Ozone Predictions in Atlanta,Georgia: Analysis of the 1999 Ozone Season

ABSTRACT

Ozone prediction has become an important activity in many U.S. ozone nonattainment areas. In this study, we describe the ozone prediction program in the Atlanta metropolitan area and analyze the performance of this program during the 1999 ozone-forecasting season. From May to September, a team of 10 air quality regulators, meteorologists, and atmospheric scientists made a daily prediction of the next-day maximum 8-hr average ozone concentration. The daily forecast was made aided by two linear regression models, a 3-dimensional air quality model, and the no-skill ozone persistence model. The team's performance is compared with the numerical models using several numerical indicators. Our analysis indicated that (1) the team correctly predicted next-day peak ozone concentrations 84% of the time, (2) the two linear regression models had a better performance than a 3-dimensional air quality model, (3) persistence was a strong predictor of ozone concentrations with a performance of 78%, and (4) about half of the team's wrong predictions could be prevented with improved meteorological predictions.     

Validation of a hybrid forecasting system for the ozone concentrations over the Paris area

A simplified hybrid statistical-deterministic chemistry-transport model, is used in real time for the prediction of ozone in the area of Paris during Summer 1999. We present here a statistical validation of this experiment. We distinguish the forecasts in the urban area from forecasts in the pollution plume downwind of the city. The validation of model forecasts, up to 3 days ahead, is performed against ground based observations within and up to 50 km outside of Paris. In the urban area, ozone levels are fairly well forecast, with correlation coefficients between forecast and observations ranging between 0.7 and 0.8 and root mean square errors in the range 15–20 μg m⁻³ at short lead times. While the bias of urban forecast is very low, the largest peaks are somehow underestimated. The ozone plume amplitude is generally well reproduced, even at long lead times (root mean square errors of about 20–30 μg m⁻³), while the direction of the plume is only captured at short lead times (about 70% of the time). The model has difficulties in forecasting the direction of the plume under stagnant weather conditions. We estimate the model ability to forecast concentrations above 180 μg m⁻³, which are of practical relevance to air quality managers. It is found that about 60% of these events are well forecast, even at long lead times, while the exact monitoring station where the exceedance is observed can only be forecast at short lead times. Finally, we found that about half of the forecast error is due to the error in the estimation of the boundary conditions, which are forecast by a simple linear regression model here.     

Ozone flux over a Norway spruce forest and correlation with net ecosystem production

Daily ozone deposition flux to a Norway spruce forest in Czech Republic was measured using the gradient method in July and August 2008. Results were in good agreement with a deposition flux model. The mean daily stomatal uptake of ozone was around 47% of total deposition. Average deposition velocity was 0.39 cm s⁻¹ and 0.36 cm s⁻¹ by the gradient method and the deposition model, respectively. Measured and modelled non-stomatal uptake was around 0.2 cm s⁻¹. In addition, net ecosystem production (NEP) was measured by using Eddy Covariance and correlations with O₃ concentrations at 15 m a.g.l., total deposition and stomatal uptake were tested. Total deposition and stomatal uptake of ozone significantly decreased NEP, especially by high intensities of solar radiation.     

Modeled and observed fine particulate matter reductions from state attainment demonstrations

States rely upon photochemical models to predict the impacts of air quality attainment strategies, but the performance of those predictions is rarely evaluated retrospectively. State implementation plans (SIPs) developed to attain the 1997 U.S. standard for fine particulate matter (PM_2.5; denoting particles smaller than 2.5 microns in diameter) by 2009 provide the first opportunity to assess modeled predictions of PM_2.5 reductions at the state level. The SIPs were the first to rely upon a speciated modeled attainment test methodology recommended by the U.S. Environmental Protection Agency to predict PM_2.5 concentrations and attainment status. Of the 23 eastern U.S. regions considered here, all but one achieved the 15 μg/m³ standard by 2009, and the other achieved it the following year, with downward trends sustained in subsequent years. The attainment tests predicted 2009 PM_2.5 design values at individual monitors with a mean bias of 0.38 μg/m³ and mean error of 0.68 μg/m³, and were 95% accurate in predicting whether a monitor would achieve the standard. All of the errors were false alarms, in which the monitor observed attainment after a modeled prediction of an exceedance; in these cases, the states used weight-of-evidence determinations to argue that attainment was likely. Overall, PM_2.5 concentrations at monitors in the SIP regions declined by 2.6 μg/m³ from 2000–2004 to 2007–2009, compared with 1.6 μg/m³ in eastern U.S. regions originally designated as attainment. Air quality improvements tended to be largest at monitors that were initially the most polluted.

ImplicationsAs states prepare to develop plans for attaining a more stringent standard for fine particulate matter, this retrospective analysis documents substantial and sustained air quality improvements achieved under the previous standard. Significantly larger air quality improvements in regions initially designated nonattainment of the 1997 standard indicate that this status prompted heightened control efforts. The speciated modeled attainment test is found to be accurate and slightly conservative in predicting particulate concentrations for the cases considered here, providing confidence for its use in upcoming attainment plans.     

夏秋季节焦化厂附近大气中臭氧及其前体物变化特征和臭氧生成潜势分析

2012年6—10月,在我国北方某焦化厂厂界附近开展了O3、NO x、CO体积分数在线监测及VOCs样品采集分析工作,获得了夏、秋两季焦化厂厂界O3及其前体物的体积分数及其日变化趋势。焦化厂厂界附近O3、NO、CO体积分数均呈单峰型日变化,O3体积分数的季节差异不明显,夏季仅略高于秋季,而NO、CO体积分数秋季高于夏季,作为二次反应产物的NO2,其变化幅度秋季比夏季强烈。夏季TVOCs在各监测时段的小时体积分数呈现先上升后下降的日变化趋势,而秋季则呈现逐渐下降的日变化趋势。由较小VOCs/NO x的比值可初步判断,该焦化厂所在区域的大气光化学臭氧生成潜势处于VOCs控制区。在焦化厂下风向厂界附近,夏、秋两季TVOCs平均体积分数分别为(43.8±45.0)×10-9和(26.7±29.6)×10-9,苯系物、烷烃、烯烃的平均体积分数分别为(34.3±28.1)×10-9和(14.4±14.8)×10-9、(5.3±11.8)×10-9和(7.0±7.7)×10-9、(4.3±5.0)×10-9和(5.3±7.1)×10-9。夏、秋两季焦化厂附近臭氧生成潜势贡献最大的是苯系物(47.6%~65.8%),其次是烯烃(28.0%~41.9%),再次是烷烃(6.3%~10.5%)。     

Ozone predictions in Atlanta, Georgia: analysis of the 1999 ozone season

Ozone prediction has become an important activity in many U.S. ozone nonattainment areas. In this study, we describe the ozone prediction program in the Atlanta metropolitan area and analyze the performance of this program during the 1999 ozone-forecasting season. From May to September, a team of 10 air quality regulators, meteorologists, and atmospheric scientists made a daily prediction of the next-day maximum 8-hr average ozone concentration. The daily forecast was made aided by two linear regression models, a 3-dimensional air quality model, and the no-skill ozone persistence model. The team's performance is compared with the numerical models using several numerical indicators. Our analysis indicated that (1) the team correctly predicted next-day peak ozone concentrations 84% of the time, (2) the two linear regression models had a better performance than a 3-dimensional air quality model, (3) persistence was a strong predictor of ozone concentrations with a performance of 78%, and (4) about half of the team's wrong predictions could be prevented with improved meteorological predictions.     

Prediction of the adsorption capability onto activated carbon of a large data set of chemicals by local lazy regression method

Accurate quantitative structure–property relationship (QSPR) models based on a large data set containing a total of 3483 organic compounds were developed to predict chemicals’ adsorption capability onto activated carbon in gas phrase. Both global multiple linear regression (MLR) method and local lazy regression (LLR) method were used to develop QSPR models. The results proved that LLR has prediction accuracy 10% higher than that of MLR model. By applying LLR method we can predict the test set (787 compounds) with Q²_ext of 0.900 and root mean square error (RMSE) of 0.129. The accurate model based on this large data set could be useful to predict adsorption property of new compounds since such model covers a highly diverse structural space.     

Ozone risk assessment for agricultural crops in Europe: Further development of stomatal flux and flux–response relationships for European wheat and potato

Applications of a parameterised Jarvis-type multiplicative stomatal conductance model with data collated from open-top chamber experiments on field grown wheat and potato were used to derive relationships between relative yield and stomatal ozone uptake. The relationships were based on thirteen experiments from four European countries for wheat and seven experiments from four European countries for potato. The parameterisation of the conductance model was based both on an extensive literature review and primary data. Application of the stomatal conductance models to the open-top chamber experiments resulted in improved linear regressions between relative yield and ozone uptake compared to earlier stomatal conductance models, both for wheat (r²=0.83) and potato (r²=0.76). The improvement was largest for potato. The relationships with the highest correlation were obtained using a stomatal ozone flux threshold. For both wheat and potato the best performing exposure index was AF_st6 (accumulated stomatal flux of ozone above a flux rate threshold of 6 nmol ozone m⁻² projected sunlit leaf area, based on hourly values of ozone flux). The results demonstrate that flux-based models are now sufficiently well calibrated to be used with confidence to predict the effects of ozone on yield loss of major arable crops across Europe. Further studies, using innovations in stomatal conductance modelling and plant exposure experimentation, are needed if these models are to be further improved.     

Surface solar ultraviolet radiation: A theoretical approach of the SUVR reaching the ground in Athens, Greece

Daily total ozone observations made during 1985–1993 by both the Total Ozone Mapping Spectrometer (TOMS) flown on the Satellite Nimbus-7 and the Dobson Spectrophotometer have been used in order to investigate the fluctuations of the daily broad-band and spectral solar ultraviolet radiation reaching the ground. This investigation has been performed by employing a recently developed parametric algorithm for the estimation of the spectral and broad-band solar ultraviolet radiation which takes the total ozone variations into consideration. Total ozone reductions during the summertime from 1985 to 1993 over Athens, Greece (37.6° N, 23.4° E), cause an increase in the ultraviolet irradiance which reaches the ground of 0.54 %, 0.98 %, 2.60 % and 0.79 % per decade for the months of July at 300 nm, 312 nm, 320 nm and UVB (280-320 nm), respectively.     

PEM式臭氧消毒在地上游泳池水处理中的应用

采用臭氧法水处理系统对地上游泳池的循环水进行灭菌消毒,研究了臭氧用量、循环水流量和运行时间等因素对臭氧法灭菌效果的影响。结果表明,3组PEM臭氧发生器应用于21.2 m3的地上游泳池,在4 m3/h的循环水流量下运行12 h后,水中的细菌总数与大肠杆菌群数达到国家标准,去除率均在99%以上。与盐电解法水处理系统相比较,臭氧法水处理系统的优势在于:杀菌快速高效、出水水质的理化指标较好和运行费用低廉。     

Cumulative effects and threshold levels in air pollution mortality: Data analysis of nine large US cities using the NMMAPS dataset

We examined the existence of thresholds, cumulative effects and the homogeneity of five air pollutants on the relative risk of three mortality outcomes using data from nine major US cities using data from NMMAPS. Overall, PM₁₀ (usually 200-day accumulation) and ozone (3-day accumulation) were the two important predictors of outcome but their effect was not uniform across the nine cities. Many models exhibited thresholds (25–45 μm g/m³ for PM₁₀, and 10–45 ppb for O₃). Our preliminary exploratory analyses suggest that the use of a linear, no threshold, model for pollution studies is not consistent with the observed data. The heterogeneity in the risk estimates across the nine cities suggests combining the local risk estimates to obtain a national risk estimate may not be justifiable and the estimate is likely to be confounded.     

Validation of road vehicle and traffic emission models – A review and meta-analysis

Road transport is often the main source of air pollution in urban areas, and there is an increasing need to estimate its contribution precisely so that pollution-reduction measures (e.g. emission standards, scrapage programs, traffic management, ITS) are designed and implemented appropriately. This paper presents a meta-analysis of 50 studies dealing with the validation of various types of traffic emission model, including ‘average speed’, ‘traffic situation’, ‘traffic variable’, ‘cycle variable’, and ‘modal’ models. The validation studies employ measurements in tunnels, ambient concentration measurements, remote sensing, laboratory tests, and mass-balance techniques. One major finding of the analysis is that several models are only partially validated or not validated at all. The mean prediction errors are generally within a factor of 1.3 of the observed values for CO₂, within a factor of 2 for HC and NO_x, and within a factor of 3 for CO and PM, although differences as high as a factor of 5 have been reported. A positive mean prediction error for NO_x (i.e. overestimation) was established for all model types and practically all validation techniques. In the case of HC, model predictions have been moving from underestimation to overestimation since the 1980s. The large prediction error for PM may be associated with different PM definitions between models and observations (e.g. size, measurement principle, exhaust/non-exhaust contribution).Statistical analyses show that the mean prediction error is generally not significantly different (p < 0.05) when the data are categorised according to model type or validation technique. Thus, there is no conclusive evidence that demonstrates that more complex models systematically perform better in terms of prediction error than less complex models. In fact, less complex models appear to perform better for PM. Moreover, the choice of validation technique does not systematically affect the result, with the exception of a CO underprediction when the validation is based on ambient concentration measurements and inverse modelling. The analysis identified two vital elements currently lacking in traffic emissions modelling: 1) guidance on the allowable error margins for different applications/scales, and 2) estimates of prediction errors. It is recommended that current and future emission models incorporate the capability to quantify prediction errors, and that clear guidelines are developed internationally with respect to expected accuracy.     

Atrazin Atmospheric deposition and air-borne concentrations

Am Beispiel des Wirkstoffes Atrazin wird die atmosph?rische Verbreitung und der atmosph?rische Eintrag von Pflanzenschutzmitteln mit einer geringen Flüchtigkeit aufgezeigt. Immissions-Konzentrationen lagen zwischen weniger als 0.005 ng·m⁻³ und maximal 0.32 ng·m⁻³ Atrazin wird fast ausschlie?lich in der Partikelphase, offensichtlich im Ungleichgewicht mit der Gasphase, verfrachtet. Dies verz?gert wahrscheinlich den photochemischen Abbau in der Atmosph?re. Die Konzentrationen im Flüssigwasser aufliegender Wolken erreichten zu den Applikationsterminen nahezu 1.6 μg·1⁻¹. Die Eintr?ge über die Atmosph?re betrugen in exponierter Lage im Fichtelgebirge mit 0.13 mg·m⁻²·a⁻¹ ca. 0.4% der Aufwandmengen in 3j?hrigen Maisfruchtfolgen. Im Alpenraum wurden mit 0.012 mg·m⁻²·a⁻¹ deutlich niedrigere Frachten gemessen als im Fichtelgebirge.Das Umweltrisiko durch die atmosph?rische Verbreitung und Deposition von Atrazin und anderen Pflanzenschutzmitteln mit vergleichbaren physikalisch-chemischen Eigenschaften ist als ?u?erst gering einzustufen. Atmospheric occurrence and deposition of atrazine are measured. During the application of atrazine, highest concentrations reached 1.6 μg·1⁻¹ in liquid water of lowlying clouds touching mountain tops. Atmospheric deposition, however, hardly amounts to 0.4% of the flux on crop land by direct spraying. Airborne concentrations ranged from less than 0.005 ng·m⁻³ to 0.32 ng·m⁻³. Contrary to theoretical expectations, almost all atrazine was found in the particulate matter, indicating nonequilibrium with the gas phase. This may inhibit a rapid photochemical decomposition. Human health concerns and environmental risks due to the atmospheric occurrence and deposition of atrazine are judged as minor. This conclusion can be applied to many other, physicochemically related pesticides.     

Soil-Atmosphere exchange of radiatively and chemically active gases

Exchanges between the soils and the atmosphere may control or significantly affect the global budgets of many environmentally important trace gases, both natural and man-made. Flux measurements, taken in several ecosystems, show that soils are a substantial source of chloroform (8 ± 4 μg/m²/d) and a sink for methyl chloride (-10 _-3 ⁺⁶ μg/m²/d). The known sources and sinks of these gases are insufficient to explain the observed concentrations. Our findings will help to balance the global budget of chloroform but may put the budget of methyl chloride further out of balance. We also found, consistent with previous research, that soils are a substantial source of nitrous oxide and carbon monoxide and take up hydrogen and methane. The uptake of man-made chlorocarbons was observed, but the rates are small. Observed fluxes of non-methane hydrocarbons showed few patterns except that soils may be a source of ethane and butane.     

Fuzzy system models combined with nonlinear regression for daily ground-level ozone predictions

This study focuses on applying a Takagi–Sugeno fuzzy system and a nonlinear regression (NLR) model for ozone predictions in six Kentucky metropolitan areas. The fuzzy “c-means” clustering technique coupled with an optimal output predefuzzification approach (least square method) was used to train the Takagi–Sugeno fuzzy system. The fuzzy system was tuned by specifying the number of rules and the fuzziness factor. The NLR models were based in part on a previously reported, trajectory-based hybrid NLR model that has been used for years for forecasting ground-level ozone in Louisville, KY. The NLR models were each composed of an interactive nonlinear term and several linear terms. Using a common meteorological parameter set as input variables, the NLR models and the Takagi–Sugeno fuzzy systems model exhibited equivalent forecasting performance on test data from 2004. For all 2004 ozone season forecasts for the six metropolitan areas, the mean absolute error was 8.1 ppb for the NLR model and 8.0 ppb for the Takagi–Sugeno fuzzy model. When a nonlinear term (which was part of the NLR model) was included in the fuzzy model, the combined NLR–fuzzy model had slightly better performance than the original NLR model. For all 2004 metropolitan area forecasts, the mean absolute error of the NLR–fuzzy model forecasts was 7.7 ppb. These small differences may be statistically significant, but for practical purposes the performance of the fuzzy models was equivalent to that of the NLR models.     

Measurement of Ambient Ground-Level Concentrations of Hydrogen Fluoride

The use of published, accepted methods for measuring ambient levels of gaseous hydrogen fluoride (HF) with a double-tape sampler led to large errors. The major source of error was found to be scrubbing In the stainless steel intake, which was avoided by substituting Teflon for the stainless steel. To avoid this and other problems encountered in the measurement of HF, we revised the double-tape sampler method and modified the double-tape sampler. We designed and constructed an HF calibrator for use in testing the revised method and modified sampler In the field and laboratory.

The results of a round robin indicated that, in the laboratory, the revised method has a single-operator precision of 3 percent at 2.6 μg/m³ and a between-laboratory precision of 4 percent. The average bias at 2.6 μg/m³ was 0.02 μg/m³ and was not significantly different from zero. Comparable precision and accuracy were obtained in the field. The response was linear, at least to 10 μg/m³. The limit of detectability, which appears to be limited by the variability in measurements of blank tapes, is 0.07 μg/m³. The revised method appears both precise and accurate.     

反应气耦合等离子体降解沙林模拟剂

采用水蒸气、氨气、过氧化氢气雾和臭氧4种气体对沙林模拟剂氟磷酸二异丙酯(DFP)进行降解研究,发现臭氧对DFP具有较好的降解作用,在流量200 L/h,DFP初始浓度50 mg/m3时,降解率最高可达56.1%。对高浓度DFP(大于80 mg/m3)进行降解研究时,等离子体单独作用最高降解率为89%,而添加臭氧后的降解率都在95%以上。计算得到臭氧作用的能量利用率为0.05 mg/(W·h),等离子体的能量利用率为0.55 mg/(W·h),而添加臭氧后的等离子体能量利用率为0.68 mg/(W·h)明显高于臭氧和等离子体能量利用率之和,因此对高浓度DFP进行处理时,臭氧与等离子体存在耦合作用。对等离子体和臭氧耦合等离子体降解DFP反应进行了产物分析,发现主要的降解产物基本一致,但是臭氧的存在能使降解更加彻底。     

Corrosion on cultural heritage buildings in Italy: A role for ozone?

Because of climatic reasons and of reduced concentrations of SO₂, ground-level ozone (O₃) is one of the main air pollutants in Southern Europe. Ozone levels are very high both in rural and urban locations. In the cities, O₃ can affect human health and materials. Regarding materials, most relevant is the exposure to pollutants of cultural heritage buildings. In particular, monuments registered on UNESCO's list of the world heritage require special monitoring. In Italy 34% and 97% of the territory is exposed to corrosion risk higher than the tolerable level for limestone and copper, respectively. The tolerable corrosion level for limestone and copper was also exceeded in the central area of Milan. In this area the tolerable O₃ concentration for copper was calculated. These concentrations (ranging between 30 and 40 μg/m³) cannot be exceeded at unchanged concentration of other pollutants to maintain corrosion levels below the tolerable ones.     

Effects of ozone fumigation treatment on the removal of residual difenoconazole from strawberries and on their quality

The effect of ozone fumigation on the reduction of difenoconazole residue on strawberries was studied. Strawberries were immersed in 1.0 L of aqueous solution containing 400 μL of the commercial product (250 g L^?1 of difenoconazole) for 1 min. Then, they were dried and exposed to ozone gas (O₃) at concentrations of 0.3, 0.6 and 0.8 mg L^?1 for 1 h. The ozone fumigation treatments reduced the difenoconazole residue on strawberries to concentrations below 0.5 mg kg^?1, which corresponds to a 95% reduction. The strawberries treated with ozone and the control group, which was not treated with ozone, were stored at 4°C for 10 days. Some characteristics of the fruit were monitored throughout this period. Among these, pH, weight loss and total color difference did not change significantly (P > 0.05). The fumigation with ozone significantly affected the soluble solids, titratable acidity and ascorbic acid content (vitamin C) of the strawberries preventing a sharp reduction of these parameters during storage.     

Meta-analysis of the Chinese studies of the association between ambient ozone and mortality

To investigate short-term effects of ambient ozone exposure on mortality in Chinese cities, we conducted a meta-analysis of 10 effect estimates of 5 short-term studies, which reported associations between ambient ozone and mortality in Chinese mainland cities. And we estimated pooled effects by non-accidental mortality, cardiovascular mortality, and respiratory mortality. Combined estimates and their 95%CI were tested by RevMan 5, and Funnel plots were used for the bias analysis. For a 10 μg m⁻³ increase of maximum 8-h average concentration of ozone, the percent change for non-accidental mortality, cardiovascular mortality, and respiratory mortality were 0.42 (95%CI, 0.32–0.52%), 0.44% (95%CI, 0.17–0.70%) and 0.50% (95%CI, 0.22–0.77%), respectively. Compared with pooled estimates from other meta-analyses on ambient ozone-associated mortality, our pooled estimate for non-accidental mortality was slightly higher than previous ones and pooled estimate for cardiovascular mortality was consistent with others. However, we observed significantly positive association between ambient ozone and respiratory mortality, which were generally nonsignificant in earlier studies. By combining estimates from published evidence, a small but substantial association between ambient ozone level and mortality was observed in Mainland China.