Modeling Cryptosporidium parvum oocyst inactivation and bromate in a flow-through ozone contactor treating natural water

A reactive transport model was developed to simultaneously predict Cryptosporidium parvum oocyst inactivation and bromate formation during ozonation of natural water. A mechanistic model previously established to predict bromate formation in organic-free synthetic waters was coupled with an empirical ozone decay model and a one-dimensional axial dispersion reactor (ADR) model to represent the performance of a lab-scale flow-through ozone bubble-diffuser contactor. Dissolved ozone concentration, bromate concentration (in flow-through experiments only), hydroxyl radical exposure and C. parvum oocyst survival were measured in batch and flow-through experiments performed with filtered Ohio River water. The model successfully represented ozone concentration and C. parvum oocyst survival ratio in the flow-through reactor using parameters independently determined from batch and semi-batch experiments. Discrepancies between model prediction and experimental data for hydroxyl radical concentration and bromate formation were attributed to unaccounted for reactions, particularly those involving natural organic matter, hydrogen peroxide and carbonate radicals. Model simulations including some of these reactions resulted in closer agreement between predictions and experimental observations for bromate formation.     

Formation of oxidation byproducts from ozonation of wastewater

Disinfection byproduct (DBP) formation in tertiary wastewater was examined after ozonation (O(3)) and advanced oxidation with O(3) and hydrogen peroxide (O(3)/H(2)O(2)). O(3) and O(3)/H(2)O(2) were applied at multiple dosages to investigate DBP formation during coliform disinfection and trace contaminant oxidation. Results showed O(3) provided superior disinfection of fecal and total coliforms compared to O(3)/H(2)O(2). Color, UV absorbance, and SUVA were reduced by O(3) and O(3)/H(2)O(2), offering wastewater utilities a few potential surrogates to monitor disinfection or trace contaminant oxidation. At equivalent O(3) dosages, O(3)/H(2)O(2) produced greater concentrations of assimilable organic carbon (5-52%), aldehydes (31-47%), and carboxylic acids (12-43%) compared to O(3) alone, indicating that organic DBP formation is largely dependent upon hydroxyl radical exposure. Bromate formation occurred when O(3) dosages exceeded the O(3) demand of the wastewater. Bench-scale tests with free chlorine showed O(3) is capable of reducing total organic halide (TOX) formation potential by at least 20%. In summary, O(3) provided superior disinfection compared to O(3)/H(2)O(2) while minimizing DBP concentrations. These are important considerations for water reuse, aquifer storage and recovery, and advanced wastewater treatment applications.     

The removal of estrogenic activity and control of brominated by-products during ozonation of secondary effluents

The purposes of this study were to investigate the behavior of brominated by-products, such as bromate ion and total organic bromide, formed during ozonation for the removal of estrogenic activity in sewage effluents and to propose operation parameters for the ozonation process. It is necessary to reduce the E(2) equivalent concentration of estrogenic activity in secondary effluent treated by 90% of the initial one. To do so, ozonation until dissolved ozone concentration increased to 0.1mg/L (which corresponds to approximately 1mg O(3)/mg DOC(0) [consumed ozone per initial DOC] of consumed ozone for the effluent in this study) is proposed as an operation parameter for ozonation without the formation of brominated by-products.     

Effect of Addition of Ammonia on theBromate Formation During Ozonation

Continuous ozonation experiments of bromide solutions have been conducted in the presence of ammonia. Solutions were prepared with phosphate-buffered NOM-free water (pH = 8) spiked with high levels of bromide and ammonium ions according variable molar ratio R= NH₄ ⁺/Br^?. Our results have shown that in the presence of tertbutanol, the bromate formation presents a delay increasing with the value of R. Bromate formation occurs when total bromine measured by the DPD colorimetric method presents a minimum level and when total bromine measured by the DPD + KI colorimetric method reaches a maximum level. The hypothesis that dibromamine was not quantitatively measured by DPD alone was first made, but unconfirmed, by complementary experiments. So we assumed that, in our experimental conditions, an unknown by-product measured by DPD + KI could be formed by ozonation of bromide in the presence of ammonia. The nitrate formation was found to be lower than expected, probably due to autonomous bromamine decomposition into nitrogen.     

Oxidation of Herbicides in Groundwater by the Fenton Process: A Realistic Alternative for O3/H2O2 Treatment?

Oxidation with O₃/H₂O₂ and Fe²⁺/H₂O₂ are optional for the degradation of herbicides and pesticides in water. The choice of which process will be applied depends upon the degree of degradation of organic micropollutants and the process conditions related to the formation of oxidation by-products, and also on the total costs and the safety and reliability of the process. Under real conditions, atrazine and some phenylureaherbicides were oxidized with O₃/H₂O₂. Comparable experiments under conditions of different pH, iron and DOC content were performed with Fe²⁺/H₂O₂, in order to gain information on the influence of these parameters. The oxidation results of both processes as well as the formation of bromate as one of the oxidation by-products are described. It was found that 80% of atrazine and >99% of some phenylureaherbicides could be degraded with O₃/H₂O₂ at pH 7.8 (H₂O₂/O₃ ratio 3.7 g/g). Under these conditions, bromate was formed up to 5 μg/1. Comparable results were obtained with Fe²⁺/H₂O₂ at a pH value of 5.5, whereas the formation of bromate was kept below 0.2 μg/L.     

Modeling of Ozonation for Dissolved Ozone Dosing

Experimental research was carried out for calibration and validation of a model describing ozone decay and ozone exposure (CT), decrease in UV absorbance at 254 nm (UVA₂₅₄), increase in assimilable organic carbon concentration and bromate formation. The model proved to be able to predict these parameters on the basis of the applied ozone dosage. The experimental ozone dosages ranged from 0.4 mg-O₃/L to 0.9 mg-O₃/L for natural water with a dissolved organic carbon concentration of 2.4 mg-C/L. The UVA₂₅₄ was found to be an effective parameter for estimation of rapid ozone decay for natural water under experimental conditions tested. The experimental setup consisted of a bench-scale plug flow reactor (approximately 100 L/h) with dissolved ozone dosing.     

Bromate Destruction by UV Irradiation and Electric Arc Discharge

Bromate ion destruction by UV irradiation using either a low pressure mercury lamp or a medium pressure mercury lamp has been evaluated. A low pressure lamp which emits radiation predominantly at < 200 nm was more effective than the UV lamp which emits radiation at 254 nm, since bromate ion has a peak absorbance of about 195 nm. Bromate ion was shown to be reduced to bromide ion with bromine as an intermediate. Bromate ion destruction using a low pressure mercury lamp (< 200 nm) ranged from 3 to 38% for doses ranging from 23 to 228 mW-s/cm²; 7-46% destruction was achieved using a medium pressure lamp with initial bromate ion concentrations of 11-38 μg/L and doses ranging from 60 to 550 mW-s/cm². A new innovative electric arc discharge method also has been evaluated and compared with UV irradiation. The electric arc discharge method destroyed 12-45% bromate ion for doses ranging from 130 to 1300 mW-s/cm².     

Modeling Bromate Formation During Ozonation

Bromate formation has been identified as a significant barrier in the application of ozone during water treatment for water sources that contain high levels of bromide. Bromate has been identified as a possible human carcinogen and bromate levels in drinking water are strictly controlled at 10 μg/L in most developed countries. Various models have been proposed to model bromate formation during ozonation based on raw water quality, ozone dose and contact time. Two main approaches for modeling have been used: an empirical regression modeling methodology and kinetic-based methodology. Currently, the benefit of the bromate models lies in their ability to show how process parameters may impact on the amount bromate formed.     

The Measurement Of Very Low Level Bromate Ion

The potential to form BrO₃ ^? as a byproduct during ozone treatment of raw water containing bromide ion is a major concern for utilities planning to use ozone. The proposed BrO₃ ^? Maximum Contaminant Level (MCL) of 10 μg/L in the USA has been established largely by using ion chromatography. A spectrophotometric method based on the oxidation of chlorpromazine in the presence of BrO₃ ^? has been developed. The method detection limit (MDL) in reagent water is 0.8 μg/L BrO₃ ^? The procedure has an operating range of 1 to 40 μg/L BrO₃. The precision of the method is calculated to be better than 2.5% with an accuracy within ± 1 μg/L BrO₃ ^?. Details of the method are presented along with data gathered by ion chromatography using borate and carbonate eluants; chlorpromazine post column studies; and low level capillary electrophoresis studies.     

离子色谱法测定瓶装矿泉水中痕量溴酸盐

建立测定饮用水中痕量溴酸盐的离子色谱法,并对北京地区超市瓶装矿泉水进行随机抽样调查。方法采用Di-onex ICS-1000型离子色谱,IonPac AS23阴离子交换柱,Na2CO3/NaHCO3等度淋洗,电导检测器,直接进样,进样体积为500μL。结果离子色谱法测定饮用水中痕量溴酸盐的检出限为0.2μg/L;在1～100μg/L范围内具有良好的线性关系（r=0.9999）;5种不同浓度标准溶液的相对标准偏差（RSD）均小于10%;对北京地区超市16种瓶装矿泉水样品中痕量溴酸盐进行了检测,加标回收率在98%～106%之间,样品检出浓度在1.78～14.49μg/L之间,其中有2种矿泉水样品溴酸盐含量超过了限值（10μg/L）。结论离子色谱法测定饮用水中痕量溴酸盐具有灵敏度高、操作简单、分离效果好、重现性卓越等特点。市售瓶装矿泉水具有一定的致癌危险性,建议相关部门依据新国标要求加强对市售瓶装矿泉水的监测和管理。