On the Budget of OH Radicals and Ozone in an Urban Plume from the Decay of C5–C8 Hydrocarbons and NOx

Simultaneous measurements of ozone and ozoneprecursors were made during a field campaign atSchauinsland in the Black Forest and in the valleynorth of Schauinsland that channels the flow ofpolluted air from the city of Freiburg to the site.From the decay of hydrocarbons and NO_x between the twomeasuring sites and the known rate coefficients, theconcentration of OH radicals was calculated. From abudget analysis of OH and HO_x it is concluded that therelatively high OH concentrations (5–8 ×10⁶cm^-3) in the presence of high NO₂concentrations cannot be explained by the knownprimary sources. The budget can be closed if efficientrecycling of OH via HO₂ is assumed to occur andthat, based on the measured hydrocarbons, 2 HO₂molecules are formed for each OH radical that reactswith a hydrocarbon molecule. This assumption is inaccordance with the budget of O_x obtained from ourmeasurements and with results from earliermeasurements of alkylnitrates and peroxy radicals atSchauinsland. A possible conclusion is that the decayof precursors and production of photooxidants in urbanplumes proceeds at a faster rate than is currentlyassumed. The potential role of biogenichydrocarbons for the radical budget is alsodiscussed.     

Interference Testing for Atmospheric HOx Measurements by Laser-induced Fluorescence

Accurate OH and HO₂ (collectively called HO_x) measurements by laser-induced fluorescence (LIF) may be contaminated by spurious signals from interfering atmospheric chemicals or from the instrument itself. Interference tests must be conducted to ensure that observed OH signal originates solely from ambient OH and is not due to instrument artifacts. Several tests were performed on the Penn State LIF HO_x instrument, both in the laboratory and in the field. Theseincluded measurements of the instrument's zero signal by using either zero air or perfluoropropylene to remove OH, examination of spectral interferences from naphthalene, sulfur dioxide, and formaldehyde, and tests of interferences by addition of suspected interfering atmospheric chemicals, including ozone, hydrogen peroxide, nitrous acid, formaldehyde, nitric acid, acetone, and organic peroxy radicals (RO₂). All tests lacked evidence ofsignificant interferences for measurements in the atmosphere, including highly polluted urban environments.     

Hydroxyl and Peroxy Radical Chemistry in a Rural Area of Central Pennsylvania: Observations and Model Comparisons

Atmospheric hydroxyl (OH), hydroperoxy (HO₂), total peroxy (HO₂ and organic peroxy radicals, RO₂) mixing ratios and OH reactivity (first order OH loss rate) were measured at a rural site in central Pennsylvania during May and June 2002. OH and HO₂ mixing ratios were measured with laser induced fluorescence (LIF); HO₂ + RO₂ mixing ratios were measured with chemical ionization mass spectrometry (CIMS). The daytime maximum mixing ratios were up to 0.6 parts per trillion by volume (pptv) for OH, 30 pptv for HO₂, and 45 pptv for HO₂ + RO₂. A parameterized RACM (Regional Atmospheric Chemistry Mechanism) box model was used to predict steady state OH, HO₂ and HO₂ + RO₂ concentrations by constraining the model to the measured OH reactivity and previously measured volatile organic compound (VOC) distributions. The averaged model calculations are generally in good agreement with the observations. For OH, the model matched the observations for day and night, with an average observed-to-modeled ratio of 0.80. In previous studies such as PROPHET98, nighttime NO was near 0 pptv and observed nighttime OH was significantly larger than modeled OH. In this study, nighttime observed and modeled OH agree to within measurement and model uncertainties because the main source of the nighttime OH was the reaction HO₂ + NO → OH + NO₂, with the NO being continually emitted from the surrounding fertilized corn field. The observed-to-modeled ratio for HO₂ is 1.0 on average, although daytime HO₂ is underpredicted by a factor of 1.2 and nighttime HO₂ is over-predicted by a factor of ∼2. The average measured and modeled HO₂ + RO₂ agree well during daytime, but the modeled value is about twice the measured value during nighttime. While measured HO₂ + RO₂ values agree with modeled values for NO mixing ratios less than a few parts per billion by volume (ppbv), it increases substantially above the expected value for NO greater than a few ppbv. This observation of the higher-than-expected HO₂ + RO₂ with the CIMS technique confirms the observed increase of HO₂ above expected values at higher NO mixing ratios in HO₂ measurements with the LIF technique. The maximum instantaneous O₃ production rate calculated from HO₂ and RO₂ reactions with NO was as high as 10–15 ppb h⁻¹ at midday; the total daily O₃ production varied from 13 to 113 ppbv d⁻¹ and was 48 ppbv d⁻¹ on average during this campaign.     

Simultaneous measurements of peroxy and nitrate radicals at Schauinsland

We present simultaneous field measurements of NO₃ and peroxy radicals made at night in a forested area (Schauinsland, Black Forest, 48° N, 8° N, 1150 ASL), together with measurements of CO, O₃, NO _x , NO _y , and hydrocarbons, as well as meteorological parameters. NO₂, NO₃, HO₂, and (RO₂) radicals are detected with matrix isolation/electron spin resonance (MIESR). NO₃ and HO₂ were found to be present in the range of 0–10 ppt, whilst organic peroxy radicals reached concentrations of 40 ppt. NO₃, RO₂, and HO₂ exhibited strong variations, in contrast to the almost constant values of the longer lived trace gases. The data suggest anticorrelation between NO₃ and RO₂ radical concentrations at night.The measured trace gas set allows the calculation of NO₃ and peroxy radical concentrations, using a chemical box model. From these simulations, it is concluded that the observed anthropogenic hydrocarbons are not sufficient to explain the observed RO₂ concentrations. The chemical budget of both NO₃ and RO₂ radicals can be understood if emissions of monoterpenes are included. The measured HO₂ can only be explained by the model, when NO concentrations at night of around 5 ppt are assumed to be present. The presence of HO₂ radicals implies the presence of hydroxyl radicals at night in concentrations of up to 10⁵ cm^–3.     

Intercomparison of Two Hydroxyl Radical Measurement Techniques at the Atmosphere Simulation Chamber SAPHIR

At the atmosphere simulation chamber SAPHIR in Jülich both Laser-Induced Fluorescence Spectroscopy (LIF) and Long-Path Differential Optical Laser Absorption Spectroscopy (DOAS) are operational for the detection of OH radicals at tropospheric levels. The two different spectroscopic techniques were compared within the controlled environment of SAPHIR based on all simultaneous measurements acquired in 2003 (13 days). Hydroxyl radicals were scavenged by added CO during four of these days in order to experimentally check the calculated precisions at the detection limit. LIF measurements have a higher precision (σ= 0.88×10⁶ cm^–3) and better time resolution (Δt = 60 s), but the DOAS method (σ= 1.24×10⁶ cm^–3, Δt = 135 s) is regarded as primary standard for comparisons because of its good accuracy. A high correlation coefficient of r = 0.95 was found for the whole data set highlighting the advantage of using a simulation chamber. The data set consists of two groups. The first one includes 3 days, where the LIF measurements yield (1 – 2) ×10⁶ cm^–3 higher OH concentrations than observed by the DOAS instrument. The experimental conditions during these days are characterized by increased NO_x concentration and a small dynamic range in OH. Excellent agreement is found within the other group of 6 days. The regression to the combined data of this large group yields unity slope without a significant offset.     

Atmospheric chemistry of alkanes

The reactions of the alkanes under atmospheric conditions and in the presence of oxides of nitrogen are reviewed and evaluated. Particular emphasis is placed upon their subsequent reactions after the initial OH radical reaction under conditions where the alkyl peroxy radicals produced react predominantly with NO, rather than with HO₂ and/or RO₂ radicals. Methods are discussed for estimating the overall OH radical rate constants, the number of molecules of NO consumed per alkane molecule reacted, and the products formed and their yields.     

Development of a Ground-Based LIF Instrument for Measuring HOx Radicals: Instrumentation and Calibrations

An instrument for measuringtropospheric OH/HO₂ radicals by laser-inducedfluorescence developed in our laboratory is presentedin detail. It is based on FAGE (fluorescence assay bygas expansion) technique and OH is both excited anddetected at 308 nm corresponding to its A-X(0,0) band.The alignment of the laser beam, the design of thesample gas inlet, and the devices for the fluorescencedetection are optimized so as to reduce the backgroundsignal while keeping the OH sensitivity as high aspossible. A thermalized position of the expanding gasbeam is probed in our system and we did not observe asevere decrease of the HO_x sensitivities under humidconditions. An optical fiber is used for deliveringthe laser light to the fluorescence detection cellmounted outside at a high position. Thus the laserbeam alignment is by far simplified and is made highlyreproducible, once settled properly. For thecalibration, two methods are employed: a system withlaser absorption measurements of OH and a system ofsimultaneous photolysis of H₂O and O₂. Thecalibration factors are compared well within thecombined uncertainty. Using the latter system, theconversion efficiency of HO₂ to OH by NO additionis measured to be around 90%. The detection limitsfor OH and HO₂ (S/N = 2) are estimated to be3.3 × 10⁶ and 3.6 × 10⁶cm^–3 at noon,respectively, with an integration time of 1 min. Theresults of test observations at our institute are alsopresented.     

Modelled and measured concentrations of peroxy radicals and nitrate radical in the U.S. Gulf Coast region during TexAQS 2006

Measurements of total peroxy radicals (HO₂?+?RO₂) and nitrate radical (NO₃) were made on the NOAA research vessel R/V?Brown along the U.S. Gulf Coast during the TexAQS 2006 field campaign. The measurements were modelled using a constrained box-model based upon the Master Chemical Mechanism (MCM). The agreement between modelled and measured HO₂?+?RO₂ was typically within ??40% and, in the unpolluted regions, within 30%. The analysis of the model results suggests that the MCM might underestimate the concentrations of some acyl peroxy radicals and other small peroxy radicals. The model underestimated the measurements of NO₃ by 60?C70%, possibly because of rapid heterogeneous uptake of N₂O₅. The MCM model results were used to estimate the composition of the peroxy radical pool and to quantify the role of DMS, isoprene and alkenes in the formation of RO₂ in the different regions. The measurements of HO₂?+?RO₂ and NO₃ were also used to calculate the gas-phase budget of NO₃ and quantify the importance of organic peroxy radicals as NO₃ sinks. RO₂ accounted, on average, for 12?C28% of the total gas-phase NO₃ losses in the unpolluted regions and for 1?C2% of the total gas-phase NO₃ losses in the polluted regions.     

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.     

A Three-Dimensional Simulation of HO x Concentrations Over East Asia During TRACE-P

The Models-3 Community Multi-scale Air Quality modeling system (CMAQ) coupled with the Regional Atmospheric Modeling System (RAMS) is used to simulate three-dimensional concentration distributions of hydroxyl (OH) and hydroperoxyl (HO₂) radicals over the western Pacific Ocean during the NASA Transport and Chemical Evolution over the Pacific (TRACE-P) field campaign. Modeled values of OH and HO₂ and their closely related chemical species and photolysis rates are compared with observational data collected onboard the DC-8 aircraft. Comparison shows that the model reasonably reproduced these observed values over a broad range of conditions with an overall tendency to overestimate the measured OH and HO₂ by a factor of 1.56 and 1.24, respectively. A case study of OH, HO₂ and their closely related chemical species and photolysis rates along the DC-8 flights 11 and 12 conducted on 17–18 March 2001 shows that the model reproduces the temporal and spatial variations reasonable well, and produces more reliable OH and HO₂ concentrations in the polluted environment than in the clean marine boundary layer.     

150年来大气甲烷浓度的长期变化

应用作者建立的全球二维大气化学模式 ,采用 2种CH4 排放源的长期增长方案 ,同时考虑了CH4 排放源以及对OH自由基浓度有重要影响的CO和NOx 排放源的长期变化 ,模拟了CH4 和OH从 1840～ 2 0 2 0年的长期变化趋势。考虑了世界人口增长的排放源方案可以更好地模拟CH4 的长期变化 ,模拟结果表明 ,工业革命前的大气CH4 浓度和年排放总量分别为 76 0× 10 -9(V/V)和 2 80× 10 9kg ,1991年大气CH4 的浓度和年排放总量分别为16 11.9× 10 -9(V/V)和 5 33 .9× 10 9kg ,对流层OH自由基数浓度从 1840年的 7.17× 10 5分子数 /cm3 下降到 1991年的 5 .79× 10 5分子数 /cm3,降低了 19%。工业革命以来大气CH4 的增长一方面是由于CH4 排放源的增长 ,另一方面是由于大气OH浓度的下降。     

Oxidation of sulphur compounds in the atmosphere: I. Rate constants of OH radical reactions with sulphur dioxide,hydrogen sulphide,aliphatic thiols and thiophenol

The reactions of OH radicals with SO₂, H₂S, thiophenol, and a series of aliphatic thiols (1–5 C-atoms) have been investigated in 201 and 381 reaction chambers at 1 atm total pressure and 300 K using a competitive kinetic technique. Initially, OH radicals were produced by photolysis of CH₃ONO/NO mixtures in air. Applying this OH source rate constants for OH with SO₂, H₂S, and thiophenol in synthetic air were determined to be (1.1±0.2)×10^-12, (5.5±0.8)×10^-12 and (1.1±0.2)×10^-11 cm³ s^-1, respectively. However, when this method was applied to the aliphatic thiols the rate constants obtained were found to be dependent on the partial pressures of O₂ and NO. These effects have been attributed to the built-up of a radical species, not yet identified, which leads to uncontrolled chain reactions in the system. Using the photolysis of H₂O₂ at wavelengths greater than 260 nm as the OH source in 1 atm N₂, rate constants for the 1–5 aliphatic thiols in the range 2.9 to 5.6×10^-11 cm³ s^-1 were obtained. The rate constants obtained in the present study are compared with recent literature values.     

A method for the selective measurement of HO<Subscript>2</Subscript> and RO<Subscript>2</Subscript> radical concentrations using a Nafion-PERCA system

An instrument is developed for the measurement of peroxy radical using chemical amplification coupled with NO₂-luminol chemiluminescence detection. The chain length of 147 ± 10 (1σ) is determined by an HO₂ source that uses the photolysis of water vapor under 184.9 nm in air. A Nafion system equipped with a Nafion tube of ~2.2 mm external diameter and 350 mm length is employed in the PERCA instrument (Nafion-PERCA system). When flowing an air sample containing HO₂ through the Nafion system, it is found that - 94.6 % of HO₂ is removed. In contrast, only 17.8 % of RO₂ radicals (a mixtures of CH₃O₂ and CH₃C(O)O₂ with a ratio of 1.1:0.9) are removed. The results indicate the Nafion system has a good selective removing performance of HO₂ radical during the PERCA measurement. Therefore, the method could be applied to ambient and laboratory measurements of absolute concentrations of RO₂ as well as the sum of HO₂ and RO₂.     

Evaluation of the Salicylic Acid—Liquid Phase Scrubbing Technique to Monitor Atmospheric Hydroxyl Radicals

A novel method has been examined for monitoring tropospheric hydroxyl radicals (OH), the most important oxidant in tropospheric chemistry. Aqueous phase salicylic acid reacts with atmospheric OH to produce 2,5-dihydroxy benzoic acid (2,5-DHBA) and other products. High Performance Liquid Chromatography (HPLC) is used to separate the post-reaction solution and the products are quantified using fluorescence detection. Unlike other methods, it has been reported to be inexpensive, portable and relatively simple. Although the sensitivity was sufficient to measure typical daytime OH concentrations of 0.04–0.4 ppt., the method was hindered by numerous interferences. Successive identification and elimination of these still resulted in a signal that was much larger than expected. Tests showed that this was not likely to be due to ozone, HO₂, NOx, H₂O₂, aerosols, light or bacteria. Experimental and numerical studies suggest that the interference could be due to methyl peroxy radicals. The effect of many other components in the atmosphere, both individual and combined, must also be tested before the method can be used reliably in the field. The validity of previous reports of ambient hydroxyl measurements using this technique is therefore brought into question.     

Determination of the Tropospheric Hydroxyl Radical by Liquidphase Scrubbing and HPLC: Preliminary Results

A preliminary study was carried out toexamine the feasibility of measuring tropospherichydroxyl radicals (OH) by liquidphase scrubbing andhigh performance liquid chromatography (HPLC). Thepotential advantages of this approach are itssimplicity, portability, and low expense. Thesampling system employs glass bubblers to trapatmospheric OH into a buffered solution of salicylicacid (o-hydroxybenzoic acid, OHBA). Rapidreaction of OH with OHBA produces a stable fluorescentproduct, 2,5-dihydroxybenzoic acid (2,5-DHBA), whichis determined by reverse-phase HPLC and fluorescencedetection. Our preliminary field results indicatethat this method is most suitable for OH measurementsin clean tropospheric air, where interferences fromother atmospheric species appear to be negligible orminor relative to polluted air. In clean air, thesampling period is about 45–90 minutes, which yieldsa detection limit of approximately 3–6 ×10⁵ radicalscm^-3. During an OHintercomparison experiment at the Caribou samplingsite in Colorado, our liquidphase scrubber method wascompared with the ion-assisted mass spectrometry (MS)method. Our results were within the same range asthose of the ion-assisted MS method (1–5 ×10⁶ radicals cm^-3) within our precision atthat time (about ±30–50%). Preliminary testsin Pullman, WA indicated that the method might alsofunction in moderately polluted air by acidifying thescrubbing solution or by adding a scavenger tosuppress interferences. In Pullman, mid-day OHconcentrations were usually in the range of 2–20 ×10⁶ radicals cm^-3. Nighttime OHconcentrations were always low, either at or slightlyabove the detection limit.     

Gas phase reactions of alkyl nitrates with hydroxyl radicals under tropospheric conditions in comparison with photolysis

Rate constants for the reaction of OH radicals with some branched alkyl nitrates have been measured applying a competitive technique. Methyl nitrite photolysis in synthetic air was used as OH radical source at 295±2 K and 1000 mbar total pressure. Using a rate constant of 2.53×10^-12 cm³ s^-1 for the reaction of OH radicals with n-butane as reference, the following rate constants were obtained (units: 10^-12 cm³ s^-1): isopropyl nitrate, 0.59±0.22; isobutyl nitrate, 1.63±0.20; 3-methyl-2-butyl nitrate, 1.95±0.15; 2-methyl-1-butyl nitrate, 2.50±0.15; 3-methyl-1-butyl nitrate, 2.55±0.35. These values have been combined with the literature data to recalculate the substituent factors F(X) for the different nitrate groups which can be used to predict OH rate constants for organic nitrates for which experimental data are not available.Preliminary measurements of the photolysis frequency of isopropyl nitrate have shown that for this nitrate as a model substance, OH reactions and direct photolysis are of equal importance under tropospheric conditions.     

Intercomparison of instruments for tropospheric measurements using differential optical absorption spectroscopy

The results of an intercomparison campaign of eight different long path UV-visible DOAS instruments measuring NO₂, O₃ and SO₂ concentrations in a moderately polluted urban site are presented. For effective optical path lengths of 230 and 780 m the overall spread of these measurements (±1) are 5×10¹⁰, 6×10¹⁰ and 1×10¹⁰ molec·cm^-3 (2.0, 2.4, and 0.4 ppb) for these molecules respectively when all instruments used a common set of absorption cross sections. The remaining differences are not completely random and the systematic differences are attributed to the different retrieval methods used for each instrument.     

Atmospheric chemistry of the monoterpene reaction products nopinone,camphenilone, and 4-acetyl-1-methylcyclohexene

Rate constants for the gas-phase reactions of OH radicals with nopinone (6,6-dimethylbicyclo[3.1.1]heptan-2-one) and camphenilone (3,3-dimethylbicyclo[2.2.1]heptan-2-one) and for the reactions of 4-acetyl-1-methylcyclohexene with OH and NO₃ radicals and O₃ have been measured at 296±2 K. The rate constants (cm³ molecule^–1 s^–1 units) obtained were, for reaction with the OH radical: nopinone, (1.43±0.37)×10^–11; camphenilone, (5.15±1.44)×10^–12; and 4-acetyl-1-methylcyclohexene, (1.29±0.33)×10^–10; for reaction with the NO₃ radical: 4-acetyl-1-methylcyclohexene, (1.05±0.38)×10^–11; and for reaction with O₃: 4-acetyl-1-methylcyclohexene, (1.50±0.53)×10^–16. These data are used to calculate the tropospheric lifetimes of these monoterpene atmospheric reaction products.