Showing papers in "Global Biogeochemical Cycles in 2015"

Explicitly representing soil microbial processes in Earth system models

Abstract: Microbes influence soil organic matter decomposition and the long-term stabilization of carbon (C) in soils. We contend that by revising the representation of microbial processes and their interactions with the physicochemical soil environment, Earth system models (ESMs) will make more realistic global C cycle projections. Explicit representation of microbial processes presents considerable challenges due to the scale at which these processes occur. Thus, applying microbial theory in ESMs requires a framework to link micro-scale process-level understanding and measurements to macro-scale models used to make decadal- to century-long projections. Here we review the diversity, advantages, and pitfalls of simulating soil biogeochemical cycles using microbial-explicit modeling approaches. We present a roadmap for how to begin building, applying, and evaluating reliable microbial-explicit model formulations that can be applied in ESMs. Drawing from experience with traditional decomposition models, we suggest the following: (1) guidelines for common model parameters and output that can facilitate future model intercomparisons; (2) development of benchmarking and model-data integration frameworks that can be used to effectively guide, inform, and evaluate model parameterizations with data from well-curated repositories; and (3) the application of scaling methods to integrate microbial-explicit soil biogeochemistry modules within ESMs. With contributions across scientific disciplines, we feel this roadmap can advance our fundamental understanding of soil biogeochemical dynamics and more realistically project likely soil C response to environmental change at global scales.

Spatial patterns in CO2 evasion from the global river network

Abstract: CO2 evasion from rivers (FCO2) is an important component of the global carbon budget. Here we present the first global maps of CO2 partial pressures (pCO2) in rivers of stream orders 3 and higher and the resulting FCO2 at 0.5° resolution constructed with a statistical model. A geographic information system based approach is used to derive a pCO2 prediction function trained on data from 1182 sampling locations. While data from Asia and Africa are scarce and the training data set is dominated by sampling locations from the Americas, Europe, and Australia, the sampling locations cover the full spectrum from high to low latitudes. The predictors of pCO2 are net primary production, population density, and slope gradient within the river catchment as well as mean air temperature at the sampling location (r2 = 0.47). The predicted pCO2 map was then combined with spatially explicit estimates of stream surface area Ariver and gas exchange velocity k calculated from published empirical equations and data sets to derive the FCO2 map. Using Monte Carlo simulations, we assessed the uncertainties of our estimates. At the global scale, we estimate an average river pCO2 of 2400 (2019-2826) μatm and a FCO2 of 650 (483-846) Tg C yr-1 (5th and 95th percentiles of confidence interval). Our global CO2 evasion is substantially lower than the recent estimate of 1800 Tg C yr-1 although the training set of pCO2 is very similar in both studies, mainly due to lower tropical pCO2 estimates in the present study. Our maps reveal strong latitudinal gradients in pCO2, Ariver, and FCO2. The zone between 10°N and 10°S contributes about half of the global CO2 evasion. Collection of pCO2 data in this zone, in particular, for African and Southeast Asian rivers is a high priority to reduce uncertainty on FCO2.

Global patterns and controls of soil organic carbon dynamics as simulated by multiple terrestrial biosphere models: Current status and future directions.

Abstract: Soil is the largest organic carbon (C) pool of terrestrial ecosystems, and C loss from soil accounts for a large proportion of land-atmosphere C exchange. Therefore, a small change in soil organic C (SOC) can affect atmospheric carbon dioxide (CO2) concentration and climate change. In the past decades, a wide variety of studies have been conducted to quantify global SOC stocks and soil C exchange with the atmosphere through site measurements, inventories, and empirical/process-based modeling. However, these estimates are highly uncertain, and identifying major driving forces controlling soil C dynamics remains a key research challenge. This study has compiled century-long (1901-2010) estimates of SOC storage and heterotrophic respiration (Rh) from 10 terrestrial biosphere models (TBMs) in the Multi-scale Synthesis and Terrestrial Model Intercomparison Project and two observation-based data sets. The 10 TBM ensemble shows that global SOC estimate ranges from 425 to 2111 Pg C (1 Pg = 1015 g) with a median value of 1158 Pg C in 2010. The models estimate a broad range of Rh from 35 to 69 Pg C yr-1 with a median value of 51 Pg C yr-1 during 2001-2010. The largest uncertainty in SOC stocks exists in the 40-65°N latitude whereas the largest cross-model divergence in Rh are in the tropics. The modeled SOC change during 1901-2010 ranges from -70 Pg C to 86 Pg C, but in some models the SOC change has a different sign from the change of total C stock, implying very different contribution of vegetation and soil pools in determining the terrestrial C budget among models. The model ensemble-estimated mean residence time of SOC shows a reduction of 3.4 years over the past century, which accelerate C cycling through the land biosphere. All the models agreed that climate and land use changes decreased SOC stocks, while elevated atmospheric CO2 and nitrogen deposition over intact ecosystems increased SOC stocks-even though the responses varied significantly among models. Model representations of temperature and moisture sensitivity, nutrient limitation, and land use partially explain the divergent estimates of global SOC stocks and soil C fluxes in this study. In addition, a major source of systematic error in model estimations relates to nonmodeled SOC storage in wetlands and peatlands, as well as to old C storage in deep soil layers.

The age of river-transported carbon: A global perspective

Abstract: The role played by river networks in regional and global carbon (C) budgets is receiving increasing attention. Despite the potential of radiocarbon measurements (Δ14C) to elucidate sources and cycling of different riverine C pools, there remain large regions for which no data are available and no comprehensive attempts to synthesize the available information and examine global patterns in the 14C content of different riverine C pools. Here we present new 14C data on particulate and dissolved organic C (POC and DOC) from six river basins in tropical and subtropical Africa and compiled >1400 literature Δ14C data and ancillary parameters from rivers globally. Our analysis reveals a consistent pattern whereby POC is progressively older in systems carrying higher sediment loads, coinciding with a lower organic carbon content. At the global scale, this pattern leads to a proposed global median Δ14C signature of −203‰, corresponding to an age of ~1800 years B.P. For DOC exported to the coastal zone, we predict a modern (decadal) age (Δ14C = +22 to +46‰), and paired data sets confirm that riverine DOC is generally more recent in origin than POC—in contrast to the situation in ocean environments. Weathering regimes complicate the interpretation of 14C ages of dissolved inorganic carbon, but the available data favor the hypothesis that in most cases, more recent organic C is preferentially mineralized.

Relevance of methodological choices for accounting of land use change carbon fluxes

Abstract: Accounting for carbon fluxes from land use and land cover change (LULCC) generally requires choosing from multiple options of how to attribute the fluxes to regions and to LULCC activities. Applying a newly developed and spatially explicit bookkeeping model BLUE (bookkeeping of land use emissions), we quantify LULCC fluxes and attribute them to land use activities and countries by a range of different accounting methods. We present results with respect to a Kyoto Protocol-like “commitment” accounting period, using land use emissions of 2008–2012 as an example scenario. We assess the effect of accounting methods that vary (1) the temporal evolution of carbon stocks, (2) the state of the carbon stocks at the beginning of the period, (3) the temporal attribution of carbon fluxes during the period, and (4) treatment of LULCC fluxes that occurred prior to the beginning of the period. We show that the methodological choices result in grossly different estimates of carbon fluxes for the different attribution definitions.

Fate of the Amazon River dissolved organic matter in the tropical Atlantic Ocean

Abstract: Constraining the fate of dissolved organic matter (DOM) delivered by rivers is a key to understand the global carbon cycle, since DOM mineralization directly influences air-sea CO2 exchange and multiple biogeochemical processes The Amazon River exports large amounts of DOM, and yet the fate of this material in the ocean remains unclear Here we investigate the molecular composition and transformations of DOM in the Amazon River-ocean continuum using ultrahigh resolution mass spectrometry and geochemical and biological tracers We show that there is a strong gradient in source and composition of DOM along the continuum, and that dilution of riverine DOM in the ocean is the dominant pattern of variability in the system Alterations in DOM composition are observed in the plume associated with the addition of new organic compounds by phytoplankton and with bacterial and photochemical transformations The relative importance of each of these drivers varies spatially and is modulated by seasonal variations in river discharge and ocean circulation We further show that a large fraction (50–76%) of the Amazon River DOM is surprisingly stable in the coastal ocean This results in a globally significant river plume with a strong terrigenous signature and in substantial export of terrestrially derived organic carbon from the continental margin, where it can be entrained in the large-scale circulation and potentially contribute to the long-term storage of terrigenous production and to the recalcitrant carbon pool found in the deep ocean

A revised global estimate of dissolved iron fluxes from marine sediments

Abstract: Literature data on benthic dissolved iron (DFe) fluxes (µmol m−2 d−1), bottom water oxygen concentrations (O2BW, μM), and sedimentary carbon oxidation rates (COX, mmol m−2 d−1) from water depths ranging from 80 to 3700 m were assembled. The data were analyzed with a diagenetic iron model to derive an empirical function for predicting benthic DFe fluxes: inline image where γ (= 170 µmol m−2 d−1) is the maximum flux for sediments at steady state located away from river mouths. This simple function unifies previous observations that COX and O2BW are important controls on DFe fluxes. Upscaling predicts a global DFe flux from continental margin sediments of 109 ± 55 Gmol yr−1, of which 72 Gmol yr−1 is contributed by the shelf ( 2000 m) of 41 ± 21 Gmol yr−1 is unsupported by empirical data. Previous estimates of benthic DFe fluxes derived using global iron models are far lower (approximately 10–30 Gmol yr−1). This can be attributed to (i) inadequate treatment of the role of oxygen on benthic DFe fluxes and (ii) improper consideration of continental shelf processes due to coarse spatial resolution. Globally averaged DFe concentrations in surface waters simulated with the intermediate-complexity University of Victoria Earth System Climate Model were a factor of 2 higher with the new function. We conclude that (i) the DFe flux from marginal sediments has been underestimated in the marine iron cycle and (ii) iron scavenging in the water column is more intense than currently presumed.

Climatological distribution of aragonite saturation state in the global oceans

Abstract: Aragonite saturation state (Ωarag) in surface and subsurface waters of the global oceans was calculated from up-to-date (through the year of 2012) ocean station dissolved inorganic carbon (DIC) and total alkalinity (TA) data. Surface Ωarag in the open ocean was always supersaturated (Ω > 1), ranging between 1.1 and 4.2. It was above 2.0 (2.0–4.2) between 40°N and 40°S but decreased toward higher latitude to below 1.5 in polar areas. The influences of water temperature on the TA/DIC ratio, combined with the temperature effects on inorganic carbon equilibrium and apparent solubility product (K′sp), explain the latitudinal differences in surface Ωarag. Vertically, Ωarag was highest in the surface mixed layer. Higher hydrostatic pressure, lower water temperature, and more CO2 buildup from biological activity in the absence of air-sea gas exchange helped maintain lower Ωarag in the deep ocean. Below the thermocline, aerobic decomposition of organic matter along the pathway of global thermohaline circulation played an important role in controlling Ωarag distributions. Seasonally, surface Ωarag above 30° latitudes was about 0.06 to 0.55 higher during warmer months than during colder months in the open-ocean waters of both hemispheres. Decadal changes of Ωarag in the Atlantic and Pacific Oceans showed that Ωarag in waters shallower than 100 m depth decreased by 0.10 ± 0.09 (−0.40 ± 0.37% yr−1) on average from the decade spanning 1989–1998 to the decade spanning 1998–2010.

Geographic variability in organic carbon stock and accumulation rate in sediments of East and Southeast Asian seagrass meadows

Abstract: Organic carbon (OC) stored in the sediments of seagrass meadows has been considered a globally significant OC reservoir. However, the sparsity and regional bias of studies on long-term OC accumulation in coastal sediments have limited reliable estimation of the capacity of seagrass meadows as a global OC sink. We evaluated the amount and accumulation rate of OC in sediment of seagrass meadows and adjacent areas in East and Southeast Asia. In temperate sites, the average OC concentration in the top 30 cm of sediment was higher in seagrass meadows (780–1080 μmol g−1) than in sediments without seagrass cover (52–430 μmol g−1). The average OC in the top 30 cm of subtropical and tropical seagrass meadow sediments ranged from 140 to 440 μmol g−1. Carbon isotope mass balancing suggested that the contribution of seagrass-derived carbon to OC stored in sediments was often relatively minor (temperate: 10–40%; subtropical: 35–82%; tropical: 4–34%) and correlated to the habitat type, being particularly low in estuarine habitats. Stock of OC in the top meter of sediment of all the studied meadows ranged from 38 to 120 Mg ha−1. The sediment accumulation rates were estimated by radiocarbon dating of six selected cores (0.32–1.34 mm yr−1). The long-term OC accumulation rates calculated from the sediment accumulation rate and the top 30 cm average OC concentration for the seagrass meadows (24–101 kg ha−1 yr−1) were considerably lower than the OC accumulation rates previously reported for Mediterranean Posidonia oceanica meadows (580 kg ha−1 yr−1 on average). Current estimates for the global carbon sink capacity of seagrass meadows, which rely largely on Mediterranean studies, may be considerable overestimations.

Modeling the fate of methane hydrates under global warming

Abstract: Large amounts of methane hydrate locked up within marine sediments are vulnerable to climate change. Changes in bottom water temperatures may lead to their destabilization and the release of methane into the water column or even the atmosphere. In a multimodel approach, the possible impact of destabilizing methane hydrates onto global climate within the next century is evaluated. The focus is set on changing bottom water temperatures to infer the response of the global methane hydrate inventory to future climate change. Present and future bottom water temperatures are evaluated by the combined use of hindcast high-resolution ocean circulation simulations and climate modeling for the next century. The changing global hydrate inventory is computed using the parameterized transfer function recently proposed by Wallmann et al. (2012). We find that the present-day world's total marine methane hydrate inventory is estimated to be 1146Gt of methane carbon. Within the next 100years this global inventory may be reduced by ∼0.03% (releasing ∼473Mt methane from the seafloor). Compared to the present-day annual emissions of anthropogenic methane, the amount of methane released from melting hydrates by 2100 is small and will not have a major impact on the global climate. On a regional scale, ocean bottom warming over the next 100years will result in a relatively large decrease in the methane hydrate deposits, with the Arctic and Blake Ridge region, offshore South Carolina, being most affected.

Is Atmospheric Phosphorus Pollution Altering Global Alpine Lake Stoichiometry

Abstract: Anthropogenic activities have significantly altered atmospheric chemistry and changed the global mobility of key macronutrients. Here we show that contemporary global patterns in nitrogen (N) and phosphorus (P) emissions drive large hemispheric variation in precipitation chemistry. These global patterns of nutrient emission and deposition (N:P) are in turn closely reflected in the water chemistry of naturally oligotrophic lakes (r2 = 0.81, p < 0.0001). Observed increases in anthropogenic N deposition play a role in nutrient concentrations (r2 = 0.20, p < 0.05); however, atmospheric deposition of P appears to be major contributor to this pattern (r2 = 0.65, p < 0.0001). Atmospheric simulations indicate a global increase in P deposition by 1.4 times the preindustrial rate largely due to increased dust and biomass burning emissions. Although changes in the mass flux of global P deposition are smaller than for N, the impacts on primary productivity may be greater because, on average, one unit of increased P deposition has 16 times the influence of one unit of N deposition. These stoichiometric considerations, combined with the evidence presented here, suggest that increases in P deposition may be a major driver of alpine Lake trophic status, particularly in the Southern Hemisphere. These results underscore the need for the broader scientific community to consider the impact of atmospheric phosphorus deposition on the water quality of naturally oligotrophic lakes.

Recent Amazon climate as background for possible ongoing and future changes of Amazon humid forests

Abstract: Recent analyses of Amazon runoff and gridded precipitation data suggest an intensification of the hydrological cycle over the past few decades in the following sense: wet-season precipitation and peak river runoff (since ∼ 1980) as well as annual-mean precipitation (since ∼ 1990) have increased while dry-season precipitation and minimum runoff have slightly decreased. There has also been an increase in the frequency of anomalously severe floods and droughts. Here we extend and expand these analyses to characterize recent climate state and change, as a background for possible ongoing and future changes of these forests. The contrasting recent changes in wet and dry season precipitation have continued and are generally consistent with changes in catchment-level peak and minimum river runoff as well as a positive trend of water vapour inflow into the basin. Consistent with the river records the increased vapour inflow is concentrated to the wet season. Temperature has been rising by 0.7∘C since 1980 with more pronounced warming during dry months. Suggestions for the cause of the observed changes of the hydrological cycle come from patterns in tropical sea surface temperatures (SST's). Tropical and North Atlantic SST's have increased rapidly and steadily since 1990, while Pacific SST's have shifted from a negative Pacific Decadal Oscillation (PDO) phase (approximately pre 1990) with warm eastern Pacific temperatures to a positive phase with cold eastern Pacific temperatures. These SST conditions have been shown to be associated with an increase in precipitation over most of the Amazon except the south and south-west. If ongoing changes continue we expect these to be generally beneficial for forests in those regions where there is an increase in precipitation with the exception of floodplain forests. An increase in flood-pulse height and duration could lead to increased mortality at higher levels of the floodplain and, over the long term, to a lateral shift of the zonally stratified floodplain forest communities. Negative effects on forests are mainly expected in the south-west and south, which have become slightly drier and hotter, consistent with tree mortality trends observed at the RAINFOR forest plot census network.

Variability in efficiency of particulate organic carbon export: A model study

Abstract: The flux of organic carbon from the surface ocean to mesopelagic depths is a key component of the global carbon cycle and is ultimately derived from primary production (PP) by phytoplankton. Only a small fraction of organic carbon produced by PP is exported from the upper ocean, referred to as the export efficiency (herein e-ratio). Limited observations of the e-ratio are available and there is thus considerable interest in using remotely-sensed parameters such as sea surface temperature to extrapolate local estimates to global annual export flux. Currently, there are large discrepancies between export estimates derived in this way; one possible explanation is spatial or temporal sampling bias in the observations. Here we examine global patterns in the spatial and seasonal variability in e-ratio and the subsequent effect on export estimates using a high resolution global biogeochemical model. NEMO-MEDUSA represents export as separate slow and fast sinking detrital material whose remineralisation is respectively temperature dependent and a function of ballasting minerals. We find that both temperature and the fraction of export carried by slow sinking particles are factors in determining e-ratio, suggesting that current empirical algorithms for e-ratio that only consider temperature are overly simple. We quantify the temporal lag between PP and export, which is greatest in regions of strong variability in PP where seasonal decoupling can result in large e-ratio variability. Extrapolating global export estimates from instantaneous measurements of e-ratio is strongly affected by seasonal variability, and can result in errors in estimated export of up to ±60%.

A new look at ocean carbon remineralization for estimating deepwater sequestration

Abstract: The “biological carbon pump” causes carbon sequestration in deep waters by downward transfer of organic matter, mostly as particles. This mechanism depends to a great extent on the uptake of CO2 by marine plankton in surface waters and subsequent sinking of particulate organic carbon (POC) through the water column. Most of the sinking POC is remineralized during its downward transit, and modest changes in remineralization have substantial feedback on atmospheric CO2 concentrations, but little is known about global variability in remineralization. Here we assess this variability based on modern underwater particle imaging combined with field POC flux data and discuss the potential sources of variations. We show a significant relationship between remineralization and the size structure of the phytoplankton assemblage. We obtain the first regionalized estimates of remineralization in biogeochemical provinces, where these estimates range between −50 and +100% of the commonly used globally uniform remineralization value. We apply the regionalized values to satellite-derived estimates of upper ocean POC export to calculate regionalized and ocean-wide deep carbon fluxes and sequestration. The resulting value of global organic carbon sequestration at 2000 m is 0.33 Pg C yr−1, and 0.72 Pg C yr−1 at the depth of the top of the permanent pycnocline, which is up to 3 times higher than the value resulting from the commonly used approach based on uniform remineralization and constant sequestration depth. These results stress that variable remineralization and sequestration depth should be used to model ocean carbon sequestration and feedback on the atmosphere.

Microbial nitrogen dynamics in organic and mineral soil horizons along a latitudinal transect in western Siberia.

Abstract: Soil N availability is constrained by the breakdown of N-containing polymers such as proteins to oligopeptides and amino acids that can be taken up by plants and microorganisms. Excess N is released from microbial cells as ammonium (N mineralization), which in turn can serve as substrate for nitrification. According to stoichiometric theory, N mineralization and nitrification are expected to increase in relation to protein depolymerization with decreasing N limitation, and thus from higher to lower latitudes and from topsoils to subsoils. To test these hypotheses, we compared gross rates of protein depolymerization, N mineralization and nitrification (determined using (15)N pool dilution assays) in organic topsoil, mineral topsoil, and mineral subsoil of seven ecosystems along a latitudinal transect in western Siberia, from tundra (67°N) to steppe (54°N). The investigated ecosystems differed strongly in N transformation rates, with highest protein depolymerization and N mineralization rates in middle and southern taiga. All N transformation rates decreased with soil depth following the decrease in organic matter content. Related to protein depolymerization, N mineralization and nitrification were significantly higher in mineral than in organic horizons, supporting a decrease in microbial N limitation with depth. In contrast, we did not find indications for a decrease in microbial N limitation from arctic to temperate ecosystems along the transect. Our findings thus challenge the perception of ubiquitous N limitation at high latitudes, but suggest a transition from N to C limitation of microorganisms with soil depth, even in high-latitude systems such as tundra and boreal forest. KEY POINTS: We compared soil N dynamics of seven ecosystems along a latitudinal transectShifts in N dynamics suggest a decrease in microbial N limitation with depthWe found no decrease in microbial N limitation from arctic to temperate zones.

Global oceanic emission of ammonia: Constraints from seawater and atmospheric observations

Abstract: Current global inventories of ammonia emissions identify the ocean as the largest natural source. This source depends on seawater pH, temperature, and the concentration of total seawater ammonia (NHx(sw)), which reflects a balance between remineralization of organic matter, uptake by plankton, and nitrification. Here we compare [NHx(sw)] from two global ocean biogeochemical models (BEC and COBALT) against extensive ocean observations. Simulated [NHx(sw)] are generally biased high. Improved simulation can be achieved in COBALT by increasing the plankton affinity for NHx within observed ranges. The resulting global ocean emissions is 2.5 TgN a−1, much lower than current literature values (7–23 TgN a−1), including the widely used Global Emissions InitiAtive (GEIA) inventory (8 TgN a−1). Such a weak ocean source implies that continental sources contribute more than half of atmospheric NHx over most of the ocean in the Northern Hemisphere. Ammonia emitted from oceanic sources is insufficient to neutralize sulfate aerosol acidity, consistent with observations. There is evidence over the Equatorial Pacific for a missing source of atmospheric ammonia that could be due to photolysis of marine organic nitrogen at the ocean surface or in the atmosphere. Accommodating this possible missing source yields a global ocean emission of ammonia in the range 2–5 TgN a−1, comparable in magnitude to other natural sources from open fires and soils.

Predicting long-term carbon sequestration in response to CO2 enrichment: How and why do current ecosystem models differ?

Abstract: Large uncertainty exists in model projections of the land carbon (C) sink response to increasing atmospheric CO2. Free-Air CO2 Enrichment (FACE) experiments lasting a decade or more have investigated ecosystem responses to a step change in atmospheric CO2 concentration. To interpret FACE results in the context of gradual increases in atmospheric CO2 over decades to centuries, we used a suite of seven models to simulate the Duke and Oak Ridge FACE experiments extended for 300 years of CO2 enrichment. We also determine key modeling assumptions that drive divergent projections of terrestrial C uptake and evaluate whether these assumptions can be constrained by experimental evidence. All models simulated increased terrestrial C pools resulting from CO2 enrichment, though there was substantial variability in quasi-equilibrium C sequestration and rates of change. In two of two models that assume that plant nitrogen (N) uptake is solely a function of soil N supply, the net primary production response to elevated CO2 became progressively N limited. In four of five models that assume that N uptake is a function of both soil N supply and plant N demand, elevated CO2 led to reduced ecosystem N losses and thus progressively relaxed nitrogen limitation. Many allocation assumptions resulted in increased wood allocation relative to leaves and roots which reduced the vegetation turnover rate and increased C sequestration. In addition, self-thinning assumptions had a substantial impact on C sequestration in two models. Accurate representation of N process dynamics (in particular N uptake), allocation, and forest self-thinning is key to minimizing uncertainty in projections of future C sequestration in response to elevated atmospheric CO2. (Less)

Biogeochemical drivers of the fate of riverine mercury discharged to the global and Arctic oceans

Abstract: Rivers discharge 28 ± 13 Mmol yr−1 of mercury (Hg) to ocean margins, an amount comparable to atmospheric deposition to the global oceans. Most of the Hg discharged by rivers is sequestered by burial of benthic sediment in estuaries or the coastal zone, but some is evaded to the atmosphere and some is exported to the open ocean. We investigate the fate of riverine Hg by developing a new global 3-D simulation for Hg in the Massachusetts Institute of Technology ocean general circulation model. The model includes plankton dynamics and carbon respiration (DARWIN project model) coupled to inorganic Hg chemistry. Results are consistent with observed spatial patterns and magnitudes of surface ocean Hg concentrations. We use observational constraints on seawater Hg concentrations and evasion to infer that most Hg from rivers is sorbed to refractory organic carbon and preferentially buried. Only 6% of Hg discharged by rivers (1.8 Mmol yr−1) is transported to the open ocean on a global basis. This fraction varies from a low of 2.6% in East Asia due to the barrier imposed by the Korean Peninsula and Japanese archipelago, up to 25% in eastern North America facilitated by the Gulf Stream. In the Arctic Ocean, low tributary particle loads and efficient degradation of particulate organic carbon by deltaic microbial communities favor a more labile riverine Hg pool. Evasion of Hg to the Arctic atmosphere is indirectly enhanced by heat transport during spring freshet that accelerates sea ice melt and ice rafting. Discharges of 0.23 Mmol Hg yr−1 from Arctic rivers can explain the observed summer maximum in the Arctic atmosphere, and this magnitude of releases is consistent with recent observations. Our work indicates that rivers are major contributors to Hg loads in the Arctic Ocean.

Net ecosystem production and organic carbon balance of U.S. East Coast estuaries: A synthesis approach

Abstract: Net ecosystem production (NEP) and the overall organic carbon budget for the estuaries along the East Coast of the United States are estimated. We focus on the open estuarine waters, excluding the fringing wetlands. We developed empirical models relating NEP to loading ratios of dissolved inorganic nitrogen to total organic carbon, and carbon burial in the sediment to estuarine water residence time and total nitrogen input across the landward boundary. Output from a data-constrained water quality model was used to estimate inputs of total nitrogen and organic carbon to the estuaries across the landward boundary, including fluvial and tidal-wetland sources. Organic carbon export from the estuaries to the continental shelf was computed by difference, assuming steady state. Uncertainties in the budget were estimated by allowing uncertainties in the supporting model relations. Collectively, U.S. East Coast estuaries are net heterotrophic, with the area-integrated NEP of −1.5 (−2.8, −1.0) Tg C yr−1 (best estimate and 95% confidence interval) and area-normalized NEP of −3.2 (−6.1, −2.3) mol C m−2 yr−1. East Coast estuaries serve as a source of organic carbon to the shelf, exporting 3.4 (2.0, 4.3) Tg C yr−1 or 7.6 (4.4, 9.5) mol C m−2 yr−1. Organic carbon inputs from fluvial and tidal-wetland sources for the region are estimated at 5.4 (4.6, 6.5) Tg C yr−1 or 12 (10, 14) mol C m−2 yr−1 and carbon burial in the open estuarine waters at 0.50 (0.33, 0.78) Tg C yr−1 or 1.1 (0.73, 1.7) mol C m−2 yr−1. Our results highlight the importance of estuarine systems in the overall coastal budget of organic carbon, suggesting that in the aggregate, U.S. East Coast estuaries assimilate (via respiration and burial) ~40% of organic carbon inputs from fluvial and tidal-wetland sources and allow ~60% to be exported to the shelf.

Preferential remineralization of dissolved organic phosphorus and non‐Redfield DOM dynamics in the global ocean: Impacts on marine productivity, nitrogen fixation, and carbon export

Abstract: Selective removal of nitrogen (N) and phosphorus (P) from the marine dissolved organic matter (DOM) pool has been reported in several regional studies. Because DOM is an important advective/mixing pathway of carbon (C) export from the ocean surface layer and its non-Redfieldian stoichiometry would affect estimates of marine export production per unit N and P, we investigated the stoichiometry of marine DOM and its remineralization globally using a compiled DOM data set. Marine DOM is enriched in C and N compared to Redfield stoichiometry, averaging 317:39:1 and 810:48:1 for C:N:P within the degradable and total bulk pools, respectively. Dissolved organic phosphorus (DOP) is found to be preferentially remineralized about twice as rapidly with respect to the enriched C:N stoichiometry of marine DOM. Biogeochemical simulations with the Biogeochemical Elemental Cycling model using Redfield and variable DOM stoichiometry corroborate the need for non-Redfield dynamics to match the observed DOM stoichiometry. From our model simulations, preferential DOP remineralization is found to increase the strength of the biological pump by ~9% versus the case of Redfield DOM cycling. Global net primary productivity increases ~10% including an increase in marine nitrogen fixation of ~26% when preferential DOP remineralization and direct utilization of DOP by phytoplankton are included. The largest increases in marine nitrogen fixation, net primary productivity, and carbon export are observed within the western subtropical gyres, suggesting the lateral transfer of P in the form of DOP from the productive eastern and poleward gyre margins may be important for sustaining these processes downstream in the subtropical gyres.

Recent decadal trends in global phytoplankton composition

Abstract: Identifying major trends in biogeochemical composition of the oceans is essential to improve our understanding of biological responses to climate forcing. Using the NASA Ocean Biogeochemical Model combined with ocean color remote sensing data assimilation, we assessed the trends in phytoplankton composition (diatoms, cyanobacteria, coccolithophores, and chlorophytes) at a global scale for the period 1998–2012. We related these trends in phytoplankton to physical conditions (surface temperature, surface photosynthetically available radiation (PAR), and mixed layer depth (MLD)) and nutrients (iron, silicate, and nitrate). We found a significant global decline in diatoms (−1.22% yr−1, p < 0.05). This trend was associated with a significant (p < 0.05) shallowing of the MLD (−0.20% yr−1), a significant increase in PAR (0.09% yr−1), and a significant decline in nitrate (−0.38% yr−1). The global decline in diatoms was mostly attributed to their decline in the North Pacific (−1.00% yr−1, p < 0.05), where the MLD shallowed significantly and resulted in a decline in all three nutrients (p < 0.05). None of the other phytoplankton groups exhibited a significant change globally, but regionally there were considerable significant trends. A decline in nutrients in the northernmost latitudes coincided with a significant decline in diatoms (North Pacific, −1.00% yr−1) and chlorophytes (North Atlantic, −9.70% yr−1). In the northern midlatitudes (North Central Pacific and Atlantic) where nutrients were more scarce, a decline in nutrients was associated with a decline in smaller phytoplankton: cyanobacteria declined significantly in the North Central Pacific (−0.72% yr−1) and Atlantic (−1.56% yr−1), and coccolithophores declined significantly in the North Central Atlantic (−2.06% yr−1). These trends represent the diversity and complexity of mechanisms that drives phytoplankton communities to adapt to variable conditions of nutrients, light, and mixed layer depth. These results provide a first insight into the existence of trends in phytoplankton composition over the maturing satellite ocean color era and illustrate how changes in the conditions of the oceans in the last ~15 years may have affected them.

Coupling atmospheric mercury isotope ratios and meteorology to identify sources of mercury impacting a coastal urban‐industrial region near Pensacola, Florida, USA

Abstract: Identifying the anthropogenic and natural sources of mercury (Hg) emissions contributing to atmospheric mercury on local, regional, and global scales continues to be a grand challenge. The relative importance of various direct anthropogenic emissions of mercury, in addition to natural geologic sources and reemission of previously released and deposited mercury, differs regionally and temporally. In this study, we used local-scale, mesoscale, and synoptic-scale meteorological analysis to couple the isotopic composition of ambient atmospheric mercury with potential sources of mercury contributing to a coastal urban-industrial setting near a coal-fired power plant in Pensacola, Florida, USA. We were able to broadly discern four influences on the isotopic composition of ambient atmospheric mercury impacting this coastal urban-industrial region: (1) local to regional urban-industrial anthropogenic emissions (mean δ202Hg = 0.44 ± 0.05‰, 1SD, n = 3), (2) marine-influenced sources derived from the Gulf of Mexico (mean δ202Hg = 0.77 ± 0.15‰, 1SD, n = 4), (3) continental sources associated with north-northwesterly flows from within the planetary boundary layer (mean δ202Hg = 0.65 ± 0.04‰, 1SD, n = 3), and (4) continental sources associated with north-northeasterly flows at higher altitudes (i.e., 2000 m above ground level; mean δ202Hg = 1.10 ± 0.21‰, 1SD, n = 8). Overall, these data, in conjunction with previous studies, suggest that the background global atmospheric mercury pool is characterized by moderately positive δ202Hg values; that urban-industrial emissions drive the isotopic composition of ambient atmospheric mercury toward lower δ202Hg values; and that air-surface exchange dynamics across vegetation and soils of terrestrial ecosystems drive the isotopic composition of ambient atmospheric mercury toward higher positive δ202Hg values. The data further suggest that mass-independent fractionation (MIF) of both even-mass- and odd-mass-number isotopes, likely generated by photochemical reactions in the atmosphere or during reemission from terrestrial and aquatic ecosystems, can be obscured by mixing with anthropogenic emissions having different MIF signatures.

Nitrogen cycling in the secondary nitrite maximum of the eastern tropical North Pacific off Costa Rica

Abstract: Nitrite is a central intermediate in the marine nitrogen cycle and represents a critical juncture where nitrogen can be reduced to the less bioavailable N2 gas or oxidized to nitrate and retained in a more bioavailable form. We present an analysis of rates of microbial nitrogen transformations in the oxygen deficient zone (ODZ) within the eastern tropical north Pacific ocean (ETNP). We determined rates using a novel one-dimensional model using the distribution of nitrite and nitrate concentrations, along with their natural abundance nitrogen (N) and oxygen (O) isotope profiles. We predict rate profiles for nitrate reduction, nitrite reduction, and nitrite oxidation throughout the ODZ, as well as the contributions of anammox to nitrite reduction and nitrite oxidation. Nitrate reduction occurs at a maximum rate of 25 nM d−1 at the top of the ODZ, at the same depth as the maximum rate of nitrite reduction, 15 nM d−1. Nitrite oxidation occurs at maximum rates of 10 nM d−1 above the secondary nitrite maximum (SNM), but also in the secondary nitrite maximum, within the ODZ. Anammox contributes to nitrite oxidation within the ODZ, but cannot account for all of it. Nitrite oxidation within the ODZ that is not through anammox is also supported by microbial gene abundance profiles. Our results suggest the presence of nitrite oxidation within the ETNP ODZ, with implications for the distribution and physiology of marine nitrite-oxidizing bacteria, and for total nitrogen loss in the largest marine ODZ.

Ammonia and nitrite oxidation in the Eastern Tropical North Pacific

Abstract: Nitrification plays a key role in the marine nitrogen (N) cycle, including in oceanic oxygen minimum zones (OMZs), which are hot spots for denitrification and anaerobic ammonia oxidation (anammox). Recent evidence suggests that nitrification links the source (remineralized organic matter) and sink (denitrification and anammox) of fixed N directly in the steep oxycline in the OMZs. We performed shipboard incubations with 15N tracers to characterize the depth distribution of nitrification in the Eastern Tropical North Pacific (ETNP). Additional experiments were conducted to investigate photoinhibition. Allylthiourea (ATU) was used to distinguish the contribution of archaeal and bacterial ammonia oxidation. The abundance of archaeal and β-proteobacterial ammonia monooxygenase gene subunit A (amoA) was determined by quantitative polymerase chain reaction. The rates of ammonia and nitrite oxidation showed distinct subsurface maxima, with the latter slightly deeper than the former. The ammonia oxidation maximum coincided with the primary nitrite concentration maximum, archaeal amoA gene maximum, and the subsurface nitrous oxide maximum. Negligible rates of ammonia oxidation were found at anoxic depths, where high rates of nitrite oxidation were measured. Archaeal amoA gene abundance was generally 1 to 2 orders of magnitude higher than bacterial amoA gene abundance, and inhibition of ammonia-oxidizing bacteria with 10 μM ATU did not affect ammonia oxidation rates, indicating the dominance of archaea in ammonia oxidation. These results depict highly dynamic activities of ammonia and nitrite oxidation in the oxycline of the ETNP OMZ.

Dissolved organic carbon pools and export from the coastal ocean

Abstract: The distribution of dissolved organic carbon (DOC) concentration across coastal waters was characterized based on the compilation of 3510 individual estimates of DOC in coastal waters worldwide. We estimated the DOC concentration in the coastal waters that directly exchange with open ocean waters in two different ways, as the DOC concentration at the edge of the shelf break and as the DOC concentration in coastal waters with salinity close to the average salinity in the open ocean. Using these estimates of DOC concentration in the coastal waters that directly exchange with open ocean waters, the mean DOC concentration in the open ocean and the estimated volume of water annually exchanged between coastal and open ocean, we estimated a median ± SE (and average ± SE) global DOC export from coastal to open ocean waters ranging from 4.4 ± 1.0 Pg C yr−1 to 27.0 ± 1.8 Pg C yr−1 (7.0 ± 5.8 Pg C yr−1 to 29.0 ± 8.0 Pg C yr−1) depending on the global hydrological exchange. These values correspond to a median and mean median (and average) range between 14.7 ± 3.3 to 90.0 ± 6.0 (23.3 ± 19.3 to 96.7 ± 26.7) Gg C yr−1 per km of shelf break, which is consistent with the range between 1.4 to 66.1 Gg C yr−1 per km of shelf break of available regional estimates of DOC export. The estimated global DOC export from coastal to open ocean waters is also consistent with independent estimates of the net metabolic balance of the coastal ocean. The DOC export from the coastal to the open ocean is likely to be a sizeable flux and is likely to be an important term in the carbon budget of the open ocean, potentially providing an important subsidy to support heterotrophic activity in the open ocean.

The stoichiometry of carbon and nutrients in peat formation

Abstract: Northern peatlands have stored large amounts (~500 Pg) of carbon (C) since the last glaciation Combined with peat C are nutrients such as nitrogen (N), phosphorus (P), calcium (Ca), magnesium (Mg), and potassium (K), each of which plays an important role in plant production, litter decomposition, and the biogeochemical functioning of peatlands Yet little attention has been given to the amounts of these nutrients stored in northern peatlands and their stoichiometry with C Here we use data on nutrient concentrations in over 400 peat profiles in Ontario, Canada, representing bogs, fens, and swamps and their vegetation We show that the C:N ratio is high (>40:1) in vegetation and litter but declines through the peat profiles to reach ratios between 22:1 and 29:1 in peat below 50 cm In contrast, the C:P ratio rises from vegetation and litter (500:1 to 1300:1) to 1500:1 to 2000:1 in the lower part of the peat profile Ratios of C to Ca, Mg, and K vary with peatland type Most of these stoichiometric changes occur in the early stages of organic matter decomposition, where the litter structure remains intact We estimate that ~18 Pg of N has been stored in northern peatlands since deglaciation, reflecting high N accumulation rates (~08 g m−2 yr−1), whereas P accumulation is small (~03 Pg, ~0016 g m−2 yr−1), indicating that P is quickly recycled in the surface layers

Strong dependence of CO2 emissions from anthropogenic land cover change on initial land cover and soil carbon parametrization

Abstract: The quantification of sources and sinks of carbon from land use and land cover changes (LULCC) is uncertain. We investigated how the parametrization of LULCC and of organic matter decomposition, as well as initial land cover, affects the historical and future carbon fluxes in an Earth System Model (ESM). Using the land component of the Max Planck Institute ESM, we found that the historical (1750–2010) LULCC flux varied up to 25% depending on the fraction of biomass which enters the atmosphere directly due to burning or is used in short-lived products. The uncertainty in the decadal LULCC fluxes of the recent past due to the parametrization of decomposition and direct emissions was 0.6 Pg C yr−1, which is 3 times larger than the uncertainty previously attributed to model and method in general. Preindustrial natural land cover had a larger effect on decadal LULCC fluxes than the aforementioned parameter sensitivity (1.0 Pg C yr−1). Regional differences between reconstructed and dynamically computed land covers, in particular, at low latitudes, led to differences in historical LULCC emissions of 84–114 Pg C, globally. This effect is larger than the effects of forest regrowth, shifting cultivation, or climate feedbacks and comparable to the effect of differences among studies in the terminology of LULCC. In general, we find that the practice of calibrating the net land carbon balance to provide realistic boundary conditions for the climate component of an ESM hampers the applicability of the land component outside its primary field of application.

Phenological characteristics of global coccolithophore blooms

Abstract: Coccolithophores are recognized as having a significant influence on the global carbon cycle through the production and export of calcium carbonate (often referred to as particulate inorganic carbon or PIC). Using remotely sensed PIC and chlorophyll data, we investigate the seasonal dynamics of coccolithophores relative to a mixed phytoplankton community. Seasonal variability in PIC, here considered to indicate changes in coccolithophore biomass, is identified across much of the global ocean. Blooms, which typically start in February–March in the low-latitude (~30°) Northern Hemisphere and last for ~6–7 months, get progressively later (April–May) and shorter (3–4 months) moving poleward. A similar pattern is observed in the Southern Hemisphere, where blooms that generally begin around August–September in the lower latitudes and which last for ~8 months get later and shorter with increasing latitude. It has previously been considered that phytoplankton blooms consist of a sequential succession of blooms of individual phytoplankton types. Comparison of PIC and chlorophyll peak dates suggests instead that in many open ocean regions, blooms of coccolithophores and other phytoplankton can co-occur, conflicting with the traditional view of species succession that is thought to take place in temperate regions such as the North Atlantic.

On the Southern Ocean CO2 uptake and the role of the biological carbon pump in the 21st century

Abstract: We use a suite of eight ocean biogeochemical/ecological general circulation models from the Marine Ecosystem Model Intercomparison Project and Coupled Model Intercomparison Project Phase 5 archives to explore the relative roles of changes in winds (positive trend of Southern Annular Mode, SAM) and in warming- and freshening-driven trends of upper ocean stratification in altering export production and CO2 uptake in the Southern Ocean at the end of the 21st century. The investigated models simulate a broad range of responses to climate change, with no agreement on a dominance of either the SAM or the warming signal south of 44°S. In the southernmost zone, i.e., south of 58°S, they concur on an increase of biological export production, while between 44 and 58°S the models lack consensus on the sign of change in export. Yet in both regions, the models show an enhanced CO2 uptake during spring and summer. This is due to a larger CO2(aq) drawdown by the same amount of summer export production at a higher Revelle factor at the end of the 21st century. This strongly increases the importance of the biological carbon pump in the entire Southern Ocean. In the temperate zone, between 30 and 44°S, all models show a predominance of the warming signal and a nutrient-driven reduction of export production. As a consequence, the share of the regions south of 44°S to the total uptake of the Southern Ocean south of 30°S is projected to increase at the end of the 21st century from 47 to 66% with a commensurable decrease to the north. Despite this major reorganization of the meridional distribution of the major regions of uptake, the total uptake increases largely in line with the rising atmospheric CO2. Simulations with the MITgcm-REcoM2 model show that this is mostly driven by the strong increase of atmospheric CO2, with the climate-driven changes of natural CO2 exchange offsetting that trend only to a limited degree (∼10%) and with negligible impact of climate effects on anthropogenic CO2 uptake when integrated over a full annual cycle south of 30°S.

Mercury species concentrations and fluxes in the Central Tropical Pacific Ocean

Abstract: The formation of the toxic and bioaccumulating monomethylmercury (MMHg) in marine systems is poorly understood, due in part to sparse data from many ocean regions. We present dissolved mercury (Hg) speciation data from 10 stations in the North and South Equatorial Pacific spanning large water mass differences and gradients in oxygen utilization. We also compare the mercury content in suspended particles from six stations and sinking particles from three stations to constrain local Hg sources and sinks. Concentrations of total Hg (THg) and methylated Hg in the surface and intermediate waters of the Equatorial and South Pacific suggest Hg cycling distinct from that of the North Pacific gyre. Maximum concentrations of 180 fM for both MMHg and dimethylmercury (DMHg) are observed in the Equatorial Pacific. South of the equator, concentrations of MMHg and DMHg are less than 100 fM. Sinking fluxes of particulate THg can reasonably explain the shape of dissolved THg profiles, but those of MMHg are too low to account for dissolved MMHg profiles. However, methylated Hg species are lower than predicted from remineralization rates based on North Pacific data, consistent with limitation of methylation in Equatorial and South Pacific waters. Full water column depth profiles were also measured for the first time in these regions. Concentrations of THg are elevated in deep waters of the North Pacific, compared to those in the intermediate and surface waters, and taper off in the South Pacific. Comparisons with previous measurements from nearby regions suggest little enrichment of THg or MMHg over the past 20 years.