We use a model of agricultural sources of ammonia (NH3) coupled to a chemical transport model to estimate the impact of U.S. food export on particulate matter concentrations (PM2.5). We find that ...food export accounts for 11% of total U.S. NH3 emissions (13% of agricultural emissions) and that it increases the population-weighted exposure of the U.S. population to PM2.5 by 0.36 μg m–3 on average. Our estimate is sensitive to the proper representation of the impact of NH3 on ammonium nitrate, which reflects the interplay between agricultural (NH3) and combustion emissions (NO, SO2). Eliminating NH3 emissions from food export would achieve greater health benefits than the reduction of the National Ambient Air Quality Standards for PM2.5 from 15 to 12 μg m–3. Valuation of the increased premature mortality associated with PM2.5 from food export (36 billion US$ (2006) per year) amounts to 50% of the gross food export value. Livestock operations in densely populated areas have particularly large health costs. Decreasing SO2 and NO x emissions will indirectly reduce health impact of food export as an ancillary benefit.
Hydrogen (H
) is expected to play a crucial role in reducing greenhouse gas emissions. However, hydrogen losses to the atmosphere impact atmospheric chemistry, including positive feedback on methane ...(CH
), the second most important greenhouse gas. Here we investigate through a minimalist model the response of atmospheric methane to fossil fuel displacement by hydrogen. We find that CH
concentration may increase or decrease depending on the amount of hydrogen lost to the atmosphere and the methane emissions associated with hydrogen production. Green H
can mitigate atmospheric methane if hydrogen losses throughout the value chain are below 9 ± 3%. Blue H
can reduce methane emissions only if methane losses are below 1%. We address and discuss the main uncertainties in our results and the implications for the decarbonization of the energy sector.
Current estimates of agricultural ammonia (NH3) emissions in China differ by more than a factor of 2, hindering our understanding of their environmental consequences. Here we apply both bottom-up ...statistical and top-down inversion methods to quantify NH3 emissions from agriculture in China for the year 2008. We first assimilate satellite observations of NH3 column concentration from the Tropospheric Emission Spectrometer (TES) using the GEOS-Chem adjoint model to optimize Chinese anthropogenic NH3 emissions at the 1∕2° × 2∕3° horizontal resolution for March–October 2008. Optimized emissions show a strong summer peak, with emissions about 50 % higher in summer than spring and fall, which is underestimated in current bottom-up NH3 emission estimates. To reconcile the latter with the top-down results, we revisit the processes of agricultural NH3 emissions and develop an improved bottom-up inventory of Chinese NH3 emissions from fertilizer application and livestock waste at the 1∕2° × 2∕3° resolution. Our bottom-up emission inventory includes more detailed information on crop-specific fertilizer application practices and better accounts for meteorological modulation of NH3 emission factors in China. We find that annual anthropogenic NH3 emissions are 11.7 Tg for 2008, with 5.05 Tg from fertilizer application and 5.31 Tg from livestock waste. The two sources together account for 88 % of total anthropogenic NH3 emissions in China. Our bottom-up emission estimates also show a distinct seasonality peaking in summer, consistent with top-down results from the satellite-based inversion. Further evaluations using surface network measurements show that the model driven by our bottom-up emissions reproduces the observed spatial and seasonal variations of NH3 gas concentrations and ammonium (NH4+) wet deposition fluxes over China well, providing additional credibility to the improvements we have made to our agricultural NH3 emission inventory.
We report experimental evidence for the formation of C(5)-hydroperoxyaldehydes (HPALDs) from 1,6-H-shift isomerizations in peroxy radicals formed from the hydroxyl radical (OH) oxidation of ...2-methyl-1,3-butadiene (isoprene). At 295 K, the isomerization rate of isoprene peroxy radicals (ISO2•) relative to the rate of reaction of ISO2• + HO2 is k(isom)(295)/(k(ISO2•+HO2)(295)) = (1.2 ± 0.6) x 10(8) mol cm(-3), or k(isom)(295) ≃ 0.002 s(-1). The temperature dependence of this rate was determined through experiments conducted at 295, 310 and 318 K and is well described by k(isom)(T)/(k(ISO2•+HO2)(T)) = 2.0 x 10(21) exp(-9000/T) mol cm(-3). The overall uncertainty in the isomerization rate (relative to k(ISO2•+HO2)) is estimated to be 50%. Peroxy radicals from the oxidation of the fully deuterated isoprene analog isomerize at a rate ∼15 times slower than non-deuterated isoprene. The fraction of isoprene peroxy radicals reacting by 1,6-H-shift isomerization is estimated to be 8-11% globally, with values up to 20% in tropical regions.
We report fluxes and dry deposition velocities for 16 atmospheric compounds above a southeastern United States forest, including: hydrogen peroxide (H₂O₂), nitric acid (HNO₃), hydrogen cyanide (HCN), ...hydroxymethyl hydroperoxide, peroxyacetic acid, organic hydroxy nitrates, and other multifunctional species derived from the oxidation of isoprene and monoterpenes. The data suggest that dry deposition is the dominant daytime sink for small, saturated oxygenates. Greater than 6 wt %C emitted as isoprene by the forest was returned by dry deposition of its oxidized products. Peroxides account for a large fraction of the oxidant flux, possibly eclipsing ozone in more pristine regions. The measured organic nitrates comprise a sizable portion (15%) of the oxidized nitrogen input into the canopy, with HNO₃ making up the balance. We observe that water-soluble compounds (e.g., strong acids and hydroperoxides) deposit with low surface resistance whereas compounds with moderate solubility (e.g., organic nitrates and hydroxycarbonyls) or poor solubility (e.g., HCN) exhibited reduced uptake at the surface of plants. To first order, the relative deposition velocities of water-soluble compounds are constrained by their molecular diffusivity. From resistance modeling, we infer a substantial emission flux of formic acid at the canopy level (∼1 nmol m⁻²·s⁻¹). GEOS–Chem, awidely used atmospheric chemical transport model, currently underestimates dry deposition for most molecules studied in this work. Reconciling GEOS–Chem deposition velocities with observations resulted in up to a 45% decrease in the simulated surface concentration of trace gases.
Emissions of nonmethane hydrocarbon compounds to the atmosphere from the biosphere exceed those from anthropogenic activity. Isoprene, a five-carbon diene, contributes more than 40% of these ...emissions. Once emitted to the atmosphere, isoprene is rapidly oxidized by the hydroxyl radical OH. We report here that under pristine conditions isoprene is oxidized primarily to hydroxyhydroperoxides. Further oxidation of these hydroxyhydroperoxides by OH leads efficiently to the formation of dihydroxyepoxides and OH reformation. Global simulations show an enormous flux--nearly 100 teragrams of carbon per year--of these epoxides to the atmosphere. The discovery of these highly soluble epoxides provides a missing link tying the gas-phase degradation of isoprene to the observed formation of organic aerosols.
This contribution describes the ocean biogeochemical component of the Geophysical Fluid Dynamics Laboratory's Earth System Model 4.1 (GFDL‐ESM4.1), assesses GFDL‐ESM4.1's capacity to capture observed ...ocean biogeochemical patterns, and documents its response to increasing atmospheric CO2. Notable differences relative to the previous generation of GFDL ESM's include enhanced resolution of plankton food web dynamics, refined particle remineralization, and a larger number of exchanges of nutrients across Earth system components. During model spin‐up, the carbon drift rapidly fell below the 10 Pg C per century equilibration criterion established by the Coupled Climate‐Carbon Cycle Model Intercomparison Project (C4MIP). Simulations robustly captured large‐scale observed nutrient distributions, plankton dynamics, and characteristics of the biological pump. The model overexpressed phosphate limitation and open ocean hypoxia in some areas but still yielded realistic surface and deep carbon system properties, including cumulative carbon uptake since preindustrial times and over the last decades that is consistent with observation‐based estimates. The model's response to the direct and radiative effects of a 200% atmospheric CO2 increase from preindustrial conditions (i.e., years 101–120 of a 1% CO2 yr−1 simulation) included (a) a weakened, shoaling organic carbon pump leading to a 38% reduction in the sinking flux at 2,000 m; (b) a two‐thirds reduction in the calcium carbonate pump that nonetheless generated only weak calcite compensation on century time‐scales; and, in contrast to previous GFDL ESMs, (c) a moderate reduction in global net primary production that was amplified at higher trophic levels. We conclude with a discussion of model limitations and priority developments.
Plain Language Summary
This paper describes and evaluates the ocean biogeochemical component of the Geophysical Fluid Dynamics Laboratory's Earth System Model 4.1 (GFDL‐ESM4.1). GFDL‐ESM4.1 was developed to study the past, present, and future evolution of the Earth system under scenarios for natural and anthropogenic drivers of Earth system change, including greenhouse gases and aerosols. The response of the ocean's vast carbon and heat reservoirs to accumulating greenhouse gases greatly reduces their atmospheric and terrestrial impacts, but also puts ocean environments and the marine resources they support at risk. Relative to previous models, GFDL‐ESM4.1 improves the representation of (a) ocean food webs connecting plankton and fish; (b) biological processes influencing the sequestration of carbon in the deep ocean; and (c) land‐atmosphere‐ocean nutrient exchanges. While simulations have biases, they capture many critical aspects of the global ocean carbon cycle and ocean ecosystem, including the observed uptake of anthropogenic carbon over the last ~150 yr. Projections suggest that continued CO2 increases could significantly decrease ocean productivity and the ocean's capacity to sequester atmospheric carbon.
Key Points
Enhanced plankton food webs, remineralization, and Earth system linkages yield skillful global carbon cycle and ecosystem simulations
Ocean productivity estimates improved, but phosphate limitation and hypoxia overestimated in some areas
High CO2 and associated warming substantially reduce the biological pump and ocean productivity across trophic levels
Anthropogenic enrichment of reactive nitrogen (Nr) deposition is an ecological concern. We use the adjoint of a global 3-D chemical transport model (GEOS-Chem) to identify the sources and processes ...that control Nr deposition to an ensemble of biodiversity hotspots worldwide and two U.S. national parks (Cuyahoga and Rocky Mountain). We find that anthropogenic sources dominate deposition at all continental sites and are mainly regional (less than 1000 km) in origin. In Hawaii, Nr supply is controlled by oceanic emissions of ammonia (50%) and anthropogenic sources (50%), with important contributions from Asia and North America. Nr deposition is also sensitive in complicated ways to emissions of SO2, which affect Nr gas–aerosol partitioning, and of volatile organic compounds (VOCs), which affect oxidant concentrations and produce organic nitrate reservoirs. For example, VOC emissions generally inhibit deposition of locally emitted NO x but significantly increase Nr deposition downwind. However, in polluted boreal regions, anthropogenic VOC emissions can promote Nr deposition in winter. Uncertainties in chemical rate constants for OH + NO2 and NO2 hydrolysis also complicate the determination of source–receptor relationships for polluted sites in winter. Application of our adjoint sensitivities to the representative concentration pathways (RCPs) scenarios for 2010–2050 indicates that future decreases in Nr deposition due to NO x emission controls will be offset by concurrent increases in ammonia emissions from agriculture.
The response of ozone (O3) dry deposition to ecosystem‐atmosphere interactions is poorly understood but is central to determining the potential for extreme pollution events under current and future ...climate conditions. Using observations and an interactive dry deposition scheme within two dynamic vegetation land models (Geophysical Fluid Dynamics Laboratory LM3.0/LM4.0) driven by observation‐based meteorological forcings over 1948–2014, we investigate the factors controlling seasonal and interannual variability (IAV) in O3 deposition velocities (Vd,O3). Stomatal activity in this scheme is determined mechanistically, depending on phenology, soil moisture, vapor pressure deficit, and CO2 concentration. Soil moisture plays a key role in modulating the observed and simulated Vd,O3 seasonal changes over evergreen forests in Mediterranean Europe, South Asia, and the Amazon. Analysis of multiyear observations at forest sites in Europe and North America reveals drought stress to reduce Vd,O3 by ~50%. Both LM3.0 and LM4.0 capture the observed Vd,O3 decreases due to drought; however, IAV is weaker by a factor of 2 in LM3.0 coupled to atmospheric models, particularly in regions with large precipitation biases. IAV in summertime Vd,O3 to forests, driven primarily by the stomatal pathway, is largest (15–35%) in semiarid regions of western Europe, eastern North America, and northeastern China. Monthly mean Vd,O3 for the highest year is 2 to 4 times that of the lowest, with significant implications for surface O3 variability and extreme events. Using Vd,O3 from LM4.0 in an atmospheric chemistry model improves the simulation of surface O3 abundance and spatial variability (reduces mean biases by ~10 ppb) relative to the widely used Wesely scheme.
Key Points
Observational analysis reveals drought stress causing 50% reduction of ozone deposition velocities
Ecosystem‐atmosphere interactions affect seasonal and interannual variability of ozone deposition
Dynamic vegetation land models with an interactive dry deposition scheme may provide mechanistic insights
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