Use of spectroscopic indicators for the monitoring of bromate generation in ozonated wastewater containing variable concentrations of bromide

Time-resolved monitoring of bromate and other by-products formed into effluents treated with ozone or advanced oxidation processes in wastewater treatment plants (WWTPs) is time-consuming and expensive. This study examined whether concentrations of bromate formed in wastewater after ozonation in the presence of widely varying bromide levels (from ca. 0.7–21.2 mg/L) can be quantified based on measurements of changes in optical properties (differential UV absorbance (ΔUVA), spectral slopes, total or regional fluorescence) of the ozonated samples. Batch ozonation was carried out using a secondary effluent produced at a major wastewater treatment plant located in the Metropolitan Seattle Area. The tests involved raw and bromide-spiked samples treated with ozone doses from 0.1 to 1 mg O3/mg DOC. Measurements of the absorbance at 254 nm (UVA254), fluorescence and bromate concentrations were performed on the treated samples. In the ozonated wastewater the concentration of bromate increased approximately linearly, from 10 mg/L) tended to inhibit the generation of bromate. Relative reduction of UVA254 and total fluorescence (TF) were found to be good predictors of bromate generation. Specifically, exponential curves could adequately fit the non-linear relationships found to exist between the concentrations of bromate and the relative reductions of the UV254 and TF, for any initial bromide concentrations used in this study. Little formation of bromate was found to occur for reduction ranges for UVA254 and TF of 30–40% and 70–80% respectively. Conversely, rapid increases in bromate generation were observed when the decrease of UVA254 or TF exceeded these threshold values

Adsorption of Uranyl on Gibbsite: A Time-Resolved Laser-Induced Fluorescence Spectroscopy Study

Uranyl adsorbed on gibbsite at pH 4.0-8.0 and ionic strengths (ISs) 0.001-0.4 M (NaClO4) in the absence of carbonate was studied using time-resolved laser-induced fluorescence spectroscopy (TRLIFS) under cryogenic conditions. TRLIFS data showed the presence of several distinct emission components. Their contributions were determined using the evolving factor analysis approach. Four components denoted as species A, B, C, and D were discerned. Each of them was characterized by a characteristic response to pH and IS changes and also by a unique combination of the values of the fundamental transition energyE0,0, vibronic spacing ∆E, and half-width of the vibronic lines ∆W. Species A and B were major contributors to the overall emission. They were mainly affected by the pH and predominated below and above pH 5.0, respectively. In contrast with that, the contribution of species C was noticeable only at IS ) 0.001 M, while it was suppressed or absent at high IS values. It was concluded that species A and B are likely to correspond to inner-sphere surface aluminol complexes ≡AIOs(UO2)+ and ≡ AIO -(UO2)OH°, while species C was hypothesized to correspond to electrostatically bound uranyl complexes (predominantly [UO2(OH)3]-)

Development of surrogate correlation models to predict trace organic contaminant oxidation and microbial inactivation during ozonation

The performance of ozonation in wastewater depends on water quality and the ability to form hydroxyl radicals ( OH) to meet disinfection or contaminant transformation objectives. Since there are no on-line methods to assess ozone and OH exposure in wastewater, many agencies are now embracing indicator frameworks and surrogate monitoring for regulatory compliance. Two of the most promising surrogate parameters for ozone-based treatment of secondary and tertiary wastewater effluents are differential UV254 absorbance (ΔUV254) and total fluorescence (ΔTF). In the current study, empirical correlations for ΔUV254 and ΔTF were developed for the oxidation of 18 trace organic contaminants (TOrCs), including 1,4-dioxane, atenolol, atrazine, bisphenol A, carbamazepine, diclofenac, gemfibrozil, ibuprofen, meprobamate, naproxen, N,N-diethyl-meta-toluamide (DEET), para-chlorobenzoic acid (pCBA), phenytoin, primidone, sulfamethoxazole, triclosan, trimethoprim, and tris-(2-chloroethyl)-phosphate (TCEP) (R2 = 0.50–0.83) and the inactivation of three microbial surrogates, including Escherichia coli, MS2, and Bacillus subtilis spores (R2 = 0.46–0.78). Nine wastewaters were tested in laboratory systems, and eight wastewaters were evaluated at pilot- and full-scale. A predictive model for OH exposure based on ΔUV254 or ΔTF was also proposed

Application of UV absorbance and fluorescence indicators to assess the formation of biodegradable dissolved organic carbon and bromate during ozonation

This study examined the significance of changes of UV absorbance and fluorescence of dissolved organic matter (DOM) as surrogate indicators for assessing the formation of bromate and biodegradable dissolved organic carbon (BDOC) during the ozonation of surface water and wastewater effluent. Spectroscopic monitoring was carried out using benchtop UV/Vis and fluorescence spectrophotometers and a newly developed miniature LED UV/fluorescence sensor capable of rapidly measuring UVA280 and protein-like and humic-like fluorescence. With the increase of O3/DOC mass ratio, the plots of BDOC formation were characterized of initial lag, transition slope and final plateau. With the decrease of UV absorbance and fluorescence, BDOC concentrations initially increased slowly and then rose more noticeably. Inflection points in plots of BDOC versus changes of spectroscopic indicators were close to 35 e45% loss of UVA254 or UVA280 and 75e85% loss of humic-like fluorescence. According to the data from size exclusion chromatography (SEC) with organic carbon detection and 2D synchronous correlation analyses, DOM fractions assigned to operationally defined large biopolymers (apparent molecular weight, AMW>20 kDa) and medium AMW humic substances (AMW 5.5e20 kDa) were transformed into medium-size building blocks (AMW 3e5.5 kDa) and other smaller AMW species (AMW<3 kDa) associated with BDOC at increasing O3/DOC ratios. Appreciable bromate formation was observed only after the values of UVA254, UVA280 and humic-like fluorescence in O3-treated samples were decreased by 45 e55%, 50e60% and 86e92% relative to their respective initial levels. No significant differences in plots of bromate concentrations versus decreases of humic-like fluorescence were observed for surface water and wastewater effluent samples. This was in contrast with the plots of bromate concentration versus UVA254 and UVA280 which exhibited sensitivity to varying initial bromide concentrations in the investigated water matrixes. These results suggest that measurements of humic-like fluorescence can provide a useful supplement to UVA indices for characterization of ozonation processes