Laboratory evaluation of the effect of nitric acid uptake on frost point hygrometer performance

Chilled mirror hygrometers (CMH) are widely used to measure water vapour in the troposphere and lower stratosphere from balloon-borne sondes. Systematic discrepancies among in situ water vapour instruments have been observed at low water vapour mixing ratios (<5 ppm) in the upper troposphere and lower stratosphere (UT/LS). Understanding the source of the measurement discrepancies is important for a more accurate and reliable determination of water vapour abundance in this region. We have conducted a laboratory study to investigate the potential interference of gas-phase nitric acid (HNO<sub>3</sub>) with the measurement of frost point temperature, and consequently the water vapour mixing ratio, determined by CMH under conditions representative of operation in the UT/LS. No detectable interference in the measured frost point temperature was found for HNO<sub>3</sub> mixing ratios of up to 4 ppb for exposure times up to 150 min. HNO<sub>3</sub> was observed to co-condense on the mirror frost, with the adsorbed mass increasing linearly with time at constant exposure levels. Over the duration of a typical balloon sonde ascent (90–120 min), the maximum accumulated HNO<sub>3</sub> amounts were comparable to monolayer coverage of the geometric mirror surface area, which corresponds to only a small fraction of the actual frost layer surface area. This small amount of co-condensed HNO<sub>3</sub> is consistent with the observed lack of HNO<sub>3</sub> interference in the frost point measurement because the CMH utilizes significant reductions (>10%) in surface reflectivity by the condensate to determine H<sub>2</sub>O

The photochemistry of acetone in the upper troposphere: A source of odd-hydrogen radicals

This paper summarizes measured photodissociation quantum yields for acetone in the 290-320 nm wavelength region for pressures and temperatures characteristic of the upper troposphere. Calculations combine this laboratory data with trace gas concentrations obtained during the NASA and NOAA sponsored Stratospheric Tracers of Atmospheric Transport (STRAT) field campaign, in which measurements of OH, HO_(2), odd-nitrogen, and other compounds were collected over Hawaii, and west of California during fall and winter of 1995/1996. OH and HO_(2) concentrations within 2 to 5 km layers just below the tropopause are ∼50% larger than expected from O_(3), CH_(4), and H_(2)O chemistry alone. Although not measured during STRAT, acetone is inferred from CO measurements and acetone-CO correlations from a previous field study. These inferred acetone levels are a significant source of odd-hydrogen radicals that can explain a large part of the discrepancy in the upper troposphere. For lower altitudes, the inferred acetone makes a negligible contribution to HO_(x) (HO+HO_(2)), but influences NO_(y) partitioning. A major fraction of HO_(x) production by acetone is through CH_(2)O formation, and the HO_(x) discrepancy can also be explained by CH_(2)O levels in the 20 to 50 pptv range, regardless of the source

Rate coefficients and product branching measurements for the reaction OH + bromopropane from 230 to 360 K

Article on rate coefficient and product branching measurements for the reaction OH + bromopropane from 230 to 360 K

Oceanic uptake and the global atmospheric acetone budget

In this study, direct measurements of the air/ sea flux of acetone were made over the North Pacific Ocean. The results demonstrate that the net flux of acetone is into, rather than out of the oceans. The extrapolated global ocean uptake of 48 Tg yr(-1) requires a major revision of the atmospheric acetone budget. This result is consistent with a recent reevaluation of acetone photodissociation quantum yields

Methane Clumped Isotopes: Progress and Potential for a New Isotopic Tracer

The isotopic composition of methane is of longstanding geochemical interest, with important implications for understanding petroleum systems, atmospheric greenhouse gas concentrations, the global carbon cycle, and life in extreme environments. Recent analytical developments focusing on multiply substituted isotopologues (‘clumped isotopes’) are opening a valuable new window into methane geochemistry. When methane forms in internal isotopic equilibrium, clumped isotopes can provide a direct record of formation temperature, making this property particularly valuable for identifying different methane origins. However, it has also become clear that in certain settings methane clumped isotope measurements record kinetic rather than equilibrium isotope effects. Here we present a substantially expanded dataset of methane clumped isotope analyses, and provide a synthesis of the current interpretive framework for this parameter. In general, clumped isotope measurements indicate plausible formation temperatures for abiotic, thermogenic, and microbial methane in many geological environments, which is encouraging for the further development of this measurement as a geothermometer, and as a tracer for the source of natural gas reservoirs and emissions. We also highlight, however, instances where clumped isotope derived temperatures are higher than expected, and discuss possible factors that could distort equilibrium formation temperature signals. In microbial methane from freshwater ecosystems, in particular, clumped isotope values appear to be controlled by kinetic effects, and may ultimately be useful to study methanogen metabolism

Photo-tautomerization of acetaldehyde as a photochemical source of formic acid in the troposphere

Organic acids play a key role in the troposphere, contributing to atmospheric aqueous-phase chemistry, aerosol formation, and precipitation acidity. Atmospheric models currently account for less than half the observed, globally averaged formic acid loading. Here we report that acetaldehyde photo-tautomerizes to vinyl alcohol under atmospherically relevant pressures of nitrogen, in the actinic wavelength range, λ = 300–330 nm, with measured quantum yields of 2–25%. Recent theoretical kinetics studies show hydroxyl-initiated oxidation of vinyl alcohol produces formic acid. Adding these pathways to an atmospheric chemistry box model (Master Chemical Mechanism) demonstrates increased formic acid concentrations by a factor of ~1.7 in the polluted troposphere and a factor of ~3 under pristine conditions. Incorporating this mechanism into the GEOS-Chem 3D global chemical transport model reveals an estimated 7% contribution to worldwide formic acid production, with up to 60% of the total modeled formic acid production over oceans arising from photo-tautomerization

Kwalitologiczna ocena jakości autobusów

Intensywnie rozwijające się miasta napotykają na różnego rodzaju problemy, w tym problemy komunikacyjne. Podejmowane są oczywiście próby rozwiązywania tych problemów. Zaliczyć do nich można koncepcję szerszego zainteresowania mieszkańców transportem publicznym. Prowadzone są też analizy, których celem jest jego optymalizacja. Chcąc zachęcić mieszkańców do korzystania z transportu publicznego, oprócz zmian organizacyjnych, należałoby zwrócić uwagę na kupowane środki transportu miejskiego. Pomocną w tym zakresie może być kwalitologia, czyli nauka zajmująca się badaniem jakości produktów

The American No-Dig Conference 2013 in Sacramento

Amerykańskie konferencje No-Dig, w odróżnieniu od polskich (www.nodigpoland.tu.kielce.pl), organizowanych co dwa lata w Kielcach, odbywają się corocznie i za każdym razem w innym mieście. W tegorocznej konferencji w Sacramento 3–7 marca 2013 r. wzięło udział 1650 uczestników.The American No-Dig Conferences, dedicated to trenchless technologies, take place annually and each time in a different city, unlike the Polish conferences, which are organized biannually in Kielce. The Conference in Sacramento from 37 March 2013 was attended by 1,650 participants