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Many studies have examined the vulnerability of calcifying organisms, such as the eastern oyster (Crassostrea virginica), to externally forced ocean acidification, but the opposite interaction whereby oysters alter their local carbonate conditions has received far less attention. We present an exploratory model for isolating the impact that net calcification and respiration of aquacultured eastern oysters can have on calcite and aragonite saturation states, in the context of varying temperature, ocean-estuary mixing, and air-sea gas exchange. We apply the model to the Damariscotta River Estuary in Maine which has experienced rapid expansion of oyster aquaculture in the last decade. Our model uses oyster shell growth over the summer season and a previously derived relationship between net calcification and respiration to quantify impacts of net oyster calcification and gross metabolism on carbonate saturation states in open tidal waters. Under 2018 industry size and climate conditions, we estimate that oysters can lower carbonate saturation states by up to 5% (i.e., 0.17 and 0.11 units on calcite and aragonite saturation states, respectively) per day in late summer, with an average of 3% over the growing season. Perturbations from temperature and air-sea exchange are similar in magnitude. Under 2050 climate conditions and 2018 industry size, calcite saturation state will decrease by up to an additional 0.54 units. If the industry expands 3-fold by 2050, the calcite and aragonite saturation states may decrease by 0.73 and 0.47 units, respectively, on average for the latter half of the growing season when compared to 2018 climate conditions and industry size. Collectively, our results indicate that dense aggregations of oysters can have a significant role on estuarine carbonate chemistry. 

Peptides and proteins were identified during a controlled laboratory degradation of the marine diatom Thalassiosira weissflogii by a surface seawater microbiome. Samples from each time point were processed both with and without the protease trypsin, allowing a partial differentiation between peptides produced naturally by microbial enzymatic degradation and peptides produced from the laboratory digestion of intact protein. Over the 12-day degradation experiment, 31% of the particulate organic carbon was depleted, and there was no preferential degradation of the overall protein pool. However, there was distinct differentiation in the cellular location, secondary structure and modifications between peptides produced by microbial vs. laboratory breakdown. During the initial period of rapid algal decay and bacterial growth, intracellular components from the cytoplasm were consumed first, resulting in the accumulation of membrane-associated proteins and peptides in the detrital pool. Accompanying the enrichment of membrane protein material was an increase in the importance of ɑ-helix motifs. Methylated arginine, a post-translational modification common in cell senescence, was found in high amounts within the microbially produced detrital peptide pool, suggesting a link between in-cell modification and resistance to immediate degradation. Another modification—asparagine deamidation—accumulated within the detrital peptides. Protein taxonomies showed the bacterial community decomposing the algal material was rich in Proteobacteria, and protein annotations showed abundant transportation of solubilized carbohydrates and small peptides across membranes. At this early stage of diagenesis, no changes in bulk amino acids (THAA) were observed, yet a proteomic approach allowed us to observe selective changes in diatom protein preservation by using amino acid sequences to infer subcellular location, secondary structures, and post-translational modifications (PTMs).