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  1. Abstract

    Riverine dissolved iron (Fe) affects water color, nutrients, and marine carbon cycling. Fe size and coupling with dissolved organic matter (DOM), in part, modulates the biogeochemical roles of riverine Fe. We used size fractionation to operationally define dissolved Fe (< 0.22 μm) into soluble (< 0.02 μm) and colloidal (0.02–0.22 μm) fractions in order to characterize the downstream drivers, concentrations, and fluxes of Fe across season and hydrologic regime at the freshwater Connecticut River mainstem, which we sampled bi‐weekly for 2 yrs. Drivers of colloidal and soluble Fe concentrations were markedly different. The response of colloidal Fe concentration to changes in discharge was modulated by water temperature; colloidal Fe decreased with increasing discharge at temperatures < 10.5°C, but increased with increasing discharge at temperatures > 10.5°C. Conversely, soluble Fe concentrations were only positively correlated to discharge at high temperatures (> 20°C). Soluble Fe was strongly positively correlated to a humic‐like DOM fluorescence component, suggesting coupling with DOM subsets, potentially through complexation. While average colloidal Fe fluxes varied twofold seasonally, soluble Fe fluxes varied ninefold; therefore, soluble Fe variability was more important to the overall dissolved Fe variability than colloidal Fe, despite lower concentrations. Seasonal Fe fluxes were decoupled from discharge: dissolved and soluble Fe fluxes were greatest in the fall, whereas discharge was greatest in the spring. Fluxes of soluble Fe, which may be more bioavailable and more likely to be exported to the ocean, were lowest in the summer when downstream biological demand is high, having implications for primary productivity and iron uptake.

     
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  2. Mean annual temperature and mean annual precipitation drive much of the variation in productivity across Earth's terrestrial ecosystems but do not explain variation in gross primary productivity (GPP) or ecosystem respiration (ER) in flowing waters. We document substantial variation in the magnitude and seasonality of GPP and ER across 222 US rivers. In contrast to their terrestrial counterparts, most river ecosystems respire far more carbon than they fix and have less pronounced and consistent seasonality in their metabolic rates. We find that variation in annual solar energy inputs and stability of flows are the primary drivers of GPP and ER across rivers. A classification schema based on these drivers advances river science and informs management. 
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  5. Abstract

    Aquatic primary productivity produces oxygen (O2) and consumes carbon dioxide (CO2) in a ratio of ~1.2. However, in aquatic ecosystems, dissolved CO2concentrations can be low, potentially limiting primary productivity. Here, results show that a large drainage basin maintains its highest levels of gross primary productivity (GPP) when dissolved CO2is diminished or undetectable due to photosynthetic uptake. Data show that, after CO2is depleted, bicarbonate, an ionized form of inorganic carbon, supports these high levels of productivity. In fact, outputs from a process‐based model suggest that bicarbonate can support up to ~58% of GPP under the most productive conditions. This is the first evidence that high levels of aquatic GPP are sustained in a riverine drainage network despite CO2depletion, which has implications for freshwater ecology, biogeochemistry, and isotopic analysis.

     
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  6. Abstract

    Streams and rivers are significant sources of carbon dioxide (CO2) and methane (CH4) to the atmosphere. However, the magnitudes of these fluxes are uncertain, in part, because dissolved greenhouse gases (GHGs) can exhibit high spatiotemporal variability. Concentration‐discharge (CQ) relationships are commonly used to describe temporal variability stemming from hydrologic controls on solute production and transport. This study assesses how the partial pressures of two GHGs—pCO2andpCH4—vary across hydrologic conditions over 4 yr in eight nested streams and rivers, at both annual and seasonal timescales. Overall, the range ofpCO2was constrained, ranging from undersaturated to nine times oversaturated, whilepCH4was highly variable, ranging from 3 to 500 times oversaturated. We show thatpCO2exhibited chemostatic behavior (i.e., no change withQ), in part, due to carbonate buffering and seasonally specific storm responses. In contrast, we show thatpCH4generally exhibited source limitation (i.e., a negative relationship withQ), which we attribute to temperature‐mediated production. However,pCH4exhibited chemostasis in a wetland‐draining stream, likely due to hydrologic connection to the CH4‐rich wetland. These findings have implications for CO2and CH4fluxes, which are controlled by concentrations and gas transfer velocities. At highQ, enhanced gas transfer velocity acts on a relatively constant CO2stock but on a diminishing CH4stock. In other words, CO2fluxes increase withQ, while CH4fluxes are modulated by the divergentQdynamics of gas transfer velocity and concentration.

     
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  7. Abstract

    Most terrestrial allochthonous organic matter enters river networks through headwater streams during high flow events. In headwaters, allochthonous inputs are substantial and variable, but become less important in streams and rivers with larger watersheds. As allochthonous dissolved organic matter (DOM) moves downstream, the proportion of less aromatic organic matter with autochthonous characteristics increases. How environmental factors converge to control this transformation of DOM at a continental scale is less certain. We hypothesized that the amount of time water has spent travelling through surface waters of inland systems (streams, rivers, lakes, and reservoirs) is correlated to DOM composition. To test this hypothesis, we used established river network scaling relationships to predict relative river network flow‐weighted travel time (FWTT) of water for 60 stream and river sites across the contiguous United States (3090 discrete samples over 10 water years). We estimated lentic contribution to travel times with upstream in‐network lake and reservoir volume. DOM composition was quantified using ultraviolet and visible absorption and fluorescence spectroscopy. A combination of FWTT and lake and reservoir volume was the best overall predictor of DOM composition among models that also incorporated discharge, specific discharge, watershed area, and upstream channel length. DOM spectral slope ratio (R2 = 0.77) and Freshness Index (R2 = 0.78) increased and specific ultraviolet absorbance at 254 nm (R2 = 0.68) and Humification Index (R2 = 0.44) decreased across sites as a function of FWTT and upstream lake volume. This indicates autochthonous‐like DOM becomes continually more dominant in waters with greater FWTT. We assert that river FWTT can be used as a metric of the continuum of DOM composition from headwaters to rivers. The nature of the changes to DOM composition detected suggest this continuum is driven by a combination of photo‐oxidation, biological processes, hydrologically varying terrestrial subsidies, and aged groundwater inputs.

     
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  8. Abstract

    The increasing availability of high‐frequency freshwater ecosystem metabolism data provides an opportunity to identify links between metabolic regimes, as gross primary production and ecosystem respiration patterns, and consumer energetics with the potential to improve our current understanding of consumer dynamics (e.g., population dynamics, community structure, trophic interactions). We describe a conceptual framework linking metabolic regimes of flowing waters with consumer community dynamics. We use this framework to identify three emerging research needs: (1) quantifying the linkage of metabolism and consumer production data via food web theory and carbon use efficiencies, (2) evaluating the roles of metabolic dynamics and other environmental regimes (e.g., hydrology, light) in consumer dynamics, and (3) determining the degree to which metabolic regimes influence the evolution of consumer traits and phenology. Addressing these needs will improve the understanding of consumer biomass and production patterns as metabolic regimes can be viewed as an emergent property of food webs.

     
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