Nitrogen deposition onto the United States and Western Europe: A synthesis of observations and models.

The documented acceleration of NH3 and NOx (NO + NO2) emissions over the last 150 years has accelerated N deposition, compromising air and water quality and altering the functioning of terrestrial and aquatic ecosystems worldwide. To construct continental-scale N budgets, we produced maps of N deposition fluxes from site-network observations for the United States and Western Europe. Increases in the rates of N cycling for these two regions of the world are large, and they have undergone profound modification of biospheric–atmospheric N exchanges, and ecosystem function. The maps are necessarily restricted to the network measured quantities and consist of statistically interpolated fields of aqueous NO3− and NH4+, gaseous HNO3 and NO2 (in Europe), and particulate NO3− and NH4+. There remain a number of gaps in the budgets, including organic N and NH3 deposition. The interpolated spatially continuous fields allow estimation of regionally integrated budget terms. Dry-deposition fluxes were the most problematic because of low station density and uncertainties associated with exchange mechanisms. We estimated dry N deposition fluxes by multiplying interpolated surface-air concentrations for each chemical species by model-calculated, spatially explicit deposition velocities. Deposition of the oxidized N species, by-products of fossil-fuel combustion, dominate the U.S. N deposition budget with 2.5 Tg of NOy-N out of a total of 3.7–4.5 Tg of N deposited annually onto the conterminous United States. Deposition of the reduced species, which are by-products of farming and animal husbandry, dominate the Western European N-deposition budget with a total of 4.3–6.3 Tg N deposited each year out of a total of 8.4–10.8 Tg N. Western Europe receives five times more N in precipitation than does the conterminous United States. Estimated N emissions exceed measured deposition in the United States by 5.3– 7.81 Tg N, suggesting significant N export or under-sampling of urban influence. In Europe, estimated emissions better balance measured deposition, with an imbalance of between −0.63 and 2.88 Tg N, suggesting that much of the N emitted in Europe is deposited there, with possible N import from the United States. The sampling network in Europe includes urban influences because of the greater population density of Western Europe. Our analysis of N deposition for both regions was limited by sampling density. The framework we present for quantification of patterns of N deposition provides a constraint on our understanding of continental biospheric–atmospheric N cycles. These spatially explicit wet and dry N fluxes also provide a tool for verifying regional and global models of atmospheric chemistry and transport, and they represent critical inputs into terrestrial models of biogeochemistry

Bromine partitioning in the tropical tropopause layer: Implications for stratospheric injection

© Author(s) 2014. Very short-lived (VSL) bromocarbons are produced at a prodigious rate by ocean biology and these source compounds (SGVSL), together with their inorganic degradation products (PGVSL), are lofted by vigorous convection to the tropical tropopause layer (TTL). Using a state-of-the-art photochemical mechanism within a global model, we calculate annual average stratospheric injection of total bromine due to VSL sources to be 5 pptv (parts per trillion by volume), with ∼ 3 pptv entering the stratosphere as PGVSL and ∼ 2 pptv as SGVSL. The geographic distribution and partitioning of VSL bromine within the TTL, and its consequent stratospheric injection, is highly dependent on the oceanic flux, the strength of convection and the occurrence of heterogeneous recycling reactions. Our calculations indicate atomic Br should be the dominant inorganic species in large regions of the TTL during daytime, due to the low ozone and cold conditions of this region. We propose the existence of a >tropical ring of atomic bromine> located approximately between 15 and 19 km and between 30°N and 30°S. Daytime Br / BrO ratios of up to ∼ 4 are predicted within this inhomogeneous ring in regions of highly convective transport, such as the tropical Western Pacific. Therefore, we suggest that experimental programs designed to quantify the bromine budget of the TTL and the stratospheric injection of VSL biogenic bromocarbons should include a strategy for the measurement of atomic Br during daytime as well as HOBr and BrCl during nighttime.Peer Reviewe

Variations in the predicted spatial distribution of atmospheric nitrogen deposition and their impact on carbon uptake by terrestrial ecosystems

Widespread mobilization of nitrogen into the atmosphere from industry, agriculture, and biomass burning and its subsequent deposition have the potential to alleviate nitrogen limitation of productivity in terrestrial ecosystems, and may contribute to enhanced terrestrial carbon uptake. To evaluate the importance of the spatial distribution of nitrogen deposition for carbon uptake and to better quantify its magnitude and uncertainty NOy-N deposition fields from five different three-dimensional chemical models, GCTM, GRANTOUR, IMAGES, MOGUNTIA, and ECHAM were used to drive NDEP, a perturbation model of terrestrial carbon uptake. Differences in atmospheric sources of NOx-N, transport, resolution, and representation of chemistry, contribute to the distinct spatial patterns of nitrogen deposition on the global land surface; these differences lead to distinct patterns of carbon uptake that vary between 0.7 and 1.3 Gt C yr−1 globally. Less than 10% of the nitrogen was deposited on forests which were most able to respond with increased carbon storage because of the wide C:N ratio of wood as well as its long lifetime. Addition of NHx-N to NOy-N deposition, increased global terrestrial carbon storage to between 1.5 and 2.0 Gt C yr−1, while the “missing terrestrial sink” is quite similar in magnitude. Thus global air pollution appears to be an important influence on the global carbon cycle. If N fertilization of the terrestrial biosphere accounts for the “missing” C sink or a substantial portion of it, we would expect significant reductions in its magnitude over the next century as terrestrial ecosystems become N saturated and O3 pollution expands

Nighttime atmospheric chemistry of iodine

Little attention has so far been paid to the nighttime atmospheric chemistry of iodine species. Current atmospheric models predict a buildup of HOI and I₂ during the night that leads to a spike of IO at sunrise, which is not observed by measurements. In this work, electronic structure calculations are used to survey possible reactions that HOI and I₂ could undergo at night in the lower troposphere, and hence reduce their nighttime accumulation. The new reaction NO₃+ HOI  →  IO + HNO₃ is proposed, with a rate coefficient calculated from statistical rate theory over the temperature range 260–300 K and at a pressure of 1000 hPa to be k(T)  =  2.7  ×  10¯¹² (300 K/T)²·⁶⁶ cm³ molecule¯¹ s¯¹. This reaction is included in two atmospheric models, along with the known reaction between I₂ and NO₃, to explore a new nocturnal iodine radical activation mechanism. The results show that this iodine scheme leads to a considerable reduction of nighttime HOI and I₂, which results in the enhancement of more than 25 % of nighttime ocean emissions of HOI +I₂ and the removal of the anomalous spike of IO at sunrise. We suggest that active nighttime iodine can also have a considerable, so far unrecognized, impact on the reduction of the NO₃ radical levels in the marine boundary layer (MBL) and hence upon the nocturnal oxidizing capacity of the marine atmosphere. The effect of this is exemplified by the indirect effect on dimethyl sulfide (DMS) oxidation

Iodine chemistry in the troposphere and its effect on ozone

Despite the potential influence of iodine chemistry on the oxidizing capacity of the troposphere, reactive iodine distributions and their impact on tropospheric ozone remain almost unexplored aspects of the global atmosphere. Here we present a comprehensive global modelling experiment aimed at estimating lower and upper limits of the inorganic iodine burden and its impact on tropospheric ozone. Two sets of simulations without and with the photolysis of IxOy oxides (i.e. I2O2, I2O3 and I2O4) were conducted to define the range of inorganic iodine loading, partitioning and impact in the troposphere. Our results show that the most abundant daytime iodine species throughout the middle to upper troposphere is atomic iodine, with an annual average tropical abundance of (0.15-0.55) pptv. We propose the existence of a "tropical ring of atomic iodine" that peaks in the tropical upper troposphere (∼11-14 km) at the equator and extends to the sub-tropics (30°N-30°S). Annual average daytime I = IO ratios larger than 3 are modelled within the tropics, reaching ratios up to ∼20 during vigorous uplift events within strong convective regions. We calculate that the integrated contribution of catalytic iodine reactions to the total rate of tropospheric ozone loss (IOx Loss) is 2-5 times larger than the combined bromine and chlorine cycles. When IxOy photolysis is included, IOx Loss represents an upper limit of approximately 27, 14 and 27% of the tropical annual ozone loss for the marine boundary layer (MBL), free troposphere (FT) and upper troposphere (UT), respectively, while the lower limit throughout the tropical troposphere is ∼9 %. Our results indicate that iodine is the second strongest ozone-depleting family throughout the global marine UT and in the tropical MBL. We suggest that (i) iodine sources and its chemistry need to be included in global tropospheric chemistry models, (ii) experimental programs designed to quantify the iodine budget in the troposphere should include a strategy for the measurement of atomic I, and (iii) laboratory programs are needed to characterize the photochemistry of higher iodine oxides to determine their atmospheric fate since they can potentially dominate halogen-catalysed ozone destruction in the troposphere

Analytic Aesthetics

Peer reviewe

The vertical distribution of ozone instantaneous radiative forcing from satellite and chemistry climate models

We evaluate the instantaneous radiative forcing (IRF) of tropospheric ozone predicted by four state-of-the-art global chemistry climate models (AM2-Chem, CAM-Chem, ECHAM5-MOZ, and GISS-PUCCINI) against ozone distribution observed from the NASA Tropospheric Emission Spectrometer (TES) during August 2006. The IRF is computed through the application of an observationally constrained instantaneous radiative forcing kernels (IRFK) to the difference between TES and model-predicted ozone. The IRFK represent the sensitivity of outgoing longwave radiation to the vertical and spatial distribution of ozone under all-sky condition. Through this technique, we find total tropospheric IRF biases from -0.4 to + 0.7 W/m(2) over large regions within the tropics and midlatitudes, due to ozone differences over the region in the lower and middle troposphere, enhanced by persistent bias in the upper troposphere-lower stratospheric region. The zonal mean biases also range from -30 to + 50 mW/m(2) for the models. However, the ensemble mean total tropospheric IRF bias is less than 0.2 W/m(2) within the entire troposphere