Studies of metal-binding sites in natural organic matter and their role in the generation of disinfection by-products using lanthanide ion probes

In this study, the complexation of Tb3+ with natural organic matter (NOM) was studied by the method of time-resolved fluorescence spectroscopy. In the presence of NOM, the excitation of Tb3+ was observed in a wide range of wavelengths, for which virtually no excitation of free Tb3+ took place. The pseudo-quantum yield spectra (excitation intensity normalized by corresponding light absorbance values) had a maximum at 282 nm. This indicated that the excitation of NOM-bound Tb3+ proceeds through energy transfer from aromatic groups in NOM. The concentration of the metal-binding sites (C(L)) was determined by titration with Tb3+ and was found to range from 0.21% to 0.83% of total moles of organic carbon. The actual number of the carbon atoms that comprise these functionalities was hypothesized to be at least seven times higher. The C(L) values were well correlated with the reactivity of NOM with chlorine quantified by total organic halogen formation potential and with the contribution of polyhydroxyaromatic moieties determined by pyrolysis-GC/MS method. The correlation of C(L) with the contributions of aromatic and carboxylic moieties in NOM determined by 13C NMR was poor. Based on the data, it was concluded that the metal binding functionalities in NOM are closely associated with halogen attack sites.     

Spectroscopic study of the degradation of antibiotics and the generation of representative EfOM oxidation products in ozonated wastewater

This study examined effects of ozonation on thirteen fluoroquinolone, macrolide and lincosamide antibiotics present in municipal wastewater. Transformations of effluent organic matter (EfOM) caused by ozonation were characterized using absorbance/fluorescence spectroscopy and high performance size exclusion chromatography (HPSEC). Concentrations of aldehydes and carboxylic acids generated via the oxidation of EfOM were also determined. The absorbance and fluorescence of ozonated wastewater decreased with increasing ozone dose or treatment time. HPSEC data showed that these phenomena corresponded to the oxidation of all EfOM fractions, with some preference towards the degradation of the EfOM molecules with high apparent molecular weight. The removal of antibiotics and production of aldehydes and carboxylic acids were strongly correlated with the changes in both EfOM absorbance and fluorescence. Applications of a model describing the concurrent degradation of trace level contaminants and relative changes of EfOM emission allowed achieving a good fitting between the experimental and modeled ΔC/C₀ vs. ΔA/A₀ and ΔC/C₀ vs. ΔF/F₀ data.     

Ozonation effects on emerging micropollutants and effluent organic matter in wastewater: characterization using changes of three-dimensional HP-SEC and EEM fluorescence data

The degradation of effluent organic matter (EfOM) in a municipal wastewater treated by ozonation was characterized using the methods of high-performance size-exclusion chromatography (HP-SEC) and excitation/emission matrix (EEM) fluorescence combined with parallel factor analysis (PARAFAC). The removal of 40 diverse trace-level contaminants of emerging concern (CEC) present in the wastewater was determined as well. Ozonation caused a rapid decrease of the absorbance and fluorescence of the wastewater, which was associated primarily with the oxidation of high and low apparent molecular weight (AMW) EfOM fractions. PARAFAC analysis also showed that components C1 and C2 decreased prominently in these conditions. The EfOM fraction of intermediate molecular weight ascribable to a terrestrial humic-like component (C3) tended to be less reactive toward ozone. Relative changes of EEM fluorescence were quantified using F _max values of PARAFAC-identified components (∆F/F ⁰ _max). Unambiguous relationships between ∆F/F ⁰ _max values and the extent of the degradation of the examined CECs (∆C/C₀) were established. This allowed correlating main parameters of the ∆C/C₀ vs. ∆F/F ⁰ _max relationships with the rates of oxidation of these CECs. The results demonstrate the potential of online measurements of EEM fluorescence for quantitating effects of ozonation on EfOM and micropollutants in wastewater effluents.

     

A spectroscopic study of the bromination of the endocrine disruptor ethynylestradiol

Bromination of ethynylestradiol (EE2) was studied using fluorescence and conventional and stopped-flow absorbance spectroscopy. EE2 transformations in the presence of bromine were determined to proceed through sequential reactions. The first step is very rapid and results in the formation of a brominated cyclohexadienone that is susceptible to reduction but in oxidative conditions it undergoes a transformation into monobromo-EE2 in a first-order OH- -accelerated reaction. The transformation from monobromo-EE2 to dibromo-EE2 follows a similar mechanism. The rates of reactions of bromine-substituted EE2 species are orders of magnitude lower than that of the parent compound indicating that these species can persist in conditions typical for water treatment operations.     

Characterization of dissolved organic matter using high-performance liquid chromatography (HPLC)-size exclusion chromatography (SEC) with a multiple wavelength absorbance detector

High-performance liquid chromatography-size exclusion chromatography (HPLC-SEC) coupled with a multiple wavelength absorbance detector (200-445 nm) was used in this study to investigate the apparent molecular weight (AMW) distributions of dissolved organic matter (DOM). Standard DOM, namely humic acid, fulvic acid and hydrophilic acid, from the Suwannee River were tested to ascertain the performance and sensitivity of the method. In addition to four compounds groups: humic substances (Peak 1, AMW 16 kD), fulvic acids (Peak 2, AMW 11 kD), low AMW acids (Peak 3, AMW 5 kD), and low AMW neutral and amphiphilic molecules, proteins and their amino acid building blocks (Peak 4, AMW 3 kD), an new group that appears to include low AMW, 6-10 kD, humic substances was found based on investigating the spectra at various elution times. The spectroscopic parameter S_>365 (slope at wavelengths >365 nm) was determined to be a good predictor of the AMW of the DOM. The detector wavelength played an important role in evaluating the AMW distribution. For some fractions, such as the humic and low AMW non-aromatic substances, the error in measurement was ±30% as determined by two-dimensional chromatograms detected at an artificially selected wavelength. HPLC-SEC with multiple wavelength absorbance detection was found to be a useful technique for DOM characterization. It characterized the AMW distributions of DOM more accurately and provided additional, potentially important information concerning the properties of DOM with varying AMWs.