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.     

Gas-phase chemistry of benzyl alcohol: Reaction rate constants and products with OH radical and ozone

A bimolecular rate constant, k_{OH+Benzyl alcohol}, of (28 ± 7) × 10^?12 cm³ molecule^?1 s^?1 was measured using the relative rate technique for the reaction of the hydroxyl radical (OH) with benzyl alcohol, at (297 ± 3) K and 1 atm total pressure. Additionally, an upper limit of the bimolecular rate constant, k_{O3+Benzyl alcohol}, of approximately 6 × 10^?19 cm³ molecule^?1 s^?1 was determined by monitoring the decrease in benzyl alcohol concentration over time in an excess of ozone (O₃). To more clearly define part of benzyl alcohol's indoor environment degradation mechanism, the products of the benzyl alcohol + OH were also investigated. The derivatizing agents O-(2,3,4,5,6-pentafluorobenzyl)hydroxylamine (PFBHA) and N,O-bis(trimethylsilyl) trifluoroacetamide (BSTFA) were used to positively identify benzaldehyde, glyoxal and 4-oxopentanal as benzyl alcohol/OH reaction products. The elucidation of other reaction products was facilitated by mass spectrometry of the derivatized reaction products coupled with plausible benzyl alcohol/OH reaction mechanisms based on previously published volatile organic compound/OH gas-phase reaction mechanisms.     

Rate constant for the reaction of ozone with diethyl sulfide

The rate constant for the reaction of diethyl sulfide (DES; C₂H₅SC₂H₅) with ozone was determined for the first time, which was (2.77±0.27)×10⁻¹⁹ cm³ molecule⁻¹ s⁻¹ under a room temperature of (289±1) K. Experiments were conducted under supposedly pseudo-first-order decay conditions, keeping [DES]₀>50[O₃]₀, but having different combinations of [DES]₀ and [O₃]₀. Cyclohexane was added into the reactor to eliminate the effect of OH radicals. The wall decay of ozone and the role of cyclohexane were also discussed in the present work.     

Vegetation exposure to ozone over the continental United States: Assessment of exposure indices by the Eta-CMAQ air quality forecast model

The main use of air quality forecast (AQF) models is to predict ozone (O₃) exceedances of the primary O₃ standard for informing the public of potential health concerns. This study presents the first evaluation of the performance of the Eta-CMAQ air quality forecast model to predict a variety of widely used seasonal mean and cumulative O₃ exposure indices associated with vegetation using the U.S. AIRNow O₃ observations. These exposure indices include two concentration-based O₃ indices, M7 and M12 (the seasonal means of daytime 7-h and 12-h O₃ concentrations, respectively), and three cumulative exposure-based indices, SUM06 (the sum of all hourly O₃ concentrations ≥ 0.06 ppm), W126 (hourly concentrations weighed by a sigmoidal weighting function), and AOT40 (O₃ concentrations accumulated over a threshold of 40 ppb during daylight hours). During a three-month simulation (July–September 2005), the model over predicted the M7 and M12 values by 8–9 ppb, or a NMB value of 19% and a NME value of 21%. The model predicts a central belt of high O₃ extending from Southern California to Middle Atlantic where the seasonal means, M7 and M12 (the seasonal means of daytime 7-h and 12-h O₃ concentrations), are higher than 50 ppbv. In contrast, the model is less capable of reproducing the observed cumulative indices. For AOT40, SUM06 and W126, the NMB and NME values are two- to three-fold of that for M7, M12 or peak 8-h O₃ concentrations. The AOT40 values range from 2 to 33 ppm h by the model and from 1 to 40 ppm h by the monitors. There is a significantly higher AOT40 value experienced in the United States in comparison to Europe. The domain-wide mean SUM06 value is 14.4 ppm h, which is about 30% higher than W126, and 40% higher than AOT40 calculated from the same 3-month hourly O₃ data. This suggests that SUM06 and W126 represent a more stringent standard than AOT40 if either the SUM06 or the W126 was used as a secondary O₃ standard. Although CMAQ considerably over predicts SUM06 and W126 values at the low end, the model under predicts the extreme high exposure values (>50 ppm h). Most of these extreme high values are found at inland California sites. Based on our analysis, further improvement of the model is needed to better capture cumulative exposure indices.     

The rate and mechanism of the gas-phase oxidation of hydroxyacetone

The rate and mechanism for gas-phase destruction of hydroxyacetone, CH₃C(O)CH₂OH, by reaction with OH, Cl-atoms, and by photolysis have been determined. The first quantitative UV absorption spectrum of hydroxyacetone is reported over the wavelength range 235 to 340 nm; the spectrum is blue-shifted by about 15 nm relative to that of acetone and peaks at 266 nm, with a maximum absorption cross section of (6.7±0.6) ×10^-20 cm² molecule^-1. Measurable absorption extends out to about 330 nm. The quantum yield for photolysis of hydroxyacetone in the region relevant to the troposphere (λ>290 nm) was found to be significantly less than unity. Rate coefficients for the reaction of hydroxyacetone with OH radicals and Cl-atoms were determined at 298 K using the relative rate technique. The rate coefficient for reaction with OH was found to be (3.0±0.7)×10^-12 cm³ molecule^-1 s^-1, while the rate coefficient for reaction with Cl-atoms was found to be (5.6±0.7)×10^-11 cm³ molecule^-1 s^-1. Both values agree well with previous studies. The data were used to determine the lifetime of hydroxyacetone in the troposphere. Reaction with OH is the major gas-phase destruction mechanism for this compound, limiting its lifetime to about 4 days, while photolysis is found to be only of minor importance.     

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.     

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.     

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.     

Surface ozone-temperature relationships in the eastern US: A monthly climatology for evaluating chemistry-climate models

We use long-term, coincident O₃ and temperature measurements at the regionally representative US Environmental Protection Agency Clean Air Status and Trends Network (CASTNet) over the eastern US from 1988 through 2009 to characterize the surface O₃ response to year-to-year fluctuations in weather, for the purpose of evaluating global chemistry-climate models. We first produce a monthly climatology for each site over all available years, defined as the slope of the best-fit line (m_O3-T) between monthly average values of maximum daily 8-hour average (MDA8) O₃ and monthly average values of daily maximum surface temperature (T_max). Applying two distinct statistical approaches to aggregate the site-specific measurements to the regional scale, we find that summer time m_O3-T is 3–6 ppb K^?1 (r = 0.5–0.8) over the Northeast, 3–4 ppb K^?1 (r = 0.5–0.9) over the Great Lakes, and 3–6 ppb K^?1 (r = 0.2–0.8) over the Mid-Atlantic. The Geophysical Fluid Dynamics Laboratory (GFDL) Atmospheric Model version 3 (AM3) global chemistry-climate model generally captures the seasonal variations in correlation coefficients and m_O3-T despite biases in both monthly mean summertime MDA8 O₃ (up to +10 to +30 ppb) and daily T_max (up to +5 K) over the eastern US. During summer, GFDL AM3 reproduces m_O3-T over the Northeast (m_O3-T = 2–6 ppb K^?1; r = 0.6–0.9), but underestimates m_O3-T by 4 ppb K^?1 over the Mid-Atlantic, in part due to excessively warm temperatures above which O₃ production saturates in the model. Combining T_max biases in GFDL AM3 with an observation-based m_O3-T estimate of 3 ppb K^?1implies that temperature biases could explain up to 5–15 ppb of the MDA8 O₃ bias in August and September though correcting for excessively cool temperatures would worsen the O₃ bias in June. We underscore the need for long-term, coincident measurements of air pollution and meteorological variables to develop process-level constraints for evaluating chemistry-climate models used to project air quality responses to climate change.     

Extent of H-atom abstraction from OH + p-cymene and upper limits to the formation of cresols from OH + m-xylene and OH + p-cymene

Aromatic hydrocarbons are important constituents of vehicle exhaust and of non-methane volatile organic compounds in ambient air in urban areas. It has recently been proposed that dealkylation is a significant pathway for the OH radical-initiated reactions, leading to the formation of phenolic compounds and/or oxepins (Noda, J., Volkamer, R., Molina, M.J., 2009. Dealkylation of alkylbenzenes: a significant pathway in the toluene, o-, m-, and p-xylene + OH reaction. Journal of Physical Chemistry A 113, 9658–9666.). We have investigated the formation of cresols from the reactions of OH radicals with m-xylene and p-cymene, and obtain upper limits of <1% for formation of each cresol isomer from OH + m-xylene and <2% for formation of each cresol isomer from OH + p-cymene. In addition, we have measured the formation yield of 4-methylacetophenone (the major product formed subsequent to H-atom abstraction from the CH(CH₃)₂ group) in the OH + p-cymene reaction to be 14.8 ± 3.2%, and estimate that H-atom abstraction from the CH₃ and CH(CH₃)₂ groups in p-cymene accounts for 20 ± 4% of the overall OH radical reaction. We also used a relative rate technique to measure the rate constant for the reaction of OH radicals with 4-methylacetophenone to be (4.50 ± 0.43) × 10^?12 cm³ molecule^?1 s^?1 at 297 ± 2 K.     

Tropical tropospheric ozone observed in Thailand

The mixing ratios of surface ozone at two rural/remote sites in Thailand, Inthanon and Srinakarin, have been measured continuously for the first time. Almost identical seasonal variations of O₃ with dry season maximum and a wet season minimum with a large seasonal amplitude are observed at both sites during 1996–1998. At Inthanon, the monthly averaged O₃ mixing ratios range 9–55 ppb, with the annual average of 27 ppb. The ozone mixing ratios at Srinakarin are in the similar range, 9–45 ppb with annual average of 28 ppb. Based on trajectory analysis of O₃ data at Inthanon, the long-range transport of O₃ under Asian monsoon regime could primarily explain the low O₃ mixing ratios of 13 ppb in clean marine air mass from Indian Ocean during wet season but only partly explain the relatively low O₃ mixing ratios, 26 ppb or less, in continental air mass from northeast Asia either in wet or dry season. The highest O₃ mixing ratios are found in air masses transported within southeast Asia, averaged 46 ppb in dry season. The high O₃ mixing ratios during the dry season are suggested to be significantly due to the local/sub-regional scale O₃ production triggered by biomass burning in southeast Asia rather than long-range transport effect.     

Production and removal of aerosol in a polluted fog layer: model evaluation and fog effect on PM

A radiation fog physics, gas- and aqueous-phase chemistry model is evaluated against measurements in three sites in the San Joaquin Valley of California (SJV) during the winter of 1995. The measurements include for the first time vertically resolved fog chemical composition measurements. Overall the model is successful in reproducing the fog dynamics as well as the temporal and spatial variability of the fog composition (pH, sulfate, nitrate, and ammonium concentrations) in the area. Sulfate production in the fog layer is relatively slow (1–4 μg m⁻³ per fog episode) compared to the episodes in the early 1980s because of the low SO₂ concentrations in the area and the lack of oxidants inside the fog layer. Sulfate production inside the fog layer is limited by the availability of oxidants in the urban areas of the valley and by SO₂ in the more remote areas. Nitrate is produced in the rural areas of the valley by the heterogeneous reaction of N₂O₅ on fog droplets, but this reaction is of secondary importance for the more polluted urban areas. The gas-phase production of HNO₃ during the daytime is sufficient to balance the nitrate removed during the nighttime fog episodes. Entrainment of air from the layer above the fog provides another source of reactants for the fog layer. Wet removal is one of most important processes inside the fog layer in SJV. We estimate based on the three episodes investigated during IMS95 that a typical fog episode removes 500–2000 μg m⁻² of sulfate, 2500–6500 μg m⁻² of nitrate, and 2000–3500 μg m⁻² of ammonium. For the winter SJV valley the net fog effect corresponds to reductions in ground ambient concentrations of 0.05–0.2 μg m⁻³ for sulfate, 3–6 μg m⁻³ for total nitrate, and 1–3 μg m⁻³ for total ammonium.     

In situ measurements of volatile aromatic hydrocarbon biodegradation rates in groundwater

Benzene and alkylbenzene biodegradation rates and patterns were measured using an in situ microcosm in a crude-oil contaminated aquifer near Bemidji, Minnesota. Benzene-D6, toluene, ethylbenzene, o-, m- and p-xylenes and four pairs of C₃- and C₄-benzenes were added to an in situ microcosm and studied over a 3-year period. The microcosm allowed for a mass-balance approach and quantification of hydrocarbon biodegradation rates within a well-defined iron-reducing zone of the anoxic plume. Among the BTEX compounds, the apparent order of persistence is ethylbenzene > benzene > m,p-xylenes > o-xylene ≥ toluene. Threshold concentrations were observed for several compounds in the in situ microcosm, below which degradation was not observed, even after hundreds of days. In addition, long lag times were observed before the onset of degradation of benzene or ethylbenzene. The isomer-specific degradation patterns were compared to observations from a multi-year study conducted using data collected from monitoring wells along a flowpath in the contaminant plume. The data were fit with both first-order and Michaelis-Menten models. First-order kinetics provided a good fit for hydrocarbons with starting concentrations below 1 mg/L and Michaelis-Menten kinetics were a better fit when starting concentrations were above 1 mg/L, as was the case for benzene. The biodegradation rate data from this study were also compared to rates from other investigations reported in the literature.     

Study of aluminium distribution and speciation in atmospheric particles of different diameters in Nanjing,China

Aluminium (Al) is one of the trace inorganic metals present in atmospheric particles. Al speciation study is essential to better evaluate the mobility, availability, and persistence of trace Al and Al species in the atmosphere. This paper reports Al distribution and speciation in atmospheric particles with aerodynamic diameters >10.0, 10.0–2.5 and <2.5 μm in the urban area of Nanjing, China. Urban particles were collected with a high-volume sampling system equipped with a cascade impactor, which effectively separates the particulate matter into three size ranges. Particulate Al was fractionated into five different forms (insoluble, oxide, organic, carbonate, and exchangeable species) by the modified five-step Tessier's sequential extraction procedure. The main points are as follows: (1) The average levels of Al in PM_2.5, PM_2.5–10 and PM_>10 are 2.02±0.35, 3.04±0.43 and 6.32±0.76 μg m⁻³, respectively, with PM_2.5, PM_2.5–10 and PM_>10 constituting respectively, 17.8±3.1%, 26.7±3.8% and 55.5±6.7% of suspended particulate matter (SPM) mass (11.38 μg m⁻³). (2) The vertical profile of airborne Al in the above three size fractions has been estimated. A significant increase in airborne Al concentrations was found for PM_2.5, PM_2.5–10 and PM_>10 as the sampling height above the ground increased from 2.5 to 17.5 m; however, there was an obvious decrease in airborne Al concentrations between 17.5 and 40.0 m. The maximum mean of total Al in PM_2.5, PM_2.5–10 and PM_>10 occurred between 12.5 and 20.0 m above the ground. (3) The distribution of Al speciation was studied. It was found that the size distribution of airborne Al species followed the order: insoluble species>oxide species>organic species>carbonate species>exchangeable species.     

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.     

Pollution events over the East Mediterranean: Synergistic use of GOME,ground-based and sonde observations and models

The behaviour of ozone (O₃) and two important precursors, nitrogen dioxide (NO₂) and formaldehyde (HCHO), over the East Mediterranean in spring from 1996 to 2002 is studied in order to characterise the buildup of tropospheric O₃. The vertical distribution of O₃ observed over Crete during the Photochemical Activity and Solar Ultraviolet Radiation (PAUR II) campaign in May 1999 has been used for validation of satellite-derived data. Retrievals of O₃ columns from measurements of backscattered radiation by Global Ozone Monitoring Experiment (GOME) are compared with Total Ozone Mapping Spectrometer (TOMS), balloon, Systeme d’Analyse par Observation Zenithale (SAOZ) and LIDAR observations. The total O₃ vertical columns vary between 270 and 402 DU and correlate well with changes in air circulation patterns. The total observed variability in tropospheric O₃ is about 25 DU. Chemical box model calculations associate the GOME-observed NO₂ and HCHO tropospheric columns with a potential of daily photochemical enhancement in the tropospheric O₃ columns of about 0.8–1 DU over Crete and estimate the daily potential of regional photochemical buildup within upwind polluted air masses at about 2–8 DU. A Langrangian analysis attributes at most 10–20 DU of tropospheric O₃ to stratosphere–troposphere exchange (STE). The remainder is attributed to long-range transport of O₃ from industrial regions in Central Europe. From 1996 to 2002, in May no significant inter-annual variation in the tropospheric NO₂ and HCHO columns over Crete has been observed by GOME suggesting no detectable increase in regionally produced tropospheric O₃.     

Influence of water quality parameters on occurrence of polybrominated diphenyl ether in sediment and sediment to biota accumulation

Polybrominated diphenyl ether (PBDE) concentrations in sediment and fish from 12 principal rivers in Taiwan were investigated to determine their association with water quality parameters as well as the biota-sediment accumulation factor (BSAF) in fish with different living patterns. The highest PBDE concentration in sediment was found in the Bajhang River (261 ng g^?1 dry weight (d.w.)) and the lowest in the Beinan River and the Da-an River (0.17 ng g^?1 d.w.). The PBDE concentrations in fish samples ranged from 1.28 ng g^?1 d.w. (Oreochromis niloticus niloticus) in the Yanshuei River to 33.7 ng g^?1 d.w. (Varico rhinos barbatulus) in the Da-an River. We conclude that PBDEs contamination in sediment was significantly affected by NH₃–N, pH, and DO. The BSAF results showed a parabolic trend from low- to high-brominated BDEs. Fish easily accumulated the congeners BDE-47, -100, -119, -126, and -154 from sediment. The BSAF decreased in the following order: PeBDE > HxBDE > TeBDE > other BDEs. Principle component analysis showed that demersal fish have different PBDE sources than do pelagic fish. We conclude that living and feeding habits are critical factors affecting PBDE accumulation in fish.     

Recreational atmospheric pollution episodes: Inhalable metalliferous particles from firework displays

The use of fireworks creates an unusual and distinctive anthropogenic atmospheric pollution event. We report on aerosol samples collected during Las Fallas in Valencia, a 6-day celebration famous for its firework displays, and add comparative data on firework- and bonfire-contaminated atmospheric aerosol samples collected from elsewhere in Spain (Barcelona, L’Alcora, and Borriana) and during the Guy Fawkes celebrations in London. Specific high-profile official firework events during Las Fallas included the afternoon Mascletà and the nightly aerial displays (especially in the climactic final 2 days of the fiesta) and were accompanied by pollution spikes in suspended particles, NO, SO₂, and the creation and dispersal of an aerosol cloud enriched in a range of metallic elements. Notable metal aerosol concentration increases recorded during Las Fallas were potassium (from 500 to 5900 ng m⁻³), aluminium (as Al₂O₃ from around 600 to 2200 ng m⁻³), titanium (from 200 to 700 ng m⁻³), magnesium (from 100 to 500 ng m⁻³), lead (from 17 to 379 ng m⁻³), barium (from 39 to 322 ng m⁻³), strontium (from 3 to 112 ng m⁻³), copper (from 12 to 71 ng m⁻³), and antimony (from 1 to 52 ng m⁻³). Firework-contaminated aerosols of similarly metalliferous composition were also identified at the other monitoring sites, although different sites show variations attributable to other sources such as bonfires and local industry. Unusual levels of the trace elements Ba, Sr and (to a lesser extent) Cu, always in proportions with Ba dominant, along with strongly enhanced K, Pb, and Sb, are identified as being particularly characteristic of firework aerosols. Although firework-related recreational pollution episodes are transient in nature, they are highly concentrated, contribute significantly to total annual metal emissions, and are on average fine enough to be easily inhaled and a health risk to susceptible individuals.     

The impact of an 8 h ozone air quality standard on ROG and NOx controls in Southern California

The new National Ambient Air Quality Standard for ozone in the US uses 8 h averaging for the concentration. Based on the 1993 ambient data for Southern California, 8 h averaging has a moderate tendency to move the location of the peak ozone concentration east of the location of the peak 1 h ozone concentration. Reducing the area-wide peak 8 h ozone concentration to 80 ppb would require an effective reduction of the area-wide peak 1 h ozone concentration to around 90 ppb. The Urban Airshed Model with improved numerical solvers, meteorological input based on a mesoscale model and an adjusted emissions inventory was used to study the effect of reactive organic gases (ROG) and NO_x controls on daily-maximum and peak 8 h ozone concentrations under the 26–28 August 1987 ozone episodic conditions in Southern California. The NO_x disbenefit remains prominent for the case of 8 h ozone concentration but is somewhat less prominent, especially when areal ozone exposure is considered, than the case for 1 h ozone concentration. The role of two indicators – O₃/NO_y and H₂O₂/HNO₃ – for NO_x- and ROG-sensitivity for 1 and 8 h ozone concentrations were also studied. In general, the indicator trends are consistent with model predictions, but the discriminating power of the indicators is rather limited.     

Biogenic nitric oxide from wastewater land application

The importance of municipal wastewater land application to nitric oxide production and transport in soil was studied through the formulation and conduct of a comprehensive laboratory testing protocol. Nitric oxide (NO) is a precursor in the formation of tropospheric ozone which can directly impact public health and the environment. It is the uncertainty in the NO budget, and its relation to O₃, that motivates the need for measurements and modeling of NO flux from soils. Wastewater-amended soil is potentially one important component of that budget. NO emissions reported here were measured from: a well-characterized unamended soil, water-amended soil, and wastewater-amended soil in the laboratory in a dynamic test chamber. Laboratory results indicate that NO emissions from the selected sandy loam soil ranged from 0.3 to 0.4 ng N m^-2 s^-1 per cm² of unamended soil, while water-amended soil emissions ranged from 0.4 to 0.7 ng N m^-2 s^-1 per cm². NO flux from wastewater-amended soil ranged from 1.0 to 1.2 ng N m^-2 s^-1 per cm² of applied soil.