Concentrations,Cumulative Exposure and Critical Levels of Ozone in Ireland

Concentrations of tropospheric ozone(O₃) and exceedance of critical levels to vegetationhave been investigated and mapped for Ireland. Hourlyozone concentration data (1995–1997) at 7 sevenmonitoring stations and the CORINE landcover database,supported by a Geographical Information System, wereused. AOT40 (Accumulated exposure Over a Threshold of 40ppb) was calculated for daylight hours for each station,and mapped using surface interpolation. Average O₃concentrations vary from year to year, and were estimatedto be 28 ppb, 26 ppb and 24 ppb for 1995, 1996 and 1997respectively. Ozone concentrations show a large diurnalvariation, with a maximum in the afternoon and a minimumat night-time. The critical level for crops and (semi-)natural vegetation was exceeded in all years examined.The highest exceedance occurred in 1995, where thecritical level was exceeded for almost 35% of the mappedarea. Approximately 15% and 1% of the mapped area wasexposed to exceedance levels during 1996 and 1997respectively. The maximum cumulative exposures (AOT40)were approximately 5000, 3890 and 3230 ppbh in 1995, 1996and 1997 respectively. The critical level for forests wasnot exceeded during the period of investigation.     

Effects of Soil Moisture Variations on Deposition Velocities Above Vegetation

The parameterized subgrid-scale surface flux (PASS) modelprovides a simplified means of using remote sensing data from satellites and limited surface meteorological information to estimate the influence of soil moisture on bulk canopy stomatalresistances to the uptake of gases over extended areas.PASS-generated estimates of bulk canopy stomatal resistance were usedin a dry deposition module to compute gas deposition velocitieswith a horizontal resolution of 200 m for approximately 5000 km² of agricultural crops and rangeland. Results were compared with measurements of O₃ flux and concentrations made during April and May 1997 at two surface stations and from an aircraft. The trend in simulated O₃ deposition velocityduring soil moisture drydown over a period of a few days matchedthe trend observed at the two surface stations. For areas underthe aircraft flight paths, the variability in simulated O₃ deposition velocity was substantially smaller than the observedvariability, while the averages over tens of kilometers were usually in agreement within 0.1 cm s^-1. Model results indicated that soil moisture can have a major role in depositionof O₃ and other substances strongly affected by canopy stomatal resistance.     

Ozone Dry Deposition Velocities for Coastal Waters

Air-sea exchange rates for ozone were measured by the eddy correlation technique at a site on the north Norfolk coast in the UK. The average surface resistance to ozone uptake was found to be, r_s(O₃) = 1,000 ± 100 s m^-1. Micrometeorological measurements of trace gas fluxes to ocean surfaces are rare but a review of available measurements suggests that we can constrain sea water surface resistance for ozone to between 1,000 (Regener (1974), and this work) and 1,890 s m^-1 (Lenschow et al., 1982), yielding surface deposition velocities between 0.53 and 1.0 mm s^-1. These values are more than an order of magnitude greater than can be explained by laboratory determined mass accommodation coefficients for ozone to water. The importance of dry deposition with respect to process air-sea exchange models is highlighted. A trend in surface deposition velocity with wind speed was also observed supporting a surface chemical enhancement mechanism of ozone uptake which in turn is enhanced by near surface mixing processes.     

Deposition Velocities of SO2 and O3 over Agricultural and Forest Ecosystems

The results of field studies that measured the flux anddeposition velocity of SO₂ and O₃ are reported. Three of the studies were over agricultural crops (pasture, corn, and soybean), and two were over forest (a deciduous forest and a mixed coniferous–deciduous forest). In all cases the deposition velocity for SO₂ was higher than that for O₃. Diurnal cycles of SO₂ deposition velocity were similar in shape, but not magnitude for all surfaces; however those for O₃ showed some difference between forest sites where the peak was in the morning, and the agricultural sites where the peak occurred at mid-day. Seasonal cycles of SO₂ were affected by deposition to surfaces when leaves were not active, yet surface conductance is significant, but not for O₃ where stomatal uptake is the primary pathway for deposition.(On assignment to the National Exposure Research Lab., US EPA) (e-mail:     

Laboratory Measurement of Dry Deposition of Ozone onto Northern Chinese Soil Samples

We used laboratory experiments to investigate surface resistance (R _c) to dry deposition of ozone (O₃) on different types of soil samples collected from the arid deserts and the Loess Plateau of northern China. Furthermore, we measured the factors that affected R _c, which depends on the physical and chemical interaction between trace constituents and the deposition surface, and evaluated deposition velocity (V _d). There was little influence of geometric surface area, soil weight, or O₃ concentration on V _d of O₃. The effect of relative humidity (RH) (i.e. moisture content of the soil) on O₃ uptake was in agreement with results reported in the literature: a distinct RH dependence of V _d and little uptake under water-saturated conditions were observed. R _c values for all the soil samples examined were in the range 0.21–3.3 s mm⁻¹ and were exponentially related to the surface area of the particles and the organic carbon content of each soil sample at RH of both <10 and 60%.     

Comparisons of Measured and Modelled Ozone Deposition to Forests in Northern Europe

The performance of a new dry deposition module, developedfor the European-scale mapping and modelling of ozone flux to vegetation, was tested against micrometeorological ozone and water vapour flux measurements. The measurement data are for twoconiferous (Scots pine in Finland, Norway spruce in Denmark) and one deciduous forest (mountain birch in Finland). On average, themodel performs well for the Scots pine forest, if local inputdata are used. The daytime deposition rates are somewhat over-predicted at the Danish site, especially in the afternoon. The mountain birch data indicate that the generic parameterisationof stomatal responses is not very representative of this northernspecies. The module was also tested by using modelled meteorological data that constitute the input for a photochemical transport model.     

Ozone Deposition at a Forest Site in NE Bavaria

The dry deposition of ozone to aconiferous forest in northeastern Bavaria(southern Germany) was quantified during 1999with both the eddy correlation method and a bigleaf model. The model included parameterizationsof the atmospheric transfer resistances fromdirect measurements, stomatal resistance from aplant ecological model, and an estimation of thecuticle resistance as function of leaf wetness.Early in the season, the measured and themodelled deposition fluxes were in goodagreement, although the modelled fluxes tended tounderestimate the measured ones. Thisunderestimation was more pronounced in the latesummer, when high nocturnal fluxes werefrequently measured. The model parameterizationof the cuticle and the stomatal resistances didnot allow for such high fluxes. In these cases,the 24 hour average of the measured fluxes wereup to 4.5 times higher than the modelled ones.The reasons for these large discrepancies remainunknown. However, assigning the unaccounted partof the deposition to a nonstomatal surfacedeposition pathway, a new parameterization of therespective resistance yielded an average value of300 s m^-1. It exhibited a decreasing trendthrough the vegetation period.     

Forest Decline Evidence in Southern Turkey and its Possible Dependence on Ozone Trends

During the period between 1991 and 1997, crown condition was monitored at an experimental forest located in Southern Turkey, near Antalya. In order to determine the nutritional status of the stands in the study area, in the years 1992, 1993 and 1998, young and old needles were collected from the labelled trees and nutrient contents (N, P, K, Ca, Mg) of the needles were determined. Between the years 1991 and 1997, the degree of defoliation of the canopies, according to the damage indexes, changes from 10–25% to 25–60%. Between the years 1992 and 1998, examination of nutrition condition of the stands reveal that, sufficient and balanced nutrition status of the trees in the year 1992, becomes insufficient or unbalanced for P, K, and N in 1998.From October 1994 to January 1996, a continuous hourly ozone sampling was performed on the Mediterranean coast of Turkey (30.34°E, 36.47°N) near Antalya. The survey carried out in the summer of 1995 reveals that AOT40_f index is 14.612 ppm.h, which exceeds the critical level of 10 ppm.h. As the measured ambient ozone levels are higher than critical level, it has been proposed that ozone may be one of the anthropogenic stress factors causing the forest decline in Southern Turkey observed within this study.     

The Control of SO2 Dry Deposition on to Natural Surfaces by NH3 and its Effects on Regional Deposition

Two years of continuous measurements of SO₂deposition fluxes to moorland vegetation are reported. The mean flux of 2.8 ng SO₂ m^-2 s^-1 is regulated predominantly by surface resistance (r _c) which, even for wet surfaces, was seldom smaller than 100 s m^-1. The control of surface resistance is shown to be regulated by the ratio of NH₃SO₂ concentrations with an excess of NH₃ generating the small surface resistances for SO₂. A dynamic surface chemistry model is used to simulate the effects of NH₃ on SO₂ deposition flux and is able to capture responses to short-term changes in ambient concentrations of SO₂, NH₃ and meteorological conditions. The coupling between surface resistance and NH₃/SO₂ concentration ratios shows that the deposition velocity for SO₂ is regulated by the regional pollution climate. Recent long-term SO₂ flux measurements in a transect over Europe demonstrate the close link between NH₃/SO₂ concentrations and rc (SO₂). The deposition velocity for SO₂ is predicted to have increased with time since the 1970s and imply a 40% increase in v _d at a site at which the annual mean ambient SO₂ concentrations declined from 47 to 3 g m^-3 between 1973 and 1998.     

Air–Soil Exchange of NO,NO2 and O3 in Forests

The exchange of NO, NO₂ and O₃ at the soil surface wasmeasured with automatic dynamic chambers in a spruce forest and in abeech forest during periods of several months.NO was emitted from the soil at a rate of0–8 ng N m^-2 s^-1(spruce) and 0–15 ng Nm^-2 s^-1(beech), but there was no simple relationship between the flux andeither soil temperature or soil moisture. NO₂ and O₃ weredeposited at the soil surface. Deposition velocities forNO₂were on average 0.3 mm s^-1 (spruce) and 0.1 mms^-1(beech), and the deposition velocities of O₃ were on average 1.6 mm s^-1 (spruce) and 1.4 mm s^-1 (beech). The depositionvelocity of O₃ is fairly constant whereas the deposition velocityof NO₂ varies greatly, but the reasons remain to be investigated.     

电化学氧化-臭氧氧化联合方法处理罗丹明B模拟染料废水

采用碳黑-聚四氟乙烯（C-PTFE）为阴极的电化学氧化-臭氧氧化联合方法处理罗丹明B模拟染料废水,考察了初始pH、电解质浓度、电流和臭氧流量对废水处理效果的影响。实验结果表明：联合体系可高效处理罗丹明B废水,在初始pH为6、Na₂SO₄浓度为0.050 mol/L、电流为300 mA、臭氧流量为873 mg/h的条件下,反应3 min时废水的脱色率可达99.64%,120 min时废水COD去除率为83.17%,分别是同条件下单一臭氧氧化和电化学氧化的9.7倍和21.7倍;COD去除过程符合一级反应动力学模型。臭氧通过破坏发色基团实现罗丹明B的降解,然后由体系产生的·OH实现废水的深度氧化处理。     

Shipboard Measurements of Nitrogen Dioxide,Nitrous Acid,Nitric Acid and Ozone in the Eastern Mediterranean Sea

Measurements of nitrogen dioxide, nitrous and nitric acids as well as ozone were made using newly developed instrumentation onboard the research vessel Aegeon in the Aegean Sea between 25th–29th July 2000. Typical nitrogen dioxide concentrations observed aboard the boat were 4–6 ppb (v/v) with a broad maximum of 20–30 ppb (v/v). Ozone concentrations typically ranged between 40 and 80 ppb (v/v). Mixing ratios of both nitric and nitrous acids in the ambient air of the Aegean Sea were mainly below 50 ppt (v/v). The data also showed a number of short pollution episodes with rapid changes in the concentration of reactive nitrogen compounds [nitrogen dioxide maximum up to 164 ppb (v/v), nitric acid maximum up to 12 ppb (v/v), nitrous acid maximum up to 2.7 ppb (v/v)] and ozone [maximum up to 88 ppb (v/v)]. These episodes were correlated with pollution plumes originating from boats upwind, at short distance, from the R/V Aegeon. The measurements revealed the importance of nitrous and nitric acids for the transport of nitrogen to marine biota in busy ship lanes.     

臭氧在循环冷却水中缓蚀作用的研究

循环冷却水处理是工业生产中的一个重要环节。臭氧作为单一的水质稳定剂在循环冷却水中具有缓蚀作用。研究结果表明：吸附在金属表面的臭氧使金属表面从活化腐蚀状态转变为钝化状态,使金属腐蚀电位由活化电位区跃变到钝化电位区,阻止金属的溶解;同时氧的传质速率加快,也可以降低由于浓差极化所产生的腐蚀作用;对于未经预膜处理的金属,臭氧改变金属表面状态,形成一层氧化钝化膜,从而起到了缓蚀作用。     

Integrated Nitrogen and Flow Modelling (INCA) in a Boreal River Basin Dominated by Forestry: Scenarios of Environmental Change

A new version (v1.7) of the Integrated Nitrogen in CAtchments model(INCA) was applied to the northern boreal Simojoki river basin (3160 km²) in Finland. The INCA model is a semi-distributed, dynamic nitrogen (N) process model which simulates N transport and processes in catchments. The INCA model was applied to model flow and seasonal inorganic N dynamics of the river Simojoki basin over the period 1994–1996, and validated for two more years. Both calibration and validation of the model were successful. The model was able to simulate annual dynamics of inorganic N concentrations in the river. The effects of forest management and atmospheric deposition on inorganic N fluxes to the sea in 2010 were studied. Three scenarios were applied for forestry practices and two for deposition. The effects of forest cutting scenarios and atmospheric deposition scenarios on inorganic N flux to the sea were small. The combination of the maximum technically possible reduction of N deposition and a decrease of 100% in forest cutting and peat mining areas decreased NO₃ ^--N flux by 6.0% and NH₄ ⁺-N flux by 3.1%.     

Inter-annual Variations of Ozone and Nitrogen Dioxide Over Europe During 1958–2003 Simulated with a Regional CTM

Inter-annual variability of surface ozone (O₃) and nitrogen dioxide (NO₂) over Europe has been studied over the period 1958–2003 using a three-dimensional Chemistry-Transport Model coupled to meteorological data from the ERA40 data set produced at the European Centre of Medium-range Weather Forecasts (ECMWF). Emissions and boundary conditions were kept at present levels throughout the simulation period. It was found that the annual mean NO₂ concentration varies between ±50% and the summer mean O₃ concentration varies between −10 and +20 percent (%) compared to the 46-year average over the model domain. There is also variation in ozone and NO₂ over longer time scales. The last 22 years display high concentrations of ozone in central and south-western Europe and low concentrations in north-eastern Europe. The first 22 years display very high concentrations of NO₂ over the North Sea. There is indication of trends in ozone and nitrogen dioxide but this has to be investigated further. Such information is one factor that should be taken into account when considering future control strategies.     

Evaluation and Improvement of a Dry Deposition Model using SO2 and O3 Measurements over a Mixed Forest

A dry deposition model (RDM) for operational application has beenevaluated and modified in the present study. Field measurements of friction velocity and dry deposition velocity of SO₂ andO₃ over a mixed forest have been used to evaluate RDM. It was found that RDM predicts friction velocities very close to measurements and thus it can predict reasonable aerodynamic resistance. RDM overestimated O₃ deposition during dry nighttime conditions and underestimated both O₃ andSO₂deposition for early morning hours. It could not predict the mean diurnal variation in deposition velocity for either O₃ or SO₂ deposition under wet surface conditions. Modifications have been made for O₃ and SO₂ dry deposition based on the comparison of results and based upon additional published data. Compared to an earlier version of RDM, the modified versionpredicts better results for O₃ and SO₂ dry deposition,especially under rain and dew conditions.     

Ozone–dioxane delignification from the cell walls of Japanese cypress (Chamaecyparis obtusa Endl.)

Delignification from the cell walls with a combination of ozone oxidation and dioxane–water extraction using thin sections of a softwood, Japanese cypress (Chamaecyparis obtusa Endl.), was studied to determine its suitability for the production of recyclable cellulose-based materials from wood waste. The visible-light absorption spectra of treated wood sections revealed that delignification from the cell walls with ozone increased with increasing ozonization time. Ozone delignification proceeded from the lumen side toward the middle lamella within the secondary wall of a cell, and it proceeded faster in early wood than in late wood within an annual ring. Mild ozonization for 10–30 min was sufficient for the removal of lignin from the cell walls when sections were extracted with dioxane after ozonization. The results obtained here demonstrate that microspectrometry coupled with the Wiesner reaction is useful for the quantitative analysis of lignin in cell walls.     

The Role of Catalyst Properties on Methanol Oxidation over V2O5–TiO2 Using Ozone

Oxidation of methanol over V₂O₅ catalysts supported on anatase TiO₂ that were prepared using sol-gel formation and impregnation procedures were investigated. The effects of incorporating Mg in sol-gel to influence the properties of the catalyst were also studied. The process provides an alternative low temperature reaction pathway for reducing emissions of hazardous air pollutant (HAPs) such as methanol and total reduced sulfur compounds (TRS) from pulp and paper mills. The bulk and surface composition of the catalysts were determined by XRD and SEM-EDAX, respectively. The X-ray diffraction patterns of the vanadia–titania catalysts showed mainly the anatase phase of TiO₂. Temperature programmed desorption of methanol from the different catalyst showed that the α and β peaks differ significantly with V content and addition of Mg. The combination of gas phase and surface reactions on the V/TiO₂ catalysts reduced the amount of ozone required for high degradation of methanol to mainly CO _x with small quantities of methyl formate. In the absence of ozone the catalysts showed very low activity. It is hypothesized that the ozone is directly influencing the V⁴⁺ and V⁵⁺ redox cycle of the catalyst. Oxidation of methanol is influenced by the operation variables and catalyst properties. The results of this study revealed that the V content has significant influence on the catalyst activity, and the optimum vanadia loading of about 6 wt%. Higher turnover frequencies were observed over sol-gel catalysts than with catalysts prepared by the impregnation method.     

Correction Factors for Covariance between Concentration and Deposition Velocity on CASTNes HNO3 Deposition Estimates

The covariance between hourly concentration (C) and depositionvelocity (V) for various atmospheric species may act to bias the dry deposition (D) computed from the product of the weeklyaverage C and V. This is a potential problem for the CASTNet filter pack (FP) species, nitric acid (HNO₃). Using ozone (O₃) behavior as a surrogate for HNO₃, correctionfactors (CF) are developed to estimate this bias. Weekly CF for O₃ depend on both site and season, and seasonal average weekly CF for O₃ at a given site may be as high as 1.25.The seasonal magnitude of this CF is generally largest in summerand is ordered: summer fall spring > winter. The CF is drivento a large extent by the diurnal correlation between C andV (i.e., both are generally higher during the day and lower at night). However, since the diurnal C profile at elevated sites is relatively constant, the resulting correlation between C and V is small, and the CF at montane sites is generally negligiblysmall. The sampling protocol using daytime integrated sampling for a week and nighttime integrated sampling for a week capturesthe diurnal correlation between C and V adequately and may be used to aggregate relatively unbiased weekly D estimates. Day-night CF for O₃ are close to unity, and limited results suggest similar behavior for HNO₃. Using these limited FP results, the site- and seasonally-specific weekly CF forO₃are refined to estimate the corresponding CF for HNO₃. Worst-case adjustments for HNO₃ as high as 30% are indicated for summer periods at a given site.     

A Coupled Land-Surface and Dry Deposition Model and Comparison to Field Measurements of Surface Heat,Moisture, and Ozone Fluxes

We have developed a coupled land-surface and drydeposition model for realistic treatment of surface fluxes ofheat, moisture, and chemical dry deposition within acomprehensive air quality modelling system. A new land-surfacemodel (LSM) with explicit treatment of soil moisture andevapotranspiration and an indirect soil moisture nudging schemehas been added to a mesoscale meteorology model. The new drydeposition model uses the same aerodynamic and bulk stomatalresistances computed for evapotranspiration in the LSM. Thisprovides consistent land-surface and boundary layer propertiesacross the meteorological and chemical components of the system. The coupled dry deposition model also has the advantage of beingable to respond to changing soil moisture and vegetationconditions. Modelled surface fluxes of sensible and latent heatas well as ozone dry deposition velocities were compared to twofield experiments: a soybean field in Kentucky during summer 1995and a mixed forest in the Adirondacks of New York in July 1998.(on assignment to the National Exposure Research Laboratory, U.S. Environmental Protection Agency) (author for correspondence, e-mail(on assignment to the National Exposure Research Laboratory, U.S. Environmental Protection Agency)