Competition between Al(III) and Fe(III) for binding onto natural organic matter: In situ monitoring by UV-Vis absorbance spectroscopy.

The ubiquitous presence of natural organic matter (NOM) in the aquatic and soil environment significantly affects the transport, fate and bioavailability of Al and Fe elements, NOM itself and other trace metals. In this study, the binding of Al(III) and Fe(III) and their competition for binding onto NOM at varying pH values were monitored in situ via UV-Vis absorbance spectroscopy. It demonstrated that the spectral parameter, e.g., the differential log-transformed absorbance at 400 nm (ΔLnA400), can quantify the amount of Al(III) and/or Fe(III) bound onto NOM in all examined cases and will show similar molar extinction coefficients that correspond to the amount of bound Al(III) and Fe(III). Therefore, this approach can not only demonstrate visibly the competition between Al(III) and Fe(III) based on their metal-specific features by evaluating differential absorbance spectra produced by metal binding but can also monitor the reaction kinetics of Al(III) and Fe(III) and their competition for binding onto NOM. To our knowledge, this study is the first to in situ monitor the competition between Al(III) and Fe(III) for binding with NOM quantitatively and at realistic environmental concentrations of both metal ions and NOM.

In-situ characterization of dissolved organic matter removal by coagulation using differential UV-Visible absorbance spectroscopy.

Removing dissolved organic matter (DOM) is of great concern due to its adverse effects on water supplies. Great effort has been given to studying DOM removal by coagulation, while the mechanism of DOM removal and the changes in its properties during coagulation have not been clearly illustrated due to the limitations of detection methods under practical environmental conditions. In this paper, the changes in DOM during coagulation were quantified using differential UV-Visible absorbance spectroscopy, and the differential spectra of DOM in the wavelength range of 200-600 nm could be deconvoluted into six Gaussian bands with maxima at approximately 200, 240, 276, 316, 385, and 457 nm after coagulation, respectively. The intensity of these maxima decreased with the type and dosage of coagulants. These observations should reflect the difference in the removability of DOM by coagulation, and this perspective was further confirmed by examining the deprotonation-protonation properties of DOM before and after coagulation. The affinity sites of DOM in coagulated waters, quantified by spectra parameter DlnA400 (differential log-transformed spectra at wavelength 400 nm) in combination with the revised NICA model, increased as the coagulant dosage, which indicates that coagulation is inclined to remove the DOM fraction with fewer functional groups. Polyaluminum chloride (PAC) and Al-aggregate (Al13) were more efficient than Alum for removing DOM due to their high efficiency for removing DOM fractions with fewer functional groups. The residual dissolved Al concentration depended on the total amount of reactive binding sites in DOM, and there was a strong linear correlation between residual dissolved Al and the total amount of reactive binding sites in DOM for Alum, while a weaker correlation was presented for PAC and Al13. This indicates that Ala was the dominant species to bind with the affinity sites in DOM to form residual dissolved Al.