Nickel Binding Affinity with Size-Fractioned Sediment Dissolved and Particulate Organic Matter and Correlation with Optical Indicators

In rivers, the distribution and reactivity of heavy metals (HMs) are affected by their binding affinity with sediment dissolved organic matter (DOM) and particulate organic matter (POM). The HM-OM binding affinity affected by the interaction between DOM and POM is not well studied. This study investigated the Ni binding affinity to size-fractioned overlaying water DOM and alkaline extracted sediment POM solution (AEOM). The DOM/AEOM filtrates (<0.45 μm) were sequentially separated into five nominal molecular weight (MW) solutions. The AEOM optical indicators had lower autochthonous, higher terrestrial sources, and lower aromaticity than the DOM. The Ni mass (72.3 ± 6.4%) was primarily distributed in the low molecular weight DOM (<1 kDa), whereas the Ni (93.5 ± 0.4%) and organic carbon (OC) mass (85.3 ± 1.0%) were predominantly distributed in the high molecular weight AEOM. The Ni and DOM binding affinity, ([Ni]/[DOC])DOM ratio ranging from 0.76 to 27.32 μmol/g-C, was significantly higher than the ([Ni]/[DOC])AEOM ratios, which ranged from 0.64 to 2.64 μmol/g-C. The ([Ni]/[DOC])AEOM ratio correlated significantly with the selected optical indicators (r = 0.87–0.92, p < 0.001), but the ([Ni]/[DOC])DOM ratio correlated weakly with the optical indicators (r = 0.13–0.40, p > 0.05). In the present study, the Ni binding affinity with size-fractioned DOM/AEOM agrees with the hypothesis of the DOM and POM exchange conceptual model in sediment. The POM underwent a hydrolysis/oxidation process; hence, AEOM had a high molecular weight and stable chemical composition and structure. The Ni mainly attached to the high molecular weight AEOM and the ([Ni]/[DOC])AEOM ratios had a strong correlation with the AEOM optical indicators. In contrast, DOM had a high ([Ni]/[DOC])DOM ratio in low molecular weight DOM.

Fluorescence of Size-Fractioned Humic Substance Extracted from Sediment and Its Effect on the Sorption of Phenanthrene

Phenanthrene (Phe) is a toxin and is ubiquitous in the environment. The sediment humic substances (HS) that bind Phe affect the fate, transport, degradation, and ecotoxicology of Phe. This study investigated Phe sorption constants on size-fractioned HS extracted from river sediment. Fractions were identified as HHS (10 kDa to 0.45 μm), MHS (1–10 kDa), and LHS (<1 kDa). A fluorescence quenching (FQ) method was used to determine the Phe log KHS on size-fractioned HS; the values ranged from 3.97 to 4.68 L/kg-C. The sorption constant (log KHS) is a surrogate of the binding capacity between HS and Phe, where a high log KHS reduces the toxicity and degradation of Phe. The log KHS values on HHS and MHS were significantly higher than the values on LHS (p = 0.015). The SUVA254 values of HHS and MHS were also significantly higher than the LHS value (p = 0.047), while fluorescence index (FI) and S275–295 values were significantly lower than the LHS values (p < 0.005). The HHS and MHS had a higher aromaticity and more terrestrial sources than LHS. The log KHS had a significant correlation with the selected optical indicators (p < 0.002), which suggested that the HS-bound Phe was positively affected by high aromaticity, terrestrial sources, and HS molecular weight. The results demonstrated that optical methods successfully obtained log KHS and the chemical properties of fractioned HS as well as the influenced factors of log KHS. Moreover, even the LHS had a capacity to bind with Phe.