Seasonal variability in carbon:234thorium ratios of suspended and sinking particles in coastal Antarctic waters: Field data and modeling synthesis

238U-234Th disequilibrium is a powerful tool for investigating particle cycling and carbon export associated with the ocean's biological carbon pump. However, the interpretation of this method is complicated by multiple processes that can modify carbon:thorium ratios over small spatial scales. We investigated seasonal variability in the thorium and carbon cycles at a coastal site in the Western Antarctic Peninsula. Throughout the ice-free summer season, we quantified carbon and 234Th vertical flux, total water column 234Th, particulate 234Th, and the C:234Th ratios of sinking material and bulk suspended material. Simultaneous identification and separation of fecal pellets from sinking material showed that fecal pellets (primarily from krill) contributed 56% of carbon flux and that as a result of lower C:234Th ratios than suspended particles, these fecal pellets were primary drivers of variability in the C:234Th ratios of sinking material. Bulk suspended particles had highly variable C:234Th ratios and were consistently elevated in the euphotic zone relative to deeper waters. The fraction of 234Th adsorbed onto particles was positively correlated with chlorophyll and particulate organic carbon (POC) concentrations. The C:234Th ratios of suspended particles were positively correlated with POC, although during the spring diatom bloom C:234Th ratios were lower than would have been predicted based on POC concentrations alone. We hypothesize that diatom production of transparent exopolymers may have led to enhanced rates of thorium adsorption during the bloom, thus decreasing the C:234Th ratios. We used a Bayesian model selection approach to develop and parameterize mechanistic models to simulate thorium sorption dynamics. The best model incorporated one slowly-sinking POC pool and rapidly-sinking fecal pellets, with second-order sorption kinetics. The model accurately simulated temporal patterns in the C:234Th ratios of sinking and suspended particles and the fraction of 234Th adsorbed to particles. However, it slightly over-estimated C:234Th ratios during the spring (diatom-dominated) bloom and underestimated C:234Th ratios during the fall (mixed-assemblage) bloom. Optimized model parameters for thorium sorption and desorption were 0.0047 +/- 0.0002 m3 mmol C-1 d-1 and 0.017 +/- 0.008 d-1, respectively. Our results highlight the important role that specific taxa can play in modifying the C:234Th ratio of sinking and suspended particles and provide guidance for future studies that use 234Th measurements to investigate the functional relationships driving the efficiency of the biological pump.

Monitoring of Sierra Nevada Caves Reveals the Potential for Stalagmites to Archive Seasonal Variability

In the southwestern United States, California (CA) is one of the most climatically sensitive regions given its low (≤250 mm/year) seasonal precipitation and its inherently variable hydroclimate, subject to large magnitude modulation. To reconstruct past climate change in CA, cave calcite deposits (stalagmites) have been utilized as an archive for environmentally sensitive proxies, such as stable isotope compositions (δ18O, δ13C) and trace element concentrations (e.g., Mg, Ba, Sr). Monitoring the cave and associated surface environments, the chemical evolution of cave drip-water, the calcite precipitated from the drip-water, and the response of these systems to seasonal variability in precipitation and temperature is imperative for interpreting stalagmite proxies. Here we present monitored drip-water and physical parameters at Lilburn Cave, Sequoia Kings Canyon National Park (Southern Sierra Nevada), CA, and measured trace element concentrations (Mg, Sr, Ba, Cu, Fe, Mn) and stable isotopic compositions (δ18O, δ2H) of drip-water and for calcite (δ18O) precipitated on glass substrates over a two-year period (November 2018 to February 2021) to better understand how chemical variability at this site is influenced by local and regional precipitation and temperature variability. Despite large variability in surface temperatures and precipitation amount and source region (North Pacific vs. subtropical Pacific), Lilburn Cave exhibits a constant cave environment year-round. At two of the three sites within the cave, drip-water δ18O and δ2H are influenced seasonally by evaporative enrichment. At a third collection site in the cave, the drip-water δ18O responds solely to precipitation δ18O variability. The Mg/Ca, Ba/Ca, and Sr/Ca ratios are seasonally responsive to prior calcite precipitation at all sites but minimally to water-rock interaction. Lastly, we examine the potential of trace metals (e.g., Mn2+ and Cu2+as a geochemical proxy of recharge and find that variability in their concentrations has high potential to denote the onset of the rainy season in the study region. The drip-water composition is recorded in the calcite, demonstrating that stalagmites from Lilburn Cave, and potentially more regionally, could record seasonal variability in weather even during periods of substantially reduced rainfall.