rowed nas of He O2one World Gnaesr, San Frarcisco 1293 4 aa ) OZONATION OF U.S. DRINKING WATER SOURCES: HO- CONCENTRATIONS AND AND OXIDATION-COMPETITION VALUES WERNER R. HAAG# and C.C. DAVID YAO. Chemistry Laboratory, SRI International 333 Ravenswood Ave., Menlo Park, CA 94025 Abstract ‘The present work provides the kinetic background for understanding product formation during ozonation of organic contaminants under water treatment conditions. The steady state [HO-}/[03] ratio during continuous ozonation of several U.S. surface waters was found to have a fairly constant value, averaging (1.3 + 0.4) x 107. The rate constant for reaction of HO: radicals with natural DOC was estimated to be (3.8 + 2.1) x 104 L(mg DOC)" 5, a value that is similar to that found earlier in Swiss surface waters The [HO-/[03] ratios can be used to estimate the relative importance of the HO- versus direct 03 reaction pathways, with the help of previously measured HO- and O3 reaction Tate constants. Introduction Products of ozonation reactions in drinking water continue to be of concem [1]. While the main products arise from the reactions of ozone-produced oxidants with the natural organic and inorganic constituents, potential products from reactions of individual contaminants also need to be considered. However, organic products are difficult to determine under drinking water treatment conditions because the contaminant concentrations are usually somewhat lower than the concentration of natural dissolved organic compounds (DOC), which can interfere in the analysis or provide a high background of ozonation products. A common procedure is to either elevate the concentration in a drinking water source, or to use organic solvents when the solubility of the organic compound in water is limited [2]. These approaches simplify the analyses and give potential product identities, but should serve only as starting points for analyses in drinking water sources at low contaminant. concentrations. Itis now well accepted that ozone treatment of water results in both direct ozone reactions and HO- radical reactions with organic and inorganic compounds [3]. These two oxidation pathways can # Present address: Purus, Inc., 2713 N. First St., San Jose, CA 95134,be expected to lead to different products. Less well understood is that natural DOC both scavenges HO: radicals and induces chain decomposition of ozone with HO: as a chain carrier [4], resulting in ozone decomposition rates that are intermediate between those of unscavenged and highly scavenged systems at the same pH [5]. When added in high concentrations, substrates can inhibit the HO: chains and favor direct reactions of ozone with the substrate. For example, it now appears that bromide oxidation to bromate is adequately modeled by molecular reactions when bromide ion is spiked into natural waters at high concentrations [6,7], but at concentrations low enough that the bromide is not a significant scavenger the oxidation takes on the behavior of a radical reactions, including inhibition by other scavengers [8]. Similarly, Gauducheau et al. [9] has given evidence that organic reaction products depend on the concentration added to the system. The present work is an initial step towards understanding product formation during ‘zonation of organic contaminants under water treatment conditions. Our approach was to first determine the steady state [HO-)[03] ratios during continuous ozonation and then use these ratios to estimate the relative importance of the HO: versus direct O3 reaction pathways, with the help of previously measured HO: and O3 reaction rate constants [10-14], for the 50 organic compounds slated for regulation under the 1986 Amendments to the Safe Drinking Water Act [15]. In the process we have also determined HO: scavenging rates in a variety of U.S. surface waters and compared them to those reported for Swiss waters [5,16]. Preliminary product data have been taken for ozonation of vinylidene chloride and naphthalene to test the hypothesis of changing product distributions with varying HO: scavenging conditions in the water. Ex thods Solutions Stock solutions of aqueous ozone (~38 ppm) were prepared using a 0.5 Lin“! oxygen feed into a Welsbach Model T-408 ozone generator and allowing the gas stream to first pass through a wash bottle containing pH 6 buffer (to remove nitrogen oxides) and then into a flask containing distilled water and cooled in an ice-water bath. Surface water samples were obtained from various areas of the U.S., filter-sterilized (0.45 HM) on receipt and stored at < 4°C until use. The characteristics of the waters are listed in Table 1. Instruments An HP8452A Diode Array Spectrophotometer with an HP89500A. UV/Vis ChemStation was used for absorption measurements. Polar and semi-polar organic compounds were determined on an HP1090 HPLC equipped with a (100 x 2.1) mm 5 jm Hypersil ODS column and a photodiode array detector. An HP5880 GC with a DB-5 capillary column and an electron capture detector was used for measuring halogenated hydrocarbons. Tonic compounds were determined on a Dionex 2000i ion chromatograph equipped with AG4A and AS4A columns and a conductivity detector.Table 1. Characteristics of Various U.S. Surface Waters Used for Ozonation Studies DOC Alkatinity Spcwa Water Sample mel! meh? ME L1 107[HO-/1031 104kyio-poc? Ozone L(mg DOCy!s"! Hetch Hetchy Res. ‘Yosemite Park, CA 14 0.065 0.70 1.56 35 L. Crystal Springs Res. Hillsborough, CA 21 0.39 0.68, 1.26 2.3 San Andreas Res. Millbrae, CA 24 041 0.72 Lit 24 San Antonio Res. Sunol, CA 2.6 0.60 0.84 0.81 2.3 Potomac River Reston, VA 3.3 0.68 1.34 1.09 2.8 Calaveras Res. Milpitas, CA alr 1.25 2.12 0.76 4.0 Eno River Durham, NC 48 0.19 2.18 2.66 3.2 Lake Hennessey Napa, CA 5.6 1.33 277 1.05 3.5 Mill Pond (Saline) Woods Hole, MA 63 0.80 (63.6) 7 = Searsville Lake Stanford, CA 7.0 1.82 10.4 1.24 10.4 Virginia Key Wastewater 141 2.13 7.62 108 38 Miami, FL Averages: 13404 38421 Aldrich Humic Acid 4.8 0 2.75 4.0 4 Initial pH values ranged from 7.0t08.2. © Calculated-using 7| = 0.67.