Photochemistry in the arctic free troposphere: Ozone budget and its dependence on nitrogen oxides and the production rate of free radicals

Abstract. Local ozone production and loss rates for the arctic free troposphere (58–85 ◦ N, 1–6 km, February–May) during the Tropospheric Ozone Production about the Spring Equinox (TOPSE) campaign were calculated using a constrained photochemical box model. Estimates were made to assess the importance of local photochemical ozone production relative to transport in accounting for the springtime maximum in arctic free tropospheric ozone. Ozone production and loss rates from our diel steady-state box model constrained by median observations were first compared to two point box models, one run to instantaneous steady-state and the other run to diel steady-state. A consistent picture of local ozone photochemistry was derived by all three box models suggesting that differences between the approaches were not critical. Our model-derived ozone production rates increased by a factor of 28 in the 1–3 km layer and a factor of 7 in the 3–6 km layer between February and May. The arctic ozone budget required net import of ozone into the arctic free troposphere throughout the campaign; however, the transport term exceeded the photochemical production only in the lower free troposphere (1–3 km) between February and March. Gross ozone production rates were calculated to increase linearly with NOx mixing ratios up to ∼300 pptv in February and for NOx mixing ratio

The Poison Pen: Bedside Diagnosis of Urinary Diquat

Diquat is a bipyridyl herbicide with nephrotoxic effects. This in vitro study demonstrates a colorimetric test for detection of diquat in human urine. Urine specimens using ten concentrations of diquat herbicide solution and controls for urine and glyphosate were prepared. A two-step assay (addition of bicarbonate followed by sodium dithionite) was performed, with a resulting color change of the original solution for each specimen. Color change intensity was noted immediately and after 30 min, by gross visual inspection. A green color with concentration-dependent intensity was detected in all specimens, in which concentrations of diquat solution ranged from 0.73 to 730 mg/L. This colorimetric effect disappeared after 30 min. The sodium bicarbonate/dithionite test may be useful as a qualitative bedside technique for the detection of urinary diquat in the appropriate clinical setting

Coupled evolution of BrOx-ClOx-HOx-NOx chemistry during bromine-catalyzed ozone depletion events in the arctic boundary layer

Extensive chemical characterization of ozone (O3) depletion events in the Arctic boundary layer during the TOPSE aircraft mission in March–May 2000 enables analysis of the coupled chemical evolution of bromine (BrOx), chlorine (ClOx), hydrogen oxide (HOx) and nitrogen oxide (NOx) radicals during these events. We project the TOPSE observations onto an O3 chemical coordinate to construct a chronology of radical chemistry during O3 depletion events, and we compare this chronology to results from a photochemical model simulation. Comparison of observed trends in ethyne (oxidized by Br) and ethane (oxidized by Cl) indicates that ClOxchemistry is only active during the early stage of O3 depletion (O3 \u3e 10 ppbv). We attribute this result to the suppression of BrCl regeneration as O3 decreases. Formaldehyde and peroxy radical concentrations decline by factors of 4 and 2 respectively during O3 depletion and we explain both trends on the basis of the reaction of CH2O with Br. Observed NOx concentrations decline abruptly in the early stages of O3 depletion and recover as O3 drops below 10 ppbv. We attribute the initial decline to BrNO3 hydrolysis in aerosol, and the subsequent recovery to suppression of BrNO3 formation as O3 drops. Under halogen-free conditions we find that HNO4 heterogeneous chemistry could provide a major NOx sink not included in standard models. Halogen radical chemistry in the model can produce under realistic conditions an oscillatory system with a period of 3 days, which we believe is the fastest oscillation ever reported for a chemical system in the atmosphere

Marine latitude/altitude OH distributions: Comparison of Pacific Ocean observations with models

Reported here are tropical/subtropical Pacific basin OH observational data presented in a latitude/altitude geographical grid. They cover two seasons of the year (spring and fall) that reflect the timing of NASA's PEM-Tropics A (1996) and B (1999) field programs. Two different OH sensors were used to collect these data, and each instrument was mounted on a different aircraft platform (i.e., NASA's P-3B and DC-8). Collectively, these chemical snapshots of the central Pacific have revealed several interesting trends. Only modest decreases (factors of 2 to 3) were found in the levels of OH with increasing altitude (0-12 km). Similarly, only modest variations were found (factors of 1.5 to 3.5) when the data were examined as a function of latitude (30° N to 30° S). Using simultaneously recorded data for CO, O3, H2O, NO, and NMHCs, comparisons with current models were also carried out. For three out of four data subsets, the results revealed a high level of correspondence. On average, the box model results agreed with the observations within a factor of 1.5. The comparison with the three-dimensional model results was found to be only slightly worse. Overall, these results suggest that current model mechanisms capture the major photochemical processes controlling OH quite well and thus provide a reasonably good representation of OH levels for tropical marine environments. They also indicate that the two OH sensors employed during the PEM-Tropics B study generally saw similar OH levels when sampling a similar tropical marine environment. However, a modest altitude bias appears to exist between these instruments. More rigorous instrument intercomparison activity would therefore seem to be justified. Further comparisons of model predictions with observations are also recommended for nontropical marine environments as well as those involving highly elevated levels of reactive non-methane hydrocarbons. Copyright 2001 by the American Geophysical Union

Accounting for convective effects in zero-Mach-number thermoacoustic models

This paper presents a methodology to account for some mean-flow effects on thermo-acoustic instabilities when using the zero-Mach-number assumption. It is shown that when a computational domain is represented under the M=0 assumption, a nonzero-Mach-number element can simply be taken into account by imposing a proper acoustic impedance at the boundaries so as to mimic the mean flow effects in the outer, not computed flow domain. A model that accounts for the coupling between acoustic and entropy waves is presented. It relies on a “delayed entropy coupled boundary condition” (DECBC) for the Helmholtz equation satisfied by the acoustic pressure. The model proves able to capture low-frequency entropic modes even without mean-flow terms in the fluctuating pressure equation

Ozone depletion events observed in the high latitude surface layer during the TOPSE aircraft program

During the Tropospheric Ozone Production about the Spring Equinox (TOPSE) aircraft program, ozone depletion events (ODEs) in the high latitude surface layer were investigated using lidar and in situ instruments. Flight legs of 100 km or longer distance were flown 32 times at 30 m altitude over a variety of regions north of 58° between early February and late May 2000. ODEs were found on each flight over the Arctic Ocean but their occurrence was rare at more southern latitudes. However, large area events with depletion to over 2 km altitude in one case were found as far south as Baffin Bay and Hudson Bay and as late as 22 May. There is good evidence that these more southern events did not form in situ but were the result of export of ozone-depleted air from the surface layer of the Arctic Ocean. Surprisingly, relatively intact transport of ODEs occurred over distances of 900–2000 km and in some cases over rough terrain. Accumulation of constituents in the frozen surface over the dark winter period cannot be a strong prerequisite of ozone depletion since latitudes south of the Arctic Ocean would also experience a long dark period. Some process unique to the Arctic Ocean surface or its coastal regions remains unidentified for the release of ozone-depleting halogens. There was no correspondence between coarse surface features such as solid ice/snow, open leads, or polynyas with the occurrence of or intensity of ozone depletion over the Arctic or subarctic regions. Depletion events also occurred in the absence of long-range transport of relatively fresh “pollution” within the high latitude surface layer, at least in spring 2000. Direct measurements of halogen radicals were not made. However, the flights do provide detailed information on the vertical structure of the surface layer and, during the constant 30 m altitude legs, measurements of a variety of constituents including hydroxyl and peroxy radicals. A summary of the behavior of these constituents is made. The measurements were consistent with a source of formaldehyde from the snow/ice surface. Median NOx in the surface layer was 15 pptv or less, suggesting that surface emissions were substantially converted to reservoir constituents by 30 m altitude and that ozone production rates were small (0.15–1.5 ppbv/d) at this altitude. Peroxyacetylnitrate (PAN) was by far the major constituent of NOy in the surface layer independent of the ozone mixing ratio