The effects of active chlorine on photooxidation of 2-methyl-2-butene.

Active chlorine comprising hypochlorite (OCl⁻), hypochlorous acid (HOCl) and chlorine (Cl2) is the active constituent in bleach formulations for a variety of industrial and consumer applications. However, the strong oxidative reactivity of active chlorine can cause adverse effects on both human health and the environment. In this study, aerosolized Oxone® [2KHSO5, KHSO4, K2SO4] with saline solution has been utilized to produce active chlorine (HOCl and Cl2). To investigate the impact of active chlorine on volatile organic compound (VOC) oxidation, 2-methyl-2-butene (MB) was photoirradiated in the presence of active chlorine using a 2-m³ Teflon film indoor chamber. The resulting carbonyl products produced from photooxidation of MB were derivatized with O-(2,3,4,5,6-pentafluorobenzyl) hydroxyamine hydrochloride (PFBHA) and analyzed using gas chromatograph-ion trap mass spectrometer (GC/ITMS). The photooxidation of MB in the presence of active chlorine was simulated with an explicit kinetic model using a chemical solver (Morpho) which included both Master Chemical Mechanism (MCM) and Cl radical reactions. The reaction rate constants of a Cl radical with MB and its oxidized products were estimated using a Structure-Reactivity Relationship method. Under dark conditions no effect of active chlorine on MB oxidation was apparent, whereas under simulated daylight conditions (UV irradiation) rapid MB oxidation was observed due to photo-dissociation of active chlorine. The model simulation agrees with chamber data showing rapid production of oxygenated products that are characterized using GC/ITMS. Ozone formation was enhanced when MB was oxidized in the presence of irradiated active chlorine and NO(x).

Inactivation of biological agents using neutral oxone-chloride solutions.

Bleach solutions containing the active ingredient hypochlorite (OCl-) serve as powerful biological disinfectants but are highly caustic and present a significant compatibility issue when applied to contaminated equipment or terrain. A neutral, bicarbonate-buffered aqueous solution of Oxone (2K2HSO5.KHSO4.K2SO4) and sodium chloride that rapidly generates hypochlorite and hypochlorous acid (HOCl) in situ was evaluated as a new alternative to bleach for the inactivation of biological agents. The solution produced a free chlorine (HOCl + OCl-) concentration of 3.3 g/L and achieved > or =5.8-log inactivation of spores of Bacillus atrophaeus, Bacillus thuringiensis, Aspergillus niger, and Escherichia coli vegetative cells in 1 min at 22 degrees C. Seawaterwas an effective substitute for solid sodium chloride and inactivated 5 to 8 logs of each organism in 10 min over temperatures ranging from -5 degrees C to 55 degrees C. Sporicidal effectiveness increased as free chlorine concentrations shifted from OCl- to HOCl. Neutrally buffered Oxone-chloride and Oxone-seawater solutions are mitigation alternatives for biologically contaminated equipment and environments that would otherwise be decontaminated using caustic bleach solutions.

Use of in situ-generated dimethyldioxirane for inactivation of biological agents.

Dimethyldioxirane (DMDO), generated in situ by adding acetone to an aqueous solution containing potassium peroxymonosulfate (Oxone) at neutral pH, was investigated for inactivation of biological warfare agent simulants. The DMDO solution inactivated bacterial spores, fungal spores, vegetative bacterial cells, viruses, and protein by 7 orders of magnitude in less than 10 min. The kill rates of DMDO were more pronounced when compared to kill rates of buffered Oxone alone. Conditions for the use of DMDO as a biological decontaminant were optimized by evaluating the effects of age and temperature on open systems. DMDO effectiveness was compared to that of current decontaminant solutions such as DS2 (used by the U.S. military), bleach, and hydrogen peroxide and was shown to be superior in achieving a 7-log kill of Bacillus atrophaeus, a Bacillus anthracis spore simulant. The results demonstrate the potential for DMDO to fill the need for a noncorrosive, nontoxic, and environmentally safe decontaminant.

Determination of in situ-generated dimethyldioxirane from an aqueous matrix using selected ion monitoring.

There is a growing interest in utilizing in situ-generated dimethyldioxirane (DMDO) as an oxidant for synthetic purposes and bleaching and decontamination applications, but the ability to quantify the organic cyclic peroxide species is often complicated by the presence of other reactive components, peroxymonosulfate and acetone, within the solution matrix. This paper is the first to report the use of a MS method for the quantitation of DMDO from these complex matrices by utilizing an isothermal 30 degrees C GC program in conjunction with selected ion monitoring (SIM). The volatile organic species is sampled from the headspace of closed batch system vials and quantified by measuring the abundance of m/z 74. The method achieves a practical quantitation limit (PQL) for DMDO of 0.033 mM, and methyl acetate is identified as a minor decomposition product from the aqueous sample matrix, contributing 9% towards the overall DMDO measurements. The spectroscopic method makes use of common analytical instrumentation and is capable of measuring other in situ-generated dioxiranes, such as those generated from 2-butanone and [2H6]acetone.

Bromate in chlorinated drinking waters: occurrence and implications for future regulation.

Bromate is a contaminant of commercially produced solutions of sodium hypochlorite used for disinfection of drinking water. However, no methodical approach has been carried out in U.S. drinking waters to determine the impact of such contamination on drinking water quality. This study utilized a recently developed method for quantitation of bromate down to 0.05 microg/L to determine the concentration of bromate present in finished waters that had been chlorinated using hypochlorite. Forty treatment plants throughout the United States using hypochlorite in the disinfection step were selected and the levels of bromate in the water both prior to and following the addition of hypochlorite were measured. The levels of bromate in the hypochlorite feedstock were also measured and together with the dosage information provided by the plants and the amount of free chlorine in the feedstock, it was possible to calculate the theoretical level of bromate that would be imparted to the water. A mass balance was performed to compare the level of bromate in finished drinking water samples to that found in the corresponding hypochlorite solution used for treatment. Additional confirmation of the source of elevated bromate levels was provided by monitoring for an increase in the level of chlorate, a co-contaminant of hypochlorite, atthe same point in the treatment plant where bromate was elevated. This study showed that bromate in hypochlorite-treated finished waters varies across the United States based on the source of the chemical feedstock, which can add as much as 3 microg/L bromate into drinking water. Although this is within the current negotiated industry standard that allows up to 50% of the maximum contaminant level (MCL) for bromate in drinking water to be contributed by hypochlorite, it would be a challenge to meet a tighter standard. Given that distribution costs encourage utilities to purchase chemical feedstocks from local suppliers, utilities in certain regions of the United States may be put at a distinct disadvantage if future lower regulations on bromate levels in finished drinking water are put into place. Moreover, with these contaminant levels it would be almost impossible to lower the maximum permissible contribution to bromate in finished water from hypochlorite to 10% of the MCL, which is the norm for other treatment chemicals. Until this issue is resolved, it will be difficult to justify a lowering of the bromate MCL from its current level of 10 to 5 microg/L or lower.