The potential occurrence of endocrine-disrupting compounds (EDCs) as well as pharmaceuticals and personal care products (PPCPs) in drinking water supplies raises concern over the removal of these compounds by common drinking water treatment processes. Three drinking water supplies were spiked with 10 to 250 ng/L of 62 different EDC/ PPCPs; one model water containing an NOM isolate was spiked with 49 different EDC/PPCPs. Compounds were detected by LC/MS/MS or GC/MS/MS. These test waters were subjected to bench-scale experimentation to simulate individual treatment processes in a water treatment plant (WTP). Aluminum sulfate and ferric chloride coagulants or chemical lime softening removed some polyaromatic hydrocarbons (PAHs) but removed <25% of most other EDC/ PPCPs. Addition of 5 mg/L of powder activated carbon (PAC) with a 4-h contact time removed 50% to >98% of GC/ MS/MS compounds (more volatile) and 10% to >95% of LC/ MS/MS compounds (more polar); higher PAC dosages improved EDC/PPCP removal. EDC/PPCP percentage removal was independent of the initial compound concentration. Octanol-water partition coefficients served as a reasonable indicator of compound removal under controlled PAC test conditions, except for EDC/PPCPs that were protonated or deprotonated at the test pH and some that contained heterocyclic or aromatic nitrogen. Separate chlorine or ozone experiments decreased the EDC/PPCP initial concentration by <10% to >90%; EDC/PPCPs were likely transformed to oxidation byproducts. Ozone oxidized steroids containing phenolic moieties (estradiol, ethynylestradiol, or estrone) more efficiently than those without aromatic or phenolic moieties (androstenedione, progesterone, and testosterone). EDC/PPCP reactivity with oxidants were separated into three general groups: (1) compounds easily oxidized (>80% reacted) by chlorine are always oxidized at least as efficiently by ozone; (2) 6 of the -60 compounds (TCEP, BHC, chlordane, dieldrin, heptachlor epoxide, musk ketone) were poorly oxidized (<20% reacted) by chlorine or ozone; (3) compounds (24 of 60) reacting preferentially (higher removals) with ozone rather than chlorine. Conventional treatment (coagulation plus chlorination) would have low removal of many EDC/PPCPs, while addition of PAC and/or ozone could substantially improve their removals. Existing strategies that predict relative removals of herbicides, pesticides, and other organic pollutants by activated carbon or oxidation can be directly applied for the removal of many EDC/PPCPs, but these strategies need to be modified to account for charged (protonated bases or deprotonated acids) and aliphatic species. Some compounds (e.g., DEET, ibuprofen, gemfibrozil) had low removals unless ozonation was used. Other compounds had low removals by all the WTP processes considered (atrazine, iopromide, meprobamate, TCEP), and removal processes capable of removing these types of compounds should be investigated.

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Ozonation is effective in improving the quality of municipal wastewater effluents by eliminating organic micropollutants. Nevertheless, ozone process design is still limited by (i) the large number of structurally diverse micropollutants and (ii) the varying quality of wastewater matrices (especially dissolved organic matter). These issues were addressed by grouping 16 micropollutants according to their ozone and hydroxyl radical ((•)OH) rate constants and normalizing the applied ozone dose to the dissolved organic carbon concentration (i.e., g O3/g DOC). Consistent elimination of micropollutants was observed in 10 secondary municipal wastewater effluents spiked with 16 micropollutants (∼2 μg/L) in the absence of ozone demand exerted by nitrite. The elimination of ozone-refractory micropollutants was well predicted by measuring the (•)OH exposure by the decrease of the probe compound p-chlorobenzoic acid. The average molar (•)OH yields (moles of (•)OH produced per mole of ozone consumed) were 21 ± 3% for g O3/g DOC = 1.0, and the average rate constant for the reaction of (•)OH with effluent organic matter was (2.1 ± 0.6) × 10(4) (mg C/L)(-1) s(-1). On the basis of these results, a DOC-normalized ozone dose, together with the rate constants for the reaction of the selected micropollutants with ozone and (•)OH, and the measurement of the (•)OH exposure are proposed as key parameters for the prediction of the elimination efficiency of micropollutants during ozonation of municipal wastewater effluents with varying water quality.

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The oxidative removal of a diverse group of trace organic contaminants from surface water and wastewater was evaluated using ozone (O 3 ) and O 3 combined with hydrogen peroxide (O 3 /H 2 O 2 ). Target compounds included estrogenic and androgenic steroids, pharmaceuticals, pesticides, and industrial chemicals. Bench-and pilot-scale experiments were conducted with surface water spiked with the target compounds and wastewater effluent containing ambient concentrations of target compounds. Full-scale water treatment plants were sampled before and after ozonation to determine if bench-and pilot-scale results accurately predict full-scale removal. In both drinking water and wastewater experiments, the majority of target compounds were removed by greater than 90% at O 3 exposures commonly used for disinfection. Atrazine, iopromide, meprobamate, and tris-chloroethylphosphate (TCEP) were the most recalcitrant compounds to oxidize using O 3 , with removals generally less than 50%. The addition of H 2 O 2 for advanced oxidation was of little benefit for contaminant removal as compared to O 3 alone. O 3 /H 2 O 2 provided a marginal increase in the removal of dilantin, diazepam, DEET, iopromide, and meprobamate, while decreasing the removal efficacy of pentoxifylline, caffeine, testosterone, progesterone, and androstenedione. In wastewater experiments, O 3 and O 3 /H 2 O 2 were shown to remove in vitro estrogenicity. Collectively, these data provide evidence that O 3 is a highly effective oxidant for removing the majority of trace organic contaminants from water.