Multi-isotopes revealing the coastal river anthropogenic pollutants and natural material flux to ocean: Sr, C, N, S, and O isotope study

Abstract

Coastal river exports massive terrestrial materials to the adjacent marine environment with information about chemical weathering, providing critical insights on riverine flux and the potential impact on marine ecosystem. In this study, the preliminary data of dissolved strontium (Sr) and ⁸⁷Sr/⁸⁶Sr in a typical coastal river in southeastern China were collected along with hydrochemistry and C, N, S, and O isotopes to discriminate the source of terrestrial weathering and the riverine flux. Sr concentrations exhibited a range of 0.084 ~ 1.307 μmol L^-1, and ⁸⁷Sr/⁸⁶Sr values ranged 0.7089 ~ 0.7164. The total cationic charge (TZ⁺) ranged 0.2 ~ 11.7 meq L^-1 with the predominant Ca²⁺ which accounted for > 50% of TZ⁺, while the anions were dominated by HCO₃^-. The extremely high Na⁺ and Cl^- near the estuary indicated seawater mixing in such a coastal river. δ¹³C-DIC, δ¹⁵N-NO₃^-, δ¹⁸O-NO₃^-, and δ³⁴S-SO₄^2- of river water ranged - 24.1‰ ~ - 9.2‰, 0.3‰ ~ 22.7‰, - 2.1‰ ~ 21.4‰, and - 9.3‰ ~ 18.0‰, respectively. δ¹³C enhanced correspondingly to decreased δ³⁴S, confirming the attendance of H₂SO₄ in carbonate weathering. Most δ¹⁸O values exhibited within ± 10‰, indicating the dominant nitrification process. δ¹⁵N presented slightly negative relationship with δ¹³C and no obvious correlation with δ³⁴S, indicating relatively limited impact of denitrification. The depleted δ¹³C and δ¹⁵N may be attributed to carbonate dissolution with nitric acids and the oxidation of organic matters into C and N pools. Quantitative analysis revealed that silicate weathering accounts for 79% of total dissolved Sr, indicating the dominant weathering process. The estimated monthly flux of dissolved Sr to the East China Sea was 138.1 tons, demonstrating an potential impact on seawater Sr isotope evolution. Overall, the investigations of multi-isotopes revealed the enhancement of weathering rates and the consequently depleted CO₂ consumption, which further proved the involvement of strong acids (H₂SO₄ and HNO₃). This study provides scientific insight in terrestrial weathering and anthropogenic impact of a typical coastal watershed and may orient the management of environmental issues related to coastal ecosystems.

Keywords: Chemical weathering; Coastal ecosystem; Jiulongjiang River; Riverine flux; Strong acids.