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

Abstract

238U-234Th disequilibrium is a powerful tool for investigating particle cycling and carbon export associated with the oceans 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. HIGHLIGHTSInvestigated thorium and carbon cycling over full ice-free season C:234Th ratios of sinking particles were controlled by low C:234Th of fecal pellets C:234Th ratios of suspended particles were correlated with chlorophyll and POC Diatom abundance may have led to high particulate thorium during spring bloom Second-order thorium sorption kinetics model accurately simulates C:234Th ratios