Synthesis of iron composites on nano-pore substrates: Identification and its application to removal of cyanide

Two types of nano-pore substrates, waste-reclaimed (WR) and soil mineral (SM) with the relatively low density, were modified by the reaction with irons (i.e. Fe(II):Fe(III) = 1:2) and the applicability of the modified substrates (i.e. Fe-WR and Fe-SM) on cyanide removal was investigated. Modification (i.e. Fe immobilization on substrate) decreased the BET surface area and PZC of the original substrates while it increased the pore diameter and the cation exchange capacity (CEC) of them. XRD analysis identified that maghemite (γ-Fe₂O₃) and iron silicate composite ((Mg, Fe)SiO₃) existed on Fe-WR, while clinoferrosilite (FeSiO₃) was identified on Fe-SM. Cyanide adsorption showed that WR adsorbed cyanide more favorably than SM. The adsorption ability of both original substrates was enhanced by the modification, which increased the negative charges of the surfaces. Without the pH adjustment, cyanide was removed as much as 97% by the only application of Fe-WR, but the undesirable transfer to hydrogen cyanide was possible because the pH was dropped to around 7.5. With a constant pH of 12, only 54% of cyanide was adsorbed on Fe-WR. On the other hand, the pH was kept as 12 without adjustment in Fe-WR/H₂O₂ system and cyanide was effectively removed by not only adsorption but also the catalytic oxidation. The observed first-order rate constant (k_obs) for cyanide removal were 0.49 (±0.081) h⁻¹. Moreover, the more cyanate production with the modified substrates indicated the iron composites, especially maghemite, on substrates had the catalytic property to increase the reactivity of H₂O₂.     

Enhanced-electrokinetic remediation of copper–pyrene co-contaminated soil with different oxidants and pH control

Electrokinetic (EK) remediation has potential to simultaneously remove heavy metals and organic compounds from soil, but the removal percent of these pollutants is very low in general if no enhancing treatment is applied. This study developed a new enhanced-EK remediation technology to decontaminate a heavy metal–organic compound co-contaminated soil by applying different oxidants and pH control. A red soil was used as a model clayed soil, and was spiked with pyrene and Cu at about 500 mg kg^?1 for both to simulate real situation. Bench-scale EK experiments were performed using four oxidants (H₂O₂, NaClO, KMnO₄, and Na₂S₂O₈) and controlling electrolyte pH at 3.5 or 10. After the treatments with 1.0 V cm^?1 of voltage gradient for 335 h, soil pH, electrical conductivity, and the concentrations and chemical fractionations of soil pyrene and Cu were analyzed. The results showed that there was significant migration of pyrene and Cu from the soil, and the removal percent of soil pyrene and Cu varied in the range of 30–52% and 8–94%, respectively. Low pH favoured the migration of soil Cu, while KMnO₄ was the best one for the degradation of pyrene among the tested oxidants, although it unfortunately prevented the migration of soil Cu by forming Cu oxide. Application of Na₂S₂O₈ and to control the catholyte pH at 3.5 were found to be the best operation conditions for decontaminating the Cu-pyrene co-contaminated soil.     

Dechlorination of hexachlorobenzene using lead–iron bimetallic particles

Synthesized lead–iron (Pb/Fe) bimetallic particles were applied to dechlorinate hexachlorobenzene (HCB) under various conditions (e.g. bimetal amount, initial pH value, reaction temperature, and reaction duration). The results showed that adding Pb onto Fe benefited the dechlorination of HCB and the bimetal with 1.4% Pb content performed best. The degradation rate decreased regularly as the initial pH value of the aqueous increased from 1.9 to 11.1 except for pH 7.0 where the fastest dechlorination rate emerged. The dechlorination could be enhanced by increasing the amount of Pb/Fe or the reaction temperature. The dechlorination ratio of HCB within 15 min increased from 24.3% to 81.3% when Pb/Fe amount increased from 0.1 g to 0.8 g. The dechlorination followed pseudo-first-order kinetics, and the dechlorination rate constants were 0.0027, 0.0064, 0.0157, and 0.0321 min^?1 at 25, 50, 70, and 85 °C, respectively, and the activation energy (E_a) of the dechlorination by Pb/Fe was 37.86 kJ mol^?1.     

Alumina-supported oxime for the degradation of sarin and diethylchlorophosphate

1-(4-Chlorophenyl))-N-hydroxymethanimine and cyclohexyl-N-hydroxymethanimine were synthesized and a well-established oxime, i.e., 2-[(hydroxyimino)methyl]-1-methylpyridinium chloride was purchased. Thereafter; all were loaded over Al₂O₃ using incipient wetness technique. The prepared systems were characterized using surface area analyzer, scanning electron microscope, energy dispersive X-ray spectrophotometer, Fourier transform infrared spectrophotometer and thermogravimetric analyzer. Kinetics of the degradation of sarin (GB) and simulant, i.e. diethylchlorophosphate (DEClP) was studied over synthesized oxime impregnated Al₂O₃ and results were compared with well reported oxime impregnated Al₂O₃. Kinetics of reaction was found to be following the pseudo first order reaction kinetics. The order of reactivity of the prepared systems was found to be cyclohexyl-N-hydroxymethanimine/Al₂O₃ > 1-(4-chlorophenyl)-N-hydroxymethanimine/Al₂O₃ > 2-[(hydroxyimino)methyl]-1-methylpyridinium chloride/Al₂O₃ > Al₂O₃. From the reaction kinetics it was observed that the reaction with DEClP was faster than with GB. Cyclohexyl-N-hydroxymethanimine/Al₂O₃ was found to be the most reactive system with half-life of 0.94 and 15 h for DEClP and GB respectively.     

The influence of ozone on atmospheric emissions of gaseous elemental mercury and reactive gaseous mercury from substrates

Experiments were performed to investigate the effect of ozone (O₃) on mercury (Hg) emission from a variety of Hg-bearing substrates. Substrates with Hg(II) as the dominant Hg phase exhibited a 1.7 to 51-fold increase in elemental Hg (Hg^o) flux and a 1.3 to 8.6-fold increase in reactive gaseous mercury (RGM) flux in the presence of O₃-enriched clean (50 ppb O₃; 8 substrates) and ambient air (up to ∼70 ppb O₃; 6 substrates), relative to clean air (oxidant and Hg free air). In contrast, Hg^o fluxes from two artificially Hg^o-amended substrates decreased by more than 75% during exposure to O₃-enriched clean air relative to clean air. Reactive gaseous mercury emissions from Hg^o-amended substrates increased immediately after exposure to O₃ but then decreased rapidly. These experimental results demonstrate that O₃ is very important in controlling Hg emissions from substrates. The chemical mechanisms that produced these trends are not known but potentially involve heterogenous reactions between O₃, the substrate, and Hg. Our experiments suggest they are not homogenous gas-phase reactions. Comparison of the influence of O₃ versus light on increasing Hg^o emissions from dry Hg(II)-bearing substrates demonstrated that they have a similar amount of influence although O₃ appeared to be slightly more dominant. Experiments using water-saturated substrates showed that the presence of high-substrate moisture content minimizes reactions between atmospheric O₃ and substrate-bound Hg. Using conservative calculations developed in this paper, we conclude that because O₃ concentrations have roughly doubled in the last 100 years, this could have increased Hg^o emissions from terrestrial substrates by 65–72%.     

Measurements and modelling of the ozone deposition velocity to concrete tiles,including the effect of diffusion

A range of models were fitted to the experimental time-dependent curves for the deposition velocity of O₃ to concrete floor tile samples. The models included modified Langmuir isotherms assuming adsorption of O₃ on the material surfaces and models assuming direct reaction on and diffusion of O₃ into the material from the air. The best fit was obtained with a simple two-parameter model assuming direct reaction of O₃ with adsorbed surface water and direct diffusion of O₃ into the material from the air. However, models assuming an additional second-order reaction of O₃ with an adsorbed surface species with a given start mass gave improved curve fit in the first 500 min. Applying the best model to experimental data obtained over the whole air humidity range resulted in markedly lower equilibrium deposition velocities than those measured after 48 h. The modelling gave a deposition velocity minimum in the 50–70% relative air humidity range in agreement with observations. The deposition velocity minimum could be explained with a reduced constant for the reaction of O₃ with water or OH⁻ ions on the surface.     

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.     

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.     

PM2.5 particles and size-segregated ionic species measured during fall season in three urban sites in Korea

Twelve hours integrated fine particles (PM_2.5) and 24-h average size-segregated particles were collected to investigate the chemical characteristics and to determine the size distribution of ionic species during October–December 1999 in three cities of different urban scale; Chongju, Kwangju, and Seoul, Korea. Concentrations of 5-min PM_2.5 black carbon (BC) and hourly criteria air pollutants (PM₁₀, CO, NO_x, SO₂, and O₃) were also measured using the Aethalometer and ambient air monitoring system, respectively.Highest PM_2.5 mass concentrations at Chongju, Kwangju, and Seoul sites were 63.0, 77.9, and 143.7 μg m⁻³, respectively. For the time period when highest PM_2.5 mass occurred, BC level out of PM_2.5 chemical species was highest at both Chongju and Kwangju, and highest NO₃⁻ (23.6 μg m⁻³) followed by BC (23.1 μg m⁻³) were observed at Seoul site, indicating that highest PM_2.5 pollution is closely associated with the traffic emissions. Strong relationships of Fe with BC and Zn at both Kwangju and Seoul sites support that the Fe and Zn measured there are originated partly from same source as BC, i.e. diesel traffics. However, it is suggested that the Fe measured at Chongju is most likely derived from dispersion of soil dust.The size distributions of SO₄²⁻, NO₃⁻, and NH₄⁺ ionic species indicated similar unimodal distributions at all sampling sites. However, different unimodal patterns in the accumulation mode size range with a peak in the smaller size (0.28–0.53 μm, condensation mode) in both Kwangju and Seoul, and in the relatively larger size (0.53–1.0 μm, droplet mode) in Chongju, were found. The potassium ion under the study sites dominates in the fine mode, and its size distribution showed unimodal character with a maximum in the size range 0.56–1.0 μm.     

Adsorption of a dye on clay and sand. Use of cyclodextrins as solubility-enhancement agents

Laboratory-scale studies were aimed at elucidating the physico-chemical aspects on the removal process of crystal violet (CV) from waters and solid substrates. The laponite clay (RD) and sand were chosen for the double aim at investigating them as CV adsorbents for water treatment and as substrates which mime the soil components. Sand is very effective in removing CV from waters. The cyclodextrins (CDs) were exploited as solubility-enhancement agents to remove CV from the solid substrates. They are powerful solvent media because they extract the CV from sand forming water-soluble CV/CD inclusion complexes and do not show affinity for sand. Optimum performance was shown by the modified CDs (i.e. hydroxypropyl-β-cyclodextrin and methyl-β-cyclodextrin). A linear correlation between the logarithm of the equilibrium constant for the CV/CD inclusion complexes formation (K_cpx) and the maximum amount of CV extracted from sand in the columns experiments at a flow rate of 1.5 ml min⁻¹ was drawn. This relationship predicts that CDs with K_cpx < 180 M⁻¹ are not suitable for CV removal from sand. CDs failed to displace CV from RD because they generate the formation of RD clusters where CV remains entrapped.     

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.     

Adsorption of NO2 on carbon aerosol particles in the low ppb range

The interaction of NO₂ on carbonaceous aerosol particles in an NO₂ concentration range relevant for the troposphere was studied. The adsorption as a function of NO₂ concentration (2.5–65 ppb) was investigated along with the dependence on time (1–600 s) and particle concentration. The results exhibit a zero-order process in NO₂ for the chemisorption over the measured time and concentration range. The results suggest that the chemisorption reaction is limited by a rapidly established steady-state coverage of a precursor in the form of reversibly adsorbed NO₂ which seems to be constant over the whole investigated NO₂ concentration range. Within the first 20 s, a chemisorption rate of 2.5×10¹¹ molecules cm^-2 s^-1 was calculated. To estimate a saturation value for the NO₂ adsorption on carbonaceous aerosol particles, bulk experiments were performed where the aerosol was deposited on a filter before exposure to NO₂. This gives a lower limit for the total NO₂ adsorption of about 1×10¹⁴ molecules cm^-2 of particle surface area. The measurements show that the concept of the often used sticking coefficient γ (i.e. the number of adsorbed molecules per number of the total gas–surface collisions) is not a useful parameter to describe the chemisorption of NO₂ at low ppb concentration on such complex surfaces as carbonaceous aerosol particles.     

Measurement and modeling of the dry deposition of peroxides

easurements of the dry deposition velocity (V_d) of hydrogen peroxide (H₂O₂) and total organic peroxides (ROOH) were made during four experiments at three forested sites. Details and uncertainties associated with the measurement of peroxide fluxes by the flux-gradient method are discussed. The results are compared to those predicted using a bulk-resistance model of the type commonly used in regional photochemical models. Good agreement between the H₂O₂ V_d measurements and a bulk resistance model is obtained when the model contains a zero surface resistance (R_c) and a common form for the laminar leaf-layer resistance (R_b) based on Schmidt and Prandtl numbers. In this case, a near-zero (<5 s m^-1) surface resistance is confirmed for H₂O₂ within experimental uncertainties. Surface resistances for ROOH were determined to be about 10–15 s m^-1 over a coniferous forest and 20–40 s m^-1 over a deciduous forest. Higher uncertainties for ROOH prevent a detailed analysis of the differences in R_c among forest types. However, the ratio of deposition velocities (ROOH/H₂O₂), computed from normalized concentration gradients, ranged from 0.28 to 0.61 (geometric mean) at the three sites. Differences in molecular diffusivities between H₂O₂ and ROOH can only account for an estimated 16% difference in V_d. Thus, the major constituent of ROOH must also be less soluble and/or less reactive than H₂O₂, which is consistent with the characteristics of methylhydroperoxide (MHP).     

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.     

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.     

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.     

Oxidative stress and arsenic toxicity: Role of NADPH oxidases

The effect of arsenic (25 and 50 μM As for 1 and 5 d) was analysed in wild type (WT) and Arabidopsis thaliana (L.) Heynh plants deficient in NADPH oxidase C (AtrbohC). The content of H₂O₂ and malondialdehyde (MDA) increased with the As concentration, while the opposite effect was found for NO in WT and AtrbohC plants. The As treatment reduced catalase and increased glutathione reductase activities to the same extent in WT and AtrbohC plants, although the induction of all SOD isoforms (mainly CuZn–SODs) was observed in WT plants, the opposite effects being found in AtrbohC plants. Glycolate oxidase (H₂O₂ producers) considerably increased with the concentration and time of treatment with As in WT and AtrbohC mutants. Arsenic induced the uptake and translocation of P, S, Cu, Zn, and Fe in WT plants, while in AtrbohC plants the opposite trend was noted and the uptake of As became considerably lower than in WT plants. These results suggest that As causes oxidative stress by inducing glycolate oxidase, while NADPH oxidase does not appear to participate in ROS overproduction but could be critical in regulating antioxidant defences as well as the transport and translocation of As and macro/micronutrients.     

Ozone sensitivity of the Mediterranean terophyte Trifolium striatum is modulated by soil nitrogen content

The influence of nitrogen (N) fertilization on the sensitivity to ozone (O₃) has been studied using the O₃ sensitive species Trifolium striatum, an annual species frequently found in therophitic grasslands of the dehesas in the central Iberian Peninsula. The experiment was carried out in open-top chambers using three different O₃ exposure treatments: charcoal-filtered air (CFA), non-filtered air (NFA) and non-filtered air plus 40 nl l⁻¹ added over ambient concentrations (NFA+). After 30 days of exposure to the different treatments, plants were placed under ambient conditions until seed ripeness was completed. Three N fertilization treatments were established receiving final doses of 10 (low), 30 (medium) or 60 (high) kg N ha⁻¹ throughout the growing period divided into four proportional doses at every 15 days. Ozone affected phenology and reduced total aerial and flower biomass and seed production in NFA and NFA+ treatments. Carry-over effects of O₃ on the reproductive ability of this species were found resulting in reductions in flower biomass and seed production detected 1 month after O₃ exposure. By contrast, N fertilization increased aerial and flower biomass. Significant O₃×N interactive effects were detected since N fertilization counterbalanced O₃-induced effects only when plants were exposed to moderate O₃ levels (NFA) but not under high O₃ concentrations (NFA+). The observed O₃ effects on reproductive ability of T. striatum might determine changes in species viability and future diversity of the ecosystem.     

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.     

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.