Sulfur (32S, 33S, 34S, 36S) and oxygen (16O,17O,18O) isotopic ratios of primary sulfate produced from combustion processes

The recent discovery of an anomalous enrichment in ¹⁷O isotope in atmospheric sulfate has opened a new way to investigate the oxidation pathways of sulfur in the atmosphere. From laboratory investigations, it has been suggested that the wet oxidation of sulfur in rain droplets was responsible for the excess ¹⁷O. In order to confirm this theory, sulfur and oxygen isotope ratios of different primary sulfates produced during fossil fuel combustion have been investigated and are reported. None of these samples exhibits any anomalous oxygen or sulfur isotopic content, as compared to urban sulfate aerosols. These results, in agreement with the laboratory investigations, reinforce the idea of an aqueous origin for the oxygen-17 anomaly found in tropospheric sulfates.     

Reconciliation of excess 14C-constrained global CO2 piston velocity estimates

Oceanic excess radiocarbon data is widely used as a constraint for air–sea gas exchange. However, recent estimates of the global mean piston velocity  〈 k 〉  from Naegler et al., Krakauer et al., Sweeney et al. and Müller et al. differ substantially despite the fact that they all are based on excess radiocarbon data from the GLODAP data base. Here I show that these estimates of  〈 k 〉  can be reconciled if first, the changing oceanic radiocarbon inventory due to net uptake of CO₂ is taken into account; second, if realistic reconstructions of sea surface  Δ¹⁴C  are used and third, if  〈 k 〉  is consistently reported with or without normalization to a Schmidt number of 660. These corrections applied, unnormalized estimates of  〈 k 〉  from these studies range between 15.1 and 18.2 cm h⁻¹. However, none of these estimates can be regarded as the only correct value for  〈 k 〉  . I thus propose to use the 'average' of the corrected values of  〈 k 〉  presented here (16.5 ± 3.2 cm h⁻¹) as the best available estimate of the global mean unnormalized piston velocity  〈 k 〉  , resulting in a gross ocean-to-atmosphere CO₂ flux of 76 ± 15 PgC yr⁻¹ for the mid-1990s.     

Projections of SO2, NOx and carbonaceous aerosols emissions in Asia

Estimates of Asian emissions of air pollutants and carbonaceous aerosols and their mid-term projections have been changing significantly in the last years. The remote sensing community has shown that increase in NO _x in Central East Asia is much stronger than any of the emission inventories or projections indicated so far. A number of studies reviewing older estimates appeared. Here, we review the key contributions and compare them to the most recent results of the GAINS model application for Asia and to the SRES projections used in the IPPC work. The recent projections indicate that the growth of emissions of SO₂ in Asia should slow down significantly towards 2010 or even stabilize at the current level. For NO _x , however, further growth is projected although it will be most likely slower that in the last decade, owing to introduction of measures in transport. Emissions of carbonaceous aerosols (black carbon and organic carbon) are expected to decline after 2010, largely due to reduced use of biofuels in residential sector and efficiency improvements. The estimates of these emissions are burdened with significantly larger uncertainties than SO₂ and NO _x ; even for the year 2000 the differences in estimates between studies are up to a factor of 2.     

Vertical profiles of biospheric and fossil fuel-derived CO2 and fossil fuel CO2 : CO ratios from airborne measurements of Δ14C, CO2 and CO above Colorado, USA

Measurements of  Δ¹⁴C  in atmospheric CO₂ are an effective method of separating CO₂ additions from fossil fuel and biospheric sources or sinks of CO₂. We illustrate this technique with vertical profiles of CO₂ and  Δ¹⁴C  analysed in whole air flask samples collected above Colorado, USA in May and July 2004. Comparison of lower tropospheric composition to cleaner air at higher altitudes (>5 km) revealed considerable additions from respiration in the morning in both urban and rural locations. Afternoon concentrations were mainly governed by fossil fuel emissions and boundary layer depth, also showing net biospheric CO₂ uptake in some cases. We estimate local industrial CO₂:CO emission ratios using in situ measurements of CO concentration. Ratios are found to vary by 100% and average 57 mole CO₂:1 mole CO, higher than expected from emissions inventories. Uncertainty in CO₂ from different sources was ±1.1 to ±4.1 ppm for addition or uptake of −4.6 to 55.8 ppm, limited by  Δ¹⁴C  measurement precision and uncertainty in background  Δ¹⁴C  and CO₂ levels.     

Diurnal variation of CO2 concentration, Δ14C and δ13C in an urban forest: estimate of the anthropogenic and biogenic CO2 contributions

Diurnal variation in the atmospheric CO₂ concentration and the carbon isotopic composition (Δ¹⁴C and δ¹³C) was measured in a forest in an urban area on 9 February 1999. The carbon isotope approach used in the present study differentiated between the quantitative contributions from anthropogenic and biogenic CO₂ sources in the urban atmosphere. The anthropogenic (fossil fuel) and biogenic (soil respiration) contributions was estimated, and they ranged from 1 to 16% and from 2 to 8% of the total atmospheric CO₂. The diurnal variation of the anthropogenic CO₂ was the major cause of the total atmospheric CO₂ variation, while the biogenic CO₂ remained relatively constant throughout the day. Estimating the contribution of soil respired CO₂ provided the mean residence time of soil respired CO₂ within the forest atmosphere.     

Seasonal and global NOx production by lightning estimated from the Optical Transient Detector (OTD)

The Optical Transient Detector (OTD) lightning data for the 12‐month period of 1996 are used to estimate the seasonal and global distributions of lightning‐produced NO _x . The relatively small viewing footprint and the low detection efficiency of the OTD sensor and other difficulties require extrapolations of the OTD data to the actual global flash distributions. Furthermore, available measurements for the ratios of intracloud (IC) to cloud‐to‐ground (CG) flashes have been used to partition lightning counts for IC versus CG flashes from the OTD observations. The resulting lightning distributions are then used to calculate the global and seasonal production of NO _x , assuming a NO production rate of 6.2×10²⁵ molecules for each CG flash and 8.7×10²⁴ molecules for each IC flash. Consequently, we find that CG flashes produce more NO _x than IC flashes despite fewer CG flashes by a factor of 3 or more. NO _x production by lightning varies seasonally in accordance with the global lightning distribution, with the maximum production occurring in the Northern Hemisphere in the local summer. The latitudinal distribution of NO _x production exhibits a strong seasonal variation outside the tropics with the production occurring mainly in the summer hemisphere, whereas in the tropics the production is high throughout the year. The annual contribution to NO _x production by lightning is higher in the Northern Hemisphere than that in the Southern Hemisphere.