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PubMed2005

Kinetic studies of the ClO + ClO association reaction as a function of temperature and pressure.

The kinetics of the association reaction of ClO radicals: ClO + ClO + M --> Cl2O2+ M (1), have been investigated as a function of temperature T between 206.0-298.0 K and pressure p between 25-760 Torr using flash photolysis with time-resolved UV absorption spectroscopy. ClO radicals were generated following the photolysis of Br2/Cl2O mixtures in nitrogen diluent gas. Charge coupled device (CCD) detection of time resolved absorptions was used to monitor ClO radicals over a broad wavelength window covering the ClO (A 2Pi<-- X 2Pi) vibronic absorption bands. The high pass filtered ClO absorption cross sections were calibrated as a function of temperature between T = 206.0-320 K, and exhibit a negative temperature dependence. The ClO association kinetics were found to be more rapid than those reported in previous studies, with limiting low and high pressure rate coefficients, in nitrogen bath gas, k0 = (2.78 +/- 0.82) x 10(-32) x (T/300)(-3.99 +/- 0.94) molecule(-2) cm6 s(-1) and k(infinity) = (3.37 +/- 1.67) x 10(-12) x (T/300)(-1.49 +/- 1.81) molecule(-1) cm3 s(-1), respectively, (obtained with the broadening factor F(c) fixed at 0.6). Errors are 2sigma. The pressure dependent ClO association rate coefficients (falloff curves) exhibited some discrepancies at low pressures, with higher than expected rate coefficients on the basis of extrapolation from high pressures (p > 100 Torr). Reanalysis of data excluding kinetic data recorded below p = 100 Torr gave k0 = (2.79 +/- 0.85) x 10(-32) x (T/300)(-3.78 +/- 0.98) molecule(-2) cm6 s(-1) and k(infinity) = (3.44 +/- 1.83)x 10(-12) x (T/300)(-1.73 +/- 1.91) molecule(-1) cm3 s(-1). Potential sources of the low pressure discrepancies are discussed. The expression for k(0) in air bath gas is k0 = (2.62 +/- 0.80) x 10(-32) x (T/300)(-3.78 +/- 0.98) molecule(-2) cm6 s(-1). These results support upward revision of the ClO association rate coefficient recommended for use in stratospheric models, and the stratospheric implications of the results reported here are briefly discussed.

Air Pressure↗
PubMed2006

Vibrational state-dependent predissociation dynamics of ClO (A (2)Pi(3/2)): Insight from correlated fine structure branching ratios.

We have studied the v'-dependent predissociation dynamics of the ClO A (2)Pi(3/2) state using velocity-map ion-imaging. Experimental final correlated state branching ratios, i.e. Cl((2)P(J=3/2,1/2)) + O((3)P(J=2,1,0)) channels, have been measured for v' = 6-11. We find that the branching ratios are highly variable and depend strongly on v', providing a window into the v'-dependent predissociation mechanism. A comparison of the experimental results with the recent model of Lane et al. (I. C. Lane, W. H. Howie and A. J. Orr-Ewing, Phys. Chem. Chem. Phys., 1999, 1, 3087) in both the diabatic and adiabatic limits suggests that the dynamics are closer to the diabatic limit. The overall Cl((2)P(J)) branching ratios are in good agreement with the diabatic model results. There are significant differences, however, between theory and experiment at the correlated state level, demonstrating the sensitivity of correlated measurements to the role of the exit channel coupling in the predissociation dynamics. The results highlight the need for more sophisticated quantum dynamical calculations to describe the correlated fine structure branching ratios in this system.

Algorithms↗
PubMed2000

In vitro inhibition of rat cauda epididymal sperm glycolytic enzymes by ornidazole, alpha-chlorohydrin and 1-chloro-3-hydroxypropanone.

Chlorinated antifertility compounds are known to inhibit glycolysis of spermatozoa as they reside in the epididymis but new compounds need to be evaluated that retain antifertility action but do not exhibit side-effects. In this study, two known antifertility agents and a related compound were compared for their inhibition of rat sperm metabolism and motility in vitro. The dose-dependent inhibition in vitro of the glycolytic enzymes glyceraldehyde-3-phosphate dehydrogenase (GAPDH) and triosephosphate isomerase (TPI) of distal cauda epididymal rat spermatozoa by (R)-, (S)- and (R,S)-ornidazole (ORN), (R,S)-alpha-chlorohydrin (ACH) and 1-chloro-3-hydroxypropanone (CHOP) was compared. The direct inhibition of GAPDH by ORN suggests that it inhibits without prior conversion outside the cell but inhibition was not stereo-specific. The GAPDH, but not TPI, activity of spermatozoa incubated with ACH and CHOP was highly correlated with kinematic parameters of spermatozoa incubated in pyruvate- and lactate-free medium. ACH only inhibited the activity of intact spermatozoa and the inhibition was not reversed by washing the particulate sperm fraction after sonication. High concentrations of ACH (100 mmol/L) killed intact rat spermatozoa and decreased the extent of GAPDH inhibition. CHOP, unlike ACH, was an effective inhibitor of both intact and sonicated cells. Pre-CHOP, the dimethylketal precursor of CHOP, and its other hydrolysis product MeOH, were both ineffective in vitro. CHOP and related ketals may be more effective inhibitors of sperm glycolysis than ACH and may prove useful for investigating sperm-specific glycolytic inhibition, a prerequisite for the development of antiglycolytic, post-testicular acting contraceptives.

Acetone↗
PubMed1999

Disinfection of hospital waste sludge using hypochlorite and chlorine dioxide.

Hypochlorite and chlorine dioxide were used to disinfect hospital waste-water sludge. Their abilities to inactivate pathogenic micro-organisms were compared. Reductions in indigenous coliform organisms and Pseudomonas aeruginosa were estimated. The results indicate that hypochlorite is a better disinfectant than chlorine dioxide for coliforms. Higher disinfection efficiency was obtained by treating a lower concentration of sludge. In addition, a higher agitation speed gave a higher disinfection efficiency with hypochlorite. The disinfection efficiencies of both disinfectants were higher against settled sludge than against thickened sludge. Therefore, it is recommended that disinfection should be performed on settled sludge rather than in a thickening tank.

Chlorine Compounds↗
PubMed2000

Isolation, purification and characterization of xylanasefrom Staphylococcus sp. SG-13 and its application in biobleaching of kraft pulp.

A haloalkalophilic Staphylococcus sp. SG-13 produced an alkalistable xylanase in wheat bran medium. A 12-fold purification was achieved by using standard purification techniques. The purified xylanase exhibited a dual pH optima of 7.5 and 9.2. The optimum temperature for enzyme activity was 50 degrees C. The enzyme was stable at 50 degrees C for more than 4 h. The xylanase exhibited Km and Vmax values of 4 mg ml-1, 90 micromol min-1 per mg for birchwood xylan and 7 mg ml-1, 55 micromol min-1 per mg for oatspelt xylan, respectively. The substrate binding affinity of xylanase was more for oatspelt xylan but birchwood xylan was hydrolysed more rapidly. The xylanase activity was stimulated by Fe2+, Ni2+, Cu2+ and dithiothreitol up to 60% and was strongly inhibited in the presence of Co2+, Hg2+, Pb2+, phenyl methane sulphonyl fluoride, ethylenediaminetetraacetic acid, and acetic anhydride up to 100%. The xylanase dose of 1.8 U g-1 moisture free pulp, exhibited bleach boosting of kraft pulps optimally at pH 9.5-10.0 and 50 degrees C after 4 h of reaction time. Pretreatment of pulp with xylanase and its subsequent treatment with 8% hypochlorite, reduced the kappa number by 30%, enhanced the brightness and viscosity by 11% and 1.8%, respectively, and improved the paper properties such as tensile strength and burst factor up to 10% and 17%, respectively.

Chlorine Compounds↗
PubMed2002

Differential efficacy of a chlorine dioxide-containing sanitizer against single species and binary biofilms of a dairy-associated Bacillus cereus and a Pseudomonas fluorescens isolate.

AIMS: Daily exposure to 100 p.p.m. chlorine dioxide of single species and binary biofilms of dairy-associated Bacillus cereus DL5 and Pseudomonas fluorescens M2, attached to stainless steel surfaces in a laboratory flow system, was studied. METHODS AND RESULTS: Surfaces were sampled daily before and after sanitizer treatment and cells and spores dislodged and enumerated by standard methods. Duplicate surfaces were prepared for confocal scanning laser microscopy (CSLM) and scanning electron microscopy. Higher counts of Ps. fluorescens M2 were obtained in single species biofilms, microcolonies stained green (viable) in CSLM images and were closely packed on attachment surfaces. By contrast, higher counts of B. cereus DL5 were obtained in binary biofilms, microcolonies stained green in CSLM images, but were more spread out. Lower spore counts were obtained for B. cereus DL5 in binary biofilms. The survival of Ps. fluorescens M2 cells after exposure to chlorine dioxide was apparently enhanced by the presence of B. cereus DL5 in binary biofilms. By contrast, B. cereus DL5 showed increased susceptibility to sanitizer treatment in the presence of Ps. fluorescens M2. CONCLUSIONS: Co-cultured bacteria in biofilms influence each other with respect to attachment capabilities and sanitizer resistance/susceptibility. SIGNIFICANCE AND IMPACT OF THE STUDY: Binary biofilms endemic in food-processing industries can survive sanitation regimes and may represent reservoirs of product contamination leading to subsequent spoilage and/or food safety risks.

Animals↗
PubMed2002

Peracetic acid as an alternative wastewater disinfectant to chlorine dioxide.

AIMS: The aim of this study was to compare the efficiency of peracetic acid with that of chlorine dioxide in the disinfection of wastewater from a sewage treatment plant (serving about 650 000 inhabitants) that has been using peracetic acid as a disinfectant since 1998. METHODS AND RESULTS: A total of 23 samplings were made, each consisting of three samples: from secondary effluent, effluent disinfected with 2 mg l(-1) of peracetic acid and effluent disinfected with 2.2 mg l(-1) of chlorine dioxide (contact time 20 min). For each sample, measurements were made of the heterotrophic plate count at 36 degrees C, total and faecal coliforms, Escherichia coli, enterococci, pH, suspended solids and chemical oxygen demand (COD). During the first phase of the experiment the peracetic acid was seen to be less efficient than chlorine dioxide. To improve the disinfectant action a system of mechanical agitation was added which led to a greater efficiency in the inactivation of bacteria of faecal origin. CONCLUSIONS: Both products were found to be influenced by the level of microbial contamination, the amount of suspended solids and COD but not by the pH of the effluent before disinfection. The immediate mixing of the wastewater and disinfectant caused a greater reduction in enterococci. SIGNIFICANCE AND IMPACT OF THE STUDY: Since peracetic acid was seen to produce a high abatement of micro-organisms, it can be considered as a valid alternative to chlorine dioxide in the disinfection of wastewaters.

Bacteria↗
PubMed2003

Mechanisms of killing of Bacillus subtilis spores by hypochlorite and chlorine dioxide.

AIMS: To determine the mechanisms of Bacillus subtilis spore killing by hypochlorite and chlorine dioxide, and its resistance against them. METHODS AND RESULTS: Spores of B. subtilis treated with hypochlorite or chlorine dioxide did not accumulate damage to their DNA, as spores with or without the two major DNA protective alpha/beta-type small, acid soluble spore proteins exhibited similar sensitivity to these chemicals; these agents also did not cause spore mutagenesis and their efficacy in spore killing was not increased by the absence of a major DNA repair pathway. Spore killing by these two chemicals was greatly increased if spores were first chemically decoated or if spores carried a mutation in a gene encoding a protein essential for assembly of many spore coat proteins. Spores prepared at a higher temperature were also much more resistant to these agents. Neither hypochlorite nor chlorine dioxide treatment caused release of the spore core's large depot of dipicolinic acid (DPA), but hypochlorite- and chlorine dioxide-treated spores much more readily released DPA upon a subsequent normally sub-lethal heat treatment than did untreated spores. Hypochlorite-killed spores could not initiate the germination process with either nutrients or a 1 : 1 chelate of Ca2+-DPA, and these spores could not be recovered by lysozyme treatment. Chlorine dioxide-treated spores also did not germinate with Ca2+-DPA and could not be recovered by lysozyme treatment, but did germinate with nutrients. However, while germinated chlorine dioxide-killed spores released DPA and degraded their peptidoglycan cortex, they did not initiate metabolism and many of these germinated spores were dead as determined by a viability stain that discriminates live cells from dead ones on the basis of their permeability properties. CONCLUSIONS: Hypochlorite and chlorine dioxide do not kill B. subtilis spores by DNA damage, and a major factor in spore resistance to these agents appears to be the spore coat. Spore killing by hypochlorite appears to render spores defective in germination, possibly because of severe damage to the spore's inner membrane. While chlorine dioxide-killed spores can undergo the initial steps in spore germination, these germinated spores can go no further in this process probably because of some type of membrane damage. SIGNIFICANCE AND IMPACT OF THE STUDY: These results provide information on the mechanisms of the killing of bacterial spores by hypochlorite and chlorine dioxide.

Bacillus subtilis↗
PubMed2003

Formation of natural biofilms during chlorine dioxide and u.v. disinfection in a public drinking water distribution system.

AIMS: The influence of two disinfection techniques on natural biofilm development during drinking water treatment and subsequent distribution is compared with regard to the supply of a high-quality drinking water. METHODS AND RESULTS: The growth of biofilms was studied using the biofilm device technique in a real public technical drinking water asset. Different pipe materials which are commonly used in drinking water facilities (hardened polyethylene, polyvinyl chloride, steel and copper) were used as substrates for biofilm formation. Apart from young biofilms, several months old biofilms were compared in terms of material dependence, biomass and physiological state. Vital staining of biofilms with 5-cyano-2,3-ditolyl tetrazolium chloride (CTC) and the DNA-specific 4',6-diamidino-2-phenylindole (DAPI) staining resulted in a significant difference in physiological behaviour of biofilm populations depending on the disinfection technique. Compared with chlorine dioxide disinfection (0.12-0.16 mg l-1), the respiratory activities of the micro-organisms were increased on all materials during u.v. disinfection (u.v.254; 400 J m-2). The biofilm biocoenosis was analysed by in situ hybridization with labelled oligonucleotides specific for some subclasses of Proteobacteria. Using PCR and additional hybridization techniques, the biofilms were also tested for the presence of Legionella spp., atypical mycobacteria and enterococci. The results of the molecular-biological experiments in combination with cultivation tests showed that enterococci were able to pass the u.v. disinfection barrier and persist in biofilms of the distribution system, but not after chlorine dioxide disinfection. CONCLUSIONS: The results indicated that bacteria are able to regenerate and proliferate more effectively after u.v. irradiation at the waterworks, and chlorine dioxide disinfection appears to be more applicative to maintain a biological stable drinking water. SIGNIFICANCE AND IMPACT OF THE STUDY: As far as the application of u.v. disinfection is used for conditioning of critical water sources for drinking water, the efficiency of u.v. irradiation in natural systems should reach a high standard to avoid adverse impacts on human health.

Biofilms↗
PubMed2001

An evaluation of the use of chlorine dioxide (Tristel One-Shot) in an automated washer/disinfector (Medivator) fitted with a chlorine dioxide generator for decontamination of flexible endoscopes.

Microbiological tests were carried out to evaluate a new chlorine dioxide sterilant: Tristel OneShot. Preliminary in vitro suspension tests showed that solutions containing around 140 ppm chlorine dioxide achieved a reduction factor exceeding 10(6) of Staphylococcus aureus in 1min and of Bacillus subtilis spores in 2.5 min in the presence of 3g/L bovine albumin. Subsequent tests evaluated the effectiveness of Tristel One-Shot in a Medivator washer/disinfector fitted with a Tristel Generator for processing flexible endoscopes. Each test run involved three stages. In the first, the instrument and air-water channels of a gastroscope were inoculated with a suspension of Pseudomonas aeruginosa (10(8)cfu/ml) in 10% sodium glutamate and serum (0, 5 or 10%) and then drained, partially dried, and saline flushed through for total viable counts (TVCs). In the second stage, the channels were re-inoculated with test organisms; detergent was flushed through the channels which were then brushed; and saline was flushed through for TVCs. In the third stage, the channels were re-inoculated; detergent was flushed through the channels which were then brushed; the endoscope was processed in the Medivator; and saline was flushed through for TVCs. Carrying out all three stages enabled determination of (1) the contribution played by manual cleaning of channels prior to processing in the Medivator, and (2) the combined effect of manual cleaning followed by processing. Two series of test runs were done. In the first, the Tristel Generator was set to generate 230ppm chlorine dioxide, and in the second 150ppm. In the first, cleaning followed by processing in the Medivator consistently achieved a >/= 10(6)-fold reduction of test organisms, and in the second a >/= 10(5)-fold reduction. Pre-cleaning of channels was very important-when done the initial concentration of serum in the inoculum (0-10%) had no affect on the results obtained after processing.

Chlorine Compounds↗
PubMed2001

Use of chlorine dioxide to disinfect dental unit waterlines.

This paper describes a trial of chlorine dioxide in dental unit waterlines to produce potable quality water. Four treatment protocols using 50 ppm activated chlorine dioxide solution were tested. Each caused a short-term (<48 h) decline in total viable counts but did not provide potable quality water. Intermittent use of chloride dioxide is thus not suitable for long-term decontamination of dental unit waterlines. Units should be redesigned to discourage biofilm formation, and more research into practical methods of achieving potable water is required in the interim.

Chlorine Compounds↗
PubMed2003

[Pseudomonads in a new hospital building].

Testing the piping of a new hospital showed that the drinking water was contaminated with Pseudomonas aeruginosa. Because of pollution the plumbing system was treated with oxidizing biocides and air-water flushing for several times, unfortunately without stopping the bacterial recontamination. The reasons were firstly stagnation due to dead legs in the piping system, oversized pipes, very low water exchange rates and the installation of a catch water system, secondly low flow velocity because of low water pressure. After these sources of recontamination had been repaired, chlorine dioxide sanitization could be stopped successfully

Chlorine Compounds↗
PubMed1986

[Bleaching agent poisoning with sodium chlorite. The toxicology and clinical course].

A woman gardener of 49 years of age suffered an inhalational intoxication from chlorine dioxide while bleaching dried flowers. Preparation of the bleaching solutions was associated with a sharp pungent smell, coughing, pharyngeal irritation and headache. Seven hours later increasing cough and dyspnoea led to hospitalisation. Clinical findings were tachypnoea, tachycardia, and rales of auscultation; clinical chemistry revealed marked leucocytosis. Chest X-ray did not yield any abnormal findings. Initially the vital capacity and forced expiratory volume in 1 s markedly reduced and the resistance correspondingly enhanced. Blood gas analysis showed hypoxaemia despite alveolar hyperventilation. Administration of corticosteroids resulted in significant alleviation of complaints and in improved lung function with stabilisation in a highly normal range, as confirmed by follow-up examination two years later. The chlorine dioxide intoxication had been due to pH level reduction resulting from an incorrect proportioning and handling of the individual bleaching agent components when preparing the solution.

Chlorides↗
PubMed2006

Spatial bistability: a source of complex dynamics. From spatiotemporal reaction-diffusion patterns to chemomechanical structures.

We show experimentally and theoretically that reaction systems characterized by a slow induction period followed by a fast evolution to equilibrium can readily generate "spatial bistability" when operated in thin gel reactors diffusively fed from one side. This phenomenon which corresponds to the coexistence of two different stable steady states, not breaking the symmetry of the boundary conditions, can be at the origin of diverse reaction-diffusion instabilities. Using different chemical reactions, we show how stationary pulses, labyrinthine patterns or spatiotemporal oscillations can be generated. Beyond simple reaction-diffusion instabilities, we also demonstrate that the cross coupling of spatial bistability with the size responsiveness of a chemosensitive gel can give rise to autonomous spatiotemporal shape patterns, referred to as chemomechanical structures.

Catalysis↗
PubMed2003

Development of processes for environmental protection based on self-propagating reactions.

The possibility of exploiting self-propagating reactions for environmental protection is discussed in this paper. In particular, results obtained at the laboratory scale and related to the fixation and consolidation of high level radioactive wastes, the recycling of silicon sludge and aluminum dross produced by semiconductor industries and aluminum foundries, the treating and recycling of a highly toxic solid waste from electrolytic zinc plants, and the degradation of chlorinated aromatics, are examined with particular emphasis on the latter case. Specifically, the self-propagating destruction of hexachlorobenzene and 2-(2-4-dichlorophenoxy)-propanoic acid with calcium hydride as reductive substrate is demonstrated. In fact, the heat liberated by the reactions involved is large enough to guarantee the self-sustaining character of the process within a wide range of reactants compositions. Moreover, no residual chlorinated organic compounds were found in the final solid product. Some reactor engineering aspects, as well as other significant future scientific and technological issues, are also addressed in view of large-scale applicability of processes based on self-propagating reactions. To date, the batch reactor technology seems to be more easily applicable, although the use of continuous reactors is not excluded in the next future.

2,4-Dichlorophenoxyacetic Acid↗