The land-to-ocean loops of the global carbon cycle.

Carbon storage by the ocean and by the land is usually quantified separately, and does not fully take into account the land-to-ocean transport of carbon through inland waters, estuaries, tidal wetlands and continental shelf waters-the 'land-to-ocean aquatic continuum' (LOAC). Here we assess LOAC carbon cycling before the industrial period and perturbed by direct human interventions, including climate change. In our view of the global carbon cycle, the traditional 'long-range loop', which carries carbon from terrestrial ecosystems to the open ocean through rivers, is reinforced by two 'short-range loops' that carry carbon from terrestrial ecosystems to inland waters and from tidal wetlands to the open ocean. Using a mass-balance approach, we find that the pre-industrial uptake of atmospheric carbon dioxide by terrestrial ecosystems transferred to the ocean and outgassed back to the atmosphere amounts to 0.65 ± 0.30 petagrams of carbon per year (±2 sigma). Humans have accelerated the cycling of carbon between terrestrial ecosystems, inland waters and the atmosphere, and decreased the uptake of atmospheric carbon dioxide from tidal wetlands and submerged vegetation. Ignoring these changing LOAC carbon fluxes results in an overestimation of carbon storage in terrestrial ecosystems by 0.6 ± 0.4 petagrams of carbon per year, and an underestimation of sedimentary and oceanic carbon storage. We identify knowledge gaps that are key to reduce uncertainties in future assessments of LOAC fluxes.

Triple oxygen isotope constraints on atmospheric O2 and biological productivity during the mid-Proterozoic.

Reconstructing the history of biological productivity and atmospheric oxygen partial pressure (pO2) is a fundamental goal of geobiology. Recently, the mass-independent fractionation of oxygen isotopes (O-MIF) has been used as a tool for estimating pO2 and productivity during the Proterozoic. O-MIF, reported as Δ'17O, is produced during the formation of ozone and destroyed by isotopic exchange with water by biological and chemical processes. Atmospheric O-MIF can be preserved in the geologic record when pyrite (FeS2) is oxidized during weathering, and the sulfur is redeposited as sulfate. Here, sedimentary sulfates from the ∼1.4-Ga Sibley Formation are reanalyzed using a detailed one-dimensional photochemical model that includes physical constraints on air-sea gas exchange. Previous analyses of these data concluded that pO2 at that time was <1% PAL (times the present atmospheric level). Our model shows that the upper limit on pO2 is essentially unconstrained by these data. Indeed, pO2 levels below 0.8% PAL are possible only if atmospheric methane was more abundant than today (so that pCO2 could have been lower) or if the Sibley O-MIF data were diluted by reprocessing before the sulfates were deposited. Our model also shows that, contrary to previous assertions, marine productivity cannot be reliably constrained by the O-MIF data because the exchange of molecular oxygen (O2) between the atmosphere and surface ocean is controlled more by air-sea gas transfer rates than by biological productivity. Improved estimates of pCO2 and/or improved proxies for Δ'17O of atmospheric O2 would allow tighter constraints to be placed on mid-Proterozoic pO2.

Decoupling of Estuarine Hypoxia and Acidification as Revealed by Historical Water Quality Data.

Hypoxia and acidification are commonly coupled in eutrophic aquatic environments because aerobic respiration is usually dominant in bottom waters and can lower dissolved oxygen (DO) and pH simultaneously. However, the degree of coupling, which can be weakened by non-aerobic respiration and CaCO3 cycling, has not been adequately assessed. In this study, we applied a box model to 20 years of water quality monitoring data to explore the relationship between hypoxia and acidification along the mainstem of Chesapeake Bay. In the early summer, dissolved inorganic carbon (DIC) production in mid-bay bottom waters was dominated by aerobic respiration, contributing to DO and pH declines. In contrast, late-summer DIC production was higher than that expected from aerobic respiration, suggesting potential buffering processes, such as calcium carbonate dissolution, which would elevate pH in hypoxic waters. These findings are consistent with contrasting seasonal relationships between riverine nitrogen (N) loads and hypoxic and acidified volumes. The N loads were associated with increased hypoxic and acidified volumes in June, but only increased hypoxic volumes in August, when acidified volume declines instead. Our study reveals that the magnitude of this decoupling varies interannually with watershed nutrient inputs, which has implications for the management of co-stressors in estuarine systems.

The spatial distribution of soil organic carbon in tidal wetland soils of the continental United States.

Tidal wetlands contain large reservoirs of carbon in their soils and can sequester carbon dioxide (CO2 ) at a greater rate per unit area than nearly any other ecosystem. The spatial distribution of this carbon influences climate and wetland policy. To assist with international accords such as the Paris Climate Agreement, national-level assessments such as the United States (U.S.) National Greenhouse Gas Inventory, and regional, state, local, and project-level evaluation of CO2 sequestration credits, we developed a geodatabase (CoBluCarb) and high-resolution maps of soil organic carbon (SOC) distribution by linking National Wetlands Inventory data with the U.S. Soil Survey Geographic Database. For over 600,000 wetlands, the total carbon stock and organic carbon density was calculated at 5-cm vertical resolution from 0 to 300 cm of depth. Across the continental United States, there are 1,153-1,359 Tg of SOC in the upper 0-100 cm of soils across a total of 24 945.9 km2 of tidal wetland area, twice as much carbon as the most recent national estimate. Approximately 75% of this carbon was found in estuarine emergent wetlands with freshwater tidal wetlands holding about 19%. The greatest pool of SOC was found within the Atchafalaya/Vermilion Bay complex in Louisiana, containing about 10% of the U.S. total. The average density across all tidal wetlands was 0.071 g cm-3 across 0-15 cm, 0.055 g cm-3 across 0-100 cm, and 0.040 g cm-3 at the 100 cm depth. There is inherent variability between and within individual wetlands; however, we conclude that it is possible to use standardized values at a range of 0-100 cm of the soil profile, to provide first-order quantification and to evaluate future changes in carbon stocks in response to environmental perturbations. This Tier 2-oriented carbon stock assessment provides a scientific method that can be copied by other nations in support of international requirements.

Anthropogenic ocean acidification over the twenty-first century and its impact on calcifying organisms.

Today's surface ocean is saturated with respect to calcium carbonate, but increasing atmospheric carbon dioxide concentrations are reducing ocean pH and carbonate ion concentrations, and thus the level of calcium carbonate saturation. Experimental evidence suggests that if these trends continue, key marine organisms--such as corals and some plankton--will have difficulty maintaining their external calcium carbonate skeletons. Here we use 13 models of the ocean-carbon cycle to assess calcium carbonate saturation under the IS92a 'business-as-usual' scenario for future emissions of anthropogenic carbon dioxide. In our projections, Southern Ocean surface waters will begin to become undersaturated with respect to aragonite, a metastable form of calcium carbonate, by the year 2050. By 2100, this undersaturation could extend throughout the entire Southern Ocean and into the subarctic Pacific Ocean. When live pteropods were exposed to our predicted level of undersaturation during a two-day shipboard experiment, their aragonite shells showed notable dissolution. Our findings indicate that conditions detrimental to high-latitude ecosystems could develop within decades, not centuries as suggested previously.

Challenges in Quantifying Air-Water Carbon Dioxide Flux Using Estuarine Water Quality Data: Case Study for Chesapeake Bay.

Estuaries play an uncertain but potentially important role in the global carbon cycle via CO2 outgassing. The uncertainty mainly stems from the paucity of studies that document the full spatial and temporal variability of estuarine surface water partial pressure of carbon dioxide ( pCO2). Here, we explore the potential of utilizing the abundance of pH data from historical water quality monitoring programs to fill the data void via a case study of the mainstem Chesapeake Bay (eastern United States). We calculate pCO2 and the air-water CO2 flux at monthly resolution from 1998 to 2018 from tidal fresh to polyhaline waters, paying special attention to the error estimation. The biggest error is due to the pH measurement error, and errors due to the gas transfer velocity, temporal sampling, the alkalinity mixing model, and the organic alkalinity estimation are 72%, 27%, 15%, and 5%, respectively, of the error due to pH. Seasonal, interannual, and spatial variability in the air-water flux and surface pCO2 is high, and a correlation analysis with oxygen reveals that this variability is driven largely by biological processes. Averaged over 1998-2018, the mainstem bay is a weak net source of CO2 to the atmosphere of 1.2 (1.1, 1.4) mol m-2 yr-1 (best estimate and 95% confidence interval). Our findings suggest that the abundance of historical pH measurements in estuaries around the globe should be mined in order to constrain the large spatial and temporal variability of the CO2 exchange between estuaries and the atmosphere.

Impact of climate change and climate anomalies on hydrologic and biogeochemical processes in an agricultural catchment of the Chesapeake Bay watershed, USA.

Nutrient export from agricultural landscapes is a water quality concern and the cause of mitigation activities worldwide. Climate change impacts hydrology and nutrient cycling by changing soil moisture, stoichiometric nutrient ratios, and soil temperature, potentially complicating mitigation measures. This research quantifies the impact of climate change and climate anomalies on hydrology, nutrient cycling, and greenhouse gas emissions in an agricultural catchment of the Chesapeake Bay watershed. We force a calibrated model with seven downscaled and bias-corrected regional climate models and derived climate anomalies to assess their impact on hydrology and the export of nitrate (NO3-), phosphorus (P), and sediment, and emissions of nitrous oxide (N2O) and di-nitrogen (N2). Model-average (±standard deviation) results indicate that climate change, through an increase in precipitation and temperature, will result in substantial increases in winter/spring flow (10.6 ±â€¯12.3%), NO3- (17.3 ±â€¯6.4%), dissolved P (32.3 ±â€¯18.4%), total P (24.8 ±â€¯16.9%), and sediment (25.2 ±â€¯16.6%) export, and a slight increases in N2O (0.3 ±â€¯4.8%) and N2 (0.2 ±â€¯11.8%) emissions. Conversely, decreases in summer flow (-29.1 ±â€¯24.6%) and the export of dissolved P (-15.5 ±â€¯26.4%), total P (-16.3 ±â€¯20.7%), sediment (-20.7 ±â€¯18.3%), and NO3- (-29.1 ±â€¯27.8%) are driven by greater evapotranspiration from increasing summer temperatures. Decreases in N2O (-26.9 ±â€¯15.7%) and N2 (-36.6 ±â€¯22.9%) are predicted in the summer and driven by drier soils. While the changes in flow are related directly to changes in precipitation and temperature, the changes in nutrient and sediment export are, to some extent, driven by changes in agricultural management that climate change induces, such as earlier spring tillage and altered nutrient application timing and by alterations to nutrient cycling in the soil.

Dissolved organic carbon fluxes in the Middle Atlantic Bight: An integrated approach based on satellite data and ocean model products.

Continental margins play an important role in global carbon cycle, accounting for 15-21% of the global marine primary production. Since carbon fluxes across continental margins from land to the open ocean are not well constrained, we undertook a study to develop satellite algorithms to retrieve dissolved organic carbon (DOC) and combined these satellite data with physical circulation model products to quantify the shelf boundary fluxes of DOC for the U.S. Middle Atlantic Bight (MAB). Satellite DOC was computed through seasonal relationships of DOC with colored dissolved organic matter absorption coefficients, which were derived from an extensive set of in situ measurements. The multiyear time series of satellite-derived DOC stocks (4.9 Teragrams C; Tg) shows that freshwater discharge influences the magnitude and seasonal variability of DOC on the continental shelf. For the 2010-2012 period studied, the average total estuarine export of DOC into the MAB shelf is 0.77 Tg C yr-1 (year). The integrated DOC tracer fluxes across the shelf boundaries are 12.1 Tg C yr-1 entering the MAB from the southwest alongshore boundary, 18.5 Tg C yr-1 entering the MAB from the northeast alongshore boundary, and 29.0 Tg C yr-1 flowing out of the MAB across the entire length of the 100 m isobath. The magnitude of the cross-shelf DOC flux is quite variable in time (monthly) and space (north to south). The highly dynamic exchange of water along the shelf boundaries regulates the DOC budget of the MAB at subseasonal time scales.

Increasing N abundance in the northwestern Pacific Ocean due to atmospheric nitrogen deposition.

The relative abundance of nitrate (N) over phosphorus (P) has increased over the period since 1980 in the marginal seas bordering the northwestern Pacific Ocean, located downstream of the populated and industrialized Asian continent. The increase in N availability within the study area was mainly driven by increasing N concentrations and was most likely due to deposition of pollutant nitrogen from atmospheric sources. Atmospheric nitrogen deposition had a high temporal correlation with N availability in the study area (r = 0.74 to 0.88), except in selected areas wherein riverine nitrogen load may be of equal importance. The increase in N availability caused by atmospheric deposition and riverine input has switched extensive parts of the study area from being N-limited to P-limited.

Modeling the dynamics of continental shelf carbon.

Continental margin systems are important contributors to global nutrient and carbon budgets. Effort is needed to quantify this contribution and how it will be modified under changing patterns of climate and land use. Coupled models will be used to provide projections of future states of continental margin systems. Thus, it is appropriate to consider the limitations that impede the development of realistic models. Here, we provide an overview of the current state of modeling carbon cycling on continental margins as well as the processes and issues that provide the next challenges to such models. Our overview is done within the context of a coupled circulation-biogeochemical model developed for the northeastern North American continental shelf region. Particular choices of forcing and initial fields and process parameterizations are used to illustrate the consequences for simulated distributions, as revealed by comparisons to observations using quantitative statistical metrics.