Ozonation of drinking water: part I. Oxidation kinetics and product formation.

Rate constants of reactions of ozone with organic and inorganic compounds in water-II dissociating organic compounds

Pharmaceuticals in STP effluents and their solar photodegradation in aquatic environment.

Stratospheric ozone levels are near their lowest point since measurements began, so current ultraviolet-B (UV-B) radiation levels are thought to be close to their maximum. Total stratospheric content of ozone-depleting substances is expected to reach a maximum before the year 2000. All other things being equal, the current ozone losses and related UV-B increases should be close to their maximum. Increases in surface erythemal (sunburning) UV radiation relative to the values in the 1970s are estimated to be: about 7% at Northern Hemisphere mid-latitudes in winter/spring; about 4% at Northern Hemisphere mid-latitudes in summer/fall; about 6% at Southern Hemisphere mid-latitudes on a year-round basis; about 130% in the Antarctic in spring; and about 22% in the Arctic in spring. Reductions in atmospheric ozone are expected to result in higher amounts of UV-B radiation reaching the Earth's surface. The expected correlation between increases in surface UV-B radiation and decreases in overhead ozone has been further demonstrated and quantified by ground-based instruments under a wide range of conditions. Improved measurements of UV-B radiation are now providing better geographical and temporal coverage. Surface UV-B radiation levels are highly variable because of cloud cover, and also because of local effects including pollutants and surface reflections. These factors usually decrease atmospheric transmission and therefore the surface irradiances at UV-B as well as other wavelengths. Occasional cloud-induced increases have also been reported. With a few exceptions, the direct detection of UV-B trends at low- and mid-latitudes remains problematic due to this high natural variability, the relatively small ozone changes, and the practical difficulties of maintaining long-term stability in networks of UV-measuring instruments. Few reliable UV-B radiation measurements are available from pre-ozone-depletion days. Satellite-based observations of atmospheric ozone and clouds are being used, together with models of atmospheric transmission, to provide global coverage and long-term estimates of surface UV-B radiation. Estimates of long-term (1979-1992) trends in zonally averaged UV irradiances that include cloud effects are nearly identical to those for clear-sky estimates, providing evidence that clouds have not influenced the UV-B trends. However, the limitations of satellite-derived UV estimates should be recognized. To assess uncertainties inherent in this approach, additional validations involving comparisons with ground-based observations are required. Direct comparisons of ground-based UV-B radiation measurements between a few mid-latitude sites in the Northern and Southern Hemispheres have shown larger differences than those estimated using satellite data. Ground-based measurements show that summertime erythemal UV irradiances in the Southern Hemisphere exceed those at comparable latitudes of the Northern Hemisphere by up to 40%, whereas corresponding satellite-based estimates yield only 10-15% differences. Atmospheric pollution may be a factor in this discrepancy between ground-based measurements and satellite-derived estimates. UV-B measurements at more sites are required to determine whether the larger observed differences are globally representative. High levels of UV-B radiation continue to be observed in Antarctica during the recurrent spring-time ozone hole. For example, during ozone-hole episodes, measured biologically damaging radiation at Palmer Station, Antarctica (64 degrees S) has been found to approach and occasionally even exceed maximum summer values at San Diego, CA, USA (32 degrees N). Long-term predictions of future UV-B levels are difficult and uncertain. Nevertheless, current best estimates suggest that a slow recovery to pre-ozone depletion levels may be expected during the next half-century. (ABSTRACT TRUNCATED)

Changes in biologically active ultraviolet radiation reaching the Earth's surface

Thermal activation can induce persulfate (S2O82−) degradation to form sulfate radicals (SO4−•) that can undergo radical interconversion to form hydroxyl radicals (HO•) under alkaline conditions. The radicals SO4−•/HO• can be present either individually or simultaneously in the persulfate oxidation system. To identify the active radical species, a chemical probe method was developed. An excess of probe compounds was added to the system, and differences between the reactivity of the probes and the potential radical species were observed. The usage of various probes, including tert-butyl alcohol, phenol, and nitrobenzene (NB), for simultaneously identifying SO4−•/HO• was investigated. NB can only react with radicals: it cannot react with persulfate. The reaction rate of NB with HO• is 3000−3900 times greater than that of NB with SO4−•, which is a good candidate for use as a probe for differentiating between SO4−•/HO• reactivity. Furthermore, the effects of pH on the formation of SO4−•/HO• were demonstrated b...

Identification of Sulfate and Hydroxyl Radicals in Thermally Activated Persulfate

The oxidation kinetics of butyl chloride, nitrobenzene, anisole, and methylmercury in the presence of hydroxyl radical (OH) scavengers were used to determine the rate and quantum efficiency for production of OH from irradiated nitrate ions in water. The experiments were conducted under steady-state irradiations with monochromatic radiation (313 nm) and with sunlight. The mean quantum efficiency for OH production at 313 nm rises from 0.013 +/- 0.002 at 20 /sup 0/C to 0.017 +/- 0.003 at 30 /sup 0/C in the pH range 6.2-8.2. Results of this study are used to estimate nitrate-induced photooxidation rates of trace organic chemicals under a variety of environmental conditions. 27 references, 6 figures, 2 tables.

Nitrate-induced photooxidation of trace organic chemicals in water.

A laboratory study showed that ozone-initiated oxidation of ammonia in water can result from the direct reaction of ozone with ammonia as well as from the reactions of hydroxyl radicals formed upon ozone decomposition. The direct reaction of ozone predominated at pH 9, the hydroxyl ion and radical-catalyzed decomposition of ozone to the reactive hydroxyl radical intermediate determines the kinetics of the ammonia oxidation. The reaction rate constant of hydroxyl radical with ammonia is relatively small. Whenever the hydroxyl radical mechanism is involved, ammonia is easily protected by other solutes which also consume hydroxyl radicals. Even carbonate and bicarbonate ions may act as efficient hydroxyl radical scavengers. Because carbonate and organic solutes affect the lifetime of ozone in water, they consequently shift the pH range in which either the direct ozone or the hydroxyl radical mechanism predominates.

Heinz. Bader

Papers

Nitrate-induced photooxidation of trace organic chemicals in water.

Ozonation of water: kinetics of oxidation of ammonia by ozone and hydroxyl radicals