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.     

Excess 210Po in the coastal atmosphere

Many researchers have reported the widespread occurrence of excess ²¹⁰ Po in the global atmosphere and suggested probable sources such as resuspension of top soils, stratospheric aerosols, sea spray of the surface micro‐layer, volcanic emission, and bio‐volatile ²¹⁰Po species from the productive ocean. We have observed excess ²¹⁰Po on aerosols in the coastal atmosphere of the Chesapeake and Delaware Bays. On‐board measurements in the Chesapeake Bay atmosphere show that the increase of this excess ²¹⁰Po is dependent upon wind speed. Simultaneously measured activity ratios of ⁷Be/²¹⁰Pb and ²¹⁰Pb/²²²Rn argue against either higher altitude air or continental soils as the source of this excess. We hypothesize that the excess ²¹⁰Po originates mainly from surface waters either by the sea‐spray of the surface microlayer, or more likely, by gas exchange. We conclude gas exchange as the mechanism since the polonium excess increases linearly with wind speed over a threshold of 3 m s⁻¹(mean) similar to other gases (i.e., CO₂, SF₆ , and DMS). In addition, higher ²¹⁰Po excess with lower ²²²Rn is observed in on‐shore marine air at Lewes, DE. This suggests sea‐air exchange of volatile Po along with other bio‐volatile species (i.e., DMS, DMSe, and MMHg) in the coastal productive ocean during high wind speeds.     

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.