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High-throughput physiochemical and biogeochemical characterization for coastal soils and waters

Coastal environments span large biogeochemical gradients and provide critical ecosystem services worldwide, thereby having a disproportionately larger influence on global biogeochemical cycles and greenhouse gas fluxes than their geographical extent suggests. Despite this, cohesive quantitative tools to understand and describe these environments, including scalable, standardized field and laboratory methodologies are lacking. In this work, we advanced the streamlining and standardizing of quantitative approaches to measure and understand coastal physiochemical properties and biogeochemical processes across systems and scales. Outcomes of this work includes workflows for multiple complementary and in-line analyses, from basic physiochemical datasets to targeted molecular approaches and proof of concept through manipulation and analysis of coastal soils and waters with varying salinity, minerology, and biogeochemistry.

54 ENVIRONMENTAL SCIENCES↗

A new biogeochemical modelling framework (FLaMe-v1.0) for lake methane emissions on the regional scale: development and application to the European domain

This study presents a new physical-biogeochemical modelling framework for simulating lake methane (CH 4 ) emissions at regional scales. The new model, FLaMe-v1.0 (Fluxes of Lake Methane), rests on an innovative, computationally efficient lake clustering approach that enables the simulation of CH 4 emissions across a large number of lakes. Building on the Canadian Small Lake Model (CSLM) that simulates the lake physics, we develop a suite of biogeochemical modules to simulate transient dynamics of organic Carbon (C), Oxygen (O 2 ), and CH 4 . We first test the performance of FLaMe-v1.0 by analyzing physical and biogeochemical processes in two theoretical lakes with characteristics that can be considered representative for many lakes (an oligotrophic, deep lake driven by cold climate versus a eutrophic, shallow lake driven by warm climate). Next, we evaluate the model by comparing simulated and observed timeseries of CH 4 emissions in four well-surveyed lakes. We then apply FLaMe-v1.0 at the European scale to evaluate simulated diffusive and ebullitive lake CH 4 fluxes against in-situ measurements in both boreal and central European regions. Finally, we provide a first assessment of the spatio-temporal variability in CH 4 emissions from European lakes with a surface area comprised between 0.1–1000 km 2 (n= 108 407, total area = 1.33 × 105 km 2 ), indicating a total emission of 0.97 ± 0.23 Tg CH 4 yr −1 , with the uncertainty constrained by combining FLaMe-v1.0 and machine learning techniques. Moreover, 30 % and 70 % of these CH 4 emissions are through diffusive and ebullitive pathways, respectively. Annually averaged CH 4 emission rates per unit lake area during 2010–2016 have a South-to-North decreasing gradient, resulting in a mean over the European domain as 7.39 g CH 4 m −2 yr −1 . Our simulations reveal a strong seasonality (with ice-blocking effects accounted for) in European lake CH 4 emissions, with nearly ten times higher emissions during late summer than during winter. This pronounced seasonal variation highlights the importance of accounting for the sub-annual variability in CH 4 emissions to accurately constrain regional CH 4 budgets. In the future, FLaMe-v1.0 could be embedded into Earth System Models to investigate the feedback between climate warming and global lake CH 4 emissions.

Maisonnier, Manon [Free Univ. of Brussels (Belgium↗

Lambda-PFLOTRAN 1.0: a workflow for incorporating organic matter chemistry informed by ultra high resolution mass spectrometry into biogeochemical modeling

Abstract. Organic matter (OM) composition plays a central role in microbial respiration of dissolved organic matter and subsequent biogeochemical reactions. Here, a direct connection of organic matter chemistry and thermodynamics to reactive transport simulators has been achieved through the newly developed Lambda-PFLOTRAN workflow tool that succinctly incorporates carbon chemistry data generated from Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS) into reaction networks to simulate organic matter degradation and the resulting biogeochemistry. Lambda-PFLOTRAN is a Python-based workflow, executed through a Jupyter notebook interface, that digests raw FTICR-MS data, develops a representative reaction network based on substrate-explicit thermodynamic modeling (also termed lambda modeling due to its key thermodynamic parameter λ used therein), and completes a biogeochemical simulation with the open source, reactive flow and transport code PFLOTRAN. The workflow consists of the following five steps: configuration, thermodynamic (lambda) analysis, sensitivity analysis, parameter estimation, and simulation output and visualization. Two test cases are provided to demonstrate the functionality of the Lambda-PFLOTRAN workflow. The first test case uses laboratory incubation data of temporal oxygen depletion to fit lambda parameters (i.e., maximum utilization rate and microbial carrying capacity). A slightly more complex second test case fits multiple lambda formulation and soil organic matter release parameters to temporal greenhouse gas generation measured during a soil incubation. Overall, the Lambda-PFLOTRAN workflow facilitates upscaling by using molecular-scale characterization to inform biogeochemical processes occurring at larger scales.

58 GEOSCIENCES↗

Biogeochemical modeling at mass extinction boundaries

The causes of major mass extinctions is a subject of considerable interest to those concerned with the history and evolution of life on earth. The primary objectives of the proposed plan of research are: (1) to develop quantitative time-dependent biogeochemical cycle models, coupled with an ocean atmosphere in order to improve the understanding of global scale physical, chemical, and biological processes that control the distribution of elements important for life at times of mass extinctions; and (2) to develop a comprehensive data base of the best available geochemical, isotopic, and other relevant geologic data from sections across mass extinction boundaries. These data will be used to constrain and test the biogeochemical model. These modeling experiments should prove useful in: (1) determining the possible cause(s) of the environmental changes seen at bio-event boundaries; (2) identifying and quantifying little-known feedbacks among the oceans, atmosphere, and biosphere; and (3) providing additional insights into the possible responses of the earth system to perturbations of various timescales. One of the best known mass extinction events marks the Cretaceous/Tertiary (K/T) boundary (66 Myr ago). Data from the K/T boundary are used here to constrain a newly developed time-dependent biogeochemical cycle model that is designed to study transient behavior of the earth system. Model results predict significant fluctuations in ocean alkalinity, atmospheric CO2, and global temperatures caused by extinction of calcareous plankton and reduction in the sedimentation rates of pelagic carbonates and organic carbon. Oxygen-isotome and other paleoclimatic data from K/T time provide some evidence that such climatic fluctuations may have occurred, but stabilizing feedbacks may have acted to reduce the ocean alkalinity and carbon dioxide fluctuations.

Rampino, M. R.↗

Biogeochemical factors which regulate the formation and fate of sulfide in wetlands

Coastal wetland areas occupy a small percentage of the terrestrial environment yet are extremely productive regions which support rapid rates of below ground bacterial activity. Wetlands appear to be significant as biogenic sources of gaseous sulfur, carbon, and nitrogen. These gases are important as tracers of man's activities, and they influence atmospheric chemistry. The interactions among wetland biogeochemical processes regulate the anaerobic production of reduced gases and influence the fate of these volatiles. Therefore, spatial and temporal variations in hydrology, salinity, temperature, and speciation and growth of vegetation affect the type and magnitude of gas emissions thus hindering predictive estimates of gas flux. The research is divided into two major parts, the first is the biogeochemical characterization of a selected tidal wetland area in terms of factors likely to regulate sulfide flux; the second is a direct measurement of gaseous sulfur flux as related to changes in these biogeochemical conditions. Variant factors affecting sulfide flux include the wetlands' tidal range, seasonal salinity, and other hydrological conditions, grass species and plant growth, soil composition, and microbial activity.

Hines, Mark E.↗

Biogeochemical factors which regulate the formation and fate of sulfide in wetlands

Coastal wetland areas occupy a small percentage of the terrestrial environment yet are extremely productive regions which support rapid rates of belowground bacterial activity. Wetlands appear to be significant as biogenic sources of gaseous sulfur, carbon, and nitrogen. These gases are important as tracers of man's activities, and they influence atmospheric chemistry. The interactions among wetland biogeochemical processes regulate the anaerobic production of reduced gases and influence the fate of these volatiles. Therefore, spatial and temporal variations in hydrology, salinity, temperature and specification, and growth of vegetation affect the type and magnitude of gas emissions thus hindering predictive estimates of gas flux. Our research is divided into two major components, the first is the biogeochemical characterization of a selected tidal wetland area in terms of factors likely to regulate sulfide flux; the second is a direct measurement of gaseous sulfur flux as related to changes in these biogeochemical conditions. Presently, we are near completion of phase one.

Hines, Mark E.↗

Apparatus for Cold, Pressurized Biogeochemical Experiments

A laboratory apparatus has been devised as a means of studying plausible biogeochemical reactions under high-pressure, low-temperature aqueous, anaerobic conditions like those conjectured to prevail in a liquid water ocean on Europa (the fourth largest moon of the planet Jupiter). The experiments to be performed by use of this apparatus are intended to enhance understanding of how life (if any) could originate and evolve in the Europa ocean environment. Inasmuch as terrestrial barophilic, psychrophilic organisms that thrive under anaerobic conditions are used in the experiments, the experiments may also contribute to terrestrial biogeochemistry. The apparatus (see figure) includes a bolt-closure reaction vessel secured inside a refrigerator that maintains a temperature of 4 C. Pressurized water is supplied to the interior of the vessel by a hydrostatic pump, which is attached to the vessel via high-pressure fittings. The terrestrial organisms used in the experiments thus far have been several facultative barophilic, psychrophilic stains of Shewanella bacteria. In the experiments, these organisms have been tested for reduction of ferric ion by growing them in the presence of a ferric food source under optimized terrestrial conditions. The short-term goal of these experiments has been to select Shewanella strains that exhibit iron-reduction capability and test their ability to facilitate biogeochemical reduction of iron under temperature and pressure conditions imitating those in Europa s ocean. It is anticipated, that, once growth under Europa-like conditions has been achieved, the selected Shewanella strains will be used to facilitate biogeochemical reactions of sulfate and carbonate with hydrogen gas. Any disequilibrium of the products with the environment would be interpreted as signifying biogenic activity and the possibility of life in Europa s ocean.

Amashukeli, Xenia↗

Arctic Biogeochemical and Optical Properties of Dissolved Organic Matter Across River to Sea Gradients

Arctic landscapes are warming and becoming wetter due to changes in precipitation and the timing of snowmelt which consequently alters seasonal runoff and river discharge patterns. These changes in hydrology lead to increased mobilization and transport of terrestrial dissolved organic matter (DOM) to Arctic coastal seas where significant impacts on biogeochemical cycling can occur. Here, we present measurements of dissolved organic carbon (DOC) and chromophoric DOM (CDOM) in the Yukon River-to-Bering Sea system and two river plumes on the Alaska North Slope which flow into the Beaufort Sea. Our sampling characterized optical and biogeochemical properties of DOM during high and low river discharge periods for the Yukon River-Bering Sea system. The average DOC concentration at the multiple Yukon River mouths ranged from a high of 10.36 mg C L-1 during the ascending limb of the 2019 freshet (late May), 6.4 mg C L-1 during the descending limb of the 2019 freshet (late June), and a low of 3.86 mg C L-1 during low river discharge in August 2018. CDOM absorption coefficient at 412 nm (aCDOM(412)) averaged 8.23 m-1, 5.07 m-1, and 1.9 m-1, respectively. Several approaches to model DOC concentration based on its relationship with CDOM properties demonstrated cross-system seasonal and spatial robustness for these Arctic coastal systems despite spanning an order of magnitude decrease in DOC concentration from the lower Yukon River to the Northern Bering Sea as well as the North Slope systems. “Snapshot” fluxes of DOC and CDOM across the Yukon River Delta to Norton Sound were calculated from our measurements and modeled water fluxes forced with upstream USGS river gauge data. Our findings suggest that during high river flow, DOM reaches the delta largely unaltered by inputs or physical and biogeochemical processing and that the transformations of Yukon River DOM largely occur in the plume. However, during low summer discharge, multiple processes including local precipitation events, microbial decomposition, photochemistry, and likely others can alter the DOM properties within the lower Yukon River and Delta prior to flowing into Norton Sound.

Arctic↗

Biogeochemical evolution of ponded meltwater in a High Arctic subglacial tunnel

Subglacial environments comprise ∼10 % of Earth's land surface, host active microbial ecosystems, and are important components of global biogeochemical cycles. However, the broadly inaccessible nature of subglacial systems has left them vastly understudied, and research to date has been limited to laboratory experiments or field measurements using basal ice or subglacial water accessed through boreholes or from the glacier margin. In this study, we extend our understanding of subglacial biogeochemistry and microbiology to include observations of a slushy pond of water that occupied a remnant meltwater channel beneath a polythermal glacier in the Canadian High Arctic over winter. The hydraulics and geochemistry of the system suggest that the pond water originated as late-season, ice-marginal runoff with less than ∼15 % solute contribution from subglacial sources. Over the 8 months of persistent sub-zero regional temperatures, the pond gradually froze, cryo-concentrating solutes in the residual water by up to 7 times. Despite cryo-concentration and the likely influx of some subglacial solute, the pond was depleted in only the most labile and biogeochemically relevant compounds, including ammonium, phosphate, and dissolved organic matter, including a potentially labile tyrosine-like component. DNA amplicon sequencing revealed decreasing microbial diversity with distance into the meltwater channel. The pond at the terminus of the channel hosted a microbial community inherited from late-season meltwater, which was dominated by only six taxa related to known psychrophilic and psychrotolerant heterotrophs that have high metabolic diversity and broad habitat ranges. Collectively, our findings suggest that generalist microbes from the extraglacial or supraglacial environments can become established in subglacial aquatic systems and deplete reservoirs of nutrients and dissolved organic carbon over a period of months. These findings extend our understanding of the microbial and biogeochemical evolution of subglacial aquatic ecosystems and the extent of their habitability.

Ashley J Dubnick↗

The Median Isn’t the Message: soil nutrient hot spots have a disproportionate influence on biogeochemical structure across years, seasons, and depths

Abstract Soil nutrient distribution is heterogeneous in space and time, potentially altering nutrient acquisition by trees and microorganisms. Ecologists have distinguished “hot spots” (HSs) as areas with enhanced and sustained rates of nutrient fluxes relative to the surrounding soil matrix. We evaluated the spatial and temporal patterns in nutrient flux HSs in two mixed-conifer forest soils by repeatedly sampling the soil solution at the same spatial locations (horizontally and vertically) over multiple seasons and years using ion exchange resins incubated in situ. The climate of these forests is Mediterranean, with intense fall rains occurring following summers with little precipitation, and highly variable winter snowfall. Hot spots formed most often for NO 3 − and Na + . Although nutrient HSs often occurred in the same spatial location multiple times, HSs persisted more often for PO 4 3− NH 4 + , and NO 3 − , and were more transient for Ca 2+ , Mg 2+ , and Na + . Sampling year (annual precipitation ranged from 558 to 1223 mm) impacted the occurrence of HSs for most nutrients, but season was only significant for PO 4 3− , NH 4 + , NO 3 − , and Na + , with HSs forming more often after fall rains than after spring snowmelt. The frequency of HSs significantly decreased with soil depth for all nutrients, forming most commonly immediately below the surficial organic horizon. Although HSs accounted for less than 17% of the sampling volume, they were responsible for 56–88% of PO 4 3− , NH 4 + , and NO 3 − resin fluxes. Our results suggest that macronutrient HSs have a disproportional contribution to soil biogeochemical structure, with implications for vegetation nutrient acquisition strategies and biogeochemical models. Graphical abstract

54 ENVIRONMENTAL SCIENCES↗

River Dynamics Control Transit Time Distributions and Biogeochemical Reactions in a Dam-Regulated River Corridor

Residence Time Distributions (RTDs) exert an important control on biogeochemical translation in the hydrological systems. Previous tracer studies have revealed that RTDs often followed time-invariant exponential, lognormal, or heavy-tailed RTDs that have power-law behavior for long tails in headwater or low-order streams. However, there is a recognition that RTDs can be more complicated and time-variable in response to dynamic hydrological forcing. Here, we use particle tracking to estimate RTDs along the Hanford Reach of the Columbia River and to quantify the influences of river stage fluctuations. Particle tracking is conducted using the velocity field from high-resolution 3D groundwater flow simulations. The effects of hydrological forcing on the residence time distribution were evaluated by varying river flow boundary conditions and releasing particles in different time windows. Our results revealed that dynamic stage fluctuations created rapidly changing losing-gaining conditions in the river and led to highly transient RTDs, which contributes to multiple modes of RTDs. Dam-induced high-frequency (sub-daily) flow variation contributes to the short-time (sub-daily) component of the RTDs. Deviation of the reactant consumption under the single-mode assumption compared to the multimodal RTDs is relatively small (~5%) and appears when the Damköhler number was close to one.More specifically, high-frequency (daily) dam-induced stage variations have higher impacts on biogeochemical reactions with faster reaction rate, and can potentially increase the reactant consumption by 26.68%. Based on these findings, we suggest that current river basin models could be improved by including bank storage and more complex RTDs influenced by both short and long term river stage fluctuations.

54 ENVIRONMENTAL SCIENCES↗

Integrating Tide‐Driven Wetland Soil Redox and Biogeochemical Interactions Into a Land Surface Model

Abstract Redox processes, aqueous and solid‐phase chemistry, and pH dynamics are key drivers of subsurface biogeochemical cycling and methanogenesis in terrestrial and wetland ecosystems but are typically not included in terrestrial carbon cycle models. These omissions may introduce errors when simulating systems where redox interactions and pH fluctuations are important, such as wetlands where saturation of soils can produce anoxic conditions and coastal systems where sulfate inputs from seawater can influence biogeochemistry. Integrating cycling of redox‐sensitive elements could therefore allow models to better represent key elements of carbon cycling and greenhouse gas production. We describe a model framework that couples the Energy Exascale Earth System Model (E3SM) Land Model (ELM) with PFLOTRAN biogeochemistry, allowing geochemical processes and redox interactions to be integrated with land surface model simulations. We implemented a reaction network including aerobic decomposition, fermentation, sulfate reduction, sulfide oxidation, methanogenesis, and methanotrophy as well as pH dynamics along with iron oxide and iron sulfide mineral precipitation and dissolution. We simulated biogeochemical cycling in tidal wetlands subject to either saltwater or freshwater inputs driven by tidal hydrological dynamics. In simulations with saltwater tidal inputs, sulfate reduction led to accumulation of sulfide, higher dissolved inorganic carbon concentrations, lower dissolved organic carbon concentrations, and lower methane emissions than simulations with freshwater tidal inputs. Model simulations compared well with measured porewater concentrations and surface gas emissions from coastal wetlands in the Northeastern United States. These results demonstrate how simulating geochemical reaction networks can improve land surface model simulations of subsurface biogeochemistry and carbon cycling.

54 ENVIRONMENTAL SCIENCES↗

The Effects of Chlorophyll Assimilation on Carbon Fluxes in a Global Biogeochemical Model

In this paper, we investigated whether the assimilation of remotely-sensed chlorophyll data can improve the estimates of air-sea carbon dioxide fluxes (FCO2). Using a global, established biogeochemical model (NASA Ocean Biogeochemical Model, NOBM) for the period 2003-2010, we found that the global FCO2 values produced in the free-run and after assimilation were within -0.6 mol C m(sup -2) y(sup -1) of the observations. The effect of satellite chlorophyll assimilation was assessed in 12 major oceanographic regions. The region with the highest bias was the North Atlantic. Here the model underestimated the fluxes by 1.4 mol C m(sup -2) y(sup -1) whereas all the other regions were within 1 mol C m(sup -2) y(sup -1) of the data. The FCO2 values were not strongly impacted by the assimilation, and the uncertainty in FCO2 was not decreased, despite the decrease in the uncertainty in chlorophyll concentration. Chlorophyll concentrations were within approximately 25% of the database in 7 out of the 12 regions, and the assimilation improved the chlorophyll concentration in the regions with the highest bias by 10-20%. These results suggest that the assimilation of chlorophyll data does not considerably improve FCO2 estimates and that other components of the carbon cycle play a role that could further improve our FCO2 estimates.

Biogeochemical Model↗

Aerosols in Atmospheric Chemistry and Biogeochemical Cycles of Nutrients

Atmospheric aerosols have complex and variable compositions and properties.While scientific interest is centered on the health and climatic effects of atmospheric aerosols, insufficient attention is given to their involvement in multiphase chemistry that alters their contribution as carriers of nutrients in ecosystems. However, there is experimental proof that the nutrient equilibria of both land and marine ecosystems have been disturbed during the Anthropocene period. This review study first summarizes our current understanding of aerosol chemical processing in the atmosphere as relevant to biogeochemical cycles. Then it binds together results of recent modeling studies based on laboratory and field experiments, focusing on the organic and dust components of aerosols that account for multiphase chemistry, aerosol ageing in the atmosphere, nutrient (N, P, Fe) emissions, atmospheric transport, transformation and deposition. The human-driven contribution to atmospheric deposition of these nutrients, derived by global simulations using past and future anthropogenic emissions of pollutants, is put into perspective with regard to potential changes in nutrient limitations and biodiversity. Atmospheric deposition of nutrients has been suggested to result in human-induced ecosystem limitations with regard to specific nutrients. Such modifications favor the development of certain species against others and affect the overall functioning of ecosystems. Organic forms of nutrients are found to contribute to the atmospheric deposition of the nutrients N, P and Fe by 20%-40%, 35%-45% and 7%-18%, respectively. These have the potential to be key components of the biogeochemical cycles since there is initial proof of their bioavailability to ecosystems. Bioaerosols have been found to make a significant contribution to atmospheric sources of N and P, indicating potentially significant interactions between terrestrial and marine ecosystems. These results deserve further experimental and modeling studies to reduce uncertainties and understand the feedbacks induced by atmospheric deposition of nutrients to ecosystems.

dust↗

Modeling Demographic-Driven Vegetation Dynamics and Ecosystem Biogeochemical Cycling in NASA GISS’s Earth System Model (ModelE-BiomeE v.1.0)

We developed a demographic vegetation model, BiomeE, to improve the modeling of vegetation dynamics and ecosystem biogeochemical cycles in the NASA Goddard Institute of Space Studies' ModelE Earth system model. This model includes the processes of plant growth, mortality, reproduction, vegetation structural dynamics, and soil carbon and nitrogen storage and transformations. The model combines the plant physiological processes of ModelE's original vegetation model, Ent, with the plant demographic and ecosystem nitrogen processes that have been represented in the Geophysical Fluid Dynamics Laboratory's LM3-PPA. We used nine plant functional types to represent global natural vegetation functional diversity, including trees, shrubs, and grasses, and a new phenology model to simulate vegetation seasonal changes with temperature and precipitation fluctuations. Competition for light and soil resources is individual based, which makes the modeling of transient compositional dynamics and vegetation succession possible. Overall, the BiomeE model simulates, with fidelity comparable to other models, the dynamics of vegetation and soil biogeochemistry, including leaf area index, vegetation structure (e.g., height, tree density, size distribution, and crown organization), and ecosystem carbon and nitrogen storage and fluxes. This model allows ModelE to simulate transient and long-term biogeophysical and biogeochemical feedbacks between the climate system and land ecosystems. Furthermore, BiomeE also allows for the eco-evolutionary modeling of community assemblage in response to past and future climate changes with its individual-based competition and demographic processes.

Biogeochemical cycles↗

Modelling the Sensitivity of Yukon River Biogeochemical Dynamics to Environmental and Chemical Drivers: Implications for Dissolved Organic Carbon

Riverine dissolved organic carbon (DOC) is a critical biogeochemical component that transmits information from Arctic soils to the Arctic Ocean, significantly influencing carbon dynamics in this unique ecosystem. As DOC travels downstream, it undergoes transformations that alter its composition and fate. The Yukon River serves as an effective testbed for modelling these dynamics, offering sufficient scale to capture key biogeochemical processes while having a simpler hydrology than other major Arctic rivers, as well as long-term DOC observational data for model validation. To investigate DOC transformations during transit in the Yukon River, we adapted our Arctic Riverine Organic Macromolecular Model by applying regional-specific parameterisations. Our model simulates the transport and transformation of 15 organic macromolecules, including CDOM (coloured dissolved organic matter), proteins, polysaccharides, lipids, lignin phenols, and humic substances. Initial DOC concentrations were derived from observed soil organic carbon stocks in the surrounding watershed, while chemical transformations and hydrological dynamics were modelled along the river's course. Sensitivity and uncertainty analyses were conducted using a Monte Carlo approach under two experimental setups. Results revealed that variability in DOC and CDOM concentrations at the river mouth were predominantly driven by initial DOC concentration (~70% of variability explained) and dilution at confluence points (~10%). The refractory fraction of DOC explained 21%–88% of the variability in 14 macromolecular concentrations and ranked in the top five sensitive parameters for all outputs when a uniform parameter distribution was assumed. However, when a more likely variability was applied to this parameter, its influence on DOC and CDOM decreased. Given that refractory DOC accounts for ~80% of total DOC in Arctic Rivers, this suggests that most DOC resists degradation and retains its chemical composition during transport to the coastal environment. River velocity, which determines residence time, explained 8%–47% of the variability in protein, polysaccharide, lipid, pigments, and lignin phenols at the river mouth. In contrast, chemical turnover times contributed only 1%–5% to output variability. Our findings underscore the need for improved land-specific headwater observations, including seasonal soil moisture and lateral transport dynamics that control the initial tributary-specific DOC inputs. With accelerated permafrost thaw and increasing river discharge, extending our model to other Arctic River systems and seasons will enhance understanding of Arctic riverine carbon fluxes and their contributions to the Arctic Ocean.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Marine phytoplankton resilience may moderate oligotrophic ecosystem responses and biogeochemical feedbacks to climate change

Are the oceans turning into deserts? Rising temperature, increasing surface stratification, and decreasing vertical inputs of nutrients are expected to cause an expansion of warm, nutrient deplete ecosystems. Such an expansion is predicted to negatively affect a trio of key ocean biogeochemical features: phytoplankton biomass, primary productivity, and carbon export. However, phytoplankton communities are complex adaptive systems with immense diversity that could render them at least partially resilient to global changes. This can be illustrated by the biology of the Prochlorococcus “collective.” Adaptations to counter stress, use of alternative nutrient sources, and frugal resource allocation can allow Prochlorococcus to buffer climate-driven changes in nutrient availability. In contrast, cell physiology is more sensitive to temperature changes. We argue that biogeochemical models need to consider the adaptive potential of diverse phytoplankton communities. However, a full understanding of phytoplankton resilience to future ocean changes is hampered by a lack of global biogeographic observations to test theories. We propose that the resilience may in fact be greater in oligotrophic waters than currently considered with implications for future predictions of phytoplankton biomass, primary productivity, and carbon export.

54 ENVIRONMENTAL SCIENCES↗

Toward more mechanistic representations of biogeochemical processes in river networks: Implementation and demonstration of a multiscale model

A recently introduced multiscale model for representing the effects of small-scale hyporheic-zone biogeochemical processes is extended from the reach scale to river network scales. The model uses advection-dispersion-reaction equations for the channel network and one-dimensional advection-reaction subgrid models for the hyporheic zone. We summarize implementation in the integrated surface/subsurface hydrology modeling system Amanzi-ATS. The extension uses topologically defined meshes to represent stream/river networks and associates a hyporheic subgrid model with each channel grid cell. Biogeochemical reaction modeling capability residing in community software is accessed through an application programming interface. The implementation is verified against independent numerical solutions on a single reach. Mesh convergence studies show that commonly used semi-distributed representations can introduce significant spatial discretization error. Denitrification of farm runoff in a subbasin of the Portage River Basin in Ohio, USA is used to demonstrate the general-purpose reactive transport capability.

54 ENVIRONMENTAL SCIENCES↗