The stable carbon isotopic composition of Thaumarchaeota-produced crenarchaeol (δ13Ccren) is thought to reflect the δ13C of dissolved inorganic carbon (DIC) and is valuable in carbon cycle research. Recently, an isotope flux-balance model was proposed that δ13Ccren is dependent on passive CO2 uptake and a slow rate of intracellular conversion to HCO3−, which has been validated in open ocean environments. However, further studies are required in environments with larger ranges of aqueous CO2 and diverse archaeal communities to examine whether the δ13Ccren value could still be predicted by the model. Here, we report δ13C values of biphytanes chemically released from the archaeal tetraether lipids (i.e., GDGTs) in sediments along a transect exhibiting shifts in the archaeal community and showing gradients of salinity, pH, and CO2 in the Pearl River Estuary, South China. Methanogenic and methanotrophic Euryarchaeota are present in the upper estuary, although not significant, as revealed by the elevated relative abundances of GDGT-0 and higher values of methane index in suspended particulate matter (SPM) and surface sediments, as well as the more 13C-depleted C40:0, C40:1, and C40:2 biphytanes than the C40:3 biphytane released from sedimentary GDGTs. Toward the lower estuary and coastal sea, GDGT distributions in SPM and sediments tend to indicate archaeal communities under normal marine conditions. However, there are still differences in δ13C values between C40:0 and C40:3 biphytanes by up to 2.4‰ in sediments, although C40:1, C40:2, and C40:3 were similar in δ13C, likely due to the existence of marine group II Euryarchaeota. Along such a physicochemical and biogeochemical gradient, the values of sedimentary δ13C40:3 increase monotonically with the increase of mean annual pH and the decrease of mean annual CO2. This phenomenon resembles the reported δ13CGDGT profiles, along with the variations in pH and CO2, in water column in the open ocean, and hence consistent in direction with the isotope flux-balance model for Thaumarchaeota lipids. However, our estimated apparent biosynthetic isotope effect (εAr) of crenarchaeol, ranging from 15.2‰ to 19.7‰, is mostly lower than those estimated in the open ocean. With the constraints of thaumarchaeal growth rates in such a dynamic estuarine environment as well as those in the open ocean, we suggest slight reductions in catalytic efficiency and intracellular kinetic isotope effect of intracellular CO2 hydration relative to previously employed values. Such modifications would slightly change the sensitivities of εAr to archaeal growth rate and ambient CO2 concentration but might be more suitable for variable hydrology and community environments.
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