ALBERT

Description: The mid-Piacenzian climate represents the most geologically recent interval of long-term average warmth relative to the last million years, and shares similarities with the climate projected for the end of the 21st century. As such, it represents a natural experiment from which we can gain insight into potential climate change impacts, enabling more informed policy decisions for mitigation and adaptation. Here, we present the first systematic comparison of Pliocene sea surface temperature (SST) between an ensemble of eight climate model simulations produced as part of PlioMIP (Pliocene Model Intercomparison Project) with the PRISM (Pliocene Research, Interpretation and Synoptic Mapping) Project mean annual SST field. Our results highlight key regional and dynamic situations where there is discord between the palaeoenvironmental reconstruction and the climate model simulations. These differences have led to improved strategies for both experimental design and temporal refinement of the palaeoenvironmental reconstruction.

Description: A parameterization was developed for the heterogeneous reaction probability (γ) of N2O5 as a function of temperature, relative humidity (RH), particle composition, and phase state, for use in advanced air quality models. The reaction probabilities on aqueous NH4HSO4, (NH4)2SO4, and NH4NO3 were modeled statistically using data and uncertainty values compiled from seven different laboratory studies. A separate regression model was fit to laboratory data for dry NH4HSO4 and (NH4)2SO4 particles, yielding lower γ values than the corresponding aqueous parameterizations. The regression equations reproduced 80% of the laboratory data within a factor of two and 63% within a factor of 1.5. A fixed value was selected for γ on ice-containing particles based on a review of the literature. The combined parameterization was applied under atmospheric conditions representative of the eastern United States using 3-dimensional fields of temperature, RH, sulfate, nitrate, and ammonium. The resulting spatial distributions of γ were contrasted with three other parameterizations that have been applied in air quality models in the past and with atmospheric observational determinations of γ. Our equations lay the foundation for future research that will parameterize the suppression of γ when inorganic ammoniated particles are mixed or coated with organic material. Our analyses draw attention to a major uncertainty in the available laboratory data at high RH and highlight a critical need for future laboratory measurements of γ at low temperature and high RH to improve model simulations of N2O5 hydrolysis during wintertime conditions.

Description: A snapshot of the thermal structure of the mid-Piacenzian ocean is obtained by combining the Pliocene Research, Interpretation and Synoptic Mapping Project (PRISM3) multiproxy sea-surface temperature (SST) reconstruction with bottom water temperature estimates produced using Mg/Ca paleothermometry. This reconstruction assumes a Pliocene water mass framework similar to that which exists today, with several important modifications. The area of formation of present day North Atlantic Deep Water (NADW) was expanded and extended further north toward the Arctic Ocean during the mid-Piacenzian relative to today. This, combined with a deeper Greenland-Scotland Ridge, allowed a greater volume of warmer NADW to enter the Atlantic Ocean. In the Southern Ocean, the Polar Front Zone was expanded relative to present day, but shifted closer to the Antarctic continent. This, combined with at least seasonal reduction in sea ice extent, resulted in decreased Antarctic Bottom Water (AABW) production (relative to present day) as well as possible changes in the depth of intermediate waters. The reconstructed mid-Piacenzian three-dimensional ocean was warmer overall than today, and the hypothesized aerial extent of water masses appears to fit the limited stable isotopic data available for this time period.

Description: The thermal structure of the mid-Piacenzian ocean is obtained by combining the Pliocene Research, Interpretation and Synoptic Mapping Project (PRISM3) multiproxy sea-surface temperature (SST) reconstruction with bottom water temperature estimates from 27 locations produced using Mg/Ca paleothermometry based upon the ostracod genus Krithe. Deep water temperature estimates are skewed toward the Atlantic Basin (63% of the locations) and represent depths from 1000 m to 4500 m. This reconstruction, meant to serve as a validation data set as well as an initialization for coupled numerical climate models, assumes a Pliocene water mass framework similar to that which exists today, with several important modifications. The area of formation of present day North Atlantic Deep Water (NADW) was expanded and extended further north toward the Arctic Ocean during the mid-Piacenzian relative to today. This, combined with a deeper Greenland-Scotland Ridge, allowed a greater volume of warmer NADW to enter the Atlantic Ocean. In the Southern Ocean, the Polar Front Zone was expanded relative to present day, but shifted closer to the Antarctic continent. This, combined with at least seasonal reduction in sea ice extent, resulted in decreased Antarctic Bottom Water (AABW) production (relative to present day) as well as possible changes in the depth of intermediate waters. The reconstructed mid-Piacenzian three-dimensional ocean was warmer overall than today, and the hypothesized aerial extent of water masses appears to fit the limited stable isotopic data available for this time period.

Description: A comprehensive parameterization was developed for the heterogeneous reaction probability (γ) of N2O5 as a function of temperature, relative humidity, particle composition, and phase state, for use in advanced air quality models. The reaction probabilities on aqueous NH4HSO4, (NH4)2SO4, and NH4NO3 were modeled statistically using data and uncertainty values compiled from seven different laboratory studies. A separate regression model was fit to laboratory data for dry NH4HSO4 and (NH4)2SO4 particles, yielding lower γ values than the corresponding aqueous parameterizations. The regression equations reproduced 79% of the laboratory data within a factor of two and 53% within a factor of 1.25. A fixed value was selected for γ on ice-containing particles based on a review of the literature. The combined parameterization was applied under atmospheric conditions representative of the eastern United States using 3-dimensional fields of temperature, relative humidity, sulfate, nitrate, and ammonium, obtained from a recent Community Multiscale Air Quality model simulation. The resulting spatial distributions of γ were contrasted with three other parameterizations that have been applied in air quality models in the past and with atmospheric observational determinations of γ. Our results highlight a critical need for more laboratory measurements of γ at low temperature and high relative humidity to improve model simulations of N2O5 hydrolysis during wintertime conditions.

Description: Chemical processing of sea-salt particles in coastal environments significantly impacts concentrations of particle components and gas-phase species and has implications for human exposure to particulate matter and nitrogen deposition to sensitive ecosystems. Emission of sea-salt particles from the coastal surf zone is known to be elevated compared to that from the open ocean. Despite the importance of sea-salt emissions and chemical processing, the US EPA's Community Multiscale Air Quality (CMAQ) model has traditionally treated coarse sea-salt particles as chemically inert and has not accounted for enhanced surf-zone emissions. In this article, updates to CMAQ are described that enhance sea-salt emissions from the coastal surf zone and allow dynamic transfer of HNO3, H2SO4, HCl, and NH3 between coarse particles and the gas phase. Predictions of updated CMAQ models and the previous release version, CMAQv4.6, are evaluated using observations from three coastal sites during the Bay Regional Atmospheric Chemistry Experiment (BRACE) in Tampa, FL in May 2002. Model updates improve predictions of NO3−, SO42−, NH4+, Na+, and Cl− concentrations at these sites with only a 8% increase in run time. In particular, the chemically interactive coarse particle mode dramatically improves predictions of nitrate concentration and size distributions as well as the fraction of total nitrate in the particle phase. Also, the surf-zone emission parameterization improves predictions of total sodium and chloride concentration. Results of a separate study indicate that the model updates reduce the mean absolute error of nitrate predictions at coastal CASTNET and SEARCH sites in the eastern US. Although the new model features improve performance relative to CMAQv4.6, some persistent differences exist between observations and predictions. Modeled sodium concentration is biased low and causes under-prediction of coarse particle nitrate. Also, CMAQ over-predicts geometric mean diameter and standard deviation of particle modes at the BRACE sites. These over-predictions may cause too rapid particle dry deposition and partially explain the low bias in sodium predictions. Despite these shortcomings, the updates to CMAQ enable more realistic simulations of chemical processes in environments where marine air mixes with urban pollution. The model updates described in this article are included in the public release of CMAQv4.7 (http://www.cmaq-model.org).

Description: This paper examines the operational performance of the Community Multiscale Air Quality (CMAQ) model simulations for 2002–2006 using both 36-km and 12-km horizontal grid spacing with a primary focus on the performance of the CMAQ model in predicting wet deposition of sulfate (SO4=), ammonium (NH4+) and nitrate (NO3−). Performance of the wet deposition species is determined by comparing CMAQ predicted concentrations to concentrations measured by the National Acid Deposition Program (NADP), specifically the National Trends Network (NTN). For SO4= wet deposition, the CMAQ model estimates were generally comparable between the 36-km and 12-km simulations for the eastern US, with the 12-km simulation giving slightly higher estimates of SO4= wet deposition than the 36-km simulation on average. The normalized mean bias (NMB) was slightly higher for the 12-km simulation, however, both simulations had annual biases that were less than ±15% for each of the five years. The model estimated SO4= wet deposition values improved when they were adjusted to account for biases in the model estimated precipitation. The CMAQ model underestimates NH4+ wet deposition over the eastern US using both the 36-km and 12-km horizontal grid spacing, with a slightly larger underestimation in the 36-km simulation. The largest underestimations occur during the winter and spring periods, while the summer and fall have slightly smaller underestimations of NH4+ wet deposition. Annually, the NMB generally ranges between −10% and −16% for the 12-km simulation and −12% to −18% for the 36-km simulation over the five-year period for the eastern US. The underestimation in NH4+ wet deposition is likely due, in part, to the poor temporal and spatial representation of ammonia (NH3) emissions, particularly those emissions associated with fertilizer applications and NH3 bi-directional exchange. The model performance for estimates of NO3− wet deposition are mixed throughout the year, with the model largely underestimating NO3− wet deposition in the spring and summer in the eastern US, while the model has a relatively small bias in the fall and winter. Model estimates of NO3− wet deposition tend to be slightly lower for the 36-km simulation as compared to the 12-km simulation, particularly in the spring. Annually for the eastern US, the NMB ranges from roughly −12% to −20% for the 12-km simulation and −18% to −26% for the 36-km simulation. The underestimation of NO3− wet deposition in the spring and summer is due, in part, to a lack of lightning generated NO emissions in the upper troposphere, which can be a large source of NO in the spring and summer when lightning activity is the high. CMAQ model simulations that include the production of NO from lightning show a significant improvement in the NO3− wet deposition estimates in the eastern US in the summer. Model performance for the western US was generally not as good as that for the eastern US for all three wet deposition species.