Measurements of the C-H overtone transition strengths combined with estimates of the photodissociation cross sections for these transitions suggest that near-IR photodissociation of peroxy acetyl nitrate (PAN) is less significant (J(near-IR) approximate to 3 x 10(-8) s(-1) at noon) in the lower atmosphere than competing sinks resulting from unimolecular decomposition and ultraviolet photolysis. This is in contrast to the photochemical behavior of a related peroxy nitrate, pernitric acid (PNA), that undergoes rapid near-IR photolysis in the atmosphere with J(near-IR) approximate to 10(-5) s(-1) at noon (Roehl et al., 2002). This difference is attributed to the larger binding energy and larger number of vibrational degrees of freedom in PAN, which make 4 nu(CH) the lowest overtone excitation with a high photodissociation yield (as opposed to 2 nu(OH) in PNA).

Observations of the column-averaged dry molar mixing ratio of CO₂ above both Park Falls, Wisconsin and Kitt Peak, Arizona, together with partial columns derived from aircraft profiles over Eurasia and North America are used to estimate the seasonal integral of net ecosystem exchange (NEE) between the atmosphere and the terrestrial biosphere in the Northern Hemisphere. We find that NEE is ∼25% larger than predicted by the Carnegie Ames Stanford Approach (CASA) model. We show that the estimates of NEE may have been biased low by too weak vertical mixing in the transport models used to infer seasonal changes in Northern Hemisphere CO₂ mass from the surface measurements of CO₂ mixing ratio.

Observations during the 2006 dry season of highly elevated concentrations of cyanides in the atmosphere above Mexico City (MC) and the surrounding plains demonstrate that biomass burning (BB) significantly impacted air quality in the region. We find that during the period of our measurements, fires contribute more than half of the organic aerosol mass and submicron aerosol scattering, and one third of the enhancement in benzene, reactive nitrogen, and carbon monoxide in the outflow from the plateau. The combination of biomass burning and anthropogenic emissions will affect ozone chemistry in the MC outflow.

Formation of isoprene nitrates (INs) is an important free radical chain termination step ending production of ozone and possibly affecting formation of secondary organic aerosol. Isoprene nitrates also represent a potentially large, unmeasured contribution to OH reactivity and are a major pathway for the removal of nitrogen oxides from the atmosphere. Current assessments indicate that formation rates of isoprene nitrates are uncertain to a factor of 2–3 and the subsequent fate of isoprene nitrates remains largely unconstrained by laboratory, field or modeling studies. Measurements of total alkyl and multifunctional nitrates (ΣANs), NO₂, total peroxy nitrates (ΣPNs), HNO₃, CH₂O, isoprene and other VOC were obtained from the NASA DC-8 aircraft during summer 2004 over the continental US during the INTEX-NA campaign. These observations represent the first characterization of ΣANs over a wide range of land surface types and in the lower free troposphere. ΣANs were a significant, 12–20%, fraction of NO_y throughout the experimental domain and ΣANs were more abundant when isoprene was high. We use the observed hydrocarbon species to calculate the relative contributions of ΣAN precursors to their production. These calculations indicate that isoprene represents at least three quarters of the ΣAN source in the summertime continental boundary layer of the US. An observed correlation between ΣANs and CH₂O is used to place constraints on nitrate yields from isoprene oxidation, atmospheric lifetimes of the resulting nitrates and recycling efficiencies of nitrates during subsequent oxidation. We find reasonable fits to the data using sets of production rates, lifetimes and recycling efficiencies of INs as follows (4.4%, 16 h, 97%), (8%, 2.5 h, 79%) and (12%, 95 min, 67%). The analysis indicates that the lifetime of ΣANs as a pool of compounds is considerably longer than the lifetime of the individual isoprene nitrates to reaction with OH, implying that the organic nitrate functionality is at least partially maintained through a second oxidation cycle.

Formation of isoprene nitrates (INs) is an important free radical chain termination step ending production of ozone and possibly affecting formation of secondary organic aerosol. Isoprene nitrates also represent a potentially large, unmeasured contribution to OH reactivity and are a major pathway for the removal of nitrogen oxides from the atmosphere. Current assessments indicate that formation rates of isoprene nitrates are uncertain to a factor of 2-3 and the subsequent fate of isoprene nitrates remains largely unconstrained by laboratory, field or modeling studies. Measurements of total alkyl and multifunctional nitrates (Sigma ANs), NO2, total peroxy nitrates (Sigma PNs), HNO3, CH2O, isoprene and other VOC were obtained from the NASA DC-8 aircraft during summer 2004 over the continental US during the INTEX-NA campaign. These observations represent the first characterization of Sigma ANs over a wide range of land surface types and in the lower free troposphere. Sigma ANs were a significant, 12-20%, fraction of NOy throughout the experimental domain and Sigma ANs were more abundant when isoprene was high. We use the observed hydrocarbon species to calculate the relative contributions of Sigma AN precursors to their production. These calculations indicate that isoprene represents at least three quarters of the Sigma AN source in the summertime continental boundary layer of the US. An observed correlation between Sigma ANs and CH2O is used to place constraints on nitrate yields from isoprene oxidation, atmospheric lifetimes of the resulting nitrates and recycling efficiencies of nitrates during subsequent oxidation. We find reasonable fits to the data using sets of production rates, lifetimes and recycling efficiencies of INs as follows (4.4%, 16 h, 97%), (8%, 2.5h, 79%) and (12%, 95 min, 67%). The analysis indicates that the lifetime of Sigma ANs as a pool of compounds is considerably longer than the lifetime of the individual isoprene nitrates to reaction with OH, implying that the organic nitrate functionality is at least partially maintained through a second oxidation cycle.

We observe significant interannual variability in the strength of the seasonal cycle drawdown in northern midlatitudes from measurements of CO₂ made by the Total Carbon Column Observing Network (TCCON) and the Greenhouse Gases Observing Satellite (GOSAT). This variability correlates with surface temperature in the boreal regions. Using TCCON measurements, we find that the slope of the relationship between the X_CO2 seasonal cycle minima and boreal surface temperature is 1.2 ± 0.7 ppm K⁻¹. Assimilations from CarbonTracker 2011 and CO₂ simulations using the Simple Biosphere exchange Model (SiB) transported by GEOS-Chem underestimate this covariation. Both atmospheric transport and biospheric activity contribute to the observed covariation.

In-situ airborne measurements of trace gases, aerosol size distributions, chemistry and optical properties were conducted over Mexico and the Eastern North Pacific during MILAGRO and INTEX-B. Heterogeneous reactions between secondary aerosol precursor gases and mineral dust lead to sequestration of sulfur, nitrogen and chlorine in the supermicrometer particulate size range. Simultaneous measurements of aerosol size distributions and weak-acid soluble calcium result in an estimate of 11 wt% of CaCO₃ for Asian dust. During transport across the North Pacific, ~5–30% of the CaCO₃ is converted to CaSO₄ or Ca(NO₃)₂ with an additional ~4% consumed through reactions with HCl. The 1996 to 2008 record from the Mauna Loa Observatory confirm these findings, indicating that, on average, 19% of the CaCO₃ has reacted to form CaSO₄ and 7% has reacted to form Ca(NO₃)₂ and ~2% has reacted with HCl. In the nitrogen-oxide rich boundary layer near Mexico City up to 30% of the CaCO₃ has reacted to form Ca(NO₃)₂while an additional 8% has reacted with HCl. These heterogeneous reactions can result in a ~3% increase in dust solubility which has an insignificant effect on their optical properties compared to their variability in-situ. However, competition between supermicrometer dust and submicrometer primary aerosol for condensing secondary aerosol species led to a 25% smaller number median diameter for the accumulation mode aerosol. A 10–25% reduction of accumulation mode number median diameter results in a 30–70% reduction in submicrometer light scattering at relative humidities in the 80–95% range. At 80% RH submicrometer light scattering is only reduced ~3% due to a higher mass fraction of hydrophobic refractory components in the dust-affected accumulation mode aerosol. Thus reducing the geometric mean diameter of the submicrometer aerosol has a much larger effect on aerosol optical properties than changes to the hygroscopic:hydrophobic mass fractions of the accumulation mode aerosol. In the presence of dust, nitric acid concentrations are reduced to <50% of total nitrate (nitric acid plus particulate nitrate). NO_y as a fraction of total nitrogen (NO_y plus particulate nitrate), is reduced from >85% to 60–80% in the presence of dust. These observations support previous model studies which predict irreversible sequestration of reactive nitrogen species through heterogeneous reactions with mineral dust during long-range transport.