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.     

Nighttime variations in HO2 radical mixing ratios at Rishiri Island observed with elevated monoterpene mixing ratios

HO₂ radical concentrations were measured by a laser-induced fluorescence instrument for three nighttime periods during the intensive field campaign at Rishiri Island, Japan, in June 2000. The HO₂ mixing ratio had temporal variations around its average of 4.2±1.2 (1σ) pptv and showed a positive correlation with the summed mixing ratio of four monoterpene species, α-pinene, β-pinene, camphene, and limonene, that sometimes reached 1 ppbv. Our model calculations suggested that ozonolysis reactions of monoterpenes were the main source of nighttime radicals and they explained 58% of measured HO₂ concentration levels. The model roughly reproduced the dependence of the HO₂ mixing ratio on the square root of the radical production rate due to the ozonolysis reactions of the monoterpenes. However, the absolute HO₂ mixing ratio was significantly underpredicted by the model. We discuss possible reasons in terms of misunderstood RO₂ chemistry, RO₂ interference with HO₂ observations, unknown radical production process associated by high NO₂ mixing ratio, and the contribution of unmeasured olefinic species to radical production via their reactions with ozone.     

Heterogeneous SOA yield from ozonolysis of monoterpenes in the presence of inorganic acid

The secondary organic aerosol (SOA) yield of a series of montoerpenes was investigated to determine the relative amounts of organic mass, which can be attributed to mass produced by heterogeneous acid-catalyzed reactions. Five monoterpenes (α-pinene, terpinolene, d-limonene, Δ²-carene, β-pinene) were studied using a 2 m³ indoor Teflon chamber and SOA was created in the presence of both acidic and neutral inorganic seed aerosol. The relative humidity was varied to create differing acidic seed environments. The heterogeneous aerosol production was influenced by the seed mass concentration, the acidity of the inorganic seed aerosol, and also molecular structure of the monoterpene ozonolysis products. This study also can be incorporated with our previously presented model of the kinetic expression for SOA mass production from heterogeneous acid-catalyzed reactions.     

Flow patterns influencing the seasonal behavior of surface ozone and carbon monoxide at a coastal site near Hong Kong

Surface O₃ and CO were measured at Cape D’Aguilar, Hong Kong during the period of January 1994 to December1996 in order to understand the temporal variations of surface O₃ and CO in East Asia–West Pacific region. The isentropic backward trajectories were used to isolate different air masses reaching the site and to analyze the long-range transport and photochemical buildup of O₃ on a regional scale. The results show that the diurnal variation of surface O₃ was significant in all seasons with daily O₃ production being about 20 ppbv in fall and 10 ppbv in winter, indicating more active photochemical processes in the subtropical region. The distinct seasonal cycles of O₃ and CO were found with a summer minimum (16 ppbv)–fall maximum (41 ppbv) for O₃ and a summer minimum (116 ppbv)–winter maximum (489 ppbv) for CO. The isentropic backward trajectory cluster analyses suggest that the air masses (associated with regional characteristics) to the site can be categorized into five groups, which are governed by the movement of synoptic weather systems under the influence of the Asian monsoon. For marine-originated air masses (M-SW, M-SE and M-E, standing for marine-southwest, marine-southeast and marine-east, respectively) which always appear in summer and spring, the surface O₃ and CO have relatively lower mixing ratios (18, 16 and 30 ppbv for O₃, 127, 134 and 213 ppbv for CO), while the continental air masses (C-E and C-N, standing for continent-east and continent-north, respectively) usually arrive at the site in winter and fall seasons with higher O₃ (43 and 48 ppbv) and CO (286 and 329 ppbv). The 43 ppbv O₃ and 286 ppbv CO are representative of the regionally polluted continental outflow air mass due to the anthropogenic activity in East Asia, while 17 ppbv O₃ and 131 ppbv CO can be considered as the signature of the approximately clean marine background of South China Sea. The very high CO values (461–508 ppbv) during winter indicate that the long-range transport of air pollutants from China continent is important at the monitoring site. The fall maximum (35–46 ppbv) of surface O₃ was believed to be caused by the effects of the weak slowly moving high-pressure systems which underlie favorable photochemical production conditions and the long-range transport of aged air masses with higher O₃ and its precursors.     

Ambient isoprene and monoterpene concentrations in a Greek fir (Abies Borisii-regis) forest. Reconciliation with emissions measurements and effects on measured OH concentrations

Ambient biogenic hydrocarbons were monitored in a forested site in Northern Greece during the summer of 1997 as part of the AEROBIC campaign. Significant concentrations of isoprene were observed, consistent with enclosure measurements presented in the previous paper (Harrison et al., 2001, Atmospheric Environment 35, 4687–4698). In addition, significant concentrations of monoterpenes were observed (nighttime maximum of 2.9 ppbv for total monoterpene concentration). Isoprene and the monoterpenes exhibited pronounced, but different, diurnal cycles which are interpreted via enclosure and OH measurements. The combination of relatively high emission rates at a time when OH concentrations are significantly lower leads to peak isoprene concentrations (∼3.0 ppbv) during the late evening. The temporal behaviour of the biogenic hydrocarbons is used to interpret the radical chemistry at the site and may indicate the presence of high (∼1×10⁶ cm⁻³) nighttime concentrations of the OH radical. Biogenic hydrocarbon measurements were supported by a range of organic and inorganic measurements which are also presented in this paper.     

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.     

Formation of hydrogen peroxide in the ozonolysis of isoprene and simple alkenes under humid conditions

The ozonolysis of isobutene and isoprene was performed in a 570 ℓ static reactor at 295 K and 730 Torr synthetic air in the presence and absence of water vapour, with the reactant concentration ranges of 1–6 ppmv. Products were analysed by a combination of FTIR spectroscopy, GC-FID, and HPLC. For both alkenes, the yields of H₂O₂ and the primary carbonyl products (acetone for isobutene, methacrolein and methylvinyl ketone for isoprene) increased under humid conditions. In the isoprene ozonolysis, the H₂O₂ yields relative to the O₃ conversion were, as determined from the initial rate of the formation, 1 and 9% for dry and humid conditions, respectively. The increase in its yield under the humid conditions was correlated with the sum of the increase in the yields of methacrolein and methylvinyl ketone (∼13%). This was explained by rapid decomposition of the transient α-hydroxy hydroperoxides formed in the reaction of H₂O with the two stabilised C₄ Criegee intermediates. Atmospheric relevance of the results is discussed.     

Ozonolysis of monoterpenes in mechanical ventilation systems

In this investigation the ozonolysis of of three monoterpenes (α-pinene, Δ³-carene and limonene) was studied was studied in authentic mechanical ventilation systems, that included either a cross flow or a rotary heat exchanger. The effects of varying three experimental parameters were investigated: the level of ozone (25 and 75 ppb), the reaction time (25 and 75 s), and the surface area in the ventilation duct (14.8 and 29.5 m²). The initial concentration of each of the monoterpenes was 20 ppb in every experiment, and 1–16% of the α-pinene, <0.5–13% of the Δ³-carene, and <0.5–16% of the limonene reacted. The effects of humidity (g m⁻³) and temperature of the outdoor and supply air, and water losses in the ventilation duct, were also evaluated. Experiments were based on a chemometric statistical design. Comparison of the results to theoretically calculated values showed that theoretical calculations underestimated the amounts that reacted in the ventilation systems by factors of 2–13, depending on the monoterpene and experimental settings.     

Evidence of impact of aerosols on surface ozone concentration in Tianjin,China

In this study, we will present evidence that aerosol particles have strong effects on the surface ozone concentration in a highly polluted city in China. The measured aerosol (PM10), UV flux, and O₃ concentrations were analyzed from 1 November (1 Nov) to 7 November (7 Nov) 2005 in Tianjin, China. During this period, the aerosol concentration had a strong day-by-day variation, ranging from 0.2 to 0.6 mg m⁻³. The ozone concentration also shows a strong variability in correlation with the aerosol concentration. During 1 Nov, 2 Nov, 6 Nov, and 7 Nov, the ozone concentration was relatively high (about 30–35 ppbv; defined as a high-ozone period), and during 3 Nov to 5 Nov, the ozone concentration was relatively low (about 5–20 ppbv; defined as a low-ozone period). The analysis of the measurement shows that the ozone concentration is strongly correlated to the measured UV flux. Because there were near cloud-free conditions between 1 Nov and 7 Nov, the variation of the UV flux mainly resulted from the variation of aerosol concentration. The result shows that higher aerosol concentrations produce a lower UV flux and lower ozone concentrations. By contrast, the lower aerosol concentration leads to a higher UV flux and higher ozone concentrations. A chemical mechanism model (NCAR MM) is applied to interpret the measurement. The model result shows that the extremely high aerosol concentration in this polluted city has a very strong impact on photochemical activities and ozone formation. The correlation between aerosol and ozone concentrations appears in a non-linear feature. The O₃ concentration is very sensitive to aerosol loading when aerosol loading is high, and this sensitivity is reduced when aerosol loading is low. For example, the ratio of Δ[O₃]/Δ[AOD] is about −16 ppbv AOD⁻¹ when AOD is less than 2, and is only −4 ppbv AOD⁻¹ when AOD is between 2 and 5. This result implies that a future decrease in aerosol loading could lead to a rapid increase in the O₃ concentration in this region.     

Aircraft measurements of O3, NOx,CO, VOCs,and SO2 in the Yangtze River Delta region

In this study, air pollutants, including ozone (O₃), nitrogen oxides (NO_x = NO + NO₂), carbon monoxides (CO), sulfur dioxide (SO₂), and volatile organic compounds (VOCs) measured in the Yangtze River Delta (YRD) region during several air flights between September/30 and October/11 are analyzed. This measurement provides horizontal and vertical distributions of air pollutants in the YRD region. The analysis of the result shows that the measured O₃ concentrations range from 20 to 60 ppbv. These values are generally below the US national standard (84 ppbv), suggesting that at the present, the O₃ pollutions are modest in this region. The NO_x concentrations have strong spatial and temporal variations, ranging from 3 to 40 ppbv. The SO₂ concentrations also have large spatial and temporal variations, ranging from 1 to 35 ppbv. The high concentrations of CO are measured with small variations, ranging from 3 to 7 ppmv. The concentrations of VOCs are relatively low, with the total VOC concentrations of less than 6 ppbv. The relative small VOC concentrations and the relative large NO_x concentrations suggest that the O₃ chemical formation is under a strong VOC-limited regime in the YRD region. The measured O₃ and NO_x concentrations are strongly anti-correlated, indicating that enhancement in NO_x concentrations leads to decrease in O₃ concentrations. Moreover, the O₃ concentrations are more sensitive to NO_x concentrations in the rural region than in the city region. The ratios of Δ[O₃]/Δ[NO_x] are ?2.3 and ?0.25 in the rural and in the city region, respectively. In addition, the measured NO_x and SO₂ concentrations are strongly correlated, highlighting that the NO_x and SO₂ are probably originated from same emission sources. Because SO₂ emissions are significantly originated from coal burnings, the strong correlation between SO₂ and NO_x concentrations suggests that the NO_x emission sources are mostly from coal burned sources. As a result, the future automobile increases could lead to rapid enhancements in O₃ concentrations in the YRD region.     

Analysis of ozone and VOCs measured in Shanghai: A case study

Shanghai Meteorological Administration has established a volatile organic compounds (VOCs) laboratory and an observational network for VOCs and ozone (O₃) measurements in the city of Shanghai. In this study, the measured VOCs and O₃ concentrations from 15 November (15-Nov) to 26 November (26-Nov) of 2005 in Shanghai show that there are strong day-to-day and diurnal variations. The measured O₃ and VOCs concentrations have very different characterizations between the two periods. During 15-Nov to 21-Nov (defined as the first period), VOCs and O₃ concentrations are lower than the values during 22-Nov to 28-Nov (defined as the second period). There is a strong diurnal variation of O₃ during the second period with maximum concentrations of 40–80 ppbv at noontime, and minimum concentrations at nighttime. By contrast, during the first period, the diurnal variation of O₃ is in an irregular pattern with maximum concentrations of only 20–30 ppbv. The VOC concentrations change rapidly from 30–50 ppbv during the first period to 80–100 ppbv during the second period. Two chemical models are applied to interpret the measurements. One model is a regional chemical/dynamical model (WRF-Chem) and another is a detailed chemical mechanism model (NCAR MM). Model analysis shows that the meteorological conditions are very different between the two periods, and are mainly responsible for the different chemical characterizations of O₃ and VOCs between the two periods. During the first period, meteorological conditions are characterized by cloudy sky and high-surface winds in Shanghai, resulting in a higher nighttime planetary boundary layer (PBL) and faster transport of air pollutants. By contrast, during the second period, the meteorological conditions are characterized by clear sky and weak surface winds, resulting in a lower nighttime PBL and slower transport of air pollutants. The chemical mechanism model calculation shows that different VOC species has very different contributions to the high-ozone concentrations during the second period. Alkane (40 ppbv) and aromatic (30 ppbv) are among the highest VOC concentrations observed in Shanghai. The analysis suggests that the aromatic is a main contributor for the O₃ chemical production in Shanghai, with approximately 79% of the O₃ being produced by aromatic. This analysis implies that future increase in VOC (especially aromatic) emissions could lead to significant increase in O₃ concentrations in Shanghai.     

The evolution of photochemical smog in a power plant plume

The evolution of photochemical smog in a plant plume was investigated with the aid of an instrumented helicopter. Air samples were taken in the plume of the Cumberland Power Plant, located in central Tennessee, during the afternoon of 16 July 1995 as part of the Southern Oxidants Study – Nashville Middle Tennessee Ozone Study. Twelve cross-wind air sampling traverses were made at six distance groups from 35 to 116 km from the source. During the sampling period the winds were from the west–northwest and the plume drifted towards the city of Nashville TN. Ten of the traverses were made upwind of the city, where the power plant plume was isolated, and two traverses downwind of the city when the plumes were possibly mixed. The results revealed that even six hours after the release, excess ozone production was limited to the edges of the plume. Only when the plume was sufficiently dispersed, but still upwind of Nashville, was excess ozone (up to 109 ppbv, 50–60 ppbv above background levels) produced in the center of the plume. The concentrations image of the plume and a Lagrangian particle model suggests that portions of the power plant plume mixed with the urban plume. The mixed urban power plant plume began to regenerate O₃ that peaked at 120 ppbv at a short distance (15–25 km) downwind of Nashville. Ozone productivity (the ratio of excess O₃ to NO_y and NO_z) in the isolated plume was significantly lower compared with that found in the city plume. The production of nitrate, a chain termination product, was significantly higher in the power plant plume compared to the mixed plume, indicating shorter chain length of the photochemical smog chain reaction mechanism.     

FT-IR product study of the OH-initiated oxidation of DMS in the presence of NOx

The influence of NO_x (NO+NO₂) concentrations on the product distribution of the OH-initiated oxidation of DMS has been studied at room temperature using total NO_x concentrations varying from 0 to ∼1800 ppbv (30–600 ppbv NO₂ and 140–1760 ppbv NO). Clear trends in the formation yields of the products SO₂, COS, MSA, MTF (methyl thiolformate), MSPN (methanesulphonyl peroxynitrate), DMSO and DMSO₂ have been observed with variation in NO_x. The presence of low levels of NO reduces the yields of both MTF and COS to zero. The formation yields of MSA and DMSO₂ increase with increasing NO_x concentration, whereas the yields of DMSO and SO₂ decrease. The following approximate changes in the yield, not corrected for possible loss processes, have been measured for variation of NO_x between 0 and ∼1800 ppbv: DMSO decreases from 20 to 3%S; DMSO₂ increases from 3 to 15%S, SO₂ decreases from 70 to 30%S and MSA increases from 4 to 17%S. Under the experiments conditions NO_x levels of several tens of ppbv are required before a perceptible change is observed in the MSA yield. If applicable to the atmosphere such a situation is only likely to be observed near coastal areas affected by pollution. MSPN (CH₃SO₂O₂NO₂) is observed as an oxidation product in the presence of NO₂ even at low levels (e.g. 60 ppbv). Its possible role as a NO_x reservoir in the troposphere is considered.     

Measurement and analysis of atmospheric concentrations of isoprene and its reaction products in central Texas

A field experiment was conducted in August 1998 to investigate the concentrations of isoprene and isoprene reaction products in the surface and mixed layers of the atmosphere in Central Texas. Measured near ground-level concentrations of isoprene ranged from 0.3 (lower limit of detection – LLD) to 10.2 ppbv in rural regions and from 0.3 to 6.0 ppbv in the Austin urban area. Rural ambient formaldehyde levels ranged from 0.4 ppbv (LLD) to 20.0 ppbv for 160 rural samples collected, while the observed range was smaller at Austin (0.4–3.4 ppbv) for a smaller set of samples (37 urban samples collected). Methacrolein levels did not vary as widely, with rural measurements from 0.1 ppbv (LLD) to 3.7 ppbv and urban concentrations varying between 0.2 and 5.7 ppbv. Isoprene flux measurements, calculated using a simple box model and measured mixed-layer isoprene concentrations, were in reasonable agreement with emission estimates based on local ground cover data. Ozone formation attributable to biogenic hydrocarbon oxidation was also calculated. The calculations indicated that if the ozone formation occurred at low VOC/NO_x ratios, up to 20 ppbv of ozone formed could be attributable to biogenic photooxidation. In contrast, if the biogenic hydrocarbon reaction products were formed under low NO_x conditions, ozone production attributable to biogenics oxidation would be as low as 1 ppbv. This variability in ozone formation potentials implies that biogenic emissions in rural areas will not lead to peak ozone levels in the absence of transport of NO_x from urban centers or large rural NO_x sources.     

An analysis on abnormally low ozone in the upper troposphere over subtropical East Asia in spring 2004

Abnormally low ozone (O₃) mixing ratios were observed by electrochemical concentration cell (ECC) ozonesondes in the upper troposphere over subtropical East Asia in spring 2004, a season when high tropospheric O₃ is usually observed in the region. Low O₃ with a lowest mixing ratio of 13 ppbv, less than a fourth of the respective seasonal average of 60–100 ppbv, was observed at 11–18 km above ground over Hong Kong (22.31°N, 114.17°E), Sanya (18.23°N, 109.52°E) and Taipei (24.98°N, 121.43°E). The origin of the low O₃ was investigated using meteorological evidence, satellite imagery and three-dimensional backward air trajectory. We found for the first time that the low O₃ resulted from deep convective pumping of low O₃ maritime air masses near the center of typhoon Sudal from the boundary layer of the tropical region to the east of the Philippines to the upper troposphere. The low O₃ air masses were then transported to the higher latitudes far ahead of the typhoon following the long-range transport driven by the circulations associated with the typhoon and the northern Hadley cell. The findings of this study highlight that more research efforts are needed to understand the effect of the circulation associated with tropical cyclones on the distribution and budget of O₃ and other trace gases in the troposphere.     

OH and HO2 radical chemistry in a forested region of north-western Greece

This paper explores several aspects of the chemistry of a forested region in north-western Greece, from data collected during the AEROBIC97 campaign. An observationally constrained box model has been constructed to enable comparisons between modelled concentrations of OH and HO₂ and those determined by the fluorescence assay by gas expansion (FAGE) technique. These results represent the first comparison of measured and modelled OH concentrations in such an environment. The modelled OH concentrations are, on average,∼50% of those measured (range of 16–61%) over 4 days of model and measurement comparison. Possible reasons for the model-measurement discrepancy are discussed. A rate of production analysis illustrates the dominance of isoprene and the monoterpenes on OH loss, as well as the significance of the ozonolysis of biogenic species as an OH source. The measured and modelled [HO₂]/[OH] ratio averaged between 11:00 and 15:00 h is much higher than has been found previously for similar NO_x concentrations,∼75 and 340, respectively, cf. 10–20. The high ratio reflects the rapid recycling through the OH–HO₂ oxidation chain, involving biogenic species. The high biogenic concentrations result in a midday OH lifetime of∼0.15 s. Finally, for the conditions encountered during the campaign, there is high net photochemical ozone production, peaking at∼20 ppbv h⁻¹ around 09:00 h.     

Seasonal variations in VOC emission rates from gorse (Ulex europaeus)

Seasonal variations of biogenic volatile organic compound (VOC) emission rates and standardised emission factors from gorse (Ulex europaeus) have been measured at two sites in the United Kingdom, from October 1994 to September 1995, within temperature and PAR conditions ranging from 3 to 34°C and 10–1300 μmol m⁻² s⁻¹, respectively. Isoprene was the dominant emitted compound with a relative composition fluctuating from 7% of the total VOC (winter) to 97% (late summer). The monoterpenes α-pinene, camphene, sabinene, β-pinene, myrcene, limonene, trans-ocimene and γ-terpinene were also emitted, with α-pinene being the dominant monoterpene during most the year. Trans-ocimene represented 33–66% of the total monoterpene during the hottest months from June to September. VOC emissions were found to be accurately predicted using existing algorithms. Standard (normalised) emission factors of VOCs from gorse were calculated using experimental parameters measured during the experiment and found to fluctuate with season, from 13.3±2.1 to 0.1±0.1 μg C (g dwt)⁻¹ h⁻¹ in August 1995 and January 1995, respectively, for isoprene, and from 2.5±0.2 to 0.4±0.2 μg C (g dwt)⁻¹ h⁻¹ in July and November 1995, respectively, for total monoterpenes. No simple clear relation was found to allow prediction of these seasonal variations with respect to temperature and light intensity. The effects of using inappropriate algorithms to derive VOC fluxes from gorse were assessed for isoprene and monoterpenes. Although on an annual basis the discrepancies are not significant, monthly estimation of isoprene were found to be overestimated by more than a factor of 50 during wintertime when the seasonality of emission factors is not considered.     

Atmospheric alcohols and aldehydes concentrations measured in Osaka,Japan and in Sao Paulo,Brazil

The use of alcohol fuel has received much attention since 1980s. In Brazil, ethanol-fueled vehicles have been currently used on a large scale. This paper reports the atmospheric methanol, ethanol and isopropanol concentrations which were measured from May to December 1997, in Osaka, Japan, where alcohol fuel was not used, and from 3 to 9 February 1998, in Sao Paulo, Brazil, where ethanol fuel was used. The alcohols were determined by the alkyl nitrite formation reaction using gas chromatography (GC-ECD) analysis. The concentration of atmospheric alcohols, especially ethanol, measured in Sao Paulo were significantly higher than those in Osaka. In Osaka, the average concentrations of atmospheric methanol, ethanol, and isopropanol were 5.8±3.8, 8.2±4.6, and 7.2±5.9 ppbv, respectively. The average ambient levels of methanol, ethanol, and isopropanol measured in Sao Paulo were 34.1±9.2, 176.3.±38.1, and 44.2±13.7 ppbv, respectively. The ambient levels of aldehydes, which were expected to be high due to the use of alcohol fuel, were also measured at these sampling sites. The atmospheric formaldehyde average concentration measured in Osaka was 1.9±0.9 ppbv, and the average acetaldehyde concentration was 1.5±0.8 ppbv. The atmospheric formaldehyde and acetaldehyde average concentrations measured in Sao Paulo were 5.0±2.8 and 5.4±2.8 ppbv, respectively. The C₂H₅OH/CH₃OH and CH₃CHO/HCHO were compared between the two measurement sites and elsewhere in the world, which have already been reported in the literature. Due to the use of ethanol-fueled vehicles, these ratios, especially C₂H₅OH/CH₃OH, are much higher in Brazil than these measured elsewhere in the world.     

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.     

Nitrogen oxide fluxes between corn (Zea mays L.) leaves and the atmosphere

In the United States, fertilized corn fields, which make up approximately 5% of the total land area, account for approximately 45% of total soil NO_x emissions. Leaf chamber measurements were conducted of NO and NO₂ fluxes between individual corn leaves and the atmosphere in (1) field-grown plants near Champaign, IL (USA) in order to assess the potential role of corn canopies in mitigating soil–NO_x emissions to the atmosphere, and (2) greenhouse-grown plants in order to study the influence of various environmental variables and physiological factors on the dynamics of NO₂ flux. In field-grown plants, fluxes of NO were small and inconsistent from plant to plant. At ambient NO concentrations between 0.1 and 0.3 ppbv, average fluxes were zero. At ambient NO concentrations above 1 ppbv, NO uptake occurred, but fluxes were so small (14.3±0.0 pmol m⁻² s⁻¹) as to be insignificant in the NO_x inventory for this site. In field-grown plants, NO₂ was emitted to the atmosphere at ambient NO₂ concentrations below 0.9 ppbv (the NO₂ compensation point), with the highest rate of emission being 50 pmol m⁻² s⁻¹ at 0.2 ppbv. NO₂ was assimilated by corn leaves at ambient NO₂ concentrations above 0.9 ppbv, with the maximum observed uptake rate being 643 pmol m⁻² s⁻¹ at 6 ppbv. When fluxes above 0.9 ppbv are standardized for ambient NO₂ concentration, the resultant deposition velocity was 1.2±0.1 mm s⁻¹. When scaled to the entire corn canopy, NO₂ uptake rates can be estimated to be as much as 27% of the soil-emitted NO_x. In greenhouse-grown and field-grown leaves, NO₂ deposition velocity was dependent on incident photosynthetic photon flux density (PPFD; 400–700 nm), whether measured above or below the NO₂ compensation point. The shape of the PPFD dependence, and its response to ambient humidity in an experiment with greenhouse-grown plants, led to the conclusion that stomatal conductance is a primary determinant of the PPFD response. However, in field-grown leaves, measured NO₂ deposition velocities were always lower than those predicted by a model solely dependent on stomatal conductance. It is concluded that NO₂ uptake rate is highest when N availability is highest, not when the leaf deficit for N is highest. It is also concluded that the primary limitations to leaf-level NO₂ uptake concern both stomatal and mesophyll components.