Chemical speciation, reactivity, and bioavailability of trace metals in aqueous systems arestrongly influenced by dissolved organic matter (DOM). DOM is a mixture of diverse components, so a range of organic molecules potentially participates in the occurrence of dissolved trace metals. In this study, we investigated water quality variables that influence dissolved trace metal concentrations in natural and effluent water systems with a particular attention given to the relationship between DOM optical properties and dissolved copper and iron concentrations. We found that specific UV absorbance (SUVA: an indicator of DOM aromaticity) has a significant correlation with dissolved trace metal to dissolved organic carbon concentration ratios ([Me]/[DOC]) for copper and iron in natural freshwaters and treated municipal wastewater in the Sagami River basin, Japan. This trend was also prevalent for other freshwaters in temperate climates except for Fe-rich waters. Our findings indicate that the concentrations of dissolved copper and iron in natural and effluent waters are significantly influenced not only by DOM concentration, but also by aromaticity of DOM, and that this DOM property can be inferred from spectrophotometric measurements.

Oxidation and reduction kinetics of iron (Fe) and proportion of steady-state Fe(II) concentration relative to total dissolved Fe (steady-state Fe(II) fraction) were investigated in the presence of various types of standard humic substances (HS) with particular emphasis on the photochemical and thermal reduction of Fe(III) and oxidation of Fe(II) by dissolved oxygen (O2) and hydrogen peroxide (H2O2) at circumneutral pH (pH 7–8). Rates of Fe(III) reduction were spectrophotometrically determined by a ferrozine method under the simulated sunlight and dark conditions, whereas rates of Fe(II) oxidation were examined in air-saturated solution using luminol chemiluminescence technique. The reduction and oxidation rate constants were determined to substantially vary depending on the type of HS. For example, the first-order rate constants varied by up to 10-fold for photochemical reduction and 7-fold for thermal reduction. The degree of variation in Fe(II) oxidation was larger for the H2O2-mediated reaction compared to the O2-mediated reaction (e.g., 15- and 3-fold changes for the former and latter reactions, respectively, at pH 8). The steady-state Fe(II) fraction under the simulated sunlight indicated that the Fe(II) fraction varies by up to 12-fold. The correlation analysis indicated that variation of Fe(II) oxidation is significantly associated with aliphatic content of HS, suggesting that Fe(II) complexation by aliphatic components accelerates Fe(II) oxidation. The reduction rate constant and steady-state Fe(II) fractions in the presence of sunlight had relatively strong positive relations with free radical content of HS, possibly due to the reductive property of radical semiquinone in HS. Overall, the findings in this study indicated that the Fe reduction and oxidation kinetics and resultant Fe(II) formation are substantially influenced by chemical properties of HS.

No abstract

No abstract