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Abstract The particulate organic matter buried in carbonate-rich seagrass ecosystems is an important blue carbon reservoir. While carbonate sediments are affected by alkalinity produced or consumed in seagrass-mediated biogeochemical processes, little is known about the corresponding impact on organic matter. A portion of particulate organic matter is carbonate-associated organic matter. Here, we explore its biogeochemistry in a carbonate seagrass meadow in central Florida Bay, USA. We couple inorganic stable isotope analyses (δ³⁴S, δ¹⁸O) with a molecular characterization of dissolved and carbonate associated organic matter (21 tesla Fourier-transform ion cyclotron resonance mass spectrometry). We find that carbonate-associated molecular formulas are highly sulfurized compared to surface water dissolved organic matter, with multiple sulfurization pathways at play. Furthermore, 97% of the formula abundance of surface water dissolved organic matter is shared with carbonate-associated organic matter, indicating connectivity between these two pools. We estimate that 9.2% of the particulate organic matter is carbonate-associated, and readily exchangeable with the broader aquatic system as the sediment dissolves and reprecipitates. 

Estuaries function as important transporters, transformers, and producers of organic matter (OM). Along the freshwater to saltwater gradient, the composition of OM is influenced by physical and biogeochemical processes that change spatially and temporally, making it difficult to constrain OM in these ecosystems. In addition, many of the environmental parameters (temperature, precipitation, riverine discharge) controlling OM are expected to change due to climate change. To better understand the environmental drivers of OM quantity (concentration) and quality (absorbance, fluorescence), we assessed both dissolved OM (DOM) and particulate OM (POM) spatially, along the freshwater to saltwater gradient and temporally, for a full year. We found seasonal differences in salinity throughout the estuary due to elevated riverine discharge during the late fall to early spring, with corresponding changes to OM quantity and quality. Using redundancy analysis, we found DOM covaried with salinity (adjusted r2 = 0.35, 0.41 for surface and bottom), indicating terrestrial sources of DOM in riverine discharge were the dominant DOM sources throughout the estuary, while POM covaried with environmental indictors of terrestrial sources (turbidity, adjusted r2 = 0.16, 0.23 for surface and bottom) as well as phytoplankton biomass (chlorophyll-a, adjusted r2 = 0.25, 0.14 for surface and bottom). Responses in OM quantity and quality observed during the period of elevated discharge were similar to studies assessing OM quality following extreme storm events suggesting that regional changes in precipitation, as predicted by climate change, will be as important in changing the estuarine OM pool as episodic storm events in the future. 

Abstract Analysis of lignin in seawater is essential to understanding the fate of terrestrial dissolved organic matter (DOM) in the ocean and its role in the carbon cycle. Lignin is typically quantified by gas or liquid chromatography, coupled with mass spectrometry (GC‐MS or LC‐MS). MS instrumentation can be relatively expensive to purchase and maintain. Here we present an improved approach for quantification of lignin phenols using LC and absorbance detection. The approach applies a modified version of parallel factor analysis (PARAFAC2) to 2^ndderivative absorbance chromatograms. It is capable of isolating individual elution profiles of analytes despite co‐elution and overall improves sensitivity and specificity, compared to manual integration methods. For most lignin phenols, detection limits below 5 nmol L⁻¹were achieved, which is comparable to MS detection. The reproducibility across all laboratory stages for our reference material showed a relative standard deviation between 1.47% and 16.84% for all 11 lignin phenols. Changing the amount of DOM in the reaction vessel for the oxidation (dissolved organic carbon between 22 and 367 mmol L⁻¹), did not significantly affect the final lignin phenol composition. The new method was applied to seawater samples from the Kattegat and Davis Strait. The total concentration of dissolved lignin phenols measured in the two areas was between 4.3–10.1 and 2.1–3.2 nmol L⁻¹, respectively, which is within the range found by other studies. Comparison with a different oxidation approach and detection method (GC‐MS) gave similar results and underline the potential of LC and absorbance detection for analysis of dissolved lignin with our proposed method. 

Abstract. The net ecosystem productivity (NEP) of two seagrassmeadows within one of the largest seagrass ecosystems in the world, FloridaBay, was assessed using direct measurements over consecutive diel cyclesduring a short study in the fall of 2018. We report significant differencesbetween NEP determined by dissolved inorganic carbon (NEPDIC) and bydissolved oxygen (NEPDO), likely driven by differences in air–water gasexchange and contrasting responses to variations in light intensity. We alsoacknowledge the impact of advective exchange on metabolic calculations ofNEP and net ecosystem calcification (NEC) using the “open-water” approachand attempt to quantify this effect. In this first direct determination ofNEPDIC in seagrass, we found that both seagrass ecosystems were netheterotrophic, on average, despite large differences in seagrass netabove-ground primary productivity. NEC was also negative, indicating thatboth sites were net dissolving carbonate minerals. We suggest that acombination of carbonate dissolution and respiration in sediments exceededseagrass primary production and calcification, supporting our negative NEPand NEC measurements. However, given the limited spatial (two sites) andtemporal (8 d) extent of this study, our results may not berepresentative of Florida Bay as a whole and may be season-specific. Theresults of this study highlight the need for better temporal resolution,accurate carbonate chemistry accounting, and an improved understanding ofphysical mixing processes in future seagrass metabolism studies.