Search

The strength of feedbacks between a changing climate and future CO2 concentrations is uncertain and difficult to predict using Earth System Models (ESMs). We analyzed emission-driven simulations—in which atmospheric CO2levels were computed prognostically—for historical (1850–2005) and future periods (Representative Concentration Pathway (RCP) 8.5 for 2006–2100) produced by 15 ESMs for the Fifth Phase of the Coupled Model Intercomparison Project (CMIP5). Comparison of ESM prognostic atmospheric CO2 over the historical period with observations indicated that ESMs, on average, had a small positive bias in predictions of contemporary atmospheric CO2. Weak ocean carbon uptake in many ESMs contributed to this bias, based on comparisons with observations of ocean and atmospheric anthropogenic carbon inventories. We found a significant linear relationship between contemporary atmospheric CO2 biases and future CO2levels for the multimodel ensemble. We used this relationship to create a contemporary CO2 tuned model (CCTM) estimate of the atmospheric CO2 trajectory for the 21st century. The CCTM yielded CO2estimates of 600±14 ppm at 2060 and 947±35 ppm at 2100, which were 21 ppm and 32 ppm below the multimodel mean during these two time periods. Using this emergent constraint approach, the likely ranges of future atmospheric CO2, CO2-induced radiative forcing, and CO2-induced temperature increases for the RCP 8.5 scenario were considerably narrowed compared to estimates from the full ESM ensemble. Our analysis provided evidence that much of the model-to-model variation in projected CO2 during the 21st century was tied to biases that existed during the observational era and that model differences in the representation of concentration-carbon feedbacks and other slowly changing carbon cycle processes appear to be the primary driver of this variability. By improving models to more closely match the long-term time series of CO2from Mauna Loa, our analysis suggests that uncertainties in future climate projections can be reduced.

Exposure to air pollution is frequently associated with reductions in birth weight but results of available studies vary widely, possibly in part because of differences in air pollution metrics. Further insight is needed to identify the air pollution metrics most strongly and consistently associated with birth weight.We used a hospital-based obstetric database of more than 70,000 births to study the relationships between air pollution and the risk of low birth weight (LBW,

Forest fires are an important source to carbonaceous aerosols in the Western United States (WUS). We quantify the relative contribution of biomass burning to black carbon (BC) in the WUS mountain ranges by analyzing surface BC observations for 2006 from the Interagency Monitoring of PROtected Visual Environment (IMPROVE) network using the GEOS-Chem global chemical transport model. Observed surface BC concentrations show broad maxima during late June to early November. Enhanced potassium concentrations and potassium/sulfur ratios observed during the high-BC events indicate a dominant biomass burning influence during the peak fire season. Model surface BC reproduces the observed day-to day and synoptic variabilities in regions downwind of but near urban centers. Major discrepancies are found at elevated mountainous sites during the July-October fire season when simulated BC concentrations are biased low by a factor of two. We attribute these low biases largely to the underestimated (by more than a factor of two) and temporally misplaced biomass burning emissions of BC in the model. Additionally, we find that the biomass burning contribution to surface BC concentrations in the USA likely was underestimated in a previous study using GEOS-Chem (Park et al., 2003), because of the unusually low planetary boundary layer (PBL) heights in the GEOS-3 meteorological reanalysis data used to drive the model. PBL heights from GEOS-4 and GEOS-5 reanalysis data are comparable to those from the North American Regional Reanalysis (NARR). Model simulations show slightly improved agreements with the observations when driven by GEOS-5 reanalysis data, but model results are still biased low. The use of biomass burning emissions with diurnal cycle, synoptic variability, and plume injection has relatively small impact on the simulated surface BC concentrations in the WUS.

The potentially significant role of the biogenic trace gas dimethylsulfide (DMS) in determining the Earth's radiation budget makes it necessary to accurately reproduce seawater DMS distribution and quantify its global flux across the sea/air interface. Following a threefold increase of data (from 15,000 to over 47,000) in the global surface ocean DMS database over the last decade, new global monthly climatologies of surface ocean DMS concentration and sea-to-air emission flux are presented as updates of those constructed 10 years ago. Interpolation/extrapolation techniques were applied to project the discrete concentration data onto a first guess field based on Longhurst's biogeographic provinces. Further objective analysis allowed us to obtain the final monthly maps. The new climatology projects DMS concentrations typically in the range of 1–7 nM, with higher levels occurring in the high latitudes, and with a general trend toward increasing concentration in summer. The increased size and distribution of the observations in the DMS database have produced in the new climatology substantially lower DMS concentrations in the polar latitudes and generally higher DMS concentrations in regions that were severely undersampled 10 years ago, such as the southern Indian Ocean. Using the new DMS concentration climatology in conjunction with state-of-the-art parameterizations for the sea/air gas transfer velocity and climatological wind fields, we estimate that 28.1 (17.6–34.4) Tg of sulfur are transferred from the oceans into the atmosphere annually in the form of DMS. This represents a global emission increase of 17% with respect to the equivalent calculation using the previous climatology. This new DMS climatology represents a valuable tool for atmospheric chemistry, climate, and Earth System models.

New burned area datasets and top-down constraints from atmospheric concentration measurements of pyrogenic gases have decreased the large uncertainty in fire emissions estimates. However, significant gaps remain in our understanding of the contribution of deforestation, savanna, forest, agricultural waste, and peat fires to total global fire emissions. Here we used a revised version of the Carnegie-Ames-Stanford-Approach (CASA) biogeochemical model and improved satellite-derived estimates of area burned, fire activity, and plant productivity to calculate fire emissions for the 1997–2009 period on a 0.5° spatial resolution with a monthly time step. For November 2000 onwards, estimates were based on burned area, active fire detections, and plant productivity from the MODerate resolution Imaging Spectroradiometer (MODIS) sensor. For the partitioning we focused on the MODIS era. We used maps of burned area derived from the Tropical Rainfall Measuring Mission (TRMM) Visible and Infrared Scanner (VIRS) and Along-Track Scanning Radiometer (ATSR) active fire data prior to MODIS (1997–2000) and estimates of plant productivity derived from Advanced Very High Resolution Radiometer (AVHRR) observations during the same period. Average global fire carbon emissions according to this version 3 of the Global Fire Emissions Database (GFED3) were 2.0 Pg C year−1 with significant interannual variability during 1997–2001 (2.8 Pg C year−1 in 1998 and 1.6 Pg C year−1 in 2001). Globally, emissions during 2002–2007 were relatively constant (around 2.1 Pg C year−1) before declining in 2008 (1.7 Pg C year−1) and 2009 (1.5 Pg C year−1) partly due to lower deforestation fire emissions in South America and tropical Asia. On a regional basis, emissions were highly variable during 2002–2007 (e.g., boreal Asia, South America, and Indonesia), but these regional differences canceled out at a global level. During the MODIS era (2001–2009), most carbon emissions were from fires in grasslands and savannas (44%) with smaller contributions from tropical deforestation and degradation fires (20%), woodland fires (mostly confined to the tropics, 16%), forest fires (mostly in the extratropics, 15%), agricultural waste burning (3%), and tropical peat fires (3%). The contribution from agricultural waste fires was likely a lower bound because our approach for measuring burned area could not detect all of these relatively small fires. Total carbon emissions were on average 13% lower than in our previous (GFED2) work. For reduced trace gases such as CO and CH4, deforestation, degradation, and peat fires were more important contributors because of higher emissions of reduced trace gases per unit carbon combusted compared to savanna fires. Carbon emissions from tropical deforestation, degradation, and peatland fires were on average 0.5 Pg C year−1. The carbon emissions from these fires may not be balanced by regrowth following fire. Our results provide the first global assessment of the contribution of different sources to total global fire emissions for the past decade, and supply the community with an improved 13-year fire emissions time series.

Fluorescence Assay by Gas Expansion (FAGE) has been used to detect ambient levels of OH and HO2 radicals at the Cape Verde Atmospheric Observatory, located in the tropical Atlantic marine boundary layer, during May and June 2007. Midday radical concentrations were high, with maximum concentrations of 9 ×106 molecule cm−3 and 6×108 molecule cm−3 observed for OH and HO2, respectively. A box model incorporating the detailed Master Chemical Mechanism, extended to include halogen chemistry, heterogeneous loss processes and constrained by all available measurements including halogen and nitrogen oxides, has been used to assess the chemical and physical parameters controlling the radical chemistry. The model was able to reproduce the daytime radical concentrations to within the 1 σ measurement uncertainty of 20% during the latter half of the measurement period but significantly under-predicted [HO2] by 39% during the first half of the project. Sensitivity analyses demonstrate that elevated [HCHO] (~2 ppbv) on specific days during the early part of the project, which were much greater than the mean [HCHO] (328 pptv) used to constrain the model, could account for a large portion of the discrepancy between modelled and measured [HO2] at this time. IO and BrO, although present only at a few pptv, constituted ~19% of the instantaneous sinks for HO2, whilst aerosol uptake and surface deposition to the ocean accounted for a further 23% of the HO2 loss at noon. Photolysis of HOI and HOBr accounted for ~13% of the instantaneous OH formation. Taking into account that halogen oxides increase the oxidation of NOx (NO → NO2), and in turn reduce the rate of formation of OH from the reaction of HO2 with NO, OH concentrations were estimated to be 9% higher overall due to the presence of halogens. The increase in modelled OH from halogen chemistry gives an estimated 9% shorter lifetime for methane in this region, and the inclusion of halogen chemistry is necessary to model the observed daily cycle of O3 destruction that is observed at the surface. Due to surface losses, we hypothesise that HO2 concentrations increase with height and therefore contribute a larger fraction of the O3 destruction than at the surface.

Seasonal and interannual variability in atmospheric carbon dioxide (CO2) concentrations was simulated using fluxes from fossil fuel, ocean and terrestrial biogeochemical models, and a tracer transport model with time-varying winds. The atmospheric CO2 variability resulting from these surface fluxes was compared to observations from 89 GLOBALVIEW monitoring stations. At northern hemisphere stations, the model simulations captured most of the observed seasonal cycle in atmospheric CO2, with the land tracer accounting for the majority of the signal. The ocean tracer was 3–6 months out of phase with the observed cycle at these stations and had a seasonal amplitude only ∼10% on average of observed. Model and observed interannual CO2 growth anomalies were only moderately well correlated in the northern hemisphere (R ∼ 0.4–0.8), and more poorly correlated in the southern hemisphere (R < 0.6). Land dominated the interannual variability (IAV) in the northern hemisphere, and biomass burning in particular accounted for much of the strong positive CO2 growth anomaly observed during the 1997–1998 El Niño event. The signals in atmospheric CO2 from the terrestrial biosphere extended throughout the southern hemisphere, but oceanic fluxes also exerted a strong influence there, accounting for roughly half of the IAV at many extratropical stations. However, the modeled ocean tracer was generally uncorrelated with observations in either hemisphere from 1979–2004, except during the weak El Niño/post-Pinatubo period of the early 1990s. During that time, model results suggested that the ocean may have accounted for 20–25% of the observed slowdown in the atmospheric CO2 growth rate

This paper presents the first ice core measurements of methyl bromide (CH3Br). Samples from a shallow Antarctic ice core (Siple Dome, West Antarctica), ranging in mean gas dates from 1671 to 1942, had a mean CH3Br mixing ratio of 5.8 ppt. These results extend the existing historical record derived from air and Antarctic firn air to about 350 years before present. Model simulations illustrate that the ice core results are consistent with estimates of the impact of anthropogenic activity (fumigation, combustion, and biomass burning) on the atmospheric CH3Br burden, given the large current uncertainties in the modern atmospheric CH3Br budget. A preindustrial scenario assuming no fumigation, no combustion, and a 75% reduction in biomass-burning sources yields a Southern Hemisphere mean mixing ratio of 5.8 ppt, in good agreement with the ice core results. There is a significant imbalance between the known CH3Br sources and sinks in the modern atmospheric CH3Br budget. The ice core data do not sufficiently constrain the model to determine how much of the “unknown source” was present in the preindustrial budget. The results do indicate that most of the southern hemispheric component of this “unknown source” is not anthropogenic.

Alkyl nitrates have been observed in remote oceanic regions of the troposphere and in the surface ocean. The mechanism for their production in the oceans is not known. A likely source is the reaction of ROO + NO (where R is an alkyl group). Steady-state laboratory experiments show that alkyl nitrates are produced in the aqueous phase via this reaction, with branching ratios of 0.23 ± 0.04, 0.67 ± 0.03, and 0.71 ± 0.04 for methyl, ethyl, and propyl nitrate respectively. The branching ratios in aqueous solution are significantly higher than in the gas phase. Irradiation of surface seawaters yield rates of alkyl nitrate production on the order of 10−18 mol cm−3 s−1, suggesting that the reaction of ROO and NO is an important source of alkyl nitrates in seawater.

We conducted a detailed investigation of the evolution of methyl bromide concentrations, degradation rates, and ventilation rates for 26 days in a naturally contained, warm-core eddy of the North Atlantic Ocean. This is the first study of the oceanic cycling of methyl bromide in a natural, contained system with a complete suite of supporting measurements of physical and chemical variables. Methyl bromide concentrations in the mixed layer ranged from 2.3 to 4.2 nmol m−3, degradation rates ranged from 0.1 to 0.9 nmol m−3 d−1, net sea-to-air exchange rates ranged from 0 to 0.5 nmol m−3 d−1, and net loss rates through the thermocline were less than 0.1 nmol m−3 d−1. From a mass balance for methyl bromide in the mixed layer, we calculated production rates ranging from