads to localized cell death. Many studies have been conducted to discover an ideal photosensitizer, which aggregates all the desirable characteristics of a potent cell killer and generates minimal side effects. Using Density Functional Theory (DFT) implemented in the program Vienna Ab-initio Simulation Package, new chlorin derivatives with different functional groups were simulated to evaluate the different absorption wavelengths to permit resonant absorption with the incident laser. Gaussian 09 program was used to determine vibrational wave numbers and Natural Bond Orbitals. The chosen drug with the best characteristics for the photosensitizer was a modified model of the original chlorin, which was called as Thiol chlorin. According to our calculations it is stable and is 19.6% more efficient at optical absorption in 708 nm in comparison to the conventional chlorin e6. Vibrational modes, optical and electronic properties were predicted. In conclusion, this study is an attempt to improve the development of new photosensitizer drugs through computational methods that save time and contribute to decrease the numbers of animals for model application.

Synthesis of potassium ferrate using residual ferrous sulfate as iron bearing material

NASA Astrophysics Data System (ADS)

Kanari, N.; Filippov, L.; Diot, F.; Mochón, J.; Ruiz-Bustinza, I.; Allain, E.; Yvon, J.

2013-03-01

This paper summarizes the results obtained during potassium ferrate (K2FeVIO4) synthesis which is a high added value material. This compound that contains iron in the rare hexavalent state is becoming a substance of growing importance for the water and effluent treatment industries. This is due to its multi-functional nature (oxidation, flocculation, elimination of heavy metals, decomposition of organic matter, etc.). The most well known synthesis methods for potassium ferrate synthesis are those involving the chemical and/or electrochemical oxidation of iron (II) and (III) from aqueous solutions having a high alkali concentration. These methods are generally characterized by a low FeVI efficiency due to the reaction of the potassium ferrate with water, leading to the reduction of FeVI into FeIII. Concerning the work pertinent to this paper, the synthesis of K2FeVIO4 was achieved by a simultaneous reaction of two solids (iron sulfate and KOH) and one gaseous oxidant (chlorine). The synthesis process is performed in a rotary reactor at room temperature and the global synthesis reaction is exothermic. The effects of different experimental parameters on the potassium ferrate synthesis are investigated to determine the optimal conditions for the process.

An equilibrium ab initio atomistic thermodynamics study of chlorine adsorption on the Cu(001) surface.

PubMed

Suleiman, Ibrahim A; Radny, Marian W; Gladys, Michael J; Smith, Phillip V; Mackie, John C; Kennedy, Eric M; Dlugogorski, Bogdan Z

2011-06-07

The effect of chlorine (Cl) chemisorption on the energetics and atomic structure of the Cu(001) surface over a wide range of chlorine pressures and temperatures has been studied using equilibrium ab initio atomistic thermodynamics to elucidate the formation of cuprous chloride (CuCl) as part of the Deacon reaction on copper metal. The calculated surface free energies show that the 1/2 monolayer (ML) c(2 × 2)-Cl phase with chlorine atoms adsorbed at the hollow sites is the most stable structure for a wide range of Cl chemical potential, in agreement with experimental observations. It is also found that at very low pressure and exposure, but elevated temperature, the 1/9 ML and 1/4 ML phases become the most stable. By contrast, a high coverage of Cl does not lead to thermodynamically stable geometries. The subsurface adsorption of Cl atoms, however, dramatically increases the stability of the 1 ML and 2 ML adsorption configurations providing a possible pathway for the formation of the bulk-chloride surface phases in the kinetic regime.

Approaches for the Analysis of Chlorinated Lipids

PubMed Central

Wang, Wen-yi; Albert, Carolyn J.; Ford, David A.

2013-01-01

Leukocytes are key cellular mediators of human diseases through their role in inflammation. Identifying unique molecules produced by leukocytes may provide new biomarkers and mechanistic insights into the role of leukocytes in disease. Chlorinated lipids are generated as a result of myeloperoxidase-containing leukocyte-derived hypochlorous acid targeting the vinyl ether bond of plasmalogens. The initial product of this reaction is α-chlorofatty aldehyde. α -Chlorofatty aldehyde is both oxidized to α-chlorofatty acid and reduced to α-chlorofatty alcohol by cellular metabolism. This review focuses on the separation techniques and quantitative analysis for these chlorinated lipids. For α-chlorofatty acid the negative charge of carboxylic acids is exploited to detect the chlorinated lipid species of these acids by electrospray ionization mass spectrometry in the negative ion mode. In contrast, α-chlorofatty aldehyde and α-chlorofatty alcohol are converted to pentafluorobenzyl oxime and pentafluorobenzoyl ester derivatives, which are detected by negative ion-chemical ionization mass spectrometry. These two detection methods coupled with the use of stable isotope internal standards and either liquid chromatography or gas chromatography provide highly sensitive analytical approaches to measure these novel lipids. PMID:24056259

Observations of chlorine monoxide over Scott Base, Antarctica, during the ozone hole, 1996-2005

USGS Publications Warehouse

Connor, Brian; Solomon, Philip; Barrett, James; Mooney, Thomas; Parrish, Alan

2007-01-01

We report observations of chlorine monoxide, ClO, in the lower stratosphere, made from Scott Base (77.85º S, 166.77º E) in springtime during each year, 1996-2005. The ClO amounts in the atmosphere are retrieved from remote measurements of microwave emission spectra. ClO column densities of up to about 2.5 × 1015 cm-2 are recorded during September, when chlorine is present in chemically active forms due to reactions on the surface of Polar Stratospheric Cloud (PSC) particles. Maximum mixing ratios of ClO are approximately 2 ppbv. The annual average of ClO column density during the activation period is anticorrelated with similar averages of ozone column measured at nearby Arrival Heights, with correlation coefficient of –0.81, and with averages of ozone mass integrated over the entire polar region, with similar correlation coefficients. There was a substantial decrease in ClO amounts during 2002-2004. There has been no systematic change in the timing of chlorine deactivation attributable to secular change in the Antarctic vortex

Genotoxicity of drinking water treated with different disinfectants and effects of disinfection conditions detected by umu-test.

PubMed

Nie, Xuebiao; Liu, Wenjun; Zhang, Liping; Liu, Qing

2017-06-01

The genotoxicity of drinking water treated with 6 disinfection methods and the effects of disinfection conditions were investigated using the umu-test. The pretreatment procedure of samples for the umu-test was optimized for drinking water analysis. The results of the umu-test were in good correlation with those of the Ames-test. The genotoxicity and production of haloacetic acids (HAAs) were the highest for chlorinated samples. UV+chloramination is the safest disinfection method from the aspects of genotoxicity, HAA production and inactivation effects. For chloramination, the effects of the mass ratio of Cl 2 to N of chloramine on genotoxicity were also studied. The changes of genotoxicity were different from those of HAA production, which implied that HAA production cannot represent the genotoxic potential of water. The genotoxicity per chlorine decay of chlorination and chloramination had similar trends, indicating that the reaction of organic matters and chlorine made a great contribution to the genotoxicity. The results of this study are of engineering significance for optimizing the operation of waterworks. Copyright © 2016. Published by Elsevier B.V.

Inert gas rejection device for zinc-halogen battery systems

DOEpatents

Hammond, Michael J.; Arendell, Mark W.

1981-01-01

An electrolytic cell for separating chlorine gas from other (foreign) gases, having an anode, a cathode assembly, an aqueous electrolyte, a housing, and a constant voltage power supply. The cathode assembly is generally comprised of a dense graphite electrode having a winding channel formed in the face opposing the anode, a gas impermeable (but liquid permeable) membrane sealed into the side of the cathode electrode over the channel, and a packing of graphite particles contained in the channel of the cathode electrode. The housing separates and parallelly aligns the anode and cathode assembly, and provides a hermetic seal for the cell. In operation, a stream of chlorine and foreign gases enters the cell at the beginning of the cathode electrode channel. The chlorine gas is dissolved into the electrolyte and electrochemically reduced into chloride ions. The chloride ions disfuse through the gas impermeable membrane, and are electrochemically oxidized at the anode into purified chlorine gas. The foreign gases do not participate in the above electrochemical reactions, and are vented from the cell at the end of the cathode electrode channel.

Atmospheric oxidation of selected chlorinated alkenes by O3, OH, NO3 and Cl

NASA Astrophysics Data System (ADS)

Zhang, Qun; Chen, Yi; Tong, Shengrui; Ge, Maofa; Shenolikar, Justin; Johnson, Matthew S.; Wang, Yifeng; Tsona, Narcisse T.; Mellouki, Abdelwahid; Du, Lin

2017-12-01

An experimental study on the 3-chloro-2-methyl-1-propene (CMP), 2,3-dichloropropene (DCP) and 3,4-dichlorobutene (DCB) reactions with atmospheric oxidants at (298 ± 1) K and atmospheric pressure is reported. Rate constants for the gas phase reactions of the three chlorinated alkenes with O3, OH and NO3 radicals and Cl atom were determined in a 100 L Teflon reactor by gas chromatography with flame ionization detector (GC-FID). The obtained rate constants are (3.03 ± 0.15) × 10-18, (3.83 ± 1.30) × 10-11, (1.99 ± 0.19) × 10-14, and (2.40 ± 0.41) × 10-10 cm3 molecule-1 s-1 for CMP reactions with O3, OH, NO3, and Cl, respectively, (4.62 ± 1.41) × 10-20, (1.37 ± 1.02) × 10-11, (1.45 ± 0.15) × 10-15 and (1.30 ± 0.99) × 10-11 cm3 molecule-1 s-1 for DCP reactions and (2.09 ± 0.24) × 10-19, (1.45 ± 0.59) × 10-11, (3.00 ± 0.82) × 10-16 and (1.91 ± 0.19) × 10-10 cm3 molecule-1 s-1 for DCB reactions. The CMP reaction products were detected and possible reaction mechanisms of their formation were proposed. Chloroacetone was found to be the major product in all four oxidation reactions. The loss process of CMP in the atmosphere is mostly controlled by its reaction with the OH radical during daytime and with NO3 during nighttime, with lifetimes of 3.6 h and 27.9 h respectively. Atmospheric implications of both these reactions and their potential products are discussed.

Kinetic study of the gas-phase reactions of chlorine atoms with 2-chlorophenol, 2-nitrophenol, and four methyl-2-nitrophenol isomers.

PubMed

Bejan, Iustinian; Duncianu, Marius; Olariu, Romeo; Barnes, Ian; Seakins, Paul W; Wiesen, Peter

2015-05-21

Anthropogenic activities are the main source of nitrophenols and chlorophenols in the atmosphere. Nitro and chlorophenols have a high potential to form ozone and secondary organic aerosol, thus investigations on the major photo oxidation pathways of these compounds are important to assess their contribution to urban air pollution and human health. Presented here are rate coefficients determined at atmospheric pressure and (298 ± 2) K using a relative kinetic method for the reactions of chlorine atoms with 2-chlorophenol (2ClP), 2-nitrophenol (2NP) and four methyl-2-nitrophenol (2-nitrocresol, nM2NP (n = 3,4,5,6)) isomers. The following rate coefficients (in units of cm(3) molecule(-1) s(-1)) have been obtained: (5.9 ± 1.5) × 10(-12) for 2ClP, (6.8 ± 2.3) × 10(-12) for 2NP, and (14.0 ± 4.9) × 10(-11), (4.3 ± 1.5) × 10(-11), (1.94 ± 0.67) × 10(-11) and (2.68 ± 0.75) × 10(-11) for the four methyl-2-nitrophenol isomers 3M2NP, 4M2NP, 5M2NP, and 6M2NP, respectively. This study represents the first kinetic investigation for the reaction of chlorine atoms with all the nitrophenols. In addition, to assist in the interpretation of the results, rate coefficients for the reactions of Cl atoms with the cresol ortho, meta, and para isomers have been determined for the first time. The rate coefficient for the reaction with 2ClP is in good agreement with previous data and the relative reactivity of 2NP, 4M2NP, 5M2NP, and 6M2NP can be rationalized based on known substituent effects. The rate coefficient for 3M2NP is anomalously large; the observation of significant NO2 production in only this reaction suggests that an ipso substitution mechanism is the cause of the enhanced reactivity.

Stepwise syntheses of bisporphyrins, bischlorins, and biscorroles and of porphyrin-chlorin and porphyrin-corrole heterodimers

DOE Office of Scientific and Technical Information (OSTI.GOV)

Paolesse, R.; Pandey, R.K.; Forsyth, T.P.

The stepwise syntheses and characterization of a series of symmetrical and unsymmetrical bisporphyrins, bischlorins, and biscorroles, and of porphyrin-chlorin and porphyrin-corrole dyads possessing ethylene, phenyl, and stilbene linking units are described. The methodology for synthesis of 10-substituted corroles 2 and their cobalt complexes 9 via a,c-biladiene salts 1 was first developed, and then extended to provide biscorroles (e.g., 4 and 5) linked through the 10-positions with phenyl linker units. Using a similar methodology, phenyl-linked corrole-porphyrin dyads 28 and 30 were also prepared. By way of intermediate phenyl-linked unsymmetrical bisdipyrromethanes, a completely unsymmetrical heterobimetallic bisporphyrin system, 45, was synthesized. Low-valent titaniummore » coupling (McMurry) reactions were used to prepare stilbene-linked bisdipyrromethanes (e.g., 46) which were subsequently transformed into stilbene-linked bisporphyrins (e.g., 48). McMurry cross-coupling reactions of porphyrins bearing p-formylphenyl substituents also afforded an unsymmetrically substituted bisporphyrinylstilbene, 60, as well as the corresponding homodimers 56 and 59. Likewise, McMurry cross-coupling of a p-formylphenyl-substituted porphyrin, 62, with a formylchlorin, 63, afforded a stilbene-linked bisporphyrin, 64, a bischlorin, 66, and a novel porphyrin-chlorin heterodimer, 65. 54 refs., 1 fig., 1 tab.« less

Estimation of rate constants of PCB dechlorination reactions using an anaerobic dehalogenation model.

PubMed

Karakas, Filiz; Imamoglu, Ipek

2017-02-15

This study aims to estimate anaerobic dechlorination rate constants (k m ) of reactions of individual PCB congeners using data from four laboratory microcosms set up using sediment from Baltimore Harbor. Pathway k m values are estimated by modifying a previously developed model as Anaerobic Dehalogenation Model (ADM) which can be applied to any halogenated hydrophobic organic (HOC). Improvements such as handling multiple dechlorination activities (DAs) and co-elution of congeners, incorporating constraints, using new goodness of fit evaluation led to an increase in accuracy, speed and flexibility of ADM. DAs published in the literature in terms of chlorine substitutions as well as specific microorganisms and their combinations are used for identification of pathways. The best fit explaining the congener pattern changes was found for pathways of Phylotype DEH10, which has the ability to remove doubly flanked chlorines in meta and para positions, para flanked chlorines in meta position. The range of estimated k m values is between 0.0001-0.133d -1 , the median of which is found to be comparable to the few available published biologically confirmed rate constants. Compound specific modelling studies such as that performed by ADM can enable monitoring and prediction of concentration changes as well as toxicity during bioremediation. Copyright © 2016 Elsevier B.V. All rights reserved.

Spiroketals of Pestalotiopsis fici provide evidence for a biosynthetic hypothesis involving diversified Diels-Alder reaction cascades.

PubMed

Liu, Ling; Li, Yan; Li, Li; Cao, Ya; Guo, Liangdong; Liu, Gang; Che, Yongsheng

2013-04-05

Chloropestolides B-G (1-6), six new metabolites featuring the chlorinated spiro[benzo[d][1,3]dioxine-2,7'-bicyclo[2.2.2]octane]-4,8'-dione (1-3) and spiro[benzo[d][1,3]dioxine-2,1'-naphthalene]-2',4-dione (4-6) skeletons, and their putative biosynthetic precursor dechloromaldoxin (7) were isolated from the scale-up fermentation cultures of the plant endophytic fungus Pestalotiopsis fici . The structures of 1-7 were determined mainly by NMR experiments. The absolute configurations of 1-3 were deduced by analogy to the previously isolated metabolites from the same fungus (9 and 13-18), whereas those of 4, 5, and 7 were assigned by electronic circular dichroism (ECD) calculations. Structurally, the spiroketal skeletons found in 1-3 and 4-6 could be derived from 2,6-dihydroxy-4-methylbenzoic acid with chlorinated bicyclo[2.2.2]oct-2-en-5-one and 4a,5,8,8a-tetrahydronaphthalen-2(1H)-one, respectively. Biogenetically, compounds 1-6 were derived from the same Diels-Alder precursors as the previously isolated 9 and 12-18. In addition, compounds 2 and 3 were proposed as the biosynthetic intermediates of 17 and 16, respectively. Compound 1 was cytotoxic to three human tumor cell lines.

About the Barriers to Reaction of CCl4 with HFeOH and FeCl2

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ginovska-Pangovska, Bojana; Camaioni, Donald M.; Dupuis, Michel

2011-08-11

The reactivity of iron nanoparticles in aqueous environments has received considerable attention due to their potential utilization in environmental remediation technologies. As part of a broader program aiming at an improved understanding of the mechanisms involved in the degradation of harmful chlorocarbons, joint experimental and computational studies of model systems were initiated. We previously reported on the reaction of one and two Fe atoms reactions with carbon tetrachloride (CCl4) in direct mimic of “atom-dropping” experiments, with insights into the formation of novel iron-carbon-chlorine complexes, their structures and possible reaction mechanisms. Increasing the level of complexity, we report here on themore » modeling of the reaction of HFeOH and CCl4 as companion research of recent ultra high vacuum experiments of the reaction of Fe with water and CCl4. HFeOH is a stable molecular species formed in the reaction of Fe with H2O. Experimentally the (Fe, H2O, CCl4) system showed no reactivity up to the desorption temperature of CCl4. Electron correlated CCSD(T) calculations (at DFT(B3LYP) optimized structures) indicated an energy barrier to reactivity of 24.5 kcal/mol following the formation of a stable ( 7.5 kcal/mol) long-range precursor complex. This finding is consistent with the lack of experimentally detected reaction products. This work was supported by the US Department of Energy Basic Energy Sciences' Chemical Sciences, Geosciences & Biosciences Division. Pacific Northwest National Laboratory is operated by Battelle for the US Department of Energy.« less

Metagenomic insights into chlorination effects on microbial antibiotic resistance in drinking water.

PubMed

Shi, Peng; Jia, Shuyu; Zhang, Xu-Xiang; Zhang, Tong; Cheng, Shupei; Li, Aimin

2013-01-01

This study aimed to investigate the chlorination effects on microbial antibiotic resistance in a drinking water treatment plant. Biochemical identification, 16S rRNA gene cloning and metagenomic analysis consistently indicated that Proteobacteria were the main antibiotic resistant bacteria (ARB) dominating in the drinking water and chlorine disinfection greatly affected microbial community structure. After chlorination, higher proportion of the surviving bacteria was resistant to chloramphenicol, trimethoprim and cephalothin. Quantitative real-time PCRs revealed that sulI had the highest abundance among the antibiotic resistance genes (ARGs) detected in the drinking water, followed by tetA and tetG. Chlorination caused enrichment of ampC, aphA2, bla(TEM-1), tetA, tetG, ermA and ermB, but sulI was considerably removed (p < 0.05). Metagenomic analysis confirmed that drinking water chlorination could concentrate various ARGs, as well as of plasmids, insertion sequences and integrons involved in horizontal transfer of the ARGs. Water pipeline transportation tended to reduce the abundance of most ARGs, but various ARB and ARGs were still present in the tap water, which deserves more public health concerns. The results highlighted prevalence of ARB and ARGs in chlorinated drinking water and this study might be technologically useful for detecting the ARGs in water environments. Copyright © 2012 Elsevier Ltd. All rights reserved.

Cathodes for molten-salt batteries

NASA Technical Reports Server (NTRS)

Argade, Shyam D.

1993-01-01

Viewgraphs of the discussion on cathodes for molten-salt batteries are presented. For the cathode reactions in molten-salt cells, chlorine-based and sulfur-based cathodes reactants have relatively high exchange current densities. Sulfur-based cathodes, metal sulfides, and disulfides have been extensively investigated. Primary thermal batteries of the Li-alloy/FeS2 variety have been available for a number of years. Chlorine based rechargable cathodes were investigated for the pulse power application. A brief introduction is followed by the experimental aspects of research, and the results obtained. Performance projections to the battery system level are discussed and the presentation is summarized with conclusions.

The Chlorine Isotopic Composition Of Lunar UrKREEP

NASA Technical Reports Server (NTRS)

Barnes, J. J.; Tartese, R.; Anand, M.; McCubbin, F. M.; Neal, C. R.; Franchi, I. A.

2016-01-01

Since the long standing paradigm of an anhydrous Moon was challenged there has been a renewed focus on investigating volatiles in a variety of lunar samples. However, the current models for the Moon’s formation have yet to fully account for its thermal evolution in the presence of H2O and other volatiles. When compared to chondritic meteorites and terrestrial rocks, lunar samples have exotic chlorine isotope compositions, which are difficult to explain in light of the abundance and isotopic composition of other volatile species, especially H, and the current estimates for chlorine and H2O in the bulk silicate Moon. In order to better understand the processes involved in giving rise to the heavy chlorine isotope compositions of lunar samples, we have performed a comprehensive in situ high precision study of chlorine isotopes, using NanoSIMS (Nanoscale Secondary Ion Mass Spectrometry) of lunar apatite from a suite of Apollo samples covering a range of geochemical characteristics and petrologic types.

A metagenomic-based survey of microbial (de)halogenation potential in a German forest soil

PubMed Central

Weigold, Pascal; El-Hadidi, Mohamed; Ruecker, Alexander; Huson, Daniel H.; Scholten, Thomas; Jochmann, Maik; Kappler, Andreas; Behrens, Sebastian

2016-01-01

In soils halogens (fluorine, chlorine, bromine, iodine) are cycled through the transformation of inorganic halides into organohalogen compounds and vice versa. There is evidence that these reactions are microbially driven but the key enzymes and groups of microorganisms involved are largely unknown. Our aim was to uncover the diversity, abundance and distribution of genes encoding for halogenating and dehalogenating enzymes in a German forest soil by shotgun metagenomic sequencing. Metagenomic libraries of three soil horizons revealed the presence of genera known to be involved in halogenation and dehalogenation processes such as Bradyrhizobium or Pseudomonas. We detected a so far unknown diversity of genes encoding for (de)halogenating enzymes in the soil metagenome including specific and unspecific halogenases as well as metabolic and cometabolic dehalogenases. Genes for non-heme, no-metal chloroperoxidases and haloalkane dehalogenases were the most abundant halogenase and dehalogenase genes, respectively. The high diversity and abundance of (de)halogenating enzymes suggests a strong microbial contribution to natural halogen cycling. This was also confirmed in microcosm experiments in which we quantified the biotic formation of chloroform and bromoform. Knowledge on microorganisms and genes that catalyze (de)halogenation reactions is critical because they are highly relevant to industrial biotechnologies and bioremediation applications. PMID:27353292

Analysis of Halogen-Mercury Reactions in Flue Gas

DOE Office of Scientific and Technical Information (OSTI.GOV)

Paula Buitrago; Geoffrey Silcox; Constance Senior

2010-01-01

Oxidized mercury species may be formed in combustion systems through gas-phase reactions between elemental mercury and halogens, such as chorine or bromine. This study examines how bromine species affect mercury oxidation in the gas phase and examines the effects of mixtures of bromine and chlorine on extents of oxidation. Experiments were conducted in a bench-scale, laminar flow, methane-fired (300 W), quartz-lined reactor in which gas composition (HCl, HBr, NO{sub x}, SO{sub 2}) and temperature profile were varied. In the experiments, the post-combustion gases were quenched from flame temperatures to about 350 C, and then speciated mercury was measured using amore » wet conditioning system and continuous emissions monitor (CEM). Supporting kinetic calculations were performed and compared with measured levels of oxidation. A significant portion of this report is devoted to sample conditioning as part of the mercury analysis system. In combustion systems with significant amounts of Br{sub 2} in the flue gas, the impinger solutions used to speciate mercury may be biased and care must be taken in interpreting mercury oxidation results. The stannous chloride solution used in the CEM conditioning system to convert all mercury to total mercury did not provide complete conversion of oxidized mercury to elemental, when bromine was added to the combustion system, resulting in a low bias for the total mercury measurement. The use of a hydroxylamine hydrochloride and sodium hydroxide solution instead of stannous chloride showed a significant improvement in the measurement of total mercury. Bromine was shown to be much more effective in the post-flame, homogeneous oxidation of mercury than chlorine, on an equivalent molar basis. Addition of NO to the flame (up to 400 ppmv) had no impact on mercury oxidation by chlorine or bromine. Addition of SO{sub 2} had no effect on mercury oxidation by chlorine at SO{sub 2} concentrations below about 400 ppmv; some increase in mercury oxidation was observed at SO{sub 2} concentrations of 400 ppmv and higher. In contrast, SO{sub 2} concentrations as low as 50 ppmv significantly reduced mercury oxidation by bromine, this reduction could be due to both gas and liquid phase interactions between SO{sub 2} and oxidized mercury species. The simultaneous presence of chlorine and bromine in the flue gas resulted in a slight increase in mercury oxidation above that obtained with bromine alone, the extent of the observed increase is proportional to the chlorine concentration. The results of this study can be used to understand the relative importance of gas-phase mercury oxidation by bromine and chlorine in combustion systems. Two temperature profiles were tested: a low quench (210 K/s) and a high quench (440 K/s). For chlorine the effects of quench rate were slight and hard to characterize with confidence. Oxidation with bromine proved sensitive to quench rate with significantly more oxidation at the lower rate. The data generated in this program are the first homogeneous laboratory-scale data on bromine-induced oxidation of mercury in a combustion system. Five Hg-Cl and three Hg-Br mechanisms, some published and others under development, were evaluated and compared to the new data. The Hg-halogen mechanisms were combined with submechanisms from Reaction Engineering International for NO{sub x}, SO{sub x}, and hydrocarbons. The homogeneous kinetics under-predicted the levels of mercury oxidation observed in full-scale systems. This shortcoming can be corrected by including heterogeneous kinetics in the model calculations.« less

Environmental applications for the analysis of chlorinated dibenzo-p-dioxins and dibenzofurans using mass spectrometry/mass spectrometry

DOE Office of Scientific and Technical Information (OSTI.GOV)

Reiner, E.J.; Schellenberg, D.H.; Taguchi, V.Y.

1991-01-01

A mass spectrometry/mass spectrometry-multiple reaction monitoring (MS/MS-MRM) technique for the analysis of all tetra- through octachlorinated dibenzo-p-dioxins (Cl{sub x}DD, x = 4-8) and dibenzofurans (Cl{sub x}DF, x = 4-8) has been developed at the Ministry of the Environment (MOE) utilizing a triple quadrupole mass spectrometer. Optimization of instrumental parameters using the analyte of interest in a direct insertion probe (DIP) resulted in sensitivities approaching those obtainable by high-resolution mass spectrometric (HRMS) methods. All congeners of dioxins and furans were detected in the femtogram range. Results on selected samples indicated that for some matrices, fewer chemical interferences were observed by MS/MSmore » than by HRMS. The technique used to optimize the instrument for chlorinated dibenzo-p-dioxins (CDDs) and chlorinated dibenzofurans (CDFs) analysis is adaptable to other analytes.« less

Lorentz force on sodium and chlorine ions in a salt water solution flow under a transverse magnetic field

NASA Astrophysics Data System (ADS)

DeLuca, R.

2009-05-01

It is shown that, by applying elementary concepts in electromagnetism and electrochemistry to a system consisting of salt water flowing in a thin rectangular pipe at an average velocity vA under the influence of a transverse magnetic field B0, an electromotive force generator can be conceived. In fact, the Lorentz force acting on the sodium and chlorine ions in a water solution gives rise to a so-called Faraday voltage across the two metal electrodes, positioned at the sides of the pipe. The effect is carried along the following chemical reactions at the electrodes: at the cathode, water is reduced (instead of sodium ions) and hydrogen gas is generated; at the anode, chlorine gas is produced. In college physics teaching, this interdisciplinary subject can be adopted to stress analogies and differences between the Hall voltage in conductors and the Faraday voltage in electrolyte solutions.

High energy chemical laser system

DOEpatents

Gregg, D.W.; Pearson, R.K.

1975-12-23

A high energy chemical laser system is described wherein explosive gaseous mixtures of a reducing agent providing hydrogen isotopes and interhalogen compounds are uniformly ignited by means of an electrical discharge, flash- photolysis or an electron beam. The resulting chemical explosion pumps a lasing chemical species, hydrogen fluoride or deuterium fluoride which is formed in the chemical reaction. The generated lasing pulse has light frequencies in the 3- micron range. Suitable interhalogen compounds include bromine trifluoride (BrF$sub 3$), bromine pentafluoride (BrF$sub 5$), chlorine monofluoride (ClF), chlorine trifluoride (ClF$sub 3$), chlorine pentafluoride (ClF$sub 5$), iodine pentafluoride (IF$sub 5$), and iodine heptafluoride (IF$sub 7$); and suitable reducing agents include hydrogen (H$sub 2$), hydrocarbons such as methane (CH$sub 4$), deuterium (D$sub 2$), and diborane (B$sub 2$H$sub 6$), as well as combinations of the gaseous compound and/or molecular mixtures of the reducing agent.

Silicon Carbide Etching Using Chlorine Trifluoride Gas

NASA Astrophysics Data System (ADS)

Habuka, Hitoshi; Oda, Satoko; Fukai, Yasushi; Fukae, Katsuya; Takeuchi, Takashi; Aihara, Masahiko

2005-03-01

The etch rate, chemical reactions and etched surface of β-silicon carbide are studied in detail using chlorine trifluoride gas. The etch rate is greater than 10 μm min-1 at 723 K with a flow rate of 0.1 \\ell min-1 at atmospheric pressure in a horizontal reactor. The maximum etch rate at a substrate temperature of 773 K is 40 μm min-1 with a flow rate of 0.25 \\ell min-1. The step-like pattern that initially exists on the β-silicon carbide surface tends to be smoothed; the root-mean-square surface roughness decreases from its initial value of 5 μm to 1 μm within 15 min; this minimum value is maintained for more than 15 min. Therefore, chlorine trifluoride gas is considered to have a large etch rate for β-silicon carbide associated with making a rough surface smooth.

Dissection of the mechanism of manganese porphyrin-catalyzed chlorine dioxide generation.

PubMed

Umile, Thomas P; Wang, Dong; Groves, John T

2011-10-17

Chlorine dioxide, an industrially important biocide and bleach, is produced rapidly and efficiently from chlorite ion in the presence of water-soluble, manganese porphyrins and porphyrazines at neutral pH under mild conditions. The electron-deficient manganese(III) tetra-(N,N-dimethyl)imidazolium porphyrin (MnTDMImP), tetra-(N,N-dimethyl)benzimidazolium (MnTDMBImP) porphyrin, and manganese(III) tetra-N-methyl-2,3-pyridinoporphyrazine (MnTM23PyPz) were found to be the most efficient catalysts for this process. The more typical manganese tetra-4-N-methylpyridiumporphyrin (Mn-4-TMPyP) was much less effective. Rates for the best catalysts were in the range of 0.24-32 TO/s with MnTM23PyPz being the fastest. The kinetics of reactions of the various ClO(x) species (e.g., chlorite ion, hypochlorous acid, and chlorine dioxide) with authentic oxomanganese(IV) and dioxomanganese(V)MnTDMImP intermediates were studied by stopped-flow spectroscopy. Rate-limiting oxidation of the manganese(III) catalyst by chlorite ion via oxygen atom transfer is proposed to afford a trans-dioxomanganese(V) intermediate. Both trans-dioxomanganese(V)TDMImP and oxoaqua-manganese(IV)TDMImP oxidize chlorite ion by 1-electron, generating the product chlorine dioxide with bimolecular rate constants of 6.30 × 10(3) M(-1) s(-1) and 3.13 × 10(3) M(-1) s(-1), respectively, at pH 6.8. Chlorine dioxide was able to oxidize manganese(III)TDMImP to oxomanganese(IV) at a similar rate, establishing a redox steady-state equilibrium under turnover conditions. Hypochlorous acid (HOCl) produced during turnover was found to rapidly and reversibly react with manganese(III)TDMImP to give dioxoMn(V)TDMImP and chloride ion. The measured equilibrium constant for this reaction (K(eq) = 2.2 at pH 5.1) afforded a value for the oxoMn(V)/Mn(III) redox couple under catalytic conditions (E' = 1.35 V vs NHE). In subsequent processes, chlorine dioxide reacts with both oxomanganese(V) and oxomanganese(IV)TDMImP to afford chlorate ion. Kinetic simulations of the proposed mechanism using experimentally measured rate constants were in agreement with observed chlorine dioxide growth and decay curves, measured chlorate yields, and the oxoMn(IV)/Mn(III) redox potential (1.03 V vs NHE). This acid-free catalysis could form the basis for a new process to make ClO(2).

Solid state synthesis of poly(dichlorophosphazene)

DOEpatents

Allen, Christopher W.; Hneihen, Azzam S.; Peterson, Eric S.

2001-01-01

A method for making poly(dichlorophosphazene) using solid state reactants is disclosed and described. The present invention improves upon previous methods by removing the need for chlorinated hydrocarbon solvents, eliminating complicated equipment and simplifying the overall process by providing a "single pot" two step reaction sequence. This may be accomplished by the condensation reaction of raw materials in the melt phase of the reactants and in the absence of an environmentally damaging solvent.

PROCESSES OF CHLORINATION OF URANIUM OXIDES

DOEpatents

Rosenfeld, S.

1958-09-16

An improvement is described in the process fur making UCl/sub 4/ from uranium oxide and carbon tetrachloride. In that process, oxides of uranium are contacted with carbon tetrachloride vapor at an elevated temperature. It has been fuund that the reaction product and yield are improved if the uranlum oxide charge is disposed in flat trays in the reaction zone, to a depth of not more than 1/2 centimeter.

Reductive transformation of dioxins: An assessment of the contribution of dissolved organic matter to dechlorination reactions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Fu, Q.S.; Barkovskii, A.L.; Adriaens, P.

1999-11-01

The susceptibility of dioxins to dissolved organic carbon (DOC)-mediated dechlorination reactions was investigated using 1,2,3,4,6,7,9-heptachlorodibenzo-p-dioxin (HpCDD), Aldrich humic acid (AHA), and polymaleic acid (PMA) as model compounds. The dechlorination yields were on the order of 4--20% which, when normalized to phenolic acidity, was comparable to yields observed in the presence of the humic constituents catechol and resorcinol. Based on the ratio of dechlorination yields as a function of phenolic acidity and electron transfer capacity, differences in electron transfer efficiency to dioxins are likely combined effects of specific interactions with the functional groups and nonspecific hydrophobic interactions. Hexa- and pentaCDD homologuesmore » were dominant in all incubations, and diCDD constituted the final product of dechlorination. The rates of appearance of lesser chlorinated products were similar to those observed in sediment systems and followed thermodynamic considerations as they decreased with a decrease in level of chlorination. Generally, both absolute and phenolic acidity-normalized rate constants for AHA-mediated reactions were up to 2-fold higher than those effected by PMA. These results indicate that the electron shuttling capacity of sediment DOC may significantly affect the fate of dioxins, in part through dechlorination reactions.« less

Molecular dynamics simulation study of the early stages of nucleation of iron oxyhydroxide nanoparticles in aqueous solutions

DOE PAGES

Zhang, Hengzhong; Waychunas, Glenn A.; Banfield, Jillian F.

2015-07-29

Nucleation is a fundamental step in crystal growth. Of environmental and materials relevance are reactions that lead to nucleation of iron oxyhydroxides in aqueous solutions. These reactions are difficult to study experimentally due to their rapid kinetics. Here, we used classical molecular dynamics simulations to investigate nucleation of iron hydroxide/oxyhydroxide nanoparticles in aqueous solutions. Results show that in a solution containing ferric ions and hydroxyl groups, iron–hydroxyl molecular clusters form by merging ferric monomers, dimers, and other oligomers, driven by strong affinity of ferric ions to hydroxyls. When deprotonation reactions are not considered in the simulations, these clusters aggregate tomore » form small iron hydroxide nanocrystals with a six-membered ring-like layered structure allomeric to gibbsite. By comparison, in a solution containing iron chloride and sodium hydroxide, the presence of chlorine drives cluster assembly along a different direction to form long molecular chains (rather than rings) composed of Fe–O octahedra linked by edge sharing. Further, in chlorine-free solutions, when deprotonation reactions are considered, the simulations predict ultimate formation of amorphous iron oxyhydroxide nanoparticles with local atomic structure similar to that of ferrihydrite nanoparticles. Overall, our simulation results reveal that nucleation of iron oxyhydroxide nanoparticles proceeds via a cluster aggregation-based nonclassical pathway.« less

Transgenic plants and associated bacteria for phytoremediation of chlorinated compounds.

PubMed

Van Aken, Benoit; Doty, Sharon Lafferty

2010-01-01

Phytoremediation is the use of plants for the treatment of environmental pollution, including chlorinated organics. Although conceptually very attractive, removal and biodegradation of chlorinated pollutants by plants is a rather slow and inefficient process resulting in incomplete treatment and potential release of toxic metabolites into the environment. In order to overcome inherent limitations of plant metabolic capabilities, plants have been genetically modified, following a strategy similar to the development of transgenic crops: genes from bacteria, fungi, and mammals involved in the metabolism of organic contaminants, such as cytochrome P-450 and glutathione S-transferase, have been introduced into higher plants, resulting in significant improvement of tolerance, removal, and degradation of pollutants. Recently, plant-associated bacteria have been recognized playing a significant role in phytoremediation, leading to the development of genetically modified rhizospheric and endophytic bacteria with improved biodegradation capabilities. Transgenic plants and associated bacteria constitute a new generation of genetically modified organisms for efficient and environmental-friendly treatment of polluted soil and water. This review focuses on recent advances in the development of transgenic plants and bacteria for the treatment of chlorinated pollutants, including chlorinated solvents, polychlorinated phenols, and chlorinated herbicides.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Qu, Shiwei; Wang, Huan; Mo, Daize

A new family of thieno[3,4-b]thiophene benzodithiophene terpolymers (PBTClx) have been designed and synthesized, in which the chlorine/fluorine content has been adjusted and optimized. As the content of chlorine is increased in polymers, the twist angle between the donor and acceptor is increased, which leads to a diminishment in the planarity and conjugation. As a result, the UV vis absorption is continuous blue-shifted, and the band gap increases from 1.57 to 2.04 eV when the chlorinated moieties increased from 0 to 100%. The highest occupied molecular orbital (HOMO) levels of those polymers are decreased by increasing the content of chlorinated moiety,more » which opens a window to constantly modify the V-oc values and eventually meets a balance point for optimized solar energy conversion. The highest power conversion efficiency of 8.31% is obtained by using PBTCl25 as the donor and PC71BM as the acceptor in polymer solar cells (PSCs), in which the Voc increased from 0.79 to 0.82 V after 25% chlorinated monomer involved in copolymerization. Herein, the chlorine replacement could be a good method to further pump the solar conversion by increasing the open circuit voltage without reducing other factors of the polymer solar cells.« less

Analyzing Environmental Policies for Chlorinated Solvents with a Model of Markets and Regulations

DTIC Science & Technology

1991-01-01

electronics, aerospace, fabricated metal products, and dry cleaning depend heavily on chlorinated solvents in their production processes . For example...production processes . The second of the model’s components is a group of economic equations that represents all of the solvent substitutions in...Instead, the process for numerically specifying the substitution parameters involves eliciting expert judgments and then normalizing the parameters

The Market Responses to the Government Regulation of Chlorinated Solvents: A Policy Analysis

DTIC Science & Technology

1988-10-01

in the process of statistical estimation of model parameters. The results of the estimation process applied to chlorinated solvent markets show the...93 C.5. Marginal Feedstock Cost Series Estimates for Process Share of Total Production .................................. 94 F.I...poliay context for this research. Section III provides analysis necessary to understand the chemicals involved, their production processes and costs, and

Chlorination of Household Drinking Water Among Cholera Patients' Households to Prevent Transmission of Toxigenic Vibrio cholerae in Dhaka, Bangladesh: CHoBI7 Trial.

PubMed

Rashid, Mahamud-Ur; George, Christine Marie; Monira, Shirajum; Mahmud, Toslim; Rahman, Zillur; Mustafiz, Munshi; Saif-Ur-Rahman, K M; Parvin, Tahmina; Bhuyian, Sazzadul Islam; Zohura, Fatema; Begum, Farzana; Biswas, Shwapon Kumar; Akhter, Shamima; Zhang, Xiaotong; Sack, David; Sack, R Bradley; Alam, Munirul

2016-12-07

Household members of cholera patients are at a 100 times higher risk of cholera infections than the general population because of shared contaminated drinking water sources and secondary transmission through poor household hygiene practices. In this study, we investigated the bactericidal concentration of free chlorine required to inactivate Vibrio cholerae in household drinking water in Dhaka, Bangladesh. In laboratory experiments, we found that the concentrations of free chlorine required to inactivate 10 5 colony-forming units (CFU)/mL of V. cholerae serogroups O1 and O139 were 0.1 mg/L and 0.2 mg/L, respectively. The concentration of free chlorine generated by a single chlorine tablet (sodium dichloroisocyanurate [33 mg]) after a 30-minute reaction time in a 10-L sealed vessel containing Dhaka city municipal supply water was 1.8 mg/L; and the concentration declined to 0.26 mg/L after 24 hours. In field measurements, water collected from 165 households enrolled in a randomized controlled trial (RCT) of a chlorine and handwashing with soap intervention (Cholera-Hospital-Based-Intervention-for-7-Days [CHoBI7]), we observed significantly higher free chlorine concentrations in the 82 intervention arm households (mean = 1.12 mg/L, standard deviation [SD] = 0.52, range = 0.07-2.6 mg/L) compared with the 83 control households (0.017 mg/L, SD = 0.01, range = 0-0.06 mg/L) (P < 0.001) during spot check visits. These findings suggest that point-of-use chlorine tablets present an effective approach to inactivate V. cholerae from drinking water in households of cholera patients in Dhaka city. This result is consistent with the findings from the RCT of CHoBI7 which found that this intervention led to a significant reduction in symptomatic cholera infections among household members of cholera patients and no stored drinking water samples with detectable V. cholerae. © The American Society of Tropical Medicine and Hygiene.

Mutagenic activities of a chlorination by-product of butamifos, its structural isomer, and their related compounds.

PubMed

Kamoshita, Masahiro; Kosaka, Koji; Endo, Osamu; Asami, Mari; Aizawa, Takako

2010-01-01

The mutagenic activities of 5-methyl-2-nitrophenol (5M2NP), a chlorination by-product of butamifos, its structural isomer 2-methyl-5-nitrophenol (2M5NP), and related compounds were evaluated by the Ames assay. The mutagenic activities of 5M2NP and 2M5NP were negative or not particularly high. However, those of their chlorinated derivatives were increased in Salmonella typhimurium strain TA100 and the overproducer strains YG1026, and YG1029 in the absence and/or presence of a rat liver metabolic activation system (S9 mix), particularly for YG1029. The mutagenic activities of 6-chloro-2-methyl-5-nitrophenol (6C2M5NP) in YG1029 in the absence and presence of S9 mix were 70000 and 110000 revertants mg(-1), respectively. When nitro functions of 6C2M5NP and 4-chloro-5-methyl-2-nitrophenol (4C5M2NP) were reduced to amino functions, their mutagenic activities were markedly decreased. The mutagenic activities of 5M2NP and 4C5M2NP were lower than those of 2M5NP and 6C2M5NP, respectively. Thus, it was shown that substituent position is a key factor for the mutagenic activities of methylnitrophenols (MNPs) and related compounds. The mutagenic activities of the extracts of 2M5NP in chlorination increased early during the reaction time and then decreased. The main chlorination by-product contributing to the mutagenic activities of the extracts of 2M5NP in chlorination was 6C2M5NP. The results of chlorination of 2M5NP suggested that MNPs were present as their dichlorinated derivatives or further chlorination by-products in drinking water. Copyright 2009 Elsevier Ltd. All rights reserved.

Chlorination of Household Drinking Water among Cholera Patients' Households to Prevent Transmission of Toxigenic Vibrio cholerae in Dhaka, Bangladesh: CHoBI7 Trial

PubMed Central

Rashid, Mahamud-ur; George, Christine Marie; Monira, Shirajum; Mahmud, Toslim; Rahman, Zillur; Mustafiz, Munshi; Saif-Ur-Rahman, K. M.; Parvin, Tahmina; Bhuyian, Sazzadul Islam; Zohura, Fatema; Begum, Farzana; Biswas, Shwapon Kumar; Akhter, Shamima; Zhang, Xiaotong; Sack, David; Sack, R. Bradley; Alam, Munirul

2016-01-01

Household members of cholera patients are at a 100 times higher risk of cholera infections than the general population because of shared contaminated drinking water sources and secondary transmission through poor household hygiene practices. In this study, we investigated the bactericidal concentration of free chlorine required to inactivate Vibrio cholerae in household drinking water in Dhaka, Bangladesh. In laboratory experiments, we found that the concentrations of free chlorine required to inactivate 105 colony-forming units (CFU)/mL of V. cholerae serogroups O1 and O139 were 0.1 mg/L and 0.2 mg/L, respectively. The concentration of free chlorine generated by a single chlorine tablet (sodium dichloroisocyanurate [33 mg]) after a 30-minute reaction time in a 10-L sealed vessel containing Dhaka city municipal supply water was 1.8 mg/L; and the concentration declined to 0.26 mg/L after 24 hours. In field measurements, water collected from 165 households enrolled in a randomized controlled trial (RCT) of a chlorine and handwashing with soap intervention (Cholera-Hospital-Based-Intervention-for-7-Days[CHoBI7]), we observed significantly higher free chlorine concentrations in the 82 intervention arm households (mean = 1.12 mg/L, standard deviation [SD] = 0.52, range = 0.07–2.6 mg/L) compared with the 83 control households (0.017 mg/L, SD = 0.01, range = 0–0.06 mg/L) (P < 0.001) during spot check visits. These findings suggest that point-of-use chlorine tablets present an effective approach to inactivate V. cholerae from drinking water in households of cholera patients in Dhaka city. This result is consistent with the findings from the RCT of CHoBI7 which found that this intervention led to a significant reduction in symptomatic cholera infections among household members of cholera patients and no stored drinking water samples with detectable V. cholerae. PMID:27698273

Chlorine gas toxicity from mixture of bleach with other cleaning products--California.

PubMed

1991-09-13

From October 1987 through November 1989, five episodes of chlorine gas exposure with toxicity to at least 14 persons occurred at two state hospitals in California. Each hospital provides inpatient treatment to approximately 1000 forensic psychiatric patients. As part of their rehabilitation programs, selected patients perform cleaning duties under the supervision of janitors or nursing staff. Each incident occurred during the performance of these duties and involved the mixture of bleach (sodium hypochlorite) and a phosphoric acid cleaner by inpatients. This mixture produced chlorine gas and other chemical byproducts (Figure 1a and 1b) and resulted in temporary illness in exposed persons.

Short-lived chlorine-36 in a Ca- and Al-rich inclusion from the Ningqiang carbonaceous chondrite

PubMed Central

Lin, Yangting; Guan, Yunbin; Leshin, Laurie A.; Ouyang, Ziyuan; Wang, Daode

2005-01-01

Excesses of sulfur-36 in sodalite, a chlorine-rich mineral, in a calcium- and aluminum-rich inclusion from the Ningqiang carbonaceous chondrite linearly correlate with chorine/sulfur ratios, providing direct evidence for the presence of short-lived chlorine-36 (with a half-life of 0.3 million years) in the early solar system. The best inferred (36Cl/35Cl)o ratios of the sodalite are ≈5 × 10-6. Different from other short-lived radionuclides, chlorine-36 was introduced into the inclusion by solid-gas reaction during secondary alteration. The alteration reaction probably took place at least 1.5 million years after the first formation of the inclusion, based on the correlated study of the 26Al-26Mg systems of the relict primary minerals and the alteration assemblages, from which we inferred an initial ratio of (36Cl/35Cl)o > 1.6 × 10-4 at the time when calcium- and aluminum-rich inclusions formed. This discovery supports a supernova origin of short-lived nuclides [Cameron, A. G. W., Hoeflich, P., Myers, P. C. & Clayton, D. D. (1995) Astrophys. J. 447, L53; Wasserburg, G. J., Gallino, R. & Busso, M. (1998) Astrophys. J. 500, L189–L193], but presents a serious challenge for local irradiation models [Shu, F. H., Shang, H., Glassgold, A. E. & Lee, T. (1997) Science 277, 1475–1479; Gounelle, M., Shu, F. H., Shang, H., Glassgold, A. E., Rehm, K. E. & Lee, T. (2001) Astrophys. J. 548, 1051–1070]. Furthermore, the short-lived 36Cl may serve as a unique fine-scale chronometer for volatile-rock interaction in the early solar system because of its close association with aqueous and/or anhydrous alteration processes. PMID:15671168

Transformation of bisphenol A in water distribution systems: a pilot-scale study.

PubMed

Li, Cong; Wang, Zilong; Yang, Y Jeffrey; Liu, Jingqing; Mao, Xinwei; Zhang, Yan

2015-04-01

Halogenations of bisphenol A (BPA) in a pilot-scale water distribution system (WDS) of a cement-lined ductile cast iron pipe were investigated. The water in the pilot-scale WDS was chlorinated with a free chlorine concentration of 0.7 mg L(-1) using sodium hypochlorite, and with an initial BPA concentration of 100 μg L(-1) was spiked in the WDS. Halogenated compounds in the BPA experiments were identified using EI/GC/MS and GC. Several BPA congeners, including 2-chlorobisphenol A (MCBPA), dichlorobisphenol A (D2-CBPA), 2,2',6-trichlorobisphenol A (T3CBPA), 2,2',6,6'-tetrachlorobisphenol A (T4CBPA), 2-bromobisphenol A (MBBPA), and bromochlorobisphenol A (MBMCBPA) were found. Moreover, further halogenation yielded other reaction intermediates, including 2,4,6-trichlorophenol (T3CP), dichlorobisphenol A, bromodichlorophenol, and dibromochlorophenol. After halogenation for 120min, most of the abovementioned reaction intermediates disappeared and were replaced by trihalomethanes (THMs). Based on these experimental findings, the halogenation process of BPA oxidation in a WDS includes three stages: (1) halogenation on the aromatic ring; (2) chlorine or bromine substitution followed by cleavage of the α-C bond on the isopropyl moiety with a positive partial charge and a β'-C bond on the benzene moiety with a negative partial charge; and (3) THMs and a minor HAA formation from phenolic intermediates through the benzene ring opening with a chlorine and bromine substitution of the hydrogen on the carbon atoms. The oxidation mechanisms of the entire transformation from BPA to THM/HAA in the WDS were proposed. Copyright © 2014 Elsevier Ltd. All rights reserved.

Potential of isotope analysis (C, Cl) to identify dechlorination mechanisms

NASA Astrophysics Data System (ADS)

Cretnik, Stefan; Thoreson, Kristen; Bernstein, Anat; Ebert, Karin; Buchner, Daniel; Laskov, Christine; Haderlein, Stefan; Shouakar-Stash, Orfan; Kliegman, Sarah; McNeill, Kristopher; Elsner, Martin

2013-04-01

Chloroethenes are commonly used in industrial applications, and detected as carcinogenic contaminants in the environment. Their dehalogenation is of environmental importance in remediation processes. However, a detailed understanding frequently accounted problem is the accumulation of toxic degradation products such as cis-dichloroethylene (cis-DCE) at contaminated sites. Several studies have addressed the reductive dehalogenation reactions using biotic and abiotic model systems, but a crucial question in this context has remained open: Do environmental transformations occur by the same mechanism as in their corresponding in vitro model systems? The presented study shows the potential to close this research gap using the latest developments in compound specific chlorine isotope analysis, which make it possible to routinely measure chlorine isotope fractionation of chloroethenes in environmental samples and complex reaction mixtures.1,2 In particular, such chlorine isotope analysis enables the measurement of isotope fractionation for two elements (i.e., C and Cl) in chloroethenes. When isotope values of both elements are plotted against each other, different slopes reflect different underlying mechanisms and are remarkably insensitive towards masking. Our results suggest that different microbial strains (G. lovleyi strain SZ, D. hafniense Y51) and the isolated cofactor cobalamin employ similar mechanisms of reductive dechlorination of TCE. In contrast, evidence for a different mechanism was obtained with cobaloxime cautioning its use as a model for biodegradation. The study shows the potential of the dual isotope approach as a tool to directly compare transformation mechanisms of environmental scenarios, biotic transformations, and their putative chemical lab scale systems. Furthermore, it serves as an essential reference when using the dual isotope approach to assess the fate of chlorinated compounds in the environment.

Novel mechanism for scavenging of hypochlorite involving a periplasmic methionine-rich peptide and methionine sulfoxide reductase

DOE PAGES

Melnyk, Ryan A.; Youngblut, Matthew D.; Clark, Iain C.; ...

2015-05-12

Reactive chlorine species (RCS) defense mechanisms are important for bacterial fitness in diverse environments. In addition to the anthropogenic use of RCS in the form of bleach, these compounds are also produced naturally through photochemical reactions of natural organic matter and in vivo by the mammalian immune system in response to invading microorganisms. To gain insight into bacterial RCS defense mechanisms, we investigated Azospira suillum strain PS, which produces periplasmic RCS as an intermediate of perchlorate respiration. Our studies identified an RCS response involving an RCS stress-sensing sigma/anti-sigma factor system (SigF/NrsF), a soluble hypochlorite-scavenging methionine-rich periplasmic protein (MrpX), and amore » putative periplasmic methionine sulfoxide reductase (YedY1). We investigated the underlying mechanism by phenotypic characterization of appropriate gene deletions, chemogenomic profiling of barcoded transposon pools, transcriptome sequencing, and biochemical assessment of methionine oxidation. Our results demonstrated that SigF was specifically activated by RCS and initiated the transcription of a small regulon centering around yedY1 and mrpX. A yedY1 paralog ( yedY2) was found to have a similar fitness to yedY1 despite not being regulated by SigF. Markerless deletions of yedY2 confirmed its synergy with the SigF regulon. MrpX was strongly induced and rapidly oxidized by RCS, especially hypochlorite. Our results suggest a mechanism involving hypochlorite scavenging by sacrificial oxidation of the MrpX in the periplasm. Reduced MrpX is regenerated by the YedY methionine sulfoxide reductase activity. The phylogenomic distribution of this system revealed conservation in several Proteobacteria of clinical importance, including uropathogenic Escherichia coli and Brucella spp., implying a putative role in immune response evasion in vivo. In addition, bacteria are often stressed in the environment by reactive chlorine species (RCS) of either anthropogenic or natural origin, but little is known of the defense mechanisms they have evolved. Using a microorganism that generates RCS internally as part of its respiratory process allowed us to uncover a novel defense mechanism based on RCS scavenging by reductive reaction with a sacrificial methionine-rich peptide and redox recycling through a methionine sulfoxide reductase. As a result, this system is conserved in a broad diversity of organisms, including some of clinical importance, invoking a possible important role in innate immune system evasion.« less

Novel mechanism for scavenging of hypochlorite involving a periplasmic methionine-rich peptide and methionine sulfoxide reductase

DOE Office of Scientific and Technical Information (OSTI.GOV)

Melnyk, Ryan A.; Youngblut, Matthew D.; Clark, Iain C.

Reactive chlorine species (RCS) defense mechanisms are important for bacterial fitness in diverse environments. In addition to the anthropogenic use of RCS in the form of bleach, these compounds are also produced naturally through photochemical reactions of natural organic matter and in vivo by the mammalian immune system in response to invading microorganisms. To gain insight into bacterial RCS defense mechanisms, we investigated Azospira suillum strain PS, which produces periplasmic RCS as an intermediate of perchlorate respiration. Our studies identified an RCS response involving an RCS stress-sensing sigma/anti-sigma factor system (SigF/NrsF), a soluble hypochlorite-scavenging methionine-rich periplasmic protein (MrpX), and amore » putative periplasmic methionine sulfoxide reductase (YedY1). We investigated the underlying mechanism by phenotypic characterization of appropriate gene deletions, chemogenomic profiling of barcoded transposon pools, transcriptome sequencing, and biochemical assessment of methionine oxidation. Our results demonstrated that SigF was specifically activated by RCS and initiated the transcription of a small regulon centering around yedY1 and mrpX. A yedY1 paralog ( yedY2) was found to have a similar fitness to yedY1 despite not being regulated by SigF. Markerless deletions of yedY2 confirmed its synergy with the SigF regulon. MrpX was strongly induced and rapidly oxidized by RCS, especially hypochlorite. Our results suggest a mechanism involving hypochlorite scavenging by sacrificial oxidation of the MrpX in the periplasm. Reduced MrpX is regenerated by the YedY methionine sulfoxide reductase activity. The phylogenomic distribution of this system revealed conservation in several Proteobacteria of clinical importance, including uropathogenic Escherichia coli and Brucella spp., implying a putative role in immune response evasion in vivo. In addition, bacteria are often stressed in the environment by reactive chlorine species (RCS) of either anthropogenic or natural origin, but little is known of the defense mechanisms they have evolved. Using a microorganism that generates RCS internally as part of its respiratory process allowed us to uncover a novel defense mechanism based on RCS scavenging by reductive reaction with a sacrificial methionine-rich peptide and redox recycling through a methionine sulfoxide reductase. As a result, this system is conserved in a broad diversity of organisms, including some of clinical importance, invoking a possible important role in innate immune system evasion.« less

Base Oil-Extreme Pressure Additive Synergy in Lubricants

USDA-ARS?s Scientific Manuscript database

Extreme pressure (EP) additives are those containing reactive elements such as sulfur, phosphorus, and chlorine. In lubrication processes that occur under extremely severe conditions (e.g., high pressure and/or slow speed), these elements undergo chemical reactions generating new materials (tribofi...

Synthesis and evaluation of sensitizer drug photorelease chemistry: Micro-optic method applied to singlet oxygen generation and drug delivery

NASA Astrophysics Data System (ADS)

Ghosh, Goutam

This thesis summarizes a new micro-optic method for singlet oxygen generation and sensitizer drug delivery, which include i) synthesis and evaluation of a first generation device for drug delivery from native and fluorinated silica probe tips, ii) synthesis of PEG conjugated sensitizers to study phototoxicity in ovarian cancer cells, and iii) synthesis and evaluation of tris-PEGylated chlorin conjugated fluorinated silica for its future integration into the device to use as a 2nd generation device. A first generation micro-optic device was developed that works by sparging O2 gas and light generating cytotoxic singlet oxygen that cleaves the covalently attached drug (sensitizer) from the probe tip at the distal end of the fiber. The aim is to develop a 1st and 2nd generation device for site specific delivery of photosensitizer and singlet oxygen to overcome the challenges involved in systemic administration of the sensitizer. Synthesis and evaluation of drug (pheophorbide-a) delivery applying micro-optic method from native and fluorinated silica probe tip was achieved. The amount of sensitizer photocleavage depends on the loading level of sensitizer onto the probe tips. We also found that photorelease efficiency depends on the nature of the solvents where sensitizer is photocleaved. For example, no photorelease was observed in an aqueous solvent where sensitizer remained adsorbed to the native silica probe-tip. But, 90% photocleavage was obtained in octanol. A significant amount of photosensitizer (formate ester of pyropheophorbide- a) diffused into the liposome when photocleavage study was carried out in liposome. Substantial increase of photorelease was observed in organic solvent when pyropheophorbide-a (PPa) sensitizer was attached to the partially fluorinated porous Vycor glass. We also explored sensitizer photorelease from the fluorinated silica surface at various temperatures and we found that autocatalytic photorelease happened at room temperature and above. No photorelease was observed at low temperature. Chlorin e6 and its one, two and three short chain methoxy triethylene glycol (PEG) conjugated derivatives were synthesized. A comparative study of photocytotoxicity and cellular uptake between each showed that 17 3,152,131- chlorin e6 methoxy triethylene glycol triester has the highest photocytotoxic activity and uptake by ovarian OVCAR-5 cancer cells. Therefore, we decided to load three short chain PEG conjugated chlorin e6 onto the silica surface through spacer alkene for delivery via a fiber-optic probe tip. In order to load chlorin e6-triPEG ester conjugate, in chapter 4, we explored different synthetic strategies. We have been successful in synthesizing spacer alkene succinate linker conjugated chlorin e6 -tri PEG ester, which was attached to the fiber-optic probe tip. Reactions were carried out in mild conditions to avoid detachment of the PEG ester from the carboxylic acid sites of chlorin. Photocleavage of the triPEG modified fluorinated probe tip system was studied in n-butanol.

Application of an atmospheric pressure sampling mass spectrometer to chlorination reactions

NASA Technical Reports Server (NTRS)

Jacobson, N. S.

1986-01-01

An atmospheric pressure mass spectrometric sampling system, based on a free jet expansion was used to study certain M-Cl-O reactions at high temperatures. The apparatus enables the volatile species from a 1-atm chemical process to be directly identified with a mass spectrometer which operates at approx. 10 to the minus 8th power torr. Studies for both pure metals and alloys are discussed. It is shown that this mass spectrometer system aids in identifying the volatile species, and provides fundamental information on the reaction mechanism.

A Simple Primary Amine Catalyst for Enantioselective α-Hydroxylations and α-Fluorinations of Branched Aldehydes.

PubMed

Witten, Michael R; Jacobsen, Eric N

2015-06-05

A new primary amine catalyst for the asymmetric α-hydroxylation and α-fluorination of α-branched aldehydes is described. The products of the title transformations are generated in excellent yields with high enantioselectivities. Both processes can be performed within short reaction times and on gram scale. The similarity in results obtained in both reactions, combined with computational evidence, implies a common basis for stereoinduction and the possibility of a general catalytic mechanism for α-functionalizations. Promising initial results in α-amination and α-chlorination reactions support this hypothesis.

Impact of wastewater infrastructure upgrades on the urban water cycle: Reduction in halogenated reaction byproducts following conversion from chlorine gas to ultraviolet light disinfection

USGS Publications Warehouse

Barber, Larry B.; Hladik, Michelle; Vajda, Alan M.; Fitzgerald, Kevin C.; Douville, Chris

2015-01-01

The municipal wastewater treatment facility (WWTF) infrastructure of the United States is being upgraded to expand capacity and improve treatment, which provides opportunities to assess the impact of full-scale operational changes on water quality. Many WWTFs disinfect their effluent prior to discharge using chlorine gas, which reacts with natural and synthetic organic matter to form halogenated disinfection byproducts (HDBPs). Because HDBPs are ubiquitous in chlorine-disinfected drinking water and have adverse human health implications, their concentrations are regulated in potable water supplies. Less is known about the formation and occurrence of HDBPs in disinfected WWTF effluents that are discharged to surface waters and become part of the de facto wastewater reuse cycle. This study investigated HDBPs in the urban water cycle from the stream source of the chlorinated municipal tap water that comprises the WWTF inflow, to the final WWTF effluent disinfection process before discharge back to the stream. The impact of conversion from chlorine-gas to low-pressure ultraviolet light (UV) disinfection at a full-scale (68,000 m3 d−1 design flow) WWTF on HDBP concentrations in the final effluent was assessed, as was transport and attenuation in the receiving stream. Nutrients and trace elements (boron, copper, and uranium) were used to characterize the different urban source waters, and indicated that the pre-upgrade and post-upgrade water chemistry was similar and insensitive to the disinfection process. Chlorinated tap water during the pre-upgrade and post-upgrade samplings contained 11 (mean total concentration = 2.7 μg L−1; n=5) and 10 HDBPs (mean total concentration = 4.5 μg L−1), respectively. Under chlorine-gas disinfection conditions 13 HDBPs (mean total concentration = 1.4 μg L−1) were detected in the WWTF effluent, whereas under UV disinfection conditions, only one HDBP was detected. The chlorinated WWTF effluent had greater relative proportions of nitrogenous, brominated, and iodinated HDBPs than the chlorinated tap water. Conversion of the WWTF to UV disinfection reduced the loading of HDBPs to the receiving stream by >90%.

Shelf-Life of Chlorine Solutions Recommended in Ebola Virus Disease Response.

PubMed

Iqbal, Qais; Lubeck-Schricker, Maya; Wells, Emma; Wolfe, Marlene K; Lantagne, Daniele

2016-01-01

In Ebola Virus Disease (EVD) outbreaks, it is widely recommended to wash living things (handwashing) with 0.05% (500 mg/L) chlorine solution and non-living things (surfaces, personal protective equipment, dead bodies) with 0.5% (5,000 mg/L) chlorine solution. Chlorine solutions used in EVD response are primarily made from powdered calcium hypochlorite (HTH), granular sodium dichloroisocyanurate (NaDCC), and liquid sodium hypochlorite (NaOCl), and have a pH range of 5-11. Chlorine solutions degrade following a reaction highly dependent on, and unusually sensitive to, pH, temperature, and concentration. We determined the shelf-life of 0.05% and 0.5% chlorine solutions used in EVD response, including HTH, NaDCC, stabilized NaOCl, generated NaOCl, and neutralized NaOCl solutions. Solutions were stored for 30 days at 25, 30, and 35°C, and tested daily for chlorine concentration and pH. Maximum shelf-life was defined as days until initial concentration fell to <90% of initial concentration in ideal laboratory conditions. At 25-35°C, neutralized-NaOCl solutions (pH = 7) had a maximum shelf-life of a few hours, NaDCC solutions (pH = 6) 2 days, generated NaOCl solutions (pH = 9) 6 days, and HTH and stabilized NaOCl solutions (pH 9-11) >30 days. Models were developed for solutions with maximum shelf-lives between 1-30 days. Extrapolating to 40°C, the maximum predicted shelf-life for 0.05% and 0.5% NaDCC solutions were 0.38 and 0.82 hours, respectively; predicted shelf-life for 0.05% and 0.5% generated NaOCl solutions were >30 and 5.4 days, respectively. Each chlorine solution type offers advantages and disadvantages to responders, as: NaDCC is an easy-to-import high-concentration effervescent powder; HTH is similar, but forms a precipitate that may clog pipes; and, NaOCl solutions can be made locally, but are difficult to transport. We recommend responders chose the most appropriate source chlorine compound for their use, and ensure solutions are stored at appropriate temperatures and used or replaced before expiring.

Impact of wastewater infrastructure upgrades on the urban water cycle: Reduction in halogenated reaction byproducts following conversion from chlorine gas to ultraviolet light disinfection.

PubMed

Barber, Larry B; Hladik, Michelle L; Vajda, Alan M; Fitzgerald, Kevin C; Douville, Chris

2015-10-01

The municipal wastewater treatment facility (WWTF) infrastructure of the United States is being upgraded to expand capacity and improve treatment, which provides opportunities to assess the impact of full-scale operational changes on water quality. Many WWTFs disinfect their effluent prior to discharge using chlorine gas, which reacts with natural and synthetic organic matter to form halogenated disinfection byproducts (HDBPs). Because HDBPs are ubiquitous in chlorine-disinfected drinking water and have adverse human health implications, their concentrations are regulated in potable water supplies. Less is known about the formation and occurrence of HDBPs in disinfected WWTF effluents that are discharged to surface waters and become part of the de facto wastewater reuse cycle. This study investigated HDBPs in the urban water cycle from the stream source of the chlorinated municipal tap water that comprises the WWTF inflow, to the final WWTF effluent disinfection process before discharge back to the stream. The impact of conversion from chlorine-gas to low-pressure ultraviolet light (UV) disinfection at a full-scale (68,000 m(3) d(-1) design flow) WWTF on HDBP concentrations in the final effluent was assessed, as was transport and attenuation in the receiving stream. Nutrients and trace elements (boron, copper, and uranium) were used to characterize the different urban source waters, and indicated that the pre-upgrade and post-upgrade water chemistry was similar and insensitive to the disinfection process. Chlorinated tap water during the pre-upgrade and post-upgrade samplings contained 11 (mean total concentration=2.7 μg L(-1); n=5) and 10 HDBPs (mean total concentration=4.5 μg L(-1)), respectively. Under chlorine-gas disinfection conditions 13 HDBPs (mean total concentration=1.4 μg L(-1)) were detected in the WWTF effluent, whereas under UV disinfection conditions, only one HDBP was detected. The chlorinated WWTF effluent had greater relative proportions of nitrogenous, brominated, and iodinated HDBPs than the chlorinated tap water. Conversion of the WWTF to UV disinfection reduced the loading of HDBPs to the receiving stream by >90%. Copyright © 2015. Published by Elsevier B.V.

Molecular mechanisms in the pyrolysis of unsaturated chlorinated hydrocarbons: formation of benzene rings. 1. Quantum chemical studies.

PubMed

McIntosh, Grant J; Russell, Douglas K

2013-05-23

Analogues of important aromatic growth mechanisms in hydrocarbon pyrolysis and combustion systems are extended to chlorinated systems. We consider the addition of C2Cl2 to both C4Cl3 and C4Cl5 radicals at the M06-2X/6-311+G(3df,3p)//B3LYP/6-31G(d) level of theory, and we demonstrate that these reaction systems have much in common with those of nonchlorinated species. In particular, we find that these radicals appear to lead preferentially to fulvenes, and not to the observed aromatic products, as is found in nonchlorinated systems. We have therefore also considered nonradical C4/C2 channels by way of Diels-Alder cyclization of C4Cl4/C2Cl2 and C4H2Cl2/C2HCl pairs to describe aromatic formation. While the latter pair readily leads to the formation of partially chlorinated benzenes, the fully chlorinated congeners are sterically prohibited from ring closing directly; this leads to a series of novel rearrangement processes which predict the formation of hexachloro-1,5-diene-3-yne, in addition to hexachlorobenzene, in good agreement with experiment. This suggests, for the first time, that facile nonradical routes to aromatic formation are operative in partially and fully chlorinated pyrolysis and combustion systems.

A comparison between minerals-modified glutamate medium and lauryl tryptose lactose broth for the enumeration of Escherichia coli and coliform organisms in water by the multiple tube method.

PubMed Central

1980-01-01

In a multi-laboratory trial, minerals-modified glutamate medium (MMGM) was compared with lauryl tryptose lactose broth (LTLB) in the multiple tube method for the enumeration of coliform organisms, including Escherichia coli, in water. Samples of raw and chlorinated waters yielded a total of 2313 positive tube-reactions with MMGM and 2174 with LTLB. These were interpreted either as E. coli; other coliform organisms; or as false positive reactions. The results at first reading (18 or 24 h) and at 48 h have been analysed statistically in terms of (i) most probable numbers of coliform organisms; (ii) positive reactions and their interpretation; and (iii) whether or not the sample yielded any E. coli or other coliform organisms. All three analyses indicated the same trends. For the detection of E. coli in raw waters LTLB was better than MMGM at 18-24 h, but MMGM was better at 48 h with waters containing small numbers of coliform organisms; for raw waters with greater numbers of organisms, both media performed equally well. Analysis of a subset of samples read at both 18 and 24 h indicated that the superiority of LTLB over MMGM with raw waters disappeared by 24 h. For chlorinated waters, LTLB yielded more positive gas reactions at 18-24 h, but fewer of these were E. coli than with MMGM; at 48 h MMGM was clearly better than LTLB for total coliform organisms including E. coli--especially if the numbers were small. MMGM therefore remains the medium of choice for the detection of E. coli as an indicator of faecal contamination of chlorinated drinking water supplies. It is also better for the detection of small numbers of E. coli in other waters. PMID:6762395

Myeloperoxidase-derived chlorinating species induce protein carbamylation through decomposition of thiocyanate and urea: Novel pathways generating dysfunctional high-density lipoprotein

PubMed Central

Holzer, Michael; Zangger, Klaus; El-Gamal, Dalia; Binder, Veronika; Curcic, Sanja; Konya, Viktoria; Schuligoi, Rufina; Heinemann, Akos; Marsche, Gunther

2013-01-01

Aim Protein carbamylation through cyanate is thought to have a causal role in promoting cardiovascular disease. We recently observed that the phagocyte protein myeloperoxidase (MPO) specifically induces high-density lipoprotein carbamylation, rather than chlorination, in human atherosclerotic lesions, raising the possibility that MPO-derived chlorinating species are involved in cyanate formation. Results Here we show that MPO-derived chlorinating species rapidly decompose the plasma components thiocyanate and urea thereby promoting (lipo)protein carbamylation. Strikingly, the presence of physiologic concentrations of thiocyanate completely prevented MPO-induced 3-chlorotyrosine formation in HDL. Moreover, thiocyanate scavenged a 2.5-fold molar excess of hypochlorous acid, promoting HDL carbamylation, but not chlorination. Carbamylation of HDL resulted in a loss of anti-inflammatory and anti-oxidative properties. Cyanate significantly impaired (i) HDL’s ability to activate lecithin-cholesterol acyltransferase, (ii) the activity of paraoxonase, a major HDL-associated anti-inflammatory enzyme and (iii) the anti-oxidative activity of HDL. Innovation Here we report that MPO-derived chlorinating species preferentially induce protein carbamylation - rather than chlorination - in the presence of physiologically relevant thiocyanate concentrations. Carbamylation of HDL results in the loss of its anti-inflammatory and anti-oxidative activities. Conclusion MPO-mediated decomposition of thiocyanate and/or urea might be a relevant mechanism for generating dysfunctional HDL in human disease. PMID:22462773

In vivo chlorine and sodium MRI of rat brain at 21.1 T.

PubMed

Schepkin, Victor D; Elumalai, Malathy; Kitchen, Jason A; Qian, Chunqi; Gor'kov, Peter L; Brey, William W

2014-02-01

MR imaging of low-gamma nuclei at the ultrahigh magnetic field of 21.1 T provides a new opportunity for understanding a variety of biological processes. Among these, chlorine and sodium are attracting attention for their involvement in brain function and cancer development. MRI of (35)Cl and (23)Na were performed and relaxation times were measured in vivo in normal rat (n = 3) and in rat with glioma (n = 3) at 21.1 T. The concentrations of both nuclei were evaluated using the center-out back-projection method. T 1 relaxation curve of chlorine in normal rat head was fitted by bi-exponential function (T 1a = 4.8 ms (0.7) T 1b = 24.4 ± 7 ms (0.3) and compared with sodium (T 1 = 41.4 ms). Free induction decays (FID) of chlorine and sodium in vivo were bi-exponential with similar rapidly decaying components of [Formula: see text] ms and [Formula: see text] ms, respectively. Effects of small acquisition matrix and bi-exponential FIDs were assessed for quantification of chlorine (33.2 mM) and sodium (44.4 mM) in rat brain. The study modeled a dramatic effect of the bi-exponential decay on MRI results. The revealed increased chlorine concentration in glioma (~1.5 times) relative to a normal brain correlates with the hypothesis asserting the importance of chlorine for tumor progression.

Site-Directed Photoproteolysis of 8-Oxoguanine DNA Glycosylase 1 (OGG1) by Specific Porphyrin-Protein Probe Conjugates: A Strategy to Improve the Effectiveness of Photodynamic Therapy for Cancer

PubMed Central

Conlon, Kimberly A.; Berrios, Miguel

2007-01-01

The specific light-induced, non-enzymatic photolysis of mOGG1 by porphyrin-conjugated or rose bengal-conjugated streptavidin and porphyrin-conjugated or rose bengal-conjugated first specific or secondary anti-IgG antibodies is reported. The porphyrin chlorin e6 and rose bengal were conjugated to either streptavidin, rabbit anti-mOGG1 primary specific antibody fractions or goat anti-rabbit IgG secondary antibody fractions. Under our experimental conditions, visible light of wavelengths greater than 600 nm induced the non-enzymatic degradation of mOGG1 when this DNA repair enzyme either directly formed a complex with chlorin e6-conjugated anti-mOGG1 primary specific antibodies or indirectly formed complexes with either streptavidin-chlorin e6 conjugates and biotinylated first specific anti-mOGG1 antibodies or first specific anti-mOGG1antibodies and chlorin e6-conjugated anti-rabbit IgG secondary antibodies. Similar results were obtained when rose bengal was used as photosensitizer instead of chlorine e6. The rate of the photochemical reaction of mOGG1 site-directed by all three chlorine e6 antibody complexes was not affected by the presence of the singlet oxygen scavenger sodium azide. Site-directed photoactivatable probes having the capacity to generate reactive oxygen species (ROS) while destroying the DNA repair system in malignant cells and tumors may represent a powerful strategy to boost selectivity, penetration and efficacy of current photodynamic (PDT) therapy methodologies. PMID:17251034

Combustion of chlorinated volatile organic compounds (VOCs) using bimetallic chromium-copper supported on modified H-ZSM-5 catalyst.

PubMed

Abdullah, Ahmad Zuhairi; Bakar, Mohamad Zailani Abu; Bhatia, Subhash

2006-02-28

The paper reports on the performance of chromium or/and copper supported on H-ZSM-5(Si/Al = 240) modified with silicon tetrachloride (Cr1.5/SiCl4-Z, Cu1.5/SiCl4-Z and Cr1.0Cu0.5/SiCl4-Z) as catalysts in the combustion of chlorinated VOCs (Cl-VOCs). A reactor operated at a gas hourly space velocity (GHSV) of 32,000 h(-1), a temperature between 100 and 500 degrees C with 2500 ppm of dichloromethane (DCM), trichloromethane (TCM) and trichloroethylene (TCE) is used for activity studies. The deactivation study is conducted at a GHSV of 3800 h(-1), at 400 degrees C for up to 12 h with a feed concentration of 35,000 ppm. Treatment with silicon tetrachloride improves the chemical resistance of H-ZSM-5 against hydrogen chloride. TCM is more reactive compared to DCM but it produces more by-products due to its high chlorine content. The stabilization of TCE is attributed to resonance effects. Water vapor increases the carbon dioxide yield through its role as hydrolysis agent forming reactive carbocations and acting as hydrogen-supplying agent to suppress chlorine-transfer reactions. The deactivation of Cr1.0Cu0.5/SiCl4-Z is mainly due to the chlorination of its metal species, especially with higher Cl/H feed. Coking is limited, particularly with DCM and TCM. In accordance with the Mars-van Krevelen model, the weakening of overall metal reducibility due to chlorination leads to a loss of catalytic activity.

Comprehensive Model for Enhanced Biodegradation of Chlorinated Solvents in Groundwater

NASA Astrophysics Data System (ADS)

Kouznetsova, I.; Gerhard, J. I.; Mao, X.; Robinson, C.; Barry, A. D.; Harkness, M.; Mack, E. E.; Dworatzek, S.

2007-12-01

SABRE (Source Area BioREmediation) is a public/private consortium whose charter is to de-termine if enhanced anaerobic bioremediation can result in effective treatment of chlorinated solvent DNAPL source areas. The focus of this 4-year, $5.7 million research and development project is a field site in the United Kingdom containing TCE DNAPL. A comprehensive numerical model for simulating dehalogenation of chlorinated ethenes has been developed. The model considers the kinetic dissolution of DNAPL and nonaqueous organic amendments, bacterial growth and decay, and the interaction of biological and geochemical reactions that might influence biological activity. The model accounts for inhibitory effects of high chlorin-ated solvent concentrations as well as the link between fermentation and dehalogenation due to dynamic hydrogen concentration (the direct electron donor). In addition to the standard biodegradation pathways, sulphate reduction, mineral dissolution and precipitation kinetics are incorporated. These latter processes influence the soil buffering capacity and thus the net acidity generated. One-dimensional simulations were carried out to reproduce the data from columns packed with site soil and groundwater exhibiting both intermediate (250 mg/L) and near solubility (1100 mg/L) TCE concentrations. The modelling aims were to evaluate the key processes underpinning bioremediation success and provide a tool for investigating field sys-tem sensitivity to site data and design variables. This paper will present the model basis and validation and examine sensitivity to key processes including chlorinated ethene partitioning into soybean oil, sulphate reduction, and geochemical influences such as pH and the role of buffering in highly dechlorinating systems.

NDMA formation during chlorination and chloramination of aqueous diuron solutions.

PubMed

Chen, Wei-Hsiang; Young, Thomas M

2008-02-15

Formation of the potent carcinogen N-nitrosodimethylamine (NDMA) during chlorine disinfection of water containing secondary amines is now generally acknowledged. The phenylurea herbicide diuron is one of the most widely used herbicides in California, has been frequently detected in California's water sources with a transient nature of appearance, and has a structure that suggests it might be an NDMA precursor. This study sought to quantify the potential for NDMA formation from aqueous diuron solutions under varied chlorine and chloramine conditions. NDMA formation was consistently observed even in the absence of added ammonia, which has usually been the source of the nitroso-nitrogen during chloramination of other precursors. It appears that both nitrogen atoms in NDMA are donated by diuron during chlorination in the absence of added ammonia. For a given chlorine and diuron dose, NDMA formation increased in the order OCl- < NH2Cl < NHCl2, a result consistentwith previous NDMAformation studies. Significant quantities of NDMA (170 ng/L) were produced during dichloramination of diuron using a low dichloramine concentration and a diuron concentration at the upper end of typically detected concentrations in California (20 microg/L), suggesting a need for further investigation to accurately assess the human health risks posed by diuron with respect to NDMA formation potential. A reaction pathway is proposed to provide a possible explanation for NDMA formation from diuron during chlorination or chloramination. The findings in this study identify a specific potential precursor of NDMA formation, one that arises from nonpoint sources. This further highlights the difficulties associated with determining the environmental safety of chemicals and their associated byproducts.

A STUDY OF GAS-PHASE MERCURY SPECIATION USING DETAILED CHEMICAL KINETICS

EPA Science Inventory

Mercury (Hg) speciation in combustion-generated flue gas is modeled using a detailed chemical mechanism consisting of 60 reactions and 21 species. This speciation model accounts for chlorination and oxidation of key flue-gas components, including elemental mercury. Results indica...

FORMATION OF CHLORINATED ORGANICS DURING SOLID WASTE COMBUSTION

EPA Science Inventory

The formation mechanisms of the precursors of polychlorinated dibenzo-p-dioxin (PCDD) and polychlorinated dibenzofuran (PCDF) were examined in a laboratory reactor. Both homogeneous and heterogeneous reactions were studied between 200 and 800°C with HCl, Cl₂, and pheno...

COMPOUND-SPECIFIC STABLE ISOTOPE ANALYSIS TO DEMONSTRATE IN-SITU MTBE BIOTRANSFORMATION

EPA Science Inventory

Change of stable isotope composition of organic contaminants (isotopic fractionation) is a useful indicator of biotransformation. Most of applications to date are in the area of chlorinated solvents and recently BTEX, MTBE and TBA. Chemical reactions (biotic- and abiotic transfor...

DEMONSTRATION BULLETIN: GAS-PHASE CHEMICAL REDUCTION - ECO LOGIC INTERNATIONAL, INC.

EPA Science Inventory

The patented Eco Logic Process employs a gas-phase reduction reaction of hydrogen with organic and chlorinated organic compounds at elevated temperatures to convert aqueous and oily hazardous contaminants into a hydrocarbon-rich gas product. After passing through a scrubber, the ...

Integrated Stable Isotope - Reactive Transport Model Approach for Assessment of Chlorinated Solvent Degradation

DTIC Science & Technology

2016-05-01

Certification Program ETH Ethene GC Gas Chromatography GC-IRMS Gas Chromatography Isotope Ratio Mass Spectroscopy H Hydrogen IRMS Isotope...tool for attenuation of chlorinated solvents. The Demonstration Site was Operable Unit 10 at Hill AFB, Utah , a site where groundwater is impacted...techniques. The method involves extraction of the target compounds from environmental sample matrix, followed by separation of the compounds using gas

Bioavailability of Heavy Metals in Soil: Impact on Microbial Biodegradation of Organic Compounds and Possible Improvement Strategies

PubMed Central

Olaniran, Ademola O.; Balgobind, Adhika; Pillay, Balakrishna

2013-01-01

Co-contamination of the environment with toxic chlorinated organic and heavy metal pollutants is one of the major problems facing industrialized nations today. Heavy metals may inhibit biodegradation of chlorinated organics by interacting with enzymes directly involved in biodegradation or those involved in general metabolism. Predictions of metal toxicity effects on organic pollutant biodegradation in co-contaminated soil and water environments is difficult since heavy metals may be present in a variety of chemical and physical forms. Recent advances in bioremediation of co-contaminated environments have focussed on the use of metal-resistant bacteria (cell and gene bioaugmentation), treatment amendments, clay minerals and chelating agents to reduce bioavailable heavy metal concentrations. Phytoremediation has also shown promise as an emerging alternative clean-up technology for co-contaminated environments. However, despite various investigations, in both aerobic and anaerobic systems, demonstrating that metal toxicity hampers the biodegradation of the organic component, a paucity of information exists in this area of research. Therefore, in this review, we discuss the problems associated with the degradation of chlorinated organics in co-contaminated environments, owing to metal toxicity and shed light on possible improvement strategies for effective bioremediation of sites co-contaminated with chlorinated organic compounds and heavy metals. PMID:23676353

Effect of trichlorofluoromethane and molecular chlorine on ozone formation by simulated solar radiation

NASA Technical Reports Server (NTRS)

Bittker, D. A.; Wong, E. L.

1977-01-01

Mixtures of air with either Cl2 or CFCl3 were photolyzed in a reaction chamber by simulated solar radiation. Ozone formation was temporarily inhibited by Cl2 and permanently inhibited by CFCl3. A chemical mechanism including gas phase and wall reactions is proposed to explain these results. The CFCl3 is assumed to be adsorbed on the chamber walls and to poison the sites for Cl destruction.

Chemical Reactions and Properties of Organosilicon Compounds Related to New Materials.

DTIC Science & Technology

1985-10-31

out. The compound behaves like an olefin in some reactions, for in- stance addition of hydrogen halides or chlorine: C1 2 HCI Mes 2 SiCl-SiClMes2...polymers have been synthesized which contain some silicon atoms bonded to hydrogen . These become crosslinked when mixed with substances containing several...and highly efficient catalysts, very small amounts are required in this process. Moreover, photocatalysis using polysilanes produces polymers with

Perchlorate-induced combustion of organic matter with variable molecular weights: Implications for Mars missions

NASA Astrophysics Data System (ADS)

Sephton, Mark A.; Lewis, James M. T.; Watson, Jonathan S.; Montgomery, Wren; Garnier, Carole

2014-11-01

Instruments on the Viking landers and Curiosity rover analyzed samples of Mars and detected carbon dioxide and organic compounds of uncertain origin. Mineral-assisted reactions are leading to uncertainty, particularly those involving perchlorate minerals which thermally decompose to produce chlorine and oxygen which can then react with organic matter to generate organochlorine compounds and carbon dioxide. Although generally considered a problem for interpretation, the release profiles of generated gases can indicate the type of organic matter present. We have performed a set of experiments with perchlorate and organic matter of variable molecular weights. Results indicate that organic susceptibility to thermal degradation and mineral-assisted reactions is related to molecular weight. Low molecular weight organic matter reacts at lower temperatures than its high molecular weight counterparts. The natural occurrence and association of organic matter with differing molecular weights helps to discriminate between contamination (usually low molecular weight organic matter only) and indigenous carbon (commonly low and high molecular weight organic matter together). Our results can be used to provide insights into data returning from Mars.

Identification and characterization of phenylacetonitrile as a nitrogenous disinfection byproduct derived from chlorination of phenylalanine in drinking water.

PubMed

Ma, Xiaoyan; Deng, Jing; Feng, Jiao; Shanaiah, Narasimhamurthy; Smiley, Elizabeth; Dietrich, Andrea M

2016-10-01

Unregulated disinfection byproducts (DBPs), including nitrogenous disinfection byproducts (N-DBPs), originating from chlorination of the precursor amino acid phenylalanine in aqueous systems, were identified in laboratory reactions and distributed tap. The major N-DBP identified was phenylacetonitrile, and minor DBPs of benzyl chloride, phenylacetaldehyde, 2-chlorobenzyl cyanide, and 2, 6-diphenylpyridine were also formed. Phenylacetonitrile was generated through decarboxylation, dechlorination and/or hydrolysis processes. With an aromatic structure, phenylacetonitrile has an unpleasant odor of various descriptors and an odor threshold concentration of 0.2 ppt-v as measured through gas chromatography-olfactometry. The half-life of phenylacetonitrile in reagent water and chlorinated water at 19 °C were 121 h and 792 h, respectively. The occurrence of phenylacetonitrile as an N-DBP in tap water was investigated for the first time; the results revealed that μg/L concentrations were present in nine different distributed drinking waters in China and the United States. Phenylacetonitrile deteriorates the aesthetic quality of drinking water and may present risk due to its prolonged existence in drinking water, especially in the presence of residual chlorine. Copyright © 2016 Elsevier Ltd. All rights reserved.

Derivatization method of free cyanide including cyanogen chloride for the sensitive analysis of cyanide in chlorinated drinking water by liquid chromatography-tandem mass spectrometry.

PubMed

Kang, Hye-In; Shin, Ho-Sang

2015-01-20

A novel derivatization method of free cyanide (HCN + CN(-)) including cyanogen chloride in chlorinated drinking water was developed with d-cysteine and hypochlorite. The optimum conditions (0.5 mM D-cysteine, 0.5 mM hypochlorite, pH 4.5, and a reaction time of 10 min at room temperature) were established by the variation of parameters. Cyanide (C(13)N(15)) was chosen as an internal standard. The formed β-thiocyanoalanine was directly injected into a liquid chromatography-tandem mass spectrometer without any additional extraction or purification procedures. Under the established conditions, the limits of detection and the limits of quantification were 0.07 and 0.2 μg/L, respectively, and the interday relative standard deviation was less than 4% at concentrations of 4.0, 20.0, and 100.0 μg/L. The method was successfully applied to determine CN(-) in chlorinated water samples. The detected concentration range and detection frequency of CN(-) were 0.20-8.42 μg/L (14/24) in source drinking water and 0.21-1.03 μg/L (18/24) in chlorinated drinking water.

Elucidating mechanisms of chlorine toxicity: reaction kinetics, thermodynamics, and physiological implications

PubMed Central

Postlethwait, Edward M.; Matalon, Sadis

2010-01-01

Industrial and transport accidents, accidental releases during recreational swimming pool water treatment, household accidents due to mixing bleach with acidic cleaners, and, in recent years, usage of chlorine during war and in acts of terror, all contribute to the general and elevated state of alert with regard to chlorine gas. We here describe chemical and physical properties of Cl2 that are relevant to its chemical reactivity with biological molecules, including water-soluble small-molecular-weight antioxidants, amino acid residues in proteins, and amino-phospholipids such as phosphatidylethanolamine and phosphatidylserine that are present in the lining fluid layers covering the airways and alveolar spaces. We further conduct a Cl2 penetration analysis to assess how far Cl2 can penetrate the surface of the lung before it reacts with water or biological substrate molecules. Our results strongly suggest that Cl2 will predominantly react directly with biological molecules in the lung epithelial lining fluid, such as low-molecular-weight antioxidants, and that the hydrolysis of Cl2 to HOCl (and HCl) can be important only when these biological molecules have been depleted by direct chemical reaction with Cl2. The results from this theoretical analysis are then used for the assessment of the potential benefits of adjuvant antioxidant therapy in the mitigation of lung injury due to inhalation of Cl2 and are compared with recent experimental results. PMID:20525917

High-resolution Measurements of Gas-Phase Hydrogen Chloride (HCl) in the Atmosphere by Cavity Ring Down Spectroscopy

NASA Astrophysics Data System (ADS)

Hoffnagle, John; Chen, Hongbing; Lee, Jim; Rella, Chris; Kim-Hak, David; Winkler, Renato; Markovic, Milos; Veres, Patrick

2017-04-01

Halogen radical species, such as chlorine and bromine atoms and their oxides, can greatly affect the chemical composition of the troposphere. Hydrogen chloride is the dominant (gas-phase) contributor to the tropospheric chlorine inventory. Real time in situ observations of HCl can provide an important window into the complex photochemical reaction pathways for chlorine in the atmosphere, including heterogeneous reactions on aerosol surfaces. In this work, we report a novel, commercially-available HCl gas-phase analyzer (G2108, Picarro Inc. Santa Clara, CA, USA) based upon Cavity Ring Down Spectroscopy (CRDS) in the near-infrared, and discuss its performance. With a measurement interval of approximately 2 seconds, a precision of better than 40 parts-per-trillion (1 sigma, 30 seconds), and a response time of approximately 1-2 minutes (10 - 90% rise time or 90 - 10% fall time), this analyzer is well-suited for measurements of atmospherically-relevant concentrations of HCl, in both laboratory and field. CRDS provides very stable measurements and low drift, requiring infrequent calibration of the instrument, and can therefore be operated remotely for extended periods of time. In this work we also present results from a laboratory intercomparison of the Picarro G2108 analyzer and an iodide ion time-of-flight Chemical Ionization Mass Spectrometer (CIMS), and the results of the analyzer time response tests.

Disinfection byproduct formation from chlorination of pure bacterial cells and pipeline biofilms.

PubMed

Wang, Jun-Jian; Liu, Xin; Ng, Tsz Wai; Xiao, Jie-Wen; Chow, Alex T; Wong, Po Keung

2013-05-15

Disinfection byproduct (DBP) formation is commonly attributed to the reaction between natural organic matters and disinfectants, yet few have considered the contribution from disinfecting bacterial materials - the essential process of water disinfection. Here, we explored the DBP formation from chlorination and chloramination of Escherichia coli and found that most selected DBPs were detectable, including trihalomethanes, haloacetonitriles, chloral hydrate, chloropicrin, and 1,1,1-trichloro-2-propanone. A positive correlation (P = 0.08-0.09) between DBP formation and the log reduction of E. coli implied that breaking down of bacterial cells released precursors for DBP formation. As Pseudomonas aeruginosa is a dominant bacterial species in pipeline biofilms, the DBP formation potentials (DBPFPs) from its planktonic cells and biofilms were characterized. Planktonic cells formed 7-11 times greater trihalomethanes per carbon of those from biofilms but significantly lower (P < 0.05) chloral hydrate, highlighting the bacterial phenotype's impact on the bacteria-derived DBPFP. Pipe material appeared to affect the DBPFP of bacteria, with 4-28% lower bromine incorporation factor for biofilms on polyvinyl chloride compared to that on galvanized zinc. This study revealed both the in situ disinfection of bacterial planktonic cells in source water and ex situ reaction between biofilms and residual chlorine in pipeline networks as hitherto unknown DBP sources in drinking water. Copyright © 2013 Elsevier Ltd. All rights reserved.

Puerto Rico - 2002 : field studies to resolve aerosol processes.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gaffney, J. S.; Marley, N. A.; Ravelo, R.

1999-10-05

A number of questions remain concerning homogeneous aerosol formation by natural organics interacting with anthropogenic pollutants. For example, chlorine has been proposed as a potential oxidant in the troposphere because of its very high reactivity with a wide range of organics (Finlayson-Pitts, 1993). Indeed, sea salt aerosol in the presence of ozone has been shown to produce chlorine atoms in heterogeneous photochemical reactions under laboratory conditions. Whether chlorine can initiate oxidation of natural organics such as monoterpene hydrocarbons and can generate homogeneous nucleation or condensable material that contributes to aerosol loadings needs to be assessed. The nighttime reactions of ozonemore » and nitrate radical can also result in monoterpene reactions that contribute to aerosol mass. We are currently planning field studies in Puerto Rico to assess these aerosol issues and other atmospheric chemistry questions. Puerto Rico has a number of key features that make it very attractive for a field study of this sort. The principal feature is the island's very regular meteorology and its position in the Caribbean Sea relative to the easterly trade winds. This meteorology and the island's rectangular shape (100 x 35 miles) make it highly suitable for simplification of boundary layer conditions. In addition, the long stretch between Puerto Rico and the nearest pollution sources in Africa and southern Europe make the incoming background air relatively clean and constant. Furthermore, Puerto Rico has approximately 3.5 million people with a very well defined source region and a central area of rain forest vegetation. These features make Puerto Rico an ideal locale for assessing aerosol processes. The following sections describe specific areas of atmospheric chemistry that can be explored during the proposed field study.« less

Thermal dechlorination of PCB-209 over Ca species-doped Fe₂O₃.

PubMed

Su, Guijin; Huang, Linyan; Shi, Ruifang; Liu, Yexuan; Lu, Huijie; Zhao, Yuyang; Yang, Fan; Gao, Lirong; Zheng, Minghui

2016-02-01

Degradation reaction of decachlorobiphenyl (PCB-209) was investigated over the synthesized Ca species-doped Fe2O3 at 300 °C. The 1%Ca-Fe2O3 exhibited the highest activity among the four catalysts prepared with the pseudo-first order reaction at k(obs) = 0.103 min(-1). PCB-207, PCB-197, PCB-176, PCB-184, PCB-150, PCB-136, PCB-148, PCB-104, PCB-96, PCB-54, PCB-19, PCB-4 and PCB-1 were identified as the dominant isomers in their respective nonachlorobiphenyl (NonaCB) to monochlorobiphenyl (MonoCB) homologue groups. Analysis of the hydrodechlorination products indicated that dechlorination was much more favored on meta- and para-than on ortho-positions. The formation of significantly predominant NonaCB and octachlorobiphenyl (OctaCB) isomers was attributed to lower energy principles and to the 90° dihedral angles of two aromatic rings which prevented the hydrodechlorination at ortho-positions. When the number of chlorine atoms is not more than 7, the steric effect supports the formation of predominant PCB isomers having chlorines at four ortho-positions. During the dechlorination of tetrachlorobiphenyl (TetraCB) formed to generate monochlorobiphenyl (MonoCB) isomers, the chlorine atoms fully substituted at the ortho-positions have to be successively removed, with the first two dechlorinations preferentially occurring at the two different benzene rings. This is dissimilar to that of octachloronaphthalene (PCN-75) in which the hydrodechlorination reaction happened preferentially at ortho-position due to the existence of steric effects. The opposite roles of the steric effect in ortho-position between PCB-209 and PCN-75 might be due to the difference of the π-conjugated plane caused by the dihedral angle of 90° and 0° of the two aromatic rings. Copyright © 2015 Elsevier Ltd. All rights reserved.

Molecular mechanisms in the pyrolysis of unsaturated chlorinated hydrocarbons: formation of benzene rings. 2. Experimental and kinetic modeling studies.

PubMed

McIntosh, Grant J; Russell, Douglas K

2013-05-23

The mechanism of formation of benzene rings during the pyrolysis of dichloro- and trichloroethylenes has been investigated by the method of laser powered homogeneous pyrolysis coupled with product analysis by gas chromatography. Additionally, selected (co)pyrolyses between the chlorinated ethylenes, CH2Cl2, C4Cl4, C4Cl6, and C2H2 have been performed to explicitly probe the roles of 2C3 and C4/C2 reaction pairs in aromatic growth. The presence of odd-carbon products in neat C4Cl6 pyrolyses indicates that 2C3 processes are operative in these systems; however, comparison with product yields from C2HCl3 suggests that C4/C2 processes dominate most other systems. This is further evidenced by an absence of C3 and other odd-carbon species in (co)pyrolyses with dichloromethane which should seed C3-based growth. The reactions of perchlorinated C4 species C4Cl5, C4Cl3, and C4Cl4 with C2Cl2 were subsequently explored through extensive kinetic simulations of the possible reaction pathways based on previous kinetic models and the exhaustive quantum chemical investigations of our preceding work. The experimental and theoretical results strongly suggest that, at moderate temperatures, aromatic ring formation from chlorinated ethylenes normally follows a Diels-Alder coupling of C4 and C2 molecular units followed by internal shifts; the one exception is the C4Cl4 + C2Cl2 system, where steric factors lead to the formation of nonaromatic products. There is little evidence for radical-based routes in these systems.

Organotrichlorogermane synthesis by the reaction of elemental germanium, tetrachlorogermane and organic chloride via dichlorogermylene intermediate.

PubMed

Okamoto, Masaki; Asano, Takuya; Suzuki, Eiichi

2004-08-07

Organotrichlorogermanes were synthesized by the reaction of elemental germanium, tetrachlorogermane and organic chlorides, methyl, propyl, isopropyl and allyl chlorides. Dichlorogermylene formed by the reaction of elemental germanium with tetrachlorogermane was the reaction intermediate, which was inserted into the carbon-chlorine bond of the organic chloride to give organotrichlorogermane. When isopropyl or allyl chloride was used as an organic chloride, organotrichlorogermane was formed also in the absence of tetrachlorogermane. These chlorides were converted to hydrogen chloride, which subsequently reacted with elemental germanium to give the dichlorogermylene intermediate. The reaction of elemental germanium, tetrachlorogermane and organic chlorides provides a simple and easy method for synthesizing organotrichlorogermanes, and all the raw materials are easily available.

Microelectrode investigation of the reactions between metallic pipe materials and monochloramine

EPA Science Inventory

Water quality parameters (i.e., pH, dissolved oxygen [DO], and phosphate) are known to impact metal reactivity with disinfectants and therefore corrosion and metals release into drinking water supplies. With various water utilities switching from free chlorine to chloramines for ...

Simulations and Experiments Reveal the Relative Significance of the Free Chlorine/Nitrite Reaction in Chloraminated Systems

EPA Science Inventory

Nitrification can be a problem in distribution systems where chloramines are used as secondary disinfectants. A very rapid monochloramine residual loss is often associated with the onset of nitrification. During nitrification, ammonia-oxidizing bacteria biologically oxidize fre...

Relative Importance of Nitrite Oxidation by Hypochlorous Acid under Chloramination Conditions

EPA Science Inventory

The importance of nitrite’s oxidation by tree chlorine under chloramination conditions was evaluated using batch kinetic experiments and a chloramine model implemented into the computer program AWUASIM. The experimental data was best represented with the inclusion of a reaction b...

Chemistry, Toxicity and Health Risk Assessment of Drinking Water Disinfection ByProducts

EPA Science Inventory

Disinfection byproducts (DBPs) are formed by the reaction of oxidizing chemicals (such as chlorine, ozone and chloramines) used to control waterborne pathogens with natural organic material and other substances in water. DBP mixture composition varies as a function of geographic ...

40 CFR 61.51 - Definitions.

Code of Federal Regulations, 2013 CFR

2013-07-01

... produce chlorine gas, hydrogen gas, and alkali metal hydroxide. (f) Mercury chlor-alkali electrolyzer... converted to alkali metal hydroxide, mercury, and hydrogen gas in a short-circuited, electrolytic reaction. (h) Hydrogen gas stream means a hydrogen stream formed in the chlor-alkali cell denuder. (i) End box...

40 CFR 61.51 - Definitions.

Code of Federal Regulations, 2011 CFR

2011-07-01

... produce chlorine gas, hydrogen gas, and alkali metal hydroxide. (f) Mercury chlor-alkali electrolyzer... converted to alkali metal hydroxide, mercury, and hydrogen gas in a short-circuited, electrolytic reaction. (h) Hydrogen gas stream means a hydrogen stream formed in the chlor-alkali cell denuder. (i) End box...

40 CFR 61.51 - Definitions.

Code of Federal Regulations, 2010 CFR

2010-07-01

... produce chlorine gas, hydrogen gas, and alkali metal hydroxide. (f) Mercury chlor-alkali electrolyzer... converted to alkali metal hydroxide, mercury, and hydrogen gas in a short-circuited, electrolytic reaction. (h) Hydrogen gas stream means a hydrogen stream formed in the chlor-alkali cell denuder. (i) End box...

40 CFR 61.51 - Definitions.

Code of Federal Regulations, 2014 CFR

2014-07-01

... produce chlorine gas, hydrogen gas, and alkali metal hydroxide. (f) Mercury chlor-alkali electrolyzer... converted to alkali metal hydroxide, mercury, and hydrogen gas in a short-circuited, electrolytic reaction. (h) Hydrogen gas stream means a hydrogen stream formed in the chlor-alkali cell denuder. (i) End box...

40 CFR 61.51 - Definitions.

Code of Federal Regulations, 2012 CFR

2012-07-01

... produce chlorine gas, hydrogen gas, and alkali metal hydroxide. (f) Mercury chlor-alkali electrolyzer... converted to alkali metal hydroxide, mercury, and hydrogen gas in a short-circuited, electrolytic reaction. (h) Hydrogen gas stream means a hydrogen stream formed in the chlor-alkali cell denuder. (i) End box...

The Formation of Trihalomethanes.

ERIC Educational Resources Information Center

Trussell, R. Rhodes; Umphres, Mark D.

1978-01-01

Reviewed are a number of factors important in the formation of trihalomethanes (THM) including the nature of aquatic humus and the influences of preozonation, bromide, pH, and chlorine. A brief investigation is also conducted into the kinetics of the THM reaction. Several major research needs are represented. (CS)

IRIS TOXICOLOGICAL REVIEW AND SUMMARY DOCUMENTS FOR 1,4 - DIOXANE

EPA Science Inventory

1,4 -Dioxane is a cyclic ether that is primarily utilized for industrial applications. These applications include 1,4 -dioxane as a solvent, reaction medium, wetting, degreasing, and dispersing agent, and for stabilization of chlorinated solvents (e.g. 1,1,1 -trichloroethane). ...

Oxidative decomposition of aromatic hydrocarbons by electron beam irradiation

NASA Astrophysics Data System (ADS)

Han, Do-Hung; Stuchinskaya, Tatiana; Won, Yang-Soo; Park, Wan-Sik; Lim, Jae-Kyong

2003-05-01

Decomposition of aromatic volatile organic compounds (VOCs) under electron beam irradiation was studied in order to examine the kinetics of the process, to characterize the reaction product distribution and to develop a process of waste gas control technology. Toluene, ethylbenzene, o-, m-, p-xylenes and chlorobenzene were used as target materials. The experiments were carried out at doses ranging from 0.5 to 10 kGy, using a flow reactor utilized under electron beam irradiation. Maximum degrees of decomposition carried out at 10 kGy in air environment were 55-65% for “non-chlorinated” aromatic VOC and 85% for chlorobenzene. It was found that a combination of aromatic pollutants with chlorobenzene would considerably increase the degradation value up to nearly 50% compared to the same compounds in the absence of chlorine groups. Based on our experimental observation, the degradation mechanism of the aromatic compounds combined with chloro-compound suggests that a chlorine radical, formed from EB irradiation, induces a chain reaction, resulting in an accelerating oxidative destruction of aromatic VOCs.

Modelling of spatial contaminant probabilities of occurrence of chlorinated hydrocarbons in an urban aquifer.

PubMed

Greis, Tillman; Helmholz, Kathrin; Schöniger, Hans Matthias; Haarstrick, Andreas

2012-06-01

In this study, a 3D urban groundwater model is presented which serves for calculation of multispecies contaminant transport in the subsurface on the regional scale. The total model consists of two submodels, the groundwater flow and reactive transport model, and is validated against field data. The model equations are solved applying finite element method. A sensitivity analysis is carried out to perform parameter identification of flow, transport and reaction processes. Coming from the latter, stochastic variation of flow, transport, and reaction input parameters and Monte Carlo simulation are used in calculating probabilities of pollutant occurrence in the domain. These probabilities could be part of determining future spots of contamination and their measure of damages. Application and validation is exemplarily shown for a contaminated site in Braunschweig (Germany), where a vast plume of chlorinated ethenes pollutes the groundwater. With respect to field application, the methods used for modelling reveal feasible and helpful tools to assess natural attenuation (MNA) and the risk that might be reduced by remediation actions.

Halogen and Sulfur Reactions Relevant to Polar Chemistry

NASA Technical Reports Server (NTRS)

Wine, Paul H.; Nicovich, J. Michael; Stickel, Robert E.; Zhao, Z.; Shackleford, C. J.; Kreutter, K. D.; Daykin, E. P.; Wang, S.

1997-01-01

It is widely hypothesized that catalytic cycles involving BrO(x) species play an important role in the episodic destruction of ground-level ozone which is observed in the springtime Arctic boundary layer, although the exact mechanism for production of BrO(x) radicals remains an open question [Barrie et al., Bottenheim et al.; Finlayson-Pitts et al., McConnell et al.] The critical evidence linking ozone depletion with BrO(x) chemistry is an observed negative correlation between ozone and filterable bromine [Bottenheim et al., Kieser et al.] In a recent field study of springtime Arctic boundary layer chemistry [Kieser et al.] ozone concentrations and ethane concentrations were found to be correlated; this observation suggests chlorine atoms (which react rapidly with ethane) may also be an important catalyst for ozone destruction under springtime Arctic conditions.

NDMA formation by chloramination of ranitidine: kinetics and mechanism.

PubMed

Roux, Julien Le; Gallard, Hervé; Croué, Jean-Philippe; Papot, Sébastien; Deborde, Marie

2012-10-16

The kinetics of decomposition of the pharmaceutical ranitidine (a major precursor of NDMA) during chloramination was investigated and some decomposition byproducts were identified by using high performance liquid chromatography coupled with mass spectrometry (HPLC-MS). The reaction between monochloramine and ranitidine followed second order kinetics and was acid-catalyzed. Decomposition of ranitidine formed different byproducts depending on the applied monochloramine concentration. Most identified products were chlorinated and hydroxylated analogues of ranitidine. In excess of monochloramine, nucleophilic substitution between ranitidine and monochloramine led to byproducts that are critical intermediates involved in the formation of NDMA, for example, a carbocation formed from the decomposition of the methylfuran moiety of ranitidine. A complete mechanism is proposed to explain the high formation yield of NDMA from chloramination of ranitidine. These results are of great importance to understand the formation of NDMA by chloramination of tertiary amines.

Formation of 3-monochloro-1,2-propanediol (3-MCPD) di- and monoesters from tristearoylglycerol (TSG) and the potential catalytic effect of Fe²⁺ and Fe³⁺.

PubMed

Zhang, Zhongfei; Gao, Boyan; Zhang, Xiaowei; Jiang, Yuanrong; Xu, Xuebing; Yu, Liangli Lucy

2015-02-18

This study investigated whether and how triacylglycerol (TAG) may serve as a precursor for 3-monochloro-1,2-propanediol (3-MCPD) fatty acid ester formation using tristearoylglycerol (TSG). TSG was reacted with inorganic chloride compounds including NaCl, KCl, FeCl2, CuCl2, ZnCl2, FeCl3 and dry HCl, or organic chlorine compound lindane at different temperatures. Only FeCl2 and FeCl3 were able to form 3-MCPD esters from TSG. Further electron spin resonance (ESR) determination of TSG, Fe2(SO4)3 and 5,5-dimethylpyrroline-N-oxide (DMPO) reactions revealed potential of Fe ion in promoting free radical generations under the experimental conditions. To further confirm the effect of Fe ion, chelating agent (EDTA-2Na) was added to the model reactions. The results showed for the first time that EDTA-2Na was able to reduce the generation of 3-MCPD esters. In addition, FT-IR examination indicated a possible involvement of a carbonyl group during the reaction. Taking all the observations together, the possible mechanisms, involving the formation of either a cyclic acyloxonium or a glycidol ester radical intermediate, were proposed for generating 3-MCPD fatty acid di- and mono- esters from TAG under a high temperature and low moisture condition, as well as the coformation of glycidol esters. The results from this study may be useful for reducing the level of 3-MCPD esters and related toxicants in the refined edible oils and food products.

An Overview of the SOLVE-THESEO 2000 Campaign

NASA Technical Reports Server (NTRS)

Newman, Paul A.; Harris, Neil R. P.; Adriani, Alberto; Amanatidis, Georgios T.; Anderson, James G.; Braathen, Geir O.; Brune, William H.; Carslaw, Kenneth S.; Craig, Michael T.; DeCola, Philip E.

2001-01-01

Between November 1999 and April 2000, two major field experiments, the SAGE III Ozone Loss and Validation Experiment (SOLVE) and the Third European Stratospheric Experiment on Ozone (THESEO 2000), collaborated to form the largest field campaign yet mounted to study Arctic ozone loss. This international campaign involved more than 500 scientists from over 20 countries spread across the high and mid-latitudes of the northern hemisphere. The main scientific aims of SOLVE-THESEO 2000 were to study (a) the processes leading to ozone loss in the Arctic vortex and (b) the effect on ozone amounts over northern mid-latitudes. The campaign included satellites, heavy lift balloon launches, 6 different aircraft, ground stations, and scores of ozone-sonde. Campaign activities were principally conducted in 3 intensive measurement phases centered on early December 1999, late January 2000, and early March 2000. Observations made during the campaign showed that temperatures were unusually cold in the polar lower stratosphere over the course of the 1999-2000 winter. These cold temperatures resulted in the formation of extensive polar stratospheric clouds (PSCs) across the Arctic. Heterogeneous chemical reactions on the surfaces of the PSC particles produced high levels of reactive chlorine within the polar vortex by early January. This reactive chlorine catalytically destroyed about 60% of the ozone in a layer near 20 km between late January and mid-March 2000.

Rate constants for reactions of ClO/x/ of atmospheric interest

NASA Technical Reports Server (NTRS)

Watson, R. T.

1977-01-01

Chemical kinetics measurements on 82 gas phase reactions of chlorine containing species are reviewed. Recommended rate constants are given. The principal species of interest are Cl, Cl2, ClO, Cl2O, ClOO, OClO, CINO, HCl and halo derivatives of methane and ethane. Absorption spectra are given for 21 species. In addition the chemical kinetics methods used to obtain these data are discussed with regard to their applicability and reliability.

Highly Stereoselective Intermolecular Haloetherification and Haloesterification of Allyl Amides

PubMed Central

Soltanzadeh, Bardia; Jaganathan, Arvind; Staples, Richard J.

2016-01-01

An organocatalytic and highly regio-, diastereo-, and enantioselective intermolecular haloetherification and haloesterification reaction of allyl amides is reported. A variety of alkene substituents and substitution patterns are compatible with this chemistry. Notably, electronically unbiased alkene substrates exhibit exquisite regio- and diastereoselectivity for the title transformation. We also demonstrate that the same catalytic system can be used in both chlorination and bromination reactions of allyl amides with a variety of nucleophiles with little or no modification. PMID:26110812

Combined Excitatory and Inhibitory Coupling in a 1-D Array of Belousov-Zhabotinsky Droplets

DTIC Science & Technology

2014-01-01

with numerical chemical models of the BZ reaction in which components that participate in the excitatory (bromine dioxide and bromous acid) and...verify the transport through the fluorinated oil of chlorine dioxide and several weak acids, including malonic acid. 1. Introduction Recent studies1...finite element model (COMSOLs) of the reaction - diffusion equation in 1-D, 2-D and 3-D, where each drop is modeled as a point, disk or sphere

Chemical Stockpile Disposal Program. Chemical Agent and Munition Disposal. Summary of the U.S. Army’s Experience

DTIC Science & Technology

1987-09-21

a difficult process to control; continuous generation of acidic products results in the possibility of side reactions and in gaseous by- products . Ion...dissolved in hydrochlorlo acid. The acid chlorination forms non-toxic reaction products as per Figure 3-3. (2) To initiate the neutralization process ...et al, "Emission and Control of By- Products From Hazarduus Waste Combustion Processes ", Land Disposal, Remedial Action, Incineration and Treatment

In vivo chlorine and sodium MRI of rat brain at 21.1 T

PubMed Central

Elumalai, Malathy; Kitchen, Jason A.; Qian, Chunqi; Gor’kov, Peter L.; Brey, William W.

2017-01-01

Object MR imaging of low-gamma nuclei at the ultrahigh magnetic field of 21.1 T provides a new opportunity for understanding a variety of biological processes. Among these, chlorine and sodium are attracting attention for their involvement in brain function and cancer development. Materials and methods MRI of 35Cl and 23Na were performed and relaxation times were measured in vivo in normal rat (n = 3) and in rat with glioma (n = 3) at 21.1 T. The concentrations of both nuclei were evaluated using the center-out back-projection method. Results T1 relaxation curve of chlorine in normal rat head was fitted by bi-exponential function (T1a = 4.8 ms (0.7) T1b = 24.4 ± 7 ms (0.3) and compared with sodium (T1 = 41.4 ms). Free induction decays (FID) of chlorine and sodium in vivo were bi-exponential with similar rapidly decaying components of T2a∗=0.4 ms and T2a∗=0.53 ms, respectively. Effects of small acquisition matrix and bi-exponential FIDs were assessed for quantification of chlorine (33.2 mM) and sodium (44.4 mM) in rat brain. Conclusion The study modeled a dramatic effect of the bi-exponential decay on MRI results. The revealed increased chlorine concentration in glioma (~1.5 times) relative to a normal brain correlates with the hypothesis asserting the importance of chlorine for tumor progression. PMID:23748497

MEASURING AND MODELING DISINFECTION WALL DEMAND IN METALLIC PIPES

EPA Science Inventory

A field test procedure was developed and implemented in Detroit to estimate chlorine loss due to wall demand in older 6" (152 mm) and 8" (203 mm) diameter, unlined cast iron pipes. The test results produced extremely high wall reaction rate coefficients that increased significan...

Simulations and Experiments Reveal the Relative Significance of the Free Chlorine/Nitrite Reaction in Chloraminated Systems - slides

EPA Science Inventory

Nitrification can be a problem in distribution systems where chloramines are used as secondary disinfectants. A very rapid monochloramine residual loss is often associated with the onset of nitrification. During nitrification, ammonia-oxidizing bacteria biologically oxidize fre...

INTEGRATED TECHNOLOGY-BASED TOXICOLOGY STUDIES ON DRINKING WATER DISINFECTION BYPRODUCTS (DBPS)

EPA Science Inventory

DBPs are formed by reactions of chemical disinfectants with natural organic matter in the source water. Although more than 300 DBPs are known, many remain unidentified; for chlorination, known DBPs account for ~50% of the mass of total organic halide. Toxicological evaluation o...

Simultaneous determination of polycyclic aromatic hydrocarbons and their chlorination by-products in drinking water and the coatings of water pipes by automated solid-phase microextraction followed by gas chromatography-mass spectrometry.

PubMed

Tillner, Jocelyn; Hollard, Caroline; Bach, Cristina; Rosin, Christophe; Munoz, Jean-François; Dauchy, Xavier

2013-11-08

In this study, an automated method for the simultaneous determination of polycyclic aromatic hydrocarbons (PAHs) and their chlorination by-products in drinking water was developed based on online solid-phase microextraction-gas chromatography-mass spectrometry. The main focus was the optimisation of the solid-phase microextraction step. The influence of the agitation rate, type of fibre, desorption time, extraction time, extraction temperature, desorption temperature, and solvent addition was examined. The method was developed and validated using a mixture of 17 PAHs, 11 potential chlorination by-products (chlorinated and oxidised PAHs) and 6 deuterated standards. The limit of quantification was 10 ng/L for all target compounds. The validated method was used to analyse drinking water samples from three different drinking water distribution networks and the presumably coal tar-based pipe coatings of two pipe sections. A number of PAHs were detected in all three networks although individual compositions varied. Several PAH chlorination by-products (anthraquinone, fluorenone, cyclopenta[d,e,f]phenanthrenone, 3-chlorofluoranthene, and 1-chloropyrene) were also found, their presence correlating closely with that of their respective parent compounds. Their concentrations were always below 100 ng/L. In the coatings, all PAHs targeted were detected although concentrations varied between the two coatings (76-12,635 mg/kg and 12-6295 mg/kg, respectively). A number of chlorination by-products (anthraquinone, fluorenone, cyclopenta[d,e,f]phenanthrenone, 3-chlorofluoranthene, and 1-chloropyrene) were also detected (from 40 to 985 mg/kg), suggesting that the reaction of PAHs with disinfectant agents takes place in the coatings and not in the water phase after migration. Copyright © 2013 Elsevier B.V. All rights reserved.

Modeling the formation of N-nitrosodimethylamine (NDMA) from the reaction of natural organic matter (NOM) with monochloramine.

PubMed

Chen, Zhuo; Valentine, Richard L

2006-12-01

This paper presents mechanistic studies on the formation of NDMA, a newly identified chloramination disinfection byproduct, from reactions of monochloramine with natural organic matter. A kinetic model was developed to validate proposed reactions and to predict NDMA formation in chloraminated water during the time frame of 1-5 days. This involved incorporating NDMA formation reactions into an established comprehensive model describing the oxidation of humic-type natural organic matter by monochloramine. A rate-limiting step involving the oxidation of NOM is theorized to control the rate of NDMA formation which is assumed to be proportional to the rate of NOM oxidized by monochloramine. The applicability of the model to describe NDMA formation in the presence of three NOM sources over a wide range in water quality (i.e., pH, DOC, and ammonia concentrations) was evaluated. Results show that with accurate measurement of monochloramine demand for a specific supply, NDMA formation could be modeled over an extended range of experimental conditions by considering a single NOM source-specific value of thetaNDMA, a stoichiometric coefficient relating the amount of NDMA produced to the amount of NOM oxidized, and several kinetic parameters describing NOM oxidation. Furthermore, the oxidation of NOM is the rate-limiting step governing NDMA formation. This suggests that NDMA formation over a 1-5 day time frame may be estimated from information on the chloramine or free chlorine demand of the NOM and the source-specific linear relationship between this demand and NDMA formation. Although the proposed model has not yet been validated for shorter time periods that may better characterize the residence time in some distribution systems, the improved understanding of the important reactions governing NDMA formation and the resulting model should benefit the water treatment industry as a tool in developing strategies that minimize NDMA formation.

Bioanalytical assessment of the formation of disinfection byproducts in a drinking water treatment plant.

PubMed

Neale, Peta A; Antony, Alice; Bartkow, Michael E; Farré, Maria José; Heitz, Anna; Kristiana, Ina; Tang, Janet Y M; Escher, Beate I

2012-09-18

Disinfection of drinking water is the most successful measure to reduce water-borne diseases and protect health. However, disinfection byproducts (DBPs) formed from the reaction of disinfectants such as chlorine and monochloramine with organic matter may cause bladder cancer and other adverse health effects. In this study the formation of DBPs through a full-scale water treatment plant serving a metropolitan area in Australia was assessed using in vitro bioanalytical tools, as well as through quantification of halogen-specific adsorbable organic halogens (AOXs), characterization of organic matter, and analytical quantification of selected regulated and emerging DBPs. The water treatment train consisted of coagulation, sand filtration, chlorination, addition of lime and fluoride, storage, and chloramination. Nonspecific toxicity peaked midway through the treatment train after the chlorination and storage steps. The dissolved organic matter concentration decreased after the coagulation step and then essentially remained constant during the treatment train. Concentrations of AOXs increased upon initial chlorination and continued to increase through the plant, probably due to increased chlorine contact time. Most of the quantified DBPs followed a trend similar to that of AOXs, with maximum concentrations observed in the final treated water after chloramination. The mostly chlorinated and brominated DBPs formed during treatment also caused reactive toxicity to increase after chlorination. Both genotoxicity with and without metabolic activation and the induction of the oxidative stress response pathway showed the same pattern as the nonspecific toxicity, with a maximum activity midway through the treatment train. Although measured effects cannot be directly translated to adverse health outcomes, this study demonstrates the applicability of bioanalytical tools to investigate DBP formation in a drinking water treatment plant, despite bioassays and sample preparation not yet being optimized for volatile DBPs. As such, the bioassays are useful as monitoring tools as they provide sensitive responses even at low DBP levels.

Perform Tests and Document Results and Analysis of Oxide Layer Effects and Comparisons

DOE Office of Scientific and Technical Information (OSTI.GOV)

Collins, E. D.; DelCul, G. D.; Spencer, B. B.

2014-08-30

During the initial feasibility test using actual used nuclear fuel (UNF) cladding in FY 2012, an incubation period of 30–45 minutes was observed in the initial dry chlorination. The cladding hull used in the test had been previously oxidized in a dry air oxidation pretreatment prior to removal of the fuel. The cause of this incubation period was attributed to the resistance to chlorination of an oxide layer imparted by the dry oxidation pretreatment on the cladding. Subsequently in 2013, researchers at the Korea Atomic Energy Institute (KAERI) reported on their chlorination study [R1] on ~9-gram samples of unirradiated ZirloTMmore » cladding tubes that had been previously oxidized in air at 500oC for various time periods to impart oxide layers of varying thickness. In early 2014, discussions with Indefinite Delivery, Indefinite Quantity (IDIQ) contracted technical consultants from Westinghouse described their previous development (and patents) [R2] on methods of chemical washing to remove some or all of the hydrous oxide layer imparted on UNF cladding during irradiation in light water reactors (LWRs) . Thus, the Oak Ridge National Laboratory (ORNL) study, described herein, was planned to extend the KAERI study on the effects of anhydrous oxide layers, but on larger ~100-gram samples of unirradiated zirconium alloy cladding tubes, and to investigate the effects of various methods of chemical pretreatment prior to chlorination with 100% chlorine on the average reaction rates and Cl2 usage efficiencies.« less

Investigating chloroperoxidase-catalyzed formation of chloroform from humic substances using stable chlorine isotope analysis.

PubMed

Breider, Florian; Hunkeler, Daniel

2014-01-01

Chloroperoxidase (CPO) is suspected to play an important role in the biosynthesis of natural chloroform. The aims of the present study are to evaluate the variability of the δ(37)Cl value of naturally produced chloroform and to better understand the reaction steps that control the chlorine isotope signature of chloroform. The isotope analyses have shown that the chlorination of the humic substances (HS) in the presence of high H3O(+) and Cl(-) concentrations induces a large apparent kinetic isotope effect (AKIE = 1.010-1.018) likely associated with the transfer of chlorine between two heavy atoms, whereas in the presence of low H3O(+) and Cl(-) concentrations, the formation of chloroform induces a smaller AKIE (1.005-1.006) likely associated with the formation of an HOCl-ferriprotoporphyrin IX intermediate. As the concentration of H3O(+) and Cl(-) in soils are generally at submillimolar levels, the formation of the HOCl-ferriprotoporphyrin IX intermediate is likely rate-limiting in a terrestrial environment. Given that the δ(37)Cl values of naturally occurring chloride tend to range between -1 and +1‰, the δ(37)Cl value of natural chloroform should vary between -5‰ and -8‰. As the median δ(37)Cl value of industrial chloroform is -3.0‰, the present study suggests that chlorine isotopic composition of chloroform might be used to discriminate industrial and natural sources in the environment.

A Simple Primary Amine Catalyst for Enantioselective α-Hydroxylations and α-Fluorinations of Branched Aldehydes

PubMed Central

Witten, Michael R.; Jacobsen, Eric N.

2016-01-01

A new primary amine catalyst for the asymmetric α-hydroxylation and α-fluorination of α-branched aldehydes is described. The products of the title transformations are generated in excellent yields and with high enantioselectivities. Both processes can be performed within short reaction times and on gram scale. The similarity in the results obtained in both reactions, combined with computational evidence, implies a common basis for stereoinduction and the possibility of a general catalytic mechanism for α-functionalizations. Promising initial results in α-amination and α-chlorination reactions support this hypothesis. PMID:25952578

Part I. Development of a concept inventory addressing students' beliefs and reasoning difficulties regarding the greenhouse effect, Part II. Distribution of chlorine measured by the Mars Odyssey Gamma Ray Spectrometer

NASA Astrophysics Data System (ADS)

Keller, John Michael

This work presents two research efforts, one involving planetary science education research and a second involving the surface composition of Mars. In the former, student beliefs and reasoning difficulties associated with the greenhouse effect were elicited through student interviews and written survey responses from >900 US undergraduate non-science majors. This guided the development of the Greenhouse Effect Concept Inventory (GECI), an educational research tool designed to assess pre- and post-instruction conceptual understanding of the greenhouse effect. Three versions of this multiple-choice instrument were administered to >2,500 undergraduates as part of the development and validation process. In contrast to previous research efforts regarding causes, consequences, and solutions to the enhanced greenhouse effect, the GECI focuses primarily on the physics of energy flow through Earth's atmosphere. The GECI is offered to the science education community as a research tool for assessing instructional strategies on this topic. It was confirmed that the study population subscribes to several previously identified beliefs. These include correct understandings that carbon dioxide is an important greenhouse gas and the greenhouse effect increases planetary surface temperatures. Students also commonly associate the greenhouse effect with increased penetration of sunlight into and trapping of solar energy in the atmosphere. Students intermix concepts associated with the greenhouse effect, global warming, and ozone depletion. Reinforcing the latter concept, a majority believe that the Sun radiates most of its energy as ultraviolet light. Students also describe inaccurate and incomplete trapping models, which include permanent trapping, trapping through reflection, and trapping of gases and pollution. Another reasoning difficulty involves the idea that Earth's surface radiates energy primarily during the nighttime. The second research effort describes the distribution of chlorine on Mars measured by the Mars Odyssey Gamma Ray Spectrometer (GRS). The distribution of chlorine is heterogeneous across the surface, with a concentration of high chlorine centered over the Medusa Fossae Formation. The distribution of chlorine correlates positively with hydrogen and negatively with silicon and thermal inertia. Four mechanisms (aeolian, volcanic, aqueous, and hydrothermal) are discussed as possible factors influencing the distribution of chlorine measured within the upper few tens of centimeters of the surface.