The distribution of intact polar lipid-derived branched tetraethers along a freshwater-seawater pH gradient in coastal East China Sea

In view of the application of microbial branched tetraether lipids (i.e., brGDGTs) in terrestrial pH reconstructions, their potential as seawater pH proxy is investigated from the Yangtze River Estuary (YRE) to the shelf region in the East China Sea (ECS). BrGDGTs occurring as ‘fossil’ core and in ‘living’ intact polar lipids (CL-brGDGTs and IPL-brGDGTs, respectively) in surface sediments are separately analyzed. The results show that riverine IPL-brGDGTs are rapidly lost at the transition from the YRE to the marine settings and sedimentary IPL-brGDGTs are predominantly produced in situ in brackish water environments. Among environmental parameters, surface water pH is a determinant factor controlling the cyclization of IPL-brGDGTs, with higher cyclization at higher pH. Hereby, two IPL-brGDGTs-based seawater pH calibrations are established in the brackish seawater environment in this study: surface pH = 7.28 + 1.08 × #Ringstetra (n = 18, r2 = 0.87, RMSE = 0.05, p < 0.01) and surface pH = 7.13 + 3.82 × f(Ic) + 4.29 × f(IIb') + 4.21 × f(IIIa) (n = 18, r2 = 0.90, RMSE = 0.04, p < 0.01), which are different from those established in terrestrial environments. This is the first work demonstrating that in situ produced microbial brGDGTs can trace seawater pH change in marine environment, which makes it promising to apply brGDGTs for seawater pH reconstructions in marine settings where the terrestrial inputs are negligible.