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1.
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2.
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 HOx 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.  相似文献   

3.
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.  相似文献   

4.
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 NOx between the twomeasuring sites and the known rate coefficients, theconcentration of OH radicals was calculated. From abudget analysis of OH and HOx 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 Ox 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.  相似文献   

5.
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.  相似文献   

6.
Measurements of formaldehyde (HCHO) were made at the Cape Verde Atmospheric Observatory between November 2006 and June 2007 using the Long-Path Differential Optical Absorption Spectroscopy (LP-DOAS) technique. Observations show that typical HCHO mixing ratios ranged between 350 and 550 pptv (with typical 2-σ uncertainties of ~110 pptv), with several events of high HCHO, the maximum being 1,885?±?149 pptv. The observations indicate a lack of strong seasonal or diurnal variations, within the uncertainty of the measurements. A box model is employed to test whether the observations can be explained using known hydrocarbon photochemistry; the model replicates well the typical diurnal profile and monthly mean values. The model results indicate that on average 20% of HO2 production and 10% of OH destruction can be attributed to the mean HCHO levels, suggesting that even at these low average mixing ratios HCHO plays an important role in determining the HOx (HO2+OH) balance of the remote marine boundary layer.  相似文献   

7.
A new version of an atmospheric pressure chemical ionisation mass spectrometer has been developed for ground based in situ atmospheric measurements of OH and total peroxy (HO2 + organic peroxy) radicals. Based on the previously developed principle of chemical conversion of OH radicals to H2SO4 in reaction with SO2 and detection of H2SO4 using an ion molecule reaction with NO3─, the new instrument is equipped with a turbulent chemical conversion reactor allowing for measurements in moderately polluted atmosphere at NO concentrations up to several ppb. Unlike other similar devices, where the primary NO3─ ions are produced using radioactive ion sources, the new instrument is equipped with a specially developed corona discharge ion source. According to laboratory measurements, the overall accuracy and detection limits are estimated to be, respectively, 25% and 2 × 105 molecule cm-3 for OH and 30% and 1 × 105 molecule cm-3 for HO2 at 10 min integration times. The detection limit for measurements of OH radicals under polluted conditions is 5 × 105 molecules cm-3 at 10 min integration times. Examples of ambient air measurements during a field campaign near Paris in July 2007 are presented demonstrating the capability of the new instrument, although with reduced performance due to the employment of non isotopic SO2.  相似文献   

8.
A detector for the chemiluminescent measurement of NO in background air is described. A large reduction of interferences is achieved by using a stabilized ozone generator which allows operation of the instrument at lower O3 concentrations. Purification and humidification of the O3 stream further reduces interferences and shortens the instrumental clean-up time, which is important for aircraft missions. From a series of laboratory tests and from measurements performed aboard an aircraft it is demonstrated that the remaining interferences are acceptable for measurements in the undisturbed troposphere. In particular, no remnant NO signal is observed in clean air at night. During flight, a detection limit (2) of 20 ppt is achieved for a 1 min integration time.  相似文献   

9.
A photochemical box model including a detailed heterogeneous chemistrymodule has been used to analyze in detail the effects of temperature andaerosol surface area on odd oxygen production/depletion in the lowerstratosphere at 30° S. Results show that for background aerosolloading, the hydrolysis of BrONO2 and N2O5are most important atall temperatures studied except when the temperature falls below about205 K, when ClONO2 hydrolysis becomes most important. Thisprocessing leads to removal of active nitrogen to form nitric acid andenhancement of HOx, BrOx, ClOx levels. Detailed O3 budgets asa function of temperature are presented showing how ozone loss andproduction terms vary with changes in stratospheric sulfate aerosol loadingfor the individual families. For (most) aerosol loading levels, thelargest ozone losses occurred at warmer temperatures due to the strongtemperature dependence of the NOx ozone-destroying reactions. Theexception to this occurred for the conditions representative of volcanicloading, which showed a strong increase in ozone destruction due toincreases in destruction from the ClOx and HOx families.The ozoneproduction term k[NO][HO2] did not show a strong dependence oneithertemperature or aerosol loading, due to the offsetting effect of reducedNOxand increased HOx concentrations.  相似文献   

10.
In situ measurements of [OH], [HO2] (square brackets denote species concentrations), and other chemical species were made in the tropical upper troposphere (TUT). [OH] showed a robust correlation with solar zenith angle. Beyond this dependence, however, [OH] did not correlate to its primary source, the product of [O3] and [H2O] ([O3]?[H2O]), or its sink [NOy]. This suggests that [OH] is heavily buffered in the TUT. One important exception to this result is found in regions with very low [O3], [NO], and [NOy]. Under these conditions, [OH] is highly suppressed, pointing to the critical role of NO in sustaining OH in the TUT and the possibility of low [OH] over the western Pacific warm pool due to strong marine convections bringing NO-poor air to the TUT. In contrast to [OH], [HOx] ([OH] + [HO2]) correlated reasonably well with [O3]?[H2O]/[NOy], suggesting that [O3]?[H2O] and [NOy] are the significant source and sink, respectively, of [HOx].  相似文献   

11.
The HO x (OH and HO2) production rate in indoor air caused by radon decay was measured by the chemical amplification technique. The average HO x production rate was found to be (4.31±0.07)×105 HO x per Rn decay per second (Bq) within the range of relative humidity from 3.4 to 55.0 percent at 22 °C. This work providedG(HO x )-value, 7.86±0.13 #/100 eV in air by directly measuring [HO x ] from radiolysis of water vapor. It is also found that there is no obvious relationship between the HO x production rate and the relative humidity in this range. Therefore, this work provides both the basic data for the evaluation of radioactive pollution in indoor air as well as a potentially useful way to produce HO x concentrations in air.  相似文献   

12.
A detailed photochemical box model was used to investigate the key reaction pathways between OH, HO2 and RO2 radicals during the summer and winter PUMA field campaigns in the urban city-centre of Birmingham in the UK. The model employed the most recent version of the Master Chemical Mechanism and was constrained to 15-minute average measurements of long-lived species determined in situ at the site. The results showed that in the summer, OH initiation was dominated by the reactions of ozone with alkenes, nitrous acid (HONO) photolysis and the reaction of excited oxygen atoms atoms with water. In the winter, ozone+alkene reactions were the primary initiation route, with a minor contribution from HONO photolysis. Photolysis of aldehydes was the main initiation route for HO2, in both summer and winter. RO2 initiation was dominated by the photolysis of aldehydes in the summer with a smaller contribution from ozone+alkenes, a situation that was reversed in the winter. At night, ozone+alkene reactions were the main radical source. Termination, under all conditions, primarily involved reactions with NO (OH) and NO2 (OH and RCO3). These results demonstrate the importance of ozone+alkene reactions in urban atmospheres, particularly when photolysis reactions were less important during winter and at nighttime. The implications for urban atmospheric chemistry are discussed.  相似文献   

13.
A bifurcation phenomenon with relevance to atmospheric chemistry is discussed. The gasphase reactions in the troposphere exhibit two types of temporal evolution which are controlled by the strength of the source,Q, of nitric oxide, NO, via the nonlinear chemical coupling between the hydrogen oxides and nitrogen oxides chemistry. IfQ remains below a threshold value, all short-lived species, including NO, approach steady-state concentrations, while above the threshold bifurcation to another state with increasing (nonstationary) NO concentrations accompanied by a depletion of the OH and HO2 abundances takes place.  相似文献   

14.
A new instrument (LOPAP: LOng Path liquid Absorption Photometer) for the sensitive detection of nitric acid (HNO3) in the atmosphere is described. HNO3 is sampled in a temperature controlled stripping coil mounted in an external sampling module to minimize sampling artefacts in sampling lines. After conversion into a strongly absorbing dye, HNO3 is detected in long path absorption in special Teflon® AF 2400 tubes used as liquid core wave guides. For the correction of some interferences, due to for example HONO and particle nitrate, two channels are used in series. The interferences from several potential interfering compounds including particle nitrate were quantified in the laboratory and in a large outdoor simulation chamber. With the exception of the interference caused by N2O5, which is quantitatively measured by the instrument, all tested interferences can be corrected under atmospheric conditions. Thus, in the instrument only the sum of N(V) from HNO3 and N2O5 is determined, which is expected to be a common problem of wet chemical HNO3 instruments. The instrument has a detection limit of 5–30 pptv for a time response of 6–2 min, respectively and was validated against the FTIR technique in a large outdoor simulation chamber. In addition, the applicability of the instrument was demonstrated in a field campaign.  相似文献   

15.
Isoprene peroxy radical isomerizations (1,5- and 1,6-H shifts) have recently been proposed as important pathways regenerating and recycling HOx (OH?+?HO2) in the atmosphere under low-NOx conditions (Peeters et al. Phys. Chem. Chem. Phys. 28: 5935?C5939 2009; da Silva et al. Environ. Sci. Technol. 44:250?C256 2010). Evaluation and comparison of the isoprene peroxy radical isomerization mechanisms from recent studies have been performed against isoprene-NOx experiments conducted in the UNC dual outdoor smog chambers. Five different kinetic mechanisms were tested in this study, including the original Master Chemical Mechanism (MCM) v3.1; two modified MCM mechanisms both implementing isoprene peroxy radical isomerization reactions but with different rate coefficients; the Carbon Bond 6 (CB6) mechanism; and the ISO-UNC mechanism. Sensitivity analyses of the unsaturated hydroxyperoxy aldehydes (HPALDs) reaction mechanisms under fast isomerization have also been performed. The results indicate that the fast isomerization mechanism and the mechanisms with high OH yields from HPALDs photolysis both significantly enhance HOx estimates with increasing isoprene/NOx ratios. However, O3 predictions, as well the isoprene decay rates are substantially overestimated. Our results suggest that given the current state of our knowledge, it is difficult to improve both HOx levels and maintain reasonable O3 simulations using the Peeters et al. (Peeters et al. Phys. Chem. Chem. Phys. 28: 5935?C5939 2009) mechanism.  相似文献   

16.
Using long path UV absorption spectroscopy we have measured OH concentrations close to the earth's surface. The OH values observed at two locations in Germany during 1980 through 1983 range from 0.7×106 to 3.2×106 cm-3. Simultaneously we measured the concentrations of O3, H2O, NO, NO2, CH4, CO, and the light non methane hydrocarbons. We also determined the photolysis rates of O3 and NO2. This allows calculations of OH using a zero dimensional time depdendent model. The modelled OH concentrations significantly exceed the measured values for low NO x concentrations. It is argued that additional, so far unidentified. HO x loss reactions must be responsible for that discrepancy.  相似文献   

17.
Photochemical box modelling was undertaken to investigate OH and HO2 radical chemistry during summer and winter field campaigns in the urban city-centre of Birmingham in the UK. The model employed the most recent version of the Master Chemical Mechanism (v3.1) and was constrained to 15-minute average measurements of long-lived species determined in situ at the site. The model was used to predict OH and HO2 concentrations for comparison with measurements made by the fluorescence assay by gas expansion technique. Whilst there was generally good agreement between the modelled and measured OH concentrations, particularly during summer, there was sometimes a significant model under-prediction during daylight hours, which significantly skews the overall model: measured agreement. There were less measured data available for HO2, but the agreement between model and measurement for the days where measurements existed were less good than for OH, with one or two exceptions. The modelled:measured ratios between the hours of 11:00–15:00 h for OH were 0.58 and 0.50 for summer and winter respectively. For HO2, the same ratios were 0.56 in the summer and 0.49 in the winter. Sensitivity studies were conducted to attempt to understand the model-measurement discrepancy. The predicted radical concentrations were particularly sensitive to changes in NOX concentrations. Constraining the model to the observed HO2 concentrations made the OH predictions worse. These results highlight the fact that there are many complexities in urban areas and that more highly-instrumented campaigns are required in the future to further our understanding.  相似文献   

18.
Observations of the tropical atmosphere are fundamental to the understanding of global changes in air quality, atmospheric oxidation capacity and climate, yet the tropics are under-populated with long-term measurements. The first three years (October 2006–September 2009) of meteorological, trace gas and particulate data from the global WMO/Global Atmospheric Watch (GAW) Cape Verde Atmospheric Observatory Humberto Duarte Fonseca (CVAO; 16° 51′ N, 24° 52′ W) are presented, along with a characterisation of the origin and pathways of air masses arriving at the station using the NAME dispersion model and simulations of dust deposition using the COSMO-MUSCAT dust model. The observations show a strong influence from Saharan dust in winter with a maximum in super-micron aerosol and particulate iron and aluminium. The dust model results match the magnitude and daily variations of dust events, but in the region of the CVAO underestimate the measured aerosol optical thickness (AOT) because of contributions from other aerosol. The NAME model also captured the dust events, giving confidence in its ability to correctly identify air mass origins and pathways in this region. Dissolution experiments on collected dust samples showed a strong correlation between soluble Fe and Al and measured solubilities were lower at high atmospheric dust concentrations. Fine mode aerosol at the CVAO contains a significant fraction of non-sea salt components including dicarboxylic acids, methanesulfonic acid and aliphatic amines, all believed to be of oceanic origin. A marine influence is also apparent in the year-round presence of iodine and bromine monoxide (IO and BrO), with IO suggested to be confined mainly to the surface few hundred metres but BrO well mixed in the boundary layer. Enhanced CO2 and CH4 and depleted oxygen concentrations are markers for air-sea exchange over the nearby northwest African coastal upwelling area. Long-range transport results in generally higher levels of O3 and anthropogenic non-methane hydrocarbons (NMHC) in air originating from North America. Ozone/CO ratios were highest (up to 0.42) in relatively fresh European air masses. In air heavily influenced by Saharan dust the O3/CO ratio was as low as 0.13, possibly indicating O3 uptake to dust. Nitrogen oxides (NOx and NOy) show generally higher concentrations in winter when air mass origins are predominantly from Africa. High photochemical activity at the site is shown by maximum spring/summer concentrations of OH and HO2 of 9?×?106 molecule cm?3 and 6?×?108 molecule cm?3, respectively. After the primary photolysis source, the most important controls on the HOx budget in this region are IO and BrO chemistry, the abundance of HCHO, and uptake of HOx to aerosol.  相似文献   

19.
Improvements of the matrix isolation/electron spin resonance technique for the measurement of NO2, NO3, and RO2 radicals in the atmosphere are described. The use of D2O instead of H2O as the matrix yields a better spectral resolution and, as a consequence, larger a signal-to-noise ratio as well as better identification of the different species. Reference spectra of the different radicals in H2O and D2O matrices are compared. While a large degree of correlation exists amongst the spectra of the different (unsubstituted and substituted) alkylperoxy radicals, the spectra of HO2, CH3C(O)O2, and NO3 show significant differences that allow their distinction in atmospheric samples.A numerical procedure for the analysis of the composite ESR spectra obtained from atmospheric samples was developed. Subtraction of the dominant NO2 signal is performed by matching a reference NO2 spectrum with respect to amplitude, spectral position, and line width to the sample spectrum. The manipulations are performed with the virtually noise-free reference spectrum and are based on physical information. The residual spectrum is then analyzed for RO2 (and/or NO3) by simultaneously fitting up to six different reference spectra.The method was applied to laboratory samples as well as to atmospheric samples in order to demonstrate the ability of retrieving small amounts of HO2 in the presence of large amounts of NO2 and other peroxy radicals. The new algorithm allowed, for the first time, the identification of the HO2 and CH3C(O)O2 radical in tropospheric air at concentrations ranging up to 40 ppt.  相似文献   

20.
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