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.

Dissolved organic matter (DOM) is a complex and heterogeneous mixture ubiquitously present in aquatic systems. DOM affects octylphenol (OP) and bisphenol A (BPA) distribution, transport, bioavailability, and toxicity. This study investigated OP and BPA sorption constants, log KCOC, with three size-fractioned DOM. The molecular weights of the sized fractions were low molecular weight DOM (LDOM, <1 kDa), middle molecular weight DOM (MDOM, 1–10 kDa), and high molecular weight DOM (HDOM, 10 kDa–0.45 μm). The log KCOC ranged from 5.34 to 6.14 L/kg-C for OP and from 5.59 to 6.04 L/kg-C for BPA. The OP and BPA log KCOC values were insignificantly different (p = 0.37) and had a strong positive correlation (r = 0.85, p < 0.001). The OP and BPA LDOM log KCOC was significantly higher than the HDOM and MDOM log KCOC (p = 0.012 for BPA, p = 0.023 for OP). The average specific ultraviolet absorption (SUVA254) values were 32.0 ± 5.4, 13.8 ± 1.0, and 17.9 ± 2.8 L/mg-C/m for LDOM, MDOM, and HDOM, respectively. The log KCOC values for both OP and BPA had a moderately positive correlation with the SUVA254 values (r = 0.79–0.84, p < 0.002), which suggested the aromatic group content in the DOM had a positive impact on sorption behavior.

Sediment humic substance (SHS) is a highly heterogeneous and complex organic mixture with a broad molecular weight range. It is the significant component that associates distribution, transport, and biotoxicity of pollutants in a river environment. Air- and freeze-drying sediment pre-treatment may cause different biological activity and may result in different chemical quantities and sediment organic matter. This study collected sediments that received livestock wastewater discharge. The sediments were air- (AD) and freeze-dried (FD). The dried sediment organic matter was extracted with an alkaline solution and separated into three size-fractioned SHS samples. Size-fractioning is an effective method used to differentiate materials, on a molecular level. The bulk solution (<0.45 μm) was designated as BHS, and size-fractioned solutions were identified as LHS (<1 kDa), MHS (1–10 kDa), and HHS (10 kDa-0.45 μm). The AD SHS had a lower dissolved organic carbon (DOC) concentration than the FD SHS for the bulk and individual size-fractioned SHS, but the AD and FD SHS had a similar distribution of organic carbon in the size-fractioned SHS. The AD SHS had higher aromaticity (SUVA254) and an extent of humification (HIX) than the FD SHS. In addition, the high molecular weight SHS (HHS) had a higher SUVA254 but lower HIX than the MHS and LHS. The HHS had significantly lower fulvic acid but had higher humic acid-like substances than the MHS and LHS. This is possibly the reason the LHS had a higher humification degree but lower aromaticity than HHS. The size-fractioned SHS and optical indicators distinguished the difference between the chemical properties when air- or freeze-dried, due to the different degree of biological activities.