Ozone affects pollen viability and NAD(P)H oxidase release from Ambrosia artemisiifolia pollen

Air pollution is frequently proposed as a cause of the increased incidence of allergy in industrialised countries. We investigated the impact of ozone (O₃) on reactive oxygen species (ROS) and allergen content of ragweed pollen (Ambrosia artemisiifolia). Pollen was exposed to acute O₃ fumigation, with analysis of pollen viability, ROS and nitric oxide (NO) content, activity of nicotinamide adenine dinucleotide phosphate (NAD[P]H) oxidase, and expression of major allergens. There was decreased pollen viability after O₃ fumigation, which indicates damage to the pollen membrane system, although the ROS and NO contents were not changed or were only slightly induced, respectively. Ozone exposure induced a significant enhancement of the ROS-generating enzyme NAD(P)H oxidase. The expression of the allergen Amb a 1 was not affected by O₃, determined from the mRNA levels of the major allergens. We conclude that O₃ can increase ragweed pollen allergenicity through stimulation of ROS-generating NAD(P)H oxidase.     

Inorganic nanoparticles enhance the production of reactive oxygen species (ROS) during the autoxidation of L-3,4-dihydroxyphenylalanine (L-dopa)

Public concerns over the toxicity of nanoparticles (NPs) are growing due to the rapid development of nanotechnology. An important mechanism of nanotoxicity is oxidative stress resulting from reactive oxygen species (ROS). In this study, the chemical production of ROS by inorganic NPs oxidizing the mammalian phenolic compound, l-3,4-dihydroxyphenylalanine (l-dopa) was evaluated using a ROS sensitive dye, 2′,7′-diclorodihydrofluorescin (DCFH). CeO₂, Fe₂O₃ and Fe⁰ NPs enhanced ROS production during the autoxidation of l-dopa by more than four-fold in reactions that were dependent on O₂. This is the first report of chemical ROS production due to interaction of phenolic compounds with NPs. Mn₂O₃ oxidized DCFH in a reaction that did not require O₂ or l-dopa, suggesting a direct redox reaction between the Mn₂O₃ and the dye. CeO₂, Mn₂O₃ and to a lesser extent Fe⁰ formed clear electron paramagnetic resonance (EPR) signature for hydroxyl radicals when incubated in aerobic aqueous suspensions with spin traps. The results indicate that NPs can generate ROS via chemical reactions with medium components and biomolecules susceptible to oxidation, such as l-dopa. NPs were reactive whereas micron-sized particles were not. The combined assay with l-dopa and DCFH is a method proposed to screen for chemical ROS production by NPs.     

Ethylenediurea (EDU): a research tool for assessment and verification of the effects of ground level ozone on plants under natural conditions

Ethylenediurea (EDU) has been widely used to prevent ozone (O₃) injury and crop losses in crop plants and growth reductions in forest trees. Successful use requires establishing a dose/response curve for EDU and the proposed plant in the absence of O₃ and in the presence of O₃ before initiating multiple applications to prevent O₃ injury. EDU can be used to verify foliar O₃ symptoms in the field, and to screen plants for sensitivity to O₃ under ambient conditions. Despite considerable research, the mode of action of EDU remains elusive. Additional research on the mode of action of EDU in suppressing O₃ injury in plants may also be helpful in understanding the mode of action of O₃ in causing injury in plants.     

Exposure to elevated ozone levels differentially affects the antioxidant capacity and the redox homeostasis of two subtropical Phaseolus vulgaris L. varieties

Ozone (O₃) has become one of the most toxic air pollutants to plants worldwide. However, investigations on O₃ impacts on crops health and productivity in South America countries are still scarce. The present study analyzed the differences on the enzymatic and non-enzymatic antioxidant system in foliar tissue of two subtropical Phaseolus vulgaris varieties exposed to high O₃ concentration. Both varieties were negatively impacted by the pollutant, but the responses between each variety were quite distinct. Results revealed that Irai has higher constitutive levels of reactive oxygen species (ROS) and ascorbate (AsA) concentration, but lower total thiol levels and catalase immunocontent. In this variety catalase protein concentration was increased after O₃ exposure, indicating a better cellular capacity to reduce hydrogen peroxide. On the opposite, Fepagro 26-exposed plants increased ROS generation and AsA concentration, but had the levels of total thiol content and catalase protein unchanged. Furthermore, O₃ treatment reduced the levels of chlorophylls a and b, and the relationship analysis between the chlorophyll ratio (a/b) and protein concentration were positively correlated indicating that photosynthetic apparatus is compromised, and thus probably is the biomass acquisition on Fepagro 26. Differently, O₃ treatment of Irai did not affect chlorophylls a and b content, and loss on the protein content was lower. Altogether, these data suggest that early accumulation of ROS on Fepagro 26 are associated with an insufficient leaf antioxidant capacity, which leads to cell structure disruption and impairs the photosynthesis. Irai seems to be more tolerant to O₃ toxic effects than Fepagro 26, and the observed differences on O₃ sensitivity between the two varieties are apparently based on constitutive differences involved in the maintenance of intracellular redox homeostasis.     

The challenge of making ozone risk assessment for forest trees more mechanistic

Upcoming decades will experience increasing atmospheric CO₂ and likely enhanced O₃ exposure which represents a risk for the carbon sink strength of forests, so that the need for cause-effect related O₃ risk assessment increases. Although assessment will gain in reliability on an O₃ uptake basis, risk is co-determined by the effective dose, i.e. the plant's sensitivity per O₃ uptake. Recent progress in research on the molecular and metabolic control of the effective O₃ dose is reported along with advances in empirically assessing O₃ uptake at the whole-tree and stand level. Knowledge on both O₃ uptake and effective dose (measures of stress avoidance and tolerance, respectively) needs to be understood mechanistically and linked as a pre-requisite before practical use of process-based O₃ risk assessment can be implemented. To this end, perspectives are derived for validating and promoting new O₃ flux-based modelling tools.     

Ozone tolerance in Phaseolus vulgaris depends on more than one mechanism

Two bean cultivars with different sensitivity to ozone, i.e. the O₃-sensitive Cannellino and the O₃-tolerant Top Crop, were exposed to acute O₃-stress (165 nL L⁻¹) with the aim of evaluating physiological and biochemical traits that may confer O₃-tolerance. Stomatal conductance was smaller and the ability to dissipate excess energy, via regulated and unregulated nonphotochemical quenching mechanisms was greater in Top Crop than in Cannellino. These morphological and physiological-traits allowed the O₃-tolerant cultivar to compensate for the light-induced declines in Φ_PSII, to preserve photosystem II from excitation-energy, and likely to prevent the generation of ROS to a superior degree than the O₃-sensitive cultivar. Furthermore, the potential capacities to reducing the superoxide anion and H₂O₂ were significantly greater in Top Crop than in Cannellino. These findings are consistent with the early accumulation of H₂O₂, the almost complete disruption of cell structure, and irreversible damages to the photosynthetic apparatus observed in the O₃-sensitive cultivar.     

Removal of AOX, total nitrogen and chlorinated lignin from bleached Kraft mill effluents by UV oxidation in the presence of hydrogen peroxide utilizing TiO2 as photocatalyst

Background, aim, and scope  The pulp and paper industry is the sixth largest polluter discharging a variety of gaseous, liquid, and solid wastes into the environment. Effluents from bleached Kraft mill effluents (BKME) are polluting waters to a great extent These effluents cause considerable damage to the receiving waters if discharged untreated since they have high levels of biological oxygen demand (BOD), chemical oxygen demand (COD), chlorinated compounds (measured as AOX), suspended solids (mainly fibers), fatty acids, tannins, resin acids, lignin and its derivatives, sulfur and sulfur compounds, etc. This study aimed to remove adsorbed organic halogen (AOX), total nitrogen, and lignin-degrading products in the wastewater (4,500 m³/h) from the paper mill in the pulp and paper industry, which is discharged to sea from a plant located in western Turkey. Materials and methods  The photocatalytic degradation of AOX, total nitrogen, and chlorinated lignin in BKME have been investigated in different parameters, such as time, H₂O₂ and TiO₂ concentration. In addition, for investigating the effect of chlorine on the removal of lignin, pure lignin solution was prepared in equal amounts to chlorinated lignin degradation products found in BKME. The same experiments were conducted for this solution. Experiments were carried out in photocatalytic reactor made of Pyrex glass. The mercury lamp was used as a radiation source. All irradiation was carried out under constant stirring. The existence of dissolved O₂ is an important factor which increases the photocatalytic degradation. Hence, we used an air pump for the aeration of the wastewater solutions. The temperature of the wastewater was controlled and adjusted to 25°C by thermostat pump in conjunction with a cooler. At the end of all experiments, AOX, total nitrogen and lignin concentrations were analyzed according to standard methods. All experiments were performed in duplicate and average values were used. Results and discussion  When the effect of H₂O₂ and time were investigated, it was observed that the AOX concentration increased from 3.0 to 11.0 mg/L by only UV. However, when H₂O₂ was added, AOX concentration decreased from approximately 3.0 to 0.0 mg/L. The optimal conditions for the removal of AOX appear to be an initial H₂O₂ concentration of 20.0 mL/L and reaction time of 50 min. In addition, at the same experiment conditions, it was seen that the total nitrogen concentration decreased from 23.0 to 15.0 mg/L by only UV and by increasing H₂O₂ concentration, the concentration of 20.0 mL/L H₂O₂ appears to be optimal (9.0 mg/L). The AOX, total nitrogen and lignin degradation products and pure lignin go through a minimum when the concentration of H₂O₂ and TiO₂ increases at constant pH and UV intensity. The kinetics for the degradation of AOX, total nitrogen and lignin degradation products followed a pseudo-first order law with respect to the products, and the degradation rates (min⁻¹) for the UV/TiO₂/H₂O₂ system were higher than that of the corresponding values for the UV/H₂O₂ system. Conclusions  The AOX, total nitrogen and lignin concentration go through a minimum when the concentration of H₂O₂ and TiO₂ increases at constant pH and UV intensity. It was found that the UV/TiO₂/H₂O₂ system has proved capable of the degradation of total nitrogen as well as chlorinated and degraded lignin in BKME. Recommendations and perspectives  The photocatalytic process can be considered a suitable alternative for the remove of some compounds from the BKME. Nevertheless, further studies should be carried out to confirm the practical feasibility of BKME. Another result obtained from the study is that pre-purification carried out with UV/TiO₂/H₂O₂ photocatalytic process may constitute an important step for further purification processes such as adsorption, membrane processes, etc.     

Elevated CO2 response of photosynthesis depends on ozone concentration in aspen

The effect of elevated CO₂ and O₃ on apparent quantum yield (?), maximum photosynthesis (P_max), carboxylation efficiency (V_cmax) and electron transport capacity (J_max) at different canopy locations was studied in two aspen (Populus tremuloides) clones of contrasting O₃ tolerance. Local light climate at every leaf was characterized as fraction of above-canopy photosynthetic photon flux density (%PPFD). Elevated CO₂ alone did not affect ? or P_max, and increased J_max in the O₃-sensitive, but not in the O₃-tolerant clone. Elevated O₃ decreased leaf chlorophyll content and all photosynthetic parameters, particularly in the lower canopy, and the negative impact of O₃ increased through time. Significant interaction effect, whereby the negative impact of elevated O₃ was exaggerated by elevated CO₂ was seen in Chl, N and J_max, and occurred in both O₃-tolerant and O₃-sensitive clones. The clonal differences in the level of CO₂ × O₃ interaction suggest a relationship between photosynthetic acclimation and background O₃ concentration.     

Advances in understanding ozone impact on forest trees: Messages from novel phytotron and free-air fumigation studies

Recent evidence from novel phytotron and free-air ozone (O₃) fumigation experiments in Europe and America on forest tree species is highlighted in relation to previous chamber studies. Differences in O₃ sensitivity between pioneer and climax species are examined and viewed for trees growing at the harsh alpine timberline ecotone. As O₃ apparently counteracts positive effects of elevated CO₂ and mitigates productivity increases, response is governed by genotype, competitors, and ontogeny rather than species per se. Complexity in O₃ responsiveness increased under the influence of pathogens and herbivores. The new evidence does not conflict in principle with previous findings that, however, pointed to a low ecological significance. This new knowledge on trees' O₃ responsiveness beyond the juvenile stage in plantations and forests nevertheless implies limited predictability due to complexity in biotic and abiotic interactions. Unravelling underlying mechanisms is mandatory for assessing O₃ risks as an important component of climate change scenarios.     

O3/H2O2处理嘧啶废水的研究

采用O3/H2O2法对嘧啶废水进行处理,考察了不同反应条件对嘧啶和COD去除率的影响,并对O3/H2O2降解嘧啶的反应机制和动力学进行了初步探讨.实验结果表明,在pH值为11,反应时间为70 min,O3流量为4g/h,H2O2投加量为50 mmol/L的条件下,废水的嘧啶和COD的去除率分别达到86.46%和74.9...     

Are Bavarian Forests (southern Germany) at risk from ground-level ozone? Assessment using exposure and flux based ozone indices

Exposure and flux-based indices of O₃ risk were compared, at 19 forest locations across Bavaria in southern Germany from 2002 to 2005; leaf symptoms on mature beech trees found at these locations were also examined for O₃ injury. O₃ flux modelling was performed using continuously recorded O₃ concentrations in combination with meteorological and soil moisture data collected from Level II forest sites. O₃ measurements at nearby rural open-field sites proved appropriate as surrogates in cases where O₃ data were lacking at forest sites (with altitude-dependent average differences of about 10% between O₃ concentrations). Operational thresholds of biomass loss for both O₃ indices were exceeded at the majority of the forest locations, suggesting similar risk under long-term average climate conditions. However, exposure-based indices estimated higher O₃ risk during dry years as compared to the flux-based approach. In comparison, minor O₃-like leaf injury symptoms were detected only at a few of the forest sites investigated. Relationships between flux-based risk thresholds and tree response need to be established for mature forest stands for validation of predicted growth reductions under the prevailing O₃ regimes.     

微波辐射Bi2O3/沸石-H2O2体系降解废水中的硝基苯

研究了微波辐射下,以负载于沸石上的三氧化二铋为催化剂,以双氧水为氧化剂的催化氧化体系处理硝基苯工艺。通过单因素实验法,从反应催化剂负载量、pH、双氧水用量、微波功率、反应时间、催化剂用量等方面初步考察了硝基苯在该体系中的催化氧化效果。在氧化铋负载量3%（质量比）,pH=2,2 mL 30%双氧水,火力为中火,催化剂投加量为0.7 g,反应2 min,对降解过程所得的中间产物和终产物进行了分析。结果表明,该体系对硝基苯的去除率能够达到99.2%,COD去除率为73.91%。     

Co3O4/介孔分子筛催化剂对苯催化完全氧化的研究

分别以介孔分子筛MCM-41、MCM-48、SBA-15为载体,采用等体积浸渍法制备了氧化钴/介孔分子筛催化剂,利用N₂吸附、X射线衍射、程序升温还原等技术对催化剂进行了表征,考察了Co₃O₄的负载量及载体的孔结构对催化剂完全催化氧化苯的性能的影响。结果表明,Co₃O₄的负载量为20%时,催化剂的催化活性最好;载体的孔径和催化剂的可还原性能是影响催化活性的主要因素,催化剂活性顺序为Co₃O₄ /SBA-15> Co₃O₄ /MCM41> Co₃O₄ /MCM-48。     

Reductive transformation of 2,4-dichlorophenoxyacetic acid by nanoscale and microscale Fe3O4 particles

Reductive transformation of 2,4-dichlorophenoxyacetic acid (2,4-D) by nanoscale and microscale Fe₃O₄ was investigated and compared. Disappearance of the parent species and formation of reaction intermediates and products were kinetically analyzed. Results suggest that the transformation of 2,4-D followed a primary pathway of its complete reduction to phenol and a secondary pathway of sequential reductive hydrogenolysis to 2,4-dichlorophenol (2,4-DCP), chlorophenol (2-CP, 4-CP) and phenol. About 65% of 2,4-D with initial concentration of 50 μ M was transformed within 48 h in the presence of 300 mg L^?1 nanoscale Fe₃O₄, and the reaction rates increased with increasing dosage of nanoscale Fe₃O₄. The decomposition of 2,4-D proceeded rapidly at optimum pH 3.0. Chloride was identified as a reduction product for 2,4-D in the magnetite–water system. Reductive transformation of 2,4-D by microscale Fe₃O₄ was slower than that by nanoscale Fe₃O₄. The reactions apparently followed pseudo-first-order kinetics with respect to the 2,4-D transformation. The degradation rate of 2,4-D decreased with the increase of initial 2,4-D concentration. In addition, anions had a significant adverse impact on the degradation efficiency of 2,4-D.     

组合方法去除新型采油污水中有机污染物的研究

含聚丙烯酰胺采油污水的有效处理是近年来困扰油田三次采油生产的一个难题。研究采用移动床生物膜技术与O3/UV/H2O2高级氧化技术的组合方法来处理含聚丙烯酰胺采油污水。实验结果表明,移动床生物膜技术可以有效去除污水中的石油类有机物,但对聚丙烯酰胺几乎无效果。O3/UV/H2O2高级氧化技术可以降解污水中的聚丙烯酰胺。组合方法处理后的含聚丙烯酰胺采油污水水质可以达到污水综合排放标准中的一级要求。     

The use of experimental data and their uncertainty for assessing ozone photochemistry in the Eastern Iberian Peninsula

Observation-based methods are useful tools to explore the sensitivity of ozone concentrations to precursor controls. With the aim of assessing the ozone precursor sensitivity in two locations: Paterna (suburban) and Villar del Arzobispo (rural) of the Turia river basin in the east of Spain, the photochemical indicator O₃/NO_y and the Extent-of-Reaction (EOR) parameter have been calculated from field measurements. In Paterna, the O₃/NO_y ratio varied from 0 to 13 with an average value of 5.1 (SD 3.2), whereas the averaged value for the EOR was 0.43 (SD 0.14). In Villar del Arzobispo, the O₃/NO_y ratio changed from 5 to 30 with a mean value of 13.6 (SD 4.7) and the EOR gave an averaged value of 0.72 (SD 0.11). The results show two different patterns of ozone production as a function of the location. The suburban area shows a VOC-sensitive regime whereas the rural one shows a transition regime close to NO_x-sensitive conditions. No seasonal differences in these regimes are observed along the monitoring campaigns. Finally, an analysis of the influence of the measurement quality of NO_y, NO_x and O₃ on the uncertainty of the O₃/NO_y ratio and the EOR was performed showing that the uncertainty of O₃/NO_y is not dependent on either its value or the individual values of O₃ and NO_y but just on the quality of O₃ and NO_y measurements. The maximum uncertainty is 26% as long as the combined uncertainties of O₃ and NO_y remain below the 7.5%. The case of the EOR is different and its uncertainty depends on both the value of the EOR parameter and the individual concentration values of NO_y and NO_x. The uncertainty of the EOR estimation can be very high (>200%) if the combined uncertainties of both NO_y and NO_x are high (>7.5%), or especially, if u(NO_y) and u(NO_x) differ considerably from each other (>3.5%).     

Regional NOx emission inversion through a four-dimensional variational approach using SCIAMACHY tropospheric NO2 column observations

In this paper, the NOx emission scaling factors applied over the 2001 National Emissions Inventory (NEI) are estimated through a four-dimensional variational (4D-Var) approach using SCIAMACHY (Scanning Imaging Absorption spectroMeter for Atmospheric CHartographY) tropospheric NO₂ columns measured during summer 2004. In the “top-down” approach, two-month average NO₂ columns are assimilated into a regional chemical transport model (CTM), STEM, using different assimilation setups. In a basic setup, NOx emissions are adjusted by assimilating the NO₂ columns. A more general setup of emission inversion allows the initial O₃ concentrations be adjusted along with the NOx emissions. A final case is set up to assimilate both the NO₂ columns and O₃ measurement from various platforms while allowing adjustments of both the NOx emissions and the initial O₃ concentrations. It is found that the addition of O₃ measurements did not improve the NOx emission inversion. With the NOx emission at surface and upper levels being adjusted separately, results from four cases show that the elevated NOx emission reduction ranges from 8.9% to 11.4%, and the surface NOx emission reduction is up to 6.6%. All the cases show NOx emission reduction in Ohio valley and Washington, District of Columbia areas.     

超声波协同H_2O_2处理养殖场污水

为了有效地改善养猪场污水的质量,以H2O2为药剂,对污水进行了水浴加热和超声波辅助的对比实验,考察了超声波发生器输出端电流强度、处理时间、H2O2用量对污水的COD、氨气及颜色的影响,并进行正交实验优化。结果表明,超声波协同H2O2处理养殖污水是一种切实可行的方法,超声波协同H2O2处理污水的最佳工艺条件:电流0.7 A、处理时间2 min、H2O2用量3%,在此条件下降低COD量可达95%以上,氨氮的含量可降至14~15 mg/L,氨臭味大大得到了改善,并将原污水由黑色变为浅黄色。     

臭氧辅助UV/Fenton法处理电镀添加剂生产废水

采用臭氧辅助光芬顿法处理电镀添加剂生产废水,考察双氧水、FeSO₄·7H₂O、pH和反应时间等因素对废水COD和UV₂₅₄去除的影响。实验结果表明,pH=4,臭氧通入量为0.25 g,双氧水的投加量93.3 mL/L,FeSO₄·7H₂O投加量为5.3 g/L,最佳反应时间为30 min,COD和UV₂₅₄去除率分别达到92.64%和87.95%。这表明,臭氧辅助光芬顿法对电镀添加剂生产废水处理效果显著,处理时间大大减少。     

Effectiveness evaluation of glyphosate oxidation employing the H2O2/UVC process: Toxicity assays with Vibrio fischeri and Rhinella arenarum tadpoles

The H₂O₂/UVC process was applied to the photodegradation of a commercial formulation of glyphosate in water. Two organisms (Vibrio fischeri bacteria and Rhinella arenarum tadpoles) were used to investigate the toxicity of glyphosate in samples M_1, M₂, and M₃ following different photodegradation reaction times (120, 240 and 360 min, respectively) that had differing amounts of residual H₂O₂. Subsamples of M₁, M₂, and M₃ were then used to create samples M_1,E, M_2,E and M_3,E in which the H₂O₂ had been removed. Acetylcholinesterase (AChE) and butyrylcholinesterase (BChE) activities were measured in tadpoles to determine possible sub-lethal effects. In V. fischeri, M_1,E, which was collected early in the photodegradation process, caused 52% inhibition, while M_3,E, which was collected at the end of the photodegradation process, caused only 17% inhibition. Survival of tadpoles was 100% in samples M₂, M₃, and in M_1,E, M_2,E and M_3,E. The lowest percentages of enzymatic inhibition were observed in samples without removal of H₂O₂: 13.96% (AChE) and 16% (BChE) for M₂, and 24.12% (AChE) and 13.83% (BChE) for M₃. These results show the efficiency of the H₂O₂/UVC process in reducing the toxicity of water or wastewater polluted by commercial formulations of glyphosate. According to the ecotoxicity assays, the conditions corresponding to M₂ (11 ± 1 mg a.e. L^?1 glyphosate and 11 ± 1 mg L^?1 H₂O₂) could be used as a final point for glyphosate treatment with the H₂O₂/UV process.