Innovative approach to reveal source contribution of dissolved organic matter in a complex river watershed using end-member mixing analysis based on spectroscopic proxies and multi-isotopes.

Dissolved organic matter (DOM) in river watersheds dynamically changes based on its source during a monsoon period with storm event. However, the variations in DOM in urban and rural river watersheds that are dominated by point and non-point sources have not been adequately explored to date. We developed an innovative approach to reveal DOM sources in complex river watershed systems during pre-monsoon, monsoon, and post-monsoon periods using end-member mixing analysis (EMMA) by combining multi-isotope values (δ13C-DOC, δ15N-NO3 and δ18O-NO3) and spectroscopic indices (fluorescence index [FI], biological index [BIX], humification index [HIX], and specific UV absorbance [SUVA]). Several potential end-members of DOM sources were collected from watersheds, including top-soils, groundwater, plant group (fallen leaves, riparian plants, suspended algae), and different effluents (cattle and pig livestock, agricultural land, urban, industry facility, swine treatment facility and wastewater treatment facility). Concentrations of dissolved organic carbon, dissolved organic nitrogen, NO3-N, and NH4-N increased during the monsoon period with an increase in the input of anthropogenic DOM, which have higher HIX values owing to the flushing effect. The results of EMMA indicate that soil and agricultural effluents accounted for a substantial contribution of anthropogenic DOM at varying rates based on seasons. We also found that results of EMMA based on combining spectroscopic indices and δ13C-DOC isotope values were more accurate in tracing DOM sources with respect to land-use characteristics compared to applying only spectroscopic indices. The positive relationship between FI, BIX and δ15N-NO3 were revealed that nitrate would be decomposed from DOM affected by intensive agricultural activities. In addition, consistent with the EMMA results, the molecular composition of the DOM was clearly evidenced by a large number of CHON formulas, accounting for over 50% of the total characterized compounds, including pesticides and pharmaceuticals used in agriculture farmland and livestock. Our results clearly demonstrated that EMMA based on combing multi-stable isotopes and spectroscopic indices could be trace the DOM source, which is important for understanding changes in the DOM quality, and application of nitrate isotopes and molecular analysis supports in-depth interpretation. This study provides easy and intuitive techniques for the estimation of the relative impacts of DOM sources in complex river watersheds, which can be verified in various ways rather than relying on a single technique approach.

Ferric-enhanced chemical remediation of dredged marine sediment contaminated by metals and petroleum hydrocarbons.

Sediments nearby harbors are dredged regularly, and the sediments require the stringent treatment to meet the regulations on reuse and mitigate the environmental burdens from toxic pollutants. In this study, FeCl3 was chosen as an extraction agent to treat marine sediment co-contaminated with Cu, Zn, and total petroleum hydrocarbons (TPH). In chemical extraction process, the extraction efficiency of Cu and Zn by FeCl3 was compared with the conventional one using inorganic acids (H2SO4 and HCl). Despite the satisfactory level for extraction of Cu (78.8%) and Zn (73.3%) by HCl (0.5 M) through proton-enhanced dissolution, one critical demerit, particularly acidified sediment, led to the unwanted loss of Al, Fe, and Mg by dissolution. Moreover, the vast amount of HCl required the huge amounts of neutralizing agents for the post-treatment of the sediment sample via the washing process. Despite a low concentration, extraction of Cu (70.1%) and Zn (69.4%) was done by using FeCl3 (0.05 M) through proton-enhanced dissolution, ferric-organic matter complexation, and oxidative dissolution of sulfide minerals. Ferric iron (Fe3+) was reduced to ferrous iron (Fe2+) with sulfide (S2-) oxidation during FeCl3 extraction. In consecutive chemical oxidations using hydrogen peroxide (H2O2) and persulfate (S2O82-), the resultant ferrous iron was used to activate the oxidants to effectively degrade TPH. S2O82- using FeCl3 solution (molar ratio of ferrous to S2O82- is 19.8-198.3) removed 42.6% of TPH, which was higher than that by H2O2 (molar ratio of ferrous to H2O2 is 1.2-6.1). All experimental findings suggest that ferric is effectively accommodated to an acid washing step for co-contaminated marine sediments, which leads to enhanced extraction, cost-effectiveness, and less environmental burden.