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Nitryl chloride (ClNO2) is produced at night by reactions of dinitrogen pentoxide (N2O5) on chloride containing surfaces. ClNO2 is photolyzed during the morning hours after sunrise to liberate highly reactive chlorine atoms (Cl-). This chemistry takes place primarily in polluted environments where the concentrations of N2O5 precursors (nitrogen oxide radicals and ozone) are high, though it likely occurs in remote regions at lower intensities. Recent field measurements have illustrated the potential importance of ClNO2 as a daytime Cl- source and a nighttime NOx reservoir. However, the fate of the Cl- and the overall impact of ClNO2 on regional photochemistry remain unclear. To this end, we have incorporated ClNO2 production, photolysis, and subsequent Cl- reactions into an existing Master Chemical Mechanism (MCM version 3.2) box model framework using observational constraints from the CalNex 2010 field study. Cl- reactions with a set of alkenes and alcohols, and the simplified multiphase chemistry of N2O5, ClNO2, HOCl, ClONO2, and Cl2, none of which are currently part of the MCM, have been added to the mechanism. The presence of ClNO2 produces significant changes to oxidants, ozone, and nitrogen oxide partitioning, relative to model runs excluding ClNO2 formation. From a nighttime maximum of 1.5 ppbv ClNO2, the daytime maximum Cl- concentration reaches 1x105 atomscm-3 at 7 a.m., reacting mostly with a large suite of volatile organic compounds (VOC) to produce 2.2 times more organic peroxy radicals in the morning than in the absence of ClNO2. In the presence of several ppbv of nitrogen oxide radicals (NOx = NO + NO2), these perturbations lead to similar enhancements in hydrogen oxide radicals (HOx = OH + HO2). Neglecting contributions from HONO, the total integrated daytime radical source is 17% larger when including ClNO2, which leads to a similar enhancement in integrated ozone production of 15 %. Detectable levels (tens of pptv) of chlorine containing organic compounds are predicted to form as a result of Cl- addition to alkenes, which may be useful in identifying times of active Cl- chemistry. [ABSTRACT FROM AUTHOR]

A laser-based cavity ring-down spectroscopy (CRDS) sensor for measurement of hydrogen chloride (HCl) has been developed and characterized. The instrument uses light from a distributed-feedback diode laser at 1742 nm coupled to a high finesse optical cavity to make sensitive and quantifiable concentration measurements of HCl based on optical absorption. The instrument has a (1σ) limit of detection of <20 pptv in 1 min and has high specificity to HCl. The measurement response time to changes in input HCl concentration is <15 s. Validation studies with a previously calibrated permeation tube setup show an accuracy of better than 10 %. The CRDS sensor was preliminarily tested in the field with two other HCl instruments (mist chamber and chemical ionization mass spectrometry), all of which were in broad agreement. The mist chamber and CRDS sensors both showed a 400 pptv plume within 50 pptv agreement. The sensor also allows simultaneous sensitive measurements of water and methane, and minimal hardware modification would allow detection of other near-infrared absorbers. [ABSTRACT FROM AUTHOR]

We present top-down estimates of anthropogenic CO, NOx and CO2 surface fluxes at mesoscale using a Lagrangian model in combination with three different WRF model configurations, driven by data from aircraft flights during the CALNEX campaign in southern California in May- June 2010. The US EPA National Emission Inventory 2005 (NEI 2005) was the prior in the CO and NOx inversion calculations. The flux ratio inversion method, based on linear relationships between chemical species, was used to calculate the CO2 inventory without prior knowledge of CO2 surface fluxes. The inversion was applied to each flight to estimate the variability of single-flight-based flux estimates. In Los Angeles (LA) County, the uncertainties on CO and NOx fluxes were 10%and 15 %, respectively. Compared with NEI 2005, the CO posterior emissions were lower by 43% in LA County and by 37% in the South Coast Air Basin (SoCAB). NOx posterior emissions were lower by 32% in LA County and by 27% in the SoCAB. NOx posterior emissions were 40% lower on weekends relative to weekdays. The CO2 posterior estimates were 183 Tgyr-1 in SoCAB. A flight during ITCT (Intercontinental Transport and Chemical Transformation) in 2002 was used to estimate emissions in the LA Basin in 2002. From 2002 to 2010, the CO and NOx posterior emissions decreased by 41%and 37 %, respectively, in agreement with previous studies. Over the same time period, CO2 emissions increased by 10% in LA County but decreased by 4% in the SoCAB, a statistically insignificant change. Overall, the posterior estimates were in good agreement with the California Air Resources Board (CARB) inventory, with differences of 15% or less. However, the posterior spatial distribution in the basin was significantly different from CARB for NOx emissions. WRF-Chem mesoscale chemical-transport model simulations allowed an evaluation of differences in chemistry using different inventory assumptions, including NEI 2005, a gridded CARB inventory and the posterior inventories derived in this study. The biases in WRF-Chem ozone were reduced and correlations were increased using the posterior from this study compared with simulations with the two bottom-up inventories, suggesting that improving the spatial distribution of ozone precursor surface emissions is also important in mesoscale chemistry simulations. [ABSTRACT FROM AUTHOR]

The detection of atmospheric NO3 radicals is still challenging owing to its low mixing ratios (≈1 to 300 pptv) in the troposphere. While long-path differential optical absorption spectroscopy (DOAS) is a well established NO3 detection approach for over 25 yr, newly sensitive techniques have been developed in the past decade. This publication outlines the results of the first comprehensive intercomparison of seven instruments developed for the spectroscopic detection of tropospheric NO3. Four instruments were based on cavity ring-down spectroscopy (CRDS), two utilised open-path cavity enhanced absorption spectroscopy (CEAS), and one applied "classical" long-path DOAS. The intercomparison campaign "NO3Comp" was held at the atmosphere simulation chamber SAPHIR in Jülich (Germany) in June 2007. Twelve experiments were performed in the well mixed chamber for variable concentrations of NO3, N2O5, NO2, hydrocarbons, and water vapour, in the absence and in the presence of inorganic or organic aerosol. The overall precision of the cavity instruments varied between 0.5 and 5 pptv for integration times of 1 s to 5min; that of the DOAS instrument was 9 pptv for an acquisition time of 1 min. The NO3 data of all instruments correlated excellently with the NOAA-CRDS instrument, which was selected as the common reference because of its superb sensitivity, high time resolution, and most comprehensive data coverage. The median of the coefficient of determination (r2) over all experiments of the campaign (60 correlations) is r2 =0.981 (25th/75th percentiles: 0.949/0.994; min/max: 0.540/0.999). The linear regression analysis of the campaign data set yielded very small intercepts (1.2±5.3 pptv) and the average slope of the regression lines was close to unity (1.02, min: 0.72, max: 1.36). The deviation of individual regression slopes from unity was always within the combined accuracies of each instrument pair. The very good correspondence between the NO3 measurements by all instruments for aerosol-free experiments indicates that the losses of NO3 in the inlet of the instruments were determined reliably by the participants for the corresponding conditions. In the presence of inorganic or organic aerosol, however, differences in the measured NO3 mixing ratios were detectable among the instruments. In individual experiments the discrepancies increased with time, pointing to additional NO3 radical losses by aerosol deposited onto the inlet walls of the instruments. Instruments using DOAS analyses showed no significant effect of aerosol on the detection of NO3. No hint of a cross interference of NO2 was found. The effect of non-Lambert-Beer behaviour of water vapour absorption lines on the accuracy of the NO3 detection by broadband techniques was small and well controlled. The NO3Comp campaign demonstrated the high quality, reliability and robustness of performance of current state-of-the-art instrumentation for NO3 detection. [ABSTRACT FROM AUTHOR]

We present top-down estimates of anthropogenic CO, NOx and CO2 surface fluxes at mesoscale using a Lagrangian model in combination with three different WRF model configurations, driven by data from aircraft flights during the CALNEX campaign in southern California in May-June 2010. The US EPA National Emission Inventory 2005 (NEI 2005) was the prior in the CO and NOx inversion calculations. The flux ratio inversion method, based on linear relationships between chemical species, was used to calculate the CO2 inventory without prior knowledge of CO2 surface fluxes. The inversion was applied to each flight to estimate the variability of single-flight-based flux estimates. In Los Angeles (LA) County, the uncertainties on CO and NOx fluxes were 10% and 15%, respectively. Compared with NEI 2005, the CO posterior emissions were lower by 43%±6% in LA County and by 37%±10% in the South Coast Air Basin (SoCAB). NOx posterior emissions were lower by 32 % ± 10 % in LA County and by 27 % ± 15 % in the SoCAB. NOx posterior emissions were 40 % lower on weekends relative to weekdays. The CO2 posterior estimates were 183 ± 18Tgyr-1 in SoCAB. A flight during ITCT in 2002 was used to estimate emissions in the LA Basin in 2002. From 2002 to 2010, the CO and NOx posterior emissions decreased by 41 % and 37%, respectively, in agreement with previous studies. Over the same time period, CO2 emissions increased by 10%±14% in LA County but decreased by 4%±10% in the SoCAB, a statistically insignificant change. Overall, the posterior estimates were in good agreement with the California Air Resources Board (CARB) inventory, with differences of 15% or less. However, the posterior spatial distribution in the basin was significantly different from CARB for NOx emissions. WRF-Chem mesoscale chemical-transport model simulations allowed an evaluation of differences in chemistry using different inventory assumptions, including NEI 2005, CARB 2010 and the posterior inventories derived in this study. The biases in WRF-Chem ozone were reduced and correlations were increased using the posterior from this study compared with simulations with the two bottom-up inventories, showing that improving the spatial distribution of ozone precursor surface emissions is also important in mesoscale chemistry forecasts. [ABSTRACT FROM AUTHOR]

We report the ozone absolute absorption cross section between 350-470 nm, the minimum between the Huggins and Chappuis bands, where the ozone cross section is less than 10-22 cm². Ozone spectra were acquired using an incoherent broadband cavity enhanced absorption spectrometer, with three channels centered at 365, 405, and 455 nm. The accuracy of the measured cross section is 2 %. Previous measurements vary by more than an order of magnitude in this spectral region. The measurements reported here provide much greater spectral coverage than the most recent measurements. We report a minimum absorption cross section of 3.4x10-24 cm² at 381.8 nm, which is 22% lower than the previously reported value. The effect of O3 concentration and water vapor partial pressure were investigated, however there were no observable changes in the absorption spectrum most likely due to the low optical density of the complex. [ABSTRACT FROM AUTHOR]

The article presents a study on a diode laser-based, cavity ring-down spectrometer for the measurements of nitrogen oxide species in the atmosphere. It mentions that the instrument uses wave diode lasers in eliminating hazardous materials found in nitrogen oxide species. It notes that the instument is also used for the measurements of nighttime nitrogen oxides.

The formation of organic nitrates and secondary organic aerosol (SOA) were monitored during the NO3 + limonene reaction in the atmosphere simulation chamber SAPHIR at Research Center Jülich. The 24-h run began in a purged, dry, particle-free chamber and comprised two injections of limonene and oxidants, such that the first experiment measured SOA yield in the absence of seed aerosol, and the second experiment yields in the presence of 10 µg m seed organic aerosol. After each injection, two separate increases in aerosol mass were observed, corresponding to sequential oxidation of the two limonene double bonds. Analysis of the measured NO3, limonene, product nitrate concentrations, and aerosol properties provides mechanistic insight and constrains rate constants, branching ratios and vapor pressures of the products. The organic nitrate yield from NO3 + limonene is ≈30%. The SOA mass yield was observed to be 25-40%. The first injection is reproduced by a kinetic model. PMF analysis of the aerosol composition suggests that much of the aerosol mass results from combined oxidation by both O3 and NO3, e.g.. oxidation of NO3 + limonene products by O3. Further, later aerosol nitrate mass seems to derive from heterogeneous uptake of NO3 onto unreacted aerosol alkene. [ABSTRACT FROM AUTHOR]

The formation of organic nitrates and secondary organic aerosol (SOA) were monitored during the NO3+limonene reaction in the atmosphere simulation chamber SAPHIR at Research Center Julich. The 24-h run began in a purged, dry, particle-free chamber and comprised two injections of limonene and oxidants, such that the first experiment measured SOA yield in the absence of seed aerosol, and the second experiment yields in the presence of 10 µg M-3 seed organic aerosol. After each injection, two separate increases in aerosol mass were observed, corresponding to sequential oxidation of the two limonene double bonds. Analysis of the measured NO3, limonene, product nitrate concentrations, and aerosol properties provides mechanistic insight and constrains rate constants, branching ratios and vapor pressures of the products. The organic nitrate yield from NO3+limonene is ≈30%. The SOA mass yield was observed to be 25-40%. The first injection is reproduced by a kinetic model. PMF analysis of the aerosol composition suggests that much of the aerosol mass results from combined oxidation by both O3 and NO3, e.g., oxidation of NO3+limonene products by O3. Further, later aerosol nitrate mass seems to derive from heterogeneous uptake of NO3 onto unreacted aerosol alkene. [ABSTRACT FROM AUTHOR]

Telicota eurotas laconia (Waterhouse) and T. ancilla ancilla (Herrich-Schäffer) are recorded from north of Weipa on the western coast of Cape York Peninsula, extending the known northern distribution of the two species approximately 165 km west-north-west of Iron Range, near Lockhart River, Queensland. Larvae of T. e. laconia were feeding on Scleria polycarpa Boeckeler (Cyperaceae) while larvae of T. a. ancilla were found on Imperata cylindrica (L.) P.Beauv. (Poaceae). [ABSTRACT FROM AUTHOR]

The yields of organic nitrates and of secondary organic aerosol (SOA) particle formation were measured for the reaction NO3+β-pinene under dry and humid conditions in the atmosphere simulation chamber SAPHIR at Research Center Jülich. These experiments were conducted at low concentrations of NO3 (NO3+N2O5<10 ppb) and β-pinene (peak ∼15 ppb), with no seed aerosol. SOA formation was observed to be prompt and substantial (∼50% mass yield under both dry conditions and at 60% RH), and highly correlated with organic nitrate formation. The observed gas/aerosol partitioning of organic nitrates can be simulated using an absorptive partitioning model to derive an estimated vapor pressure of the condensing nitrate species of pvap∼5 x 10-6 Torr (6.67 x 10-4 Pa), which constrains speculation about the oxidation mechanism and chemical identity of the organic nitrate. Once formed the SOA in this system continues to evolve, resulting in measurable aerosol volume decrease with time. The observations of high aerosol yield from NOx-dependent oxidation of monoterpenes provide an example of a significant anthropogenic source of SOA from biogenic hydrocarbon precursors. Estimates of the NO3+β-pinene SOA source strength for California and the globe indicate that NO3 reactions with monoterpenes are likely an important source (0.5-8% of the global total) of organic aerosol on regional and global scales. [ABSTRACT FROM AUTHOR]

The shallow mixing depth and vertical stratification of the lowest levels of the atmosphere at night has implications for the chemistry of nitrogen oxides emitted from the surface. Here we report vertical profiles of NO3, N2O5 and O3 measured from in-situ instruments on a movable carriage on a 300m tower. The study offers high-resolution (<1 m) vertical distributions of both NO3 and N2O5 and shows that the nocturnal mixing ratios of these compounds vary widely over short vertical distance scales (10m or less). Furthermore, there are systematic differences in the steady state lifetimes of NO3 and N2O5 and in the partitioning among nitrogen oxides between different near-surface layers. These differences imply that NO3 and N2O5 occupy distinct chemical regimes as a function of altitude, potentially serving as sinks for nitrogen oxides and O3 near the surface but as reservoirs of NOx and O3 aloft. [ABSTRACT FROM AUTHOR]

Prolonged coma due to acute overdosage with hypnotic drugs is shown to be associated with a pronounced increase in the activity of serum creatine kinase and in the concentration of fibrin degradation products and with less pronounced abnormalities of other serum enzymes and of other indices of coagulation and fibrinolysis. Evidence is presented that skeletal muscle damage occurs and that this is related to the coagulation abnormality. These findings probably explain some of the non-specific features such as fever which commonly occur in recovery from severe poisoning. [ABSTRACT FROM PUBLISHER]

A review of the arterial acid-base status on admission to hospital of 62 adults with severe salicylate poisoning showed that arterial H was normal or high in most patients, but low in 8. The mean plasma salicylate concentrations of the acidaemic and nonacidaemic patients were similar and the difference in arterial H was associated with a marked fall in standard bicarbonate in the former group. No significant difference of Pco between the two groups was found, and hence no simple relationship exists between hypocapnia and the development of acidaemia in salicylate poisoning. Acidaemia is shown to be associated with impaired consciousness and to carry a grave prognosis. [ABSTRACT FROM PUBLISHER]