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The objective of the analytical phase is to identify those chemical compounds, other than the free and combined available halogen, which result from the addition of chlorine to fresh or saltwater. The study is composed of analytical chemistry and biological divisions with freshwater and marine biological subdivisions. The model also indicates that early-morning photolysis of molecular chlorine can yield sufficiently high concentrations of chlorine atoms to render the oxidation of common gaseous compounds by this species 100 times faster than the analogous oxidation reactions involving the OH radical, thus emphasizing the locally significant effect of chlorine atoms on the concentrations and lifetimes of atmospheric trace species in both the remote marine boundary layer and coastal urban areas. Using the observed chlorine concentrations and a simple photochemical box model, we estimate that a hitherto unrecognized chlorine source must exist that produces up to 330 p.p.t. The measured Cl2 mixing ratios range from <10 to 150 parts per 1012 (p.p.t.), exceeding those predicted for marine air by more than an order of magnitude. Here we report nighttime observations of molecular chlorine concentrations at a North American coastal site during onshore wind flow conditions that cannot be explained using known chlorine chemistry.
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In recent years, laboratory investigations, modelling studies, measured Cl deficits in marine aerosols and species-nonspecific observations of gaseous inorganic chlorine compounds other than HCl have suggested that reactive halogen species may contribute significantly to-or even locally dominate-the oxidative more » capacity of the lower marine troposphere. Ozone can contribute to the oxidation of atmospheric species during both day and night. In the daytime troposphere, these reactions are dominated by photochemically produced OH radicals at night and in polluted environments, NO3 radicals are an important oxidant. The fate of many atmospheric trace species, including pollutants such as nitrogen oxides and some volatile organic compounds, is controlled by oxidation reactions. The final chapter considers the relative efficiency and potential environmental impact of alternative chemical and physical methods for controlling biofouling in power plant cooling systems. Information on biological effects, derived mainly from the results of laboratory bioassays, consists primarily of more » acute toxicity data, but also included are discussions of biological and environmental factors affecting species' tolerance levels sublethal effects on reproduction, growth, behavior, and physiological processes such as respiration and osmoregulation and possible mechanisms of oxidant toxicity at the cellular or biochemical level. Analytical methods for differentiating and measuring chlorine-produced residual oxidants are discussed in a separate section. Information is provided on aqueous chlorine chemistry including the types and relative concentrations of residual oxidants formed under varying environmental conditions the stability, persistence, and reactivity of these oxidants and their potential for forming halogenated organic compounds.
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The pre-1980 open literature on the chemistry and biological effects of chlorine in marine, freshwater, and estuarine systems is reviewed with special emphasis placed on the potential impacts of power plant chlorination practices.