Sensitivity of ozone concentrations to diurnal variations of surface emissions in Mexico City: A WRF/Chem modeling study

Sensitivity of ozone (O₃) concentrations in the Mexico City area to diurnal variations of surface air pollutant emissions is investigated using the WRF/Chem model. Our analysis shows that diurnal variations of nitrogen oxides (NO_x = NO + NO₂) and volatile organic compound (VOC) emissions play an important role in controlling the O₃ concentrations in the Mexico City area. The contributions of NO_x and VOC emissions to daytime O₃ concentrations are very sensitive to the morning emissions of NO_x and VOCs. Increase in morning NO_x emissions leads to decrease in daytime O₃ concentrations as well as the afternoon O₃ maximum, while increase in morning VOC emissions tends to increase in O₃ concentrations in late morning and early afternoon, indicating that O₃ production in Mexico City is under VOC-limited regime. It is also found that the nighttime O₃ is independent of VOCs, but is sensitive to NO_x. The emissions of VOCs during other periods (early morning, evening, and night) have only small impacts on O₃ concentrations, while the emissions of NO_x have important impacts on O₃ concentrations in the evening and the early morning.This study suggests that shifting emission pattern, while keeping the total emissions unchanged, has important impacts on air quality. For example, delaying the morning emission peak from 8 am to 10 am significantly reduced the morning peaks of NO_x and VOCs, as well as the afternoon O₃ maxima. It suggests that without reduction of total emission, the daytime O₃ concentrations can be significantly reduced by changing the diurnal variations of the emissions of O₃ precursors.     

Seasonal and shorter-term variations in particulate atmospheric nitrate in Baltimore

Fine particle nitrate concentrations were measured at 10-min intervals for approximately 9.5 months beginning on 14 February 2002, at the Baltimore Supersite Ponca St. location using an R&P 8400N semi-continuous monitor. The measurement results were used to characterize seasonal and shorter-term excursions in nitrate concentrations and determine their influence on PM_2.5 concentrations. Over the 9.5-month study period, nitrate levels of 1.7±1.6 μg m⁻³ accounted for 11.4% of the PM_2.5 mass. Monthly averages ranged from 0.8 μg m⁻³ in August to 2.9 μg m⁻³ in November, and accounted for 4.7–17.3% of monthly PM_2.5 mass. Hourly averages, however, were often larger, especially in the colder months, owing to numerous relatively short-term transients, where hourly nitrate concentrations exceeded 5.0 μg m⁻³. These often occurred along with NO_x and ultrafine particle transients during the morning commute hours.A total of 275 short-term transients (31.7% of the total) exceeding 1.0 μg m⁻³ were identified. These were associated with one of three sets of conditions. The first, most typical (177, i.e. 64.4% of the 275 incidences), is characterized by high NO_x typically between 0500 and 0800EST and is attributed to early morning commute traffic activity. The second type occurred during the afternoon due to photochemical activity. The excursions in the afternoon occurred infrequently (only 9.5% of all the observed transients) during the study period and were characterized by less elevated nitrate concentrations than morning and nighttime transients. The third (72, i.e. 26.2% of the 275 transients) occurred at night, typically between 2000EST and 0200EST.Multiple linear regression analysis between nitrate excursions and volume size distributions indicates that particulate nitrate observed is closely related to the near accumulation (0.1–0.2 μm) and droplet modes (0.5–1.0 μm) in the morning hours, and associated with the droplet (0.5–1.0 μm) and coarse modes (1.0–2.5 μm) for nighttime transients, suggesting that processes governing particulate nitrate formation depend on time-of-day.     

Aerosol optical properties based on ground measurements over the Chinese Yangtze Delta Region

The characteristics of Aerosol Optical Depth (AOD) and Angstrom exponent were analyzed and compared using Cimel sunphotometer data from 2007 to 2008 at five sites located in the Yangtze River Delta region of China. The simultaneous measurements between Lin’an and ZFU showed a very high consistency of AOD at all wavelengths. The differences are less than 0.02 for Angstrom exponent and AOD at all wavelengths. The mean values of AOD at 440 nm at the Pudong, Taihu and Lin’an were about 0.74 ± 0.43, 0.85 ± 0.46, and 0.89 ± 0.46, respectively. The mean values of Angstrom exponents were about 1.27 ± 0.30, 1.20 ± 0.28 and 1.32 ± 0.35, respectively. The variation of monthly averaged AOD over Pudong showed a single peak distribution, with the maximum value occurring in July (AOD_440nm 1.26 ± 0.61) and minimum in January (AOD_440nm 0.50 ± 0.27). However, the variations of monthly averaged AOD at Taihu and Lin’an showed a bi-modal distribution. There were peak values of AOD occurring in July (AOD_440nm 1.41 ± 0.49) and September (AOD_440nm 1.22 ± 0.52) for Taihu. For Lin’an, the two peak values of AOD occurred in June (AOD_440nm 1.17 ± 0.69) and September (AOD_440nm 1.28 ± 0.46). The AOD accumulated mainly between 0.30–0.90(68%), 0.30–1.20(75%) and 0.30–1.20 (～75%) at Pudong, Taihu, and Lin’an, respectively. The Angstrom exponent accumulated mainly between 1.10–1.60 (75%), 1.10–1.50 (63%) and 1.20–1.60, 50% (50%) at Pudong, Taihu, and Lin’an, respectively.The synchronized observation showed that the AOD at Pudong was larger than those at Dongtan by 0.03, 0.03, 0.04, 0.07, and 0.08 at wavelengths of 1020 nm, 870 nm, 670 nm, 500 nm and 440 nm, respectively. The synchronized observations at Pudong, Taihu and Lin’an showed that the three stations had high level AOD with means at 440 nm about 0.68, 0.73, and 0.78, respectively. The relationship between MODIS retrieved and ground-based measured AOD shows good agreement with R² ranging from 0.68 to 0.79 at Pudong, Taihu, Lin’an and Dongtan. The MODIS results were overestimated comparing the ground measurements at Pudong, Taihu, and Dongtan but exceptional at Lin’an.The analysis results between aerosol optical properties and wind measurement at Pudong showed that the wind speed from the east correlates with the lower observed AOD. The back trajectory analysis indicates that more than 50% airmasses were from the marine area at Pudong, while back trajectories distribution is relatively homogeneous at Lin’an.     

Factors controlling the diurnal variation of CO above a forested area in southeast Europe

Carbon monoxide (CO) measurements have been performed in a forested site in central Greece in the framework of the AEROBIC (AEROsol formation from Biogenic Carbon) campaign in summer 1997. The mean CO observed during the whole campaign ranged between 114 and 250 ppbv (mean of 170±27 ppbv), reflecting continental influence. The observed mean diurnal cycle of CO presented a minimum in the early morning due to the efficient deposition of CO in a shallow nocturnal layer sealed from the free tropospheric air during the night (loss rates of about 2 ppbv h⁻¹). In the early morning and in the late afternoon, a sharp and fluctuating increase of CO was observed as the consequence of CO primary sources, likely by local traffic as suggested by the concomitant enhancements of black carbon (BC) and other combustion tracers. The morning pollution peak (6:30–8:30 local time) preceded slightly the opening of the nocturnal layer to the free troposphere, which resulted in CO reduction down to background levels at about 10:00. During the day (10:00–17:00), a slight but regular increase was observed on CO levels. For lack of simultaneous increase of other anthropogenic tracers, this CO enhancement has been attributed to its photochemical formation initiated by the oxidation of reactive biogenic hydrocarbons. This observed net production of CO averaging 1.2 ppbv h⁻¹ is quite well reproduced by a box model containing an explicit chemical scheme of isoprene and α- and β-pinene and taking into account the measured mixing ratios and the reactivity of all biogenic organic reactive compounds when uncertainties in measurements and modelling are considered.     

On the optical properties of the polluted Athens atmosphere,during May 1995

Using ground-based spectral solar extinction data taken over the Athens atmosphere, reduced (total minus Rayleigh) and aerosol (Angstrom) spectral optical depths of the atmosphere, have been retrieved, under different polluted conditions. The results suggest that the optical depth, on days with relatively low pollution, exhibits slight variation with wavelength denoting that aerosols deplete all wavelengths almost equally. In contrast, under dense pollution, small particles scattering and trace gases absorption, are the dominant processes, resulting in steeper optical depth’s slopes, mainly in the ultraviolet domain. The Angstrom’s parameters β and α were determined through a least-squares fitting method. The turbidity β coefficient always shows a temporal pattern with high values in the morning and afternoon and low values midday.     

Trends in size classified particle number concentration in subtropical Brisbane,Australia, based on a 5 year study

Particle number size distribution data in the range from 0.015 to 0.630 μm were collected over a 5-year period in the central business district (CBD) of Brisbane, Australia. Particle size distribution was summarised by total number concentration and number median diameter (NMD) as well as the number concentration of the 0.015–0.030 (N_15–30), 0.030–0.050 (N_30–50), 0.050–0.100 (N_50–100), 0.100–0.300 (N_100–300) and 0.300–0.630 (N_300–630) μm size classes. Morning (6:00–10:00) and afternoon (16:00–19:00) measurements, the former representing fresh traffic emissions (based on the local meteorological conditions) and the latter well-mixed emissions from the CBD, during weekdays were extracted and the respective monthly mean values were estimated for time series analysis. For all size fractions, average morning concentrations were about 1.5 higher than in the afternoon whereas NMD did not vary between the morning and afternoon. The trend and seasonal components were extracted through weighted linear regression models, using the monthly variance as weights. Only the morning measurements exhibited significant trends. During this time of the day, total particle number increased by 105.7% and the increase was greater for larger particles, resulting in a shift in NMD by 7.9%. Although no seasonal component was detected the evidence against it remained weak due to the limitations of the database.     

Aerosol optical properties of regional background atmosphere in Northeast China

Aerosol optical properties from 2005 to 2008 at the Longfengshan regional background station in Northeast China were measured and analyzed. The annual mean of aerosol optical depth (AOD) at 440 nm for the four years was about 0.27 ± 0.25, 0.39 ± 0.37, 0.35 ± 0.34, and 0.38 ± 0.38, respectively, and the corresponding annual mean for the Angstrom exponent between 440 nm and 870 nm was about 1.43 ± 0.48, 1.23 ± 0.37, 1.53 ± 0.47, and 1.55 ± 0.42. The average monthly AOD_440nm showed similar seasonal variation with a maximum in spring and a minimum in autumn. The monthly means of AOD at 440, 675, 870 and 1020 nm increase from the January to March with the maxima about 0.77 ± 0.04, 0.65 ± 0.04, 0.58 ± 0.06, 0.57 ± 0.07, respectively and decrease from September to February with the minima about 0.32 ± 0.12, 0.22 ± 0.09, 0.15 ± 0.08, and 0.13 ± 0.07 in January. The monthly mean of Angstrom exponent shows a minimum in March (0.97 ± 0.52) and a maximum in September (1.66 ± 0.29). Both the AOD and Angstrom exponent presents single peak distributions of occurrence frequencies. The Longfenshan data showed high AODs (>1.00) both clustering in the fine mode growth wing and the coarse mode. Two typical cases under dust and haze conditions showed that the AOD under dusty day decreased from 2.20 to 1.20 and the Angstrom exponent increased from 0.10 to 1.00. On the contrast, the AOD under haze day remained relatively stable about 0.90 and the Angstrom exponent was around 1.40. The 3-day backtrajectory analysis at Longfengshan illustrated that the air-masses near ground on the dust day were from Bohai Sea and passed through Liaodong Peninsula and Northeast plain in China. But the air-masses on 500 m AGL were originated from western Mongolia and crossed Gobi deserts, Otindag Sand Land and Horqin Sand Land in Northeast China. The air-masses at Longfengshan near ground 500 m and 1000 m AGL on the haze days were from North China Region and passed through Northeast Heavy Industrial Base in Northeast China.     

Volatile organic compound emissions from Siberian larch

We determined hourly emissions of isoprene, monoterpenes and sesquiterpenes from Siberian larch, one of the major tree species in Siberian forests. Summer volatile organic compounds (VOCs) emission from Siberian larch consisted mainly of monoterpenes (about 90%). The monoterpene emission spectrum remained constant during the measurement period, almost half was sabinene and other major monoterpenes were Δ³-carene, β- and α-pinene. During spring and summer, about 10% of the VOCs were sesquiterpenes, mainly α-farnesene. The sesquiterpene emissions declined to 3% in the fall. Isoprene, 2-methyl-3-buten-2-ol (MBO) and 1,8-cineole contributed to less than 3% of the VOC emission during the whole period. The diurnal variation of the emissions could be explained using a temperature-dependent parameterization. Emission potentials normalized to 30 °C were 5.2–21 μg g_dw⁻¹ h⁻¹ (using β-value of 0.09 °C⁻¹) for monoterpenes and 0.4–1.8 μg g_dw⁻¹ h⁻¹ (using β-value of 0.143 °C⁻¹, mean of determined values) for sesquiterpenes. Normalized monoterpene emission potentials were highest in late summer and elevated again in late fall. Sesquiterpene emission potentials were also highest in late summer, but decreased towards fall.     

Peroxyacetyl nitrate and peroxypropionyl nitrate in Porto Alegre,Brazil

For 41 days between 25 May 1996 and 27 March 1997, peroxyacetyl nitrate (PAN) and peroxypropionyl nitrate (PPN) have been measured by electron capture gas chromatography at Santa Rita near Porto Alegre, RS, Brazil, where light-duty vehicles used either ethanol or a gasoline–MTBE blend. Daily maximum concentrations ranged from 0.19 to 6.67 ppb for PAN and 0.06 to 0.72 ppb for PPN. Linear regression of maximum PPN vs. maximum PAN yielded a slope of 0.105±0.004 (R²=0.974). Diurnal variations of ambient PAN often followed those of ozone with respect to time of day but not with respect to amplitude. This was reflected in the large relative standard deviations associated with the study-averaged PAN/ozone concentration ratio, 0.037±0.105 (ppb/ppb, n=789) and the maximum PAN/maximum ozone concentration ratio, 0.028±0.015 (ppb/ppb, range 0.005–0.078, n=41). On several days PAN accounted for large fractions of the total ambient NO_x in the late morning and afternoon hours, e.g., PAN/NO_x⩽0.58 and PAN/(NO_x–NO) ⩽0.76 on 27 March 1997. The amount of PAN lost by thermal decomposition (TPAN) was comparable in magnitude to that present in ambient air. The ratios TPAN/(PAN+TPAN) were up to 0.53, 0.67 and 0.64 during the warm afternoons of 25, 26 and 27 March 1997, respectively. The highest calculated value of TPAN was 5.6 ppb on 27 March 1997. On that day the 24 h-averaged value of TPAN (1.01 ppb) was nearly the same as that of PAN (1.09 ppb). Using computer kinetic modeling (SAPRC 97 chemical mechanism) and sensitivity analysis of VOC incremental reactivity, we ranked VOC present in Porto Alegre ambient air for their importance as precursors to PAN and to PPN. Using as input data the averages of VOC concentrations measured in downtown Porto Alegre during the ca. 1 yr period March 1996–April 1997, we calculated that the most important precursors to PAN and PPN were the SAPRC 97 model species ARO2 (which includes the aromatics xylenes, trimethylbenzenes, ethyltoluenes, etc.), which accounted for ca. 17% of the total PAN and total PPN formation potentials. Overall, the results indicate a major role for aromatics and alkenes and a minor role for acetaldehyde and ethanol as precursors to peroxyacyl nitrates in the Porto Alegre urban area.     

On applicability of model aerosol distributions for urban region of Bratislava city

Long-term measurements of spectral atmospheric transparency are analysed to describe the aerosol size distribution as well as the aerosol optical thickness in the urban region of Bratislava city, capital of Slovak Republic. Aerosol characteristics are related to the most frequent air masses, especially to the continental polar (cP—with a 54% occurrence) and maritime polar (mP—with 34% occurrence), to the wind direction and speed, as well as to the relative humidity. Including both random and systematic errors of the observations into the calculation procedures, the aerosol optical thickness is obtained with approximately 4% error at all wavelengths. Averaged values of the aerosol optical thickness τ_a(λ) at reference wavelength λ=520 nm vary over a wide range, from 0.1 to 0.7. Besides, the aerosol optical thickness of the continental polar air mass is obviously higher than corresponding values in the maritime polar air mass. It is shown that the transformation inside the air mass reflects the changes of the optical characteristics of aerosols, especially during decay of air mass. The function τ_a(λ) seems to be monomodal in the majority of cases, with the mode position about λ≈400 nm for cP, and λ≈500 nm for mP. A value of power parameter δ of the function τ_a(λ)≈λ^−δ is about 0.8–1.6 for maritime polar and about 0.3–1.2 for continental polar. Two simple model functions (Junge and gamma) are examined to find a best fit of real distribution retrieved from the aerosol optical thickness data using the inverse techniques based on Mellin transform. The gamma function much better than Junge's function supply the real aerosol component of all studied air masses (mainly for cP and mP). The average modal radius of gamma distribution practically does not exceed the value of 0.06 μm. Real distributions retrieved using a Mellin transform give an averaged morning value of particle modal radius r_m about 0.084 μm, and averaged daily value r_m about 0.054 μm.     

Variability-lifetime relationship of VOCs observed at the Sonnblick Observatory 1999—estimation of HO-densities

An extensive dataset of VOC measurements was collected at the Sonnblick Observatory, Austria (3106 m) in Fall/Winter 1999/2000, showing high mixing ratios of anthropogenic and biogenic VOCs at this high altitude site due to upward mixing of air masses (Geophys. Res. Lett. 2F (2001) 507). Here we give an interpretation of proton-transfer-reaction (PTR-MS) mass scans obtained in November 1999 based on fragmentation data, GC-PTR-MS analysis and the variability-lifetime relationship, described by the power law, σ(ln(x))=Aτ^−b. The variability-lifetime plot of anthropogenic VOCs gave a proportionality factor A of 1.40 and a,b exponent (sink term) of 0.44 and allowed an estimate of average HO-densities on the order of (1.5±0.4)×10⁵ molecules cm⁻³. Additionally we were able to indirectly determine a diurnal HO-profile with peak values of (1.3±0.5)×10⁶ molecules cm⁻³ around midday. HO-reaction rate coefficients for higher aldehydes (heptanal to nonanal) were estimated due to photochemical losses during a stagnant air episode (27 November) and from the variability-lifetime relationship. Combining long term PTR-MS analysis of VOCs and the variability-lifetime method provides a valuable tool for assessing the dominant cause of the variability in VOC concentrations. This information is essential in understanding the sources and photochemical processing of VOCs detected in ambient air at field measurement sites.     

A study of the variation of urban mixed layer heights

The AERMET model is used to estimate hourly mixing heights during the Joint URBAN (2003) experiment in Oklahoma City, Oklahoma. AERMET is a simple 2-D model that requires only routine meteorological observations and an early morning atmospheric sounding to estimate convective boundary layer (CBL) growth. Estimated mixing heights are compared with observed mixing heights measured during Joint URBAN 2003. Observed CBL heights are derived from profiler data using a peak signal-to-noise ratio method. The method of deriving mixing heights from profiler data is validated using daily atmospheric sounding data. Estimated mixing heights using AERMET show good agreement with observations on days of varying temperature and cloud cover. AERMET was able to estimate the rapid boundary layer growth observed in the late morning and early afternoon hours during highly convective conditions. CBL heights of over 3000 m are observed in sounding data during the late afternoon. Estimated CBL heights of over 3000 m during the late afternoon agreed well with observations from the sounding and profiler data.     

Aerosol scattering properties in northern China

The aerosol scattering properties were investigated at two continental sites in northern China in 2004. Aerosol light scattering coefficient (σ_sp) at 525 nm, PM₁₀, and aerosol mass scattering efficiencies (α) at Dunhuang had a mean value of 165.1±148.8 M m⁻¹, 157.6±270.0 μg m⁻³, and 2.30±3.41 m² g⁻¹, respectively, while these values at Dongsheng were, respectively, 180.2±151.9 M m⁻¹, 119.0±112.9 μg m⁻³, and 1.87±1.41 m² g⁻¹. There existed a seasonal variability of aerosol scattering properties. In spring, at Dunhuang PM₁₀, σ_sp, and α were 184.1±211.548 μg m⁻³, 126.3±89.6 M m⁻¹, and 1.05±0.97 m² g⁻¹, respectively, and these values at Dongsheng were 146.4±142.1 μg m⁻³, 183.4±81.7 M m⁻¹, and 1.98±1.52 m² g⁻¹, respectively. However, in winter at Dunhuang PM₁₀, σ_sp, and α were 158.1±261.4 μg m⁻³, 303.3±165.2 M m⁻¹, and 3.17±1.93 m² g⁻¹, respectively, and these values at Dongsheng were 155.7±170.1 μg m⁻³, 304.4±158.1 M m⁻¹, and 2.90±1.72 m² g⁻¹, respectively. σ_sp and α in winter were higher than that in spring at both the sites, which coincides with the characteristics of dust aerosol and pollution aerosol. Overall, the dominant aerosol types in spring and winter at both sites in northern China are dust aerosol and pollution aerosol, respectively.     

Air quality measurements in urban green areas – a case study

The influence of traffic-induced pollutants (e.g. CO, NO, NO₂ and O₃) on the air quality of urban areas was investigated in the city of Essen, North Rhine-Westphalia (NRW), Germany. Twelve air hygiene profile measuring trips were made to analyse the trace gas distribution in the urban area with high spatial resolution and to compare the air hygiene situation of urban green areas with the overall situation of urban pollution. Seventeen measurements were made to determine the diurnal concentration courses within urban parks (summer conditions: 13 measurements, 530 30 min mean values, winter conditions: 4 measurements, 128 30 min mean values). The measurements were carried out during mainly calm wind and cloudless conditions between February 1995 and March 1996. It was possible to establish highly differentiated spatial concentration patterns within the urban area. These patterns were correlated with five general types of land use (motorway, main road, secondary road, residential area, green area) which were influenced to varying degrees by traffic emissions. Urban parks downwind from the main emission sources show the following typical temporal concentration courses: In summer rush-hour-dependent CO, NO and NO₂ maxima only occurred in the morning. A high NO₂/NO ratio was established during weather conditions with high global radiation intensities (K>800 W m⁻²), which may result in a high O₃ formation potential. Some of the values measured found in one of the parks investigated (Gruga Park, Essen, area: 0.7 km²), which were as high as 275 μg m⁻³ O₃ (30-min mean value) were significantly higher than the German air quality standard of 120 μg m⁻³ (30-min mean value, VDI Guideline 2310, 1996) which currently applies in Germany and about 20% above the maximum values measured on the same day by the network of the North Rhine–Westphalian State Environment Agency. In winter high CO and NO concentrations occur in the morning and during the afternoon rush-hour. The highest concentrations (CO=4.3 mg m⁻³, NO=368 μg m⁻³, 30-min mean values) coincide with the increase in the evening inversion. The maximum measured values for CO, NO and NO₂ do not, however, exceed the German air quality standards in winter and summer.     

Measurements of aerosol optical properties in central Tokyo during summertime using cavity ring-down spectroscopy: Comparison with conventional techniques

A highly sensitive cavity ring-down spectrometer (CRDS) was used to monitor the aerosol extinction coefficient at 532 nm. The performance of the spectrometer was evaluated using measurements of nearly monodisperse polystyrene particles with diameters between 150 and 500 nm. By comparing the observed results with those determined using Mie theory, the accuracy of the CRDS instrument was determined to be >97%, while the upper limit for the precision of the instrument was estimated to be 0.6–3.5% (typically 2%), depending on the particle number concentration, which was in the range of 30–2300 particles cm^?3. Simultaneous measurements of the extinction (b_ext), scattering (b_sca) and absorption (b_abs) coefficients of ambient aerosols were performed in central Tokyo from 14 August to 2 September 2007 using the CRDS instrument, two nephelometers and a particle/soot absorption photometer (PSAP), respectively. The value of b_ext measured using the CRDS instrument was compared with the sum of the b_sca and b_abs values measured with a nephelometer and a PSAP, respectively. Good agreement between the b_ext and b_sca + b_abs values was obtained except for data on days when high ozone mixing ratios (>130 ppbv) were observed. During the high-O₃ days, the values for b_sca + b_abs were ～7% larger than the value for b_ext, possibly because the value for b_abs measured by the PSAP was overestimated due to interference from coexisting non-absorbing aerosols such as secondary organic aerosols.     

Particle size and time of the day influences on the morphology distributions of atmospheric fine particles at the Baltimore supersite

The morphology of size-classified ambient particulate matter less than 2.5 μm in aerodynamic diameter (PM_2.5) was studied in samples collected at the USEPA supersite located in Baltimore, MD. Size classification was accomplished through the use of a low pressure impactor to produce samples with cut-off diameters of 0.10, 0.15, 0.55, and 2.0 μm. Sampling was conducted in two campaigns during the fall of 2002, with separate sampling occurring during early morning, mid-day, late afternoon, and evening periods. Particles with cut-off diameters of 2 μm were generally round in shape, with a border fractal dimension close to 1 based on the analysis of transmission electron microscope (TEM) images of collected samples. Particles with a cut-off diameter of 0.15 μm had on average higher fractal dimensions than the other size classes considered, regardless of time of day associated with the sample. As expected, the time of the day influenced the shape of particle populations sampled. Particles collected during early morning were found to have higher fractal dimension than those collected at other sampling times. At night, particles presented mostly round shapes. This difference was particularly pronounced in particles with cut-off diameters of 0.15 μm.     

Isoprene and monoterpene fluxes measured above Amazonian rainforest and their dependence on light and temperature

Canopy scale emissions of isoprene and monoterpenes from Amazonian rainforest were measured by eddy covariance and eddy accumulation techniques. The peak mixing ratios at about 10 m above the canopy occurred in the afternoon and were typically about 90 ppt_v of α-pinene and 4–5 ppb_v of isoprene. α-pinene was the most abundant monoterpene in the air above the canopy comprising ≈50% of the total monoterpene mixing ratio. Measured isoprene fluxes were almost 10 times higher than α-pinene fluxes. Normalized conditions of 30°C and 1000 μmol m⁻² s⁻¹ were associated with an isoprene flux of 2.4 mg m⁻² h⁻¹ and a β-pinene flux of 0.26 mg m⁻² h⁻¹. Both fluxes were lower than values that have been specified for Amazon rainforests in global emission models. Isoprene flux correlated with a light- and temperature-dependent emission activity factor, and even better with measured sensible heat flux. The variation in the measured α-pinene fluxes, as well as the diurnal cycle of mixing ratio, suggest emissions that are dependent on both light and temperature. The light and temperature dependence can have a significant effect on the modeled diurnal cycle of monoterpene emission as well as on the total monoterpene emission.     

Isoprene and monoterpene emission from the coniferous species Abies Borisii-regis—implications for regional air chemistry in Greece

The emission of isoprene has been studied from a forest of Abies Borisii-regis, a Mediterranean fir species previously thought to emit only monoterpenes. Emission studies from two independent enclosure experiments indicated a standardised isoprene emission rate of (18.4±3.8) μg g_dry-weight⁻¹ h⁻¹, similar in magnitude to species such as eucalyptus and oak which are considered to be strong isoprene emitters. Isoprene emission depended strongly on both leaf temperature (2°C–34°C) and photosynthetically active radiation (PAR) below 250 μmol m⁻² s⁻¹, becoming saturated with respect to PAR above this value. The annual isoprene emission rate was estimated to be (132±29) kT yr⁻¹ for those trees growing within Greece, comparable to current estimates of the total isoprene budget of Greece as a whole, and contributing significantly to regional ozone and carbon monoxide budgets. Monoterpene emission exhibited exponential temperature dependence, with 1,8-cineole, α-pinene, β-pinene and limonene forming the primary emissions. A standardised total monoterpene emission rate of (2.7±1.1) μg g_dry-weight⁻¹ h⁻¹ was calculated, corresponding to an annual monoterpene emission rate of (24±12) kT yr⁻¹. Research was conducted as part of the AEROBIC’97 (AEROsol formation from BIogenic organic Carbon) series of field campaigns.     

Ozone response to precursor controls: comparison of data analysis methods with the predictions of photochemical air quality simulation models

Comparisons were made between the predictions of six photochemical air quality simulation models (PAQSMs) and three indicators of ozone response to emission reductions: the ratios of O₃/NO_z and O₃/NO_y and the extent of reaction. The values of the two indicator ratios and the extent of reaction were computed from the model-predicted mixing ratios of ozone and oxidized nitrogen species and were compared to the changes in peak 1 and 8 h ozone mixing ratios predicted by the PAQSMs. The ozone changes were determined from the ozone levels predicted for base-case emission levels and for reduced emissions of volatile organic compounds (VOCs) and oxides of nitrogen (NO_x). For all simulations, the model-predicted responses of peak 1 and 8 h ozone mixing ratios to VOC or NO_x emission reductions were correlated with the base-case extent of reaction and ratios of O₃/NO_z and O₃/NO_y. Peak ozone values increased following NO_x control in 95% (median over all simulations) of the high-ozone (>80 ppbv hourly mixing ratio in the base-case) grid cells having mean afternoon O₃/NO_z ratios less than 5 : 1, O₃/NO_y less than 4 : 1, or extent less than 0.6. Peak ozone levels decreased in response to NO_x reductions in 95% (median over all simulations) of the grid cells having peak hourly ozone mixing ratios greater than 80 ppbv and where mean afternoon O₃/NO_z exceeded 10 : 1, O₃/NO_y was greater than 8 : 1, or extent exceeded 0.8. Ozone responses varied in grid cells where O₃/NO_z was between 5 : 1 and 10 : 1, O₃/NO_y was between 4 : 1 and 8 : 1, or extent was between 0.6 and 0.8. The responses in such grid cells were affected by ozone responses in upwind grid cells and by the changes in ozone levels along the upwind boundaries of the modeling domains.     

Surface ozone and NOx concentrations at a high altitude Mediterranean site,Greece

Ozone was measured in six- and NO_x in five sampling periods in 1996–97, mostly during summer, at a 1070 m altitude site in northern Peloponnese. Mean values in each sampling period ranged from 43–48 ppb exceeding the European Union 24 h plant protection standard. The background ozone concentration of 43 ppb derived from the correlation of ozone with NO^′_x also exceeded the EU plant protection standard. Ozone exhibited maxima in the afternoon and minima during the night; in certain 24–48 h periods, however, the ozone concentrations remained practically constant; in these short periods air mass back trajectories indicated air masses which originated in north Africa. NO^′_x concentrations had maximum of 24 h around noon. Their mean concentrations ranged from 0.5–0.7 ppb, smaller than respective concentrations in north-central Europe.