F. Holland

Amplified Trace Gas Removal in the Troposphere

Going Faster The concentrations of most tropospheric pollutants and trace gases are kept in check by their reactions with hydroxyl radicals (OH). OH is a short-lived, highly reactive species that is produced in the atmosphere by photochemical processes, and regenerated in the chain of chemical reactions that follows the oxidative destruction of those molecules. These regeneration mechanisms were thought to be fairly well understood, but now Hofzumahaus et al. (p. 1702, published online 4 June) present evidence of a pathway not previously recognized. In a study of atmospheric composition in the Pearl River Delta, a highly polluted region of China, greatly elevated OH concentrations were observed without the correspondingly high levels of ozone expected from current models. Thus, OH concentrations may be augmented by a process that speeds the regeneration of OH without producing ozone. A yet undescribed pathway for hydroxyl radical production is needed to account for reaction rates of highly polluted air. The degradation of trace gases and pollutants in the troposphere is dominated by their reaction with hydroxyl radicals (OH). The importance of OH rests on its high reactivity, its ubiquitous photochemical production in the sunlit atmosphere, and most importantly on its regeneration in the oxidation chain of the trace gases. In the current understanding, the recycling of OH proceeds through HO2 reacting with NO, thereby forming ozone. A recent field campaign in the Pearl River Delta, China, quantified tropospheric OH and HO2 concentrations and turnover rates by direct measurements. We report that concentrations of OH were three to five times greater than expected, and we propose the existence of a pathway for the regeneration of OH independent of NO, which amplifies the degradation of pollutants without producing ozone.

Rapid aerosol particle growth and increase of cloud condensation nucleus activity by secondary aerosol formation and condensation: A case study for regional air pollution in northeastern China

[1] This study was part of the international field measurement Campaigns of Air Quality Research in Beijing and Surrounding Region 2006 (CAREBeijing-2006). We investigated a new particle formation event in a highly polluted air mass at a regional site south of the megacity Beijing and its impact on the abundance and properties of cloud condensation nuclei (CCN). During the 1-month observation, particle nucleation followed by significant particle growth on a regional scale was observed frequently (~30%), and we chose 23 August 2006 as a representative case study. Secondary aerosol mass was produced continuously, with sulfate, ammonium, and organics as major components. The aerosol mass growth rate was on average 19 μg m -3 h -1 during the late hours of the day. This growth rate was observed several times during the 1-month intensive measurements. The nucleation mode grew very quickly into the size range of CCN, and the CCN size distribution was dominated by the growing nucleation mode (up to 80% of the total CCN number concentration) and not as usual by the accumulation mode. At water vapor supersaturations of 0.07-0.86%, the CCN number concentrations reached maximum values of 4000-19,000 cm -3 only 6-14 h after the nucleation event. During particle formation and growth, the effective hygroscopicity parameter κ increased from about 0.1-0.3 to 0.35-0.5 for particles with diameters of 40-90 nm, but it remained nearly constant at ~0.45 for particles with diameters of ~190 nm. This result is consistent with aerosol chemical composition data, showing a pronounced increase of sulfate.

The measurement of tropospheric OH radicals by laser‐induced fluorescence spectroscopy during the POPCORN Field Campaign

A highly sensitive OH measurement instrument has been developed. It is based on laser-induced fluorescence (LIF) detection of OH using the A²Σ+v′ = 0-X²Π v″ = 0 transition at 308.15 nm at low pressure. The LIF instrument detects OH directly and with high specificity, a fact that was demonstrated by recording laser excitation spectra (Q1(3), Q21(3) and P1(1) lines) of ambient OH. For high time resolution (typ. 60–100 s), the laser wavelength was modulated on-/off- resonance with the P1(1) line. Here, we report some of the OH measurements obtained by this technique during its first application in a tropospheric field campaign (“POPCORN”), which was conducted in August 1994 in a rural environment in the North-East of Germany. These include diurnal OH concentration profiles with maximum OH concentrations up to 1.4×107cm−3at noon. Minimum OH concentrations were measured in the morning and evening down to the detection limit of (3–6) × 105cm−3(SNR=2, measurement time 1 min.). During the day, OH fluctuations were observed on a time scale of minutes and hours. These were highly correlated to the flux of the solar UV radiation which is responsible for the primary OH production by photolysis.

Missing gas-phase source of hono inferred from zeppelin measurements in the troposphere

On a Zeppelin Nitrous acid (HONO) is an important atmospheric trace gas that acts as a precursor of tropospheric hydroxyl-radicals (OH), which is responsible for the self-cleansing capacity of the atmosphere and which also controls the concentrations of greenhouse gases, such as methane and ozone. How HONO is made is a mystery. Flying onboard a Zeppelin over the Po Valley in Northern Italy, Li et al. (p. 292) discovered HONO in the undisturbed morning troposphere, indicating that HONO must be produced there, rather than mixed from the surface. The high HONO concentrations are likely to have been formed by a light-dependent gas-phase source that probably consumed OH or HO2 radicals, which hints that the impact of HONO on the abundance of OH in the entire troposphere may be substantially overestimated. The tropospheric production of HONO from a light-dependent gas-phase source raises questions about its impact on OH. Gaseous nitrous acid (HONO) is an important precursor of tropospheric hydroxyl radicals (OH). OH is responsible for atmospheric self-cleansing and controls the concentrations of greenhouse gases like methane and ozone. Due to lack of measurements, vertical distributions of HONO and its sources in the troposphere remain unclear. Here, we present a set of observations of HONO and its budget made onboard a Zeppelin airship. In a sunlit layer separated from Earth’s surface processes by temperature inversion, we found high HONO concentrations providing evidence for a strong gas-phase source of HONO consuming nitrogen oxides and potentially hydrogen oxide radicals. The observed properties of this production process suggest that the generally assumed impact of HONO on the abundance of OH in the troposphere is substantially overestimated.

Free radicals and fast photochemistry during BERLIOZ

The free radicals OH, HO2, RO2, and NO3 are known to be the driving force for most chemical processes in the atmosphere. Since the low concentration of the above radicals makes measurements particularly difficult, only relatively few direct measurements of free radical concentrations have been reported to date. We present a comprehensive set of simultaneous radical measurements performed by Laser Induced Fluorescence (LIF), Matrix Isolation — Electron spin Resonance (MI-ESR), Peroxy Radical Chemical Amplification (PERCA), and Differential Optical Absorption Spectroscopy (DOAS) during the BERLIner OZonexperiment (BERLIOZ) during July and August of 1998 near Berlin, Germany. Most of the above radical species were measured by more than one technique and an intercomparison gave good agreement. This data set offered the possibility to study and quantify the role of each radical at a rural, semi-polluted site in the continental boundary layer and to investigate interconnections and dependencies among these free radicals. In general (box) modelled diurnal profiles of the different radicals reproduced the measurements quite well, however measured absolute levels are frequently lower than model predictions. These discrepancies point to disturbing deficiencies in our understanding of the chemical system in urban air masses. In addition considerable night-time peroxy radical production related to VOC reactions with NO3 and O3 could be quantified.

In Situ Measurement of Tropospheric OH Radicals by Laser-Induced Fluorescence—A Description of the KFA Instrument

Abstract An instrument for the measurement of tropospheric OH radical concentrations by laser-induced fluorescence spectroscopy has been developed. Ambient air is expanded through a nozzle into a low-pressure fluorescence cell and is irradiated by a frequency-doubled dye laser, which is pulsed with a high repetition rate of 8.5 kHz. The laser wavelength is tunable to selectively excite single rovibronic transitions of the OH radicals at 308 nm [A2∑+(ν′ = 0) ← X2 Π (ν″=0)]. The OH resonance fluorescence, emitted mostly between 307 and 311 nm, is detected by gated photon counting. From laboratory calibrations and ambient air measurements the authors infer a detection limit (S/N = 2) of 8 × 105 OH cm−3 for 1-minute data integration time. First tests of the new instrument in ambient air revealed the existence of an interference problem due to generation of OH by a dark reaction of ozone inside the detection cell. Improvements of the instrument reduced the spurious OH signal to a level corresponding to an ambi...

Highly Time Resolved Measurements of OH during POPCORN Using Laser-Induced Fluorescence Spectroscopy

Tropospheric hydroxyl radical (OH) concentrations were measured by laser-induced fluorescence (LIF) during the POPCORN field campaign in August 1994 at a rural site in the North East of Germany. Ambient air spectra were recorded by tuning the laser wavelength over a spectral region covering the Q11(3), Q21(3), and P11(1) rotational transitions of the (0-0) band in the A-X system of OH around 308 nm. The observed spectra clearly identify the OH radical in the atmosphere. Besides the OH absorption lines there was no sign of any other narrow-band spectral structure nearby demonstrating the high specificity of the method. For OH measurements with a typical time resolution of 60–100 seconds per data point the laser wavelength was tuned repetitively over small spectral intervals covering the peak position of the P11(1) OH-line and background positions. A total of 2300 measurements were recorded including diurnal cycles of OH with more than 300 data points. The OH as well as the LIF background signal data will be presented. In a first analysis the background signal will be characterized and the correlation between OH and the ozone photolysis frequency will be derived.

Intercomparison of tropospheric OH radical measurements by multiple folded long‐path laser absorption and laser induced fluorescence

An intercomparison of in-situ OH measurements by differential optical absorption spectroscopy (DOAS) and laser-induced fluorescence spectroscopy (LIF) was carried out in August 1994 in a clean rural environment in North-East Germany. A large data set of temporally overlapping OH measurements with well defined measurement errors was obtained and compared. Both instruments encountered the same air masses, except when the wind came from NNW and caused a perturbation of the DOAS measurements. Excluding that wind sector, the weighted regression analysis of 137 data pairs (70% of all available data pairs) yields a linear relationship between the DOAS and LIF measurements with a correlation coefficientr = 0.90. The unity slope (1.01±0.04) and the non-significant intercept (0.28±0.15) × 106 cm−3 demonstrate that both OH instruments agreed excellently in their calibrations and accurately measured OH.

Kinetic Study of the OH-isoprene and O3-isoprene reaction in the atmosphere simulation chamber, SAPHIR

Kinetic studies conducted in the new atmosphere simulation chamber SAPHIR at the Research Center Julich allow a thorough investigation of oxidation of isoprene induced by O 3 and the OH radical under atmospheric conditions. Rate coefficients for the 03-isoprene and OH-isoprene reaction are determined from measured concentration-time profiles. For the reaction of O 3 with isoprene the rate coefficient is determined to be (9.6 ± 0.7) x 10 -18 cm 3 molecule -1 s -1 at 286 K. The rate coefficient for the reaction OH + isoprene is (10.0 ± 1.2) x 10 -11 cm 3 molecule -1 s -1 at 294 K. The kinetic parameters determined in SAPHIR at atmospheric concentrations agree well with recent recommendations.

Measurement of tropospheric RO2 and HO2 radicals by a laser-induced fluorescence instrument.

A new method (ROxLIF) for the measurement of atmospheric peroxy radicals (HO(2) and RO(2)) was developed using a two-step chemical conversion scheme and laser-induced fluorescence (LIF) for radical detection. Ambient air is sampled into a differentially pumped flow reactor, in which atmospheric RO(x) radicals (=RO(2)+RO+HO(2)+OH) are chemically converted to HO(2) by a large excess of NO and CO at reduced pressures (ROx mode). When only CO is added as a reagent, the sum of atmospheric HO(2)+OH is converted to HO(2) (HOx mode). At the reactor outlet, part of the air flow is transferred into a low-pressure detection chamber, where the HO(2) is further converted by reaction with NO to OH, which is then detected with high sensitivity by LIF at 308 nm. The ROxLIF technique has been implemented in an existing LIF instrument that is also capable of measuring atmospheric OH. From the concurrent measurements of RO(x), HO(x) and OH, concentrations of HO(2) and RO(2) can be determined. The system is calibrated using the quantitative photolysis of water vapor at 185 nm as a radical source. Addition of CO or hydrocarbons to the calibration gas yields well-defined concentrations of HO(2) or RO(2), respectively, providing an estimated accuracy for the calibration of about 20%. The ROxLIF technique is extremely sensitive and has detection limits (signal-to-noise ratio=2) of about 0.1 pptv of HO(2) or RO(2) at a time resolution of 1 min. The paper describes the technique and its calibration, discusses the chemistry in the conversion reactor and possible interferences, and gives an example of ambient air measurements to demonstrate the performance of the new technique.